Research ArticleSynthesis X-Ray Crystallography Thermal Analysis and DFTStudies of Ni(II) Complex with 1-Vinylimidazole Ligand
Fatih Fen1 Ramazan Fahin2 Muharrem Dinccediler3 Oumlmer Andaccedil2 and Murat TaG4
1 Department of Opticianry Vocational High School of Health Services Kilis 7 Aralık University 79000 Kilis Turkey2Department of Chemistry Arts and Sciences Faculty Ondokuz Mayıs University 55139 Samsun Turkey3 Department of Physics Arts and Sciences Faculty Ondokuz Mayıs University 55139 Samsun Turkey4Department of Chemistry Arts and Sciences Faculty Giresun University 28100 Giresun Turkey
Correspondence should be addressed to Fatih Sen fatihsen55gmailcom
Received 12 September 2013 Revised 23 December 2013 Accepted 11 January 2014 Published 14 April 2014
Academic Editor Hasan Kucukbay
Copyright copy 2014 Fatih Sen et alThis is an open access article distributed under the Creative CommonsAttribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
The paper presents a combined experimental and computational study of hexa(1-vinylimidazole)Ni(II) perchlorate complex Thecomplex was prepared in the laboratory and crystallized in the monoclinic space group P21n with 119886 = 8442(5) 119887 = 13686(8)119888 = 16041(9) A 120572 = 120574 = 90 120573 = 96638(5) and 119885 = 1 The complex has been characterized structurally (by single-crystal X-Raydiffraction) and its molecular structure in the ground state has been calculated using the density functional theory (DFT) methodswith 6-31G(d) and LanL2DZbasis setsThermal behaviour and stability of the complexwere studied byTGADTAanalyses Besidesthe nonlinear optical effects (NLO) molecular electrostatic potential (MEP) frontier molecular orbitals (FMO) and the Mullikencharge distribution were investigated theoretically
1 Introduction
Imidazole was first reported in 1858 although various imi-dazole derivatives had been discovered as early as the 1840s[1] Derivatives of imidazole represent a class of heterocycliccompounds of great importance Both imidazole and itsderivatives have found widespread applications in industryand pharmacy [2ndash5] For example imidazole has been usedextensively as a corrosion inhibitor on certain transitionmetals such as copper in industry [1] and also the substitutedimidazole derivatives are valuable in treatment of manysystemic fungal infections in pharmacy [6] The imidazoleligand is of particular interest due to its important role inmany biological systems especially as the side group inhistidine which plays an essential role in the active motif ofmany enzymes [7] Imidazole in polymers has traditionallybeen utilized in a variety of applications such as immobilizedcatalysts [8 9] redox reactions [10] water purification [11 12]hydrometallurgymetal recovery [13 14] and ion and protonconductors [15]
Imidazoles are useful ligands in coordination chemistryand the synthesis of the compounds containing the imidazolering is an important area of scientific investigation [16ndash19] Numerous complexes derived from 119889-block metals andimidazole ligands are well known [7] A large numberof investigations on the complexation of copper(II) withimidazole ligands and vinylimidazole ligands have beenreported with some of them reporting structures determinedcrystallographically [20] The title compound is a novelcomplex firstly synthesized by us
Determination of the structural and spectroscopic prop-erties of compounds using both experimental techniques andtheoretical methods has attracted interest for many years Inrecent years among the computational methods calculatingthe electronic structure of molecular systems DFT has beenthe favorite one due to its great accuracy in reproducingthe experimental values of in molecule geometry vibrationalfrequencies atomic charges dipole moment and so forth[21 22]
Hindawi Publishing CorporationJournal of CrystallographyVolume 2014 Article ID 856498 9 pageshttpdxdoiorg1011552014856498
2 Journal of Crystallography
In this present study hexa(1-vinylimidazole)Ni(II) per-chlorate has been investigated both experimentally and the-oretically In experimental study the complex was synthe-sized and characterized by single-crystal X-ray diffractionmethods In theoretical study the geometric parameters ofthe title complex in the ground state have been calculatedusing the density functional method (DFT) (UB3LYP) with6-31G(d) and LanL2DZ basis sets The calculated optimizedstructures were compared with their X-ray structure Itwas noted here that the experimental results belong tosolid phase and theoretical calculations belong to gaseousphase In the solid state the existence of the crystal fieldalong with the intermolecular interactions has connected themolecules together which result in the differences of bondparameters between the calculated and experimental values[23]
(ClO4)2 1-vinylimidazole and ethanol were purchased from
commercial sources and used without further purificationPerkin Elmer Diamond TGDTA thermal analyzer was usedto record simultaneous TG DTG and DTA curves in thestatic air atmosphere at a heating rate of 10 Kmin 21 in thetemperature range 30ndash750∘C using platinum crucibles
22 Synthesis Nickel(II) perchlorate hexahydrate (036 g10mmol) was dissolved in 20mL ethanol and 1-vinylimida-zole (056 g 60mmol) was added slowly The mixturewas stirred for 1 h filtered and left for crystallizationSingle crystals of hexa(1-vinylimidazole)Ni(II) perchloratesuitable for X-ray analysis were obtained after one week(yield 56)
23 Crystal Structure Analysis Diffraction data for com-plex was collected on Agilent Diffraction SuperNova (sin-gle source at offset) Eos diffractometer using graphitemonochromated Mo Ka radiation (120582 = 071073 A) at 296KThe structure was solved by direct methods using SHELXS-97 [24] and implemented in the WinGX [25] programsuite The refinement was carried out by full-matrix least-squares method on the positional and anisotropic tempera-ture parameters of the nonhydrogen atoms or equivalentlycorresponding to 241 crystallographic parameters usingSHELXL-97 [26] All H atoms were positioned geometricallyand treated using a riding model fixing the bond lengthsat 086 093 097 and 096 A for NH CH and CH
2atoms
respectively All otherH atomswere positioned geometricallyand refined with a riding model with Uiso 12 times that ofattached atoms Data collection is by CrysAlis PRO [27]cell refinement by CrysAlis RED [28] and data reductionby CrysAlis RED [28] The general-purpose crystallographictool PLATON [29] was used for the structure analysis andpresentation of the results Details of the data collectionconditions and the parameters of the refinement process aregiven in Table 1
Table 1 Crystal data and structure refinement parameters for thetitle complex
Chemical formula C30H36N12Ni 2(ClO4)Formula weight 82232Temperature (K) 296Wavelength (A) 071073MoK120572Crystal system MonoclinicSpace group P 21nUnit cell parameters119886 = 119887 = 119888 (A) 8442(5) 13686(8) 16041(9)120573 (∘) 96638(5)Volume (A3) 184085(18)119885 1Calculated density (Mgm3) 1484120583 (mmminus1) 074119879min 119879max 0882 1119865000
852Crystal size (mm) 01 times 01 times 01
ℎmin ℎmax minus6 10119896min 119896max minus16 14119897min 119897max minus19 19Theta range for data collection (∘) 32 le 120579 le 26
Measured reflections 7193Independentobserved reflections 3525Refinement method Full-matrix least-squares on 1198652
119908119877(1198652) 0119
119877int 0036Δ120588max Δ120588min (eA
3) 051 minus028
24 Computational Procedures All the calculations wereperformed by using Gaussian 03 package [30] and Gauss-View molecular visualization programs [31] on the personalcomputer without restricting any symmetry for the titlecomplex For modeling the initial guess of the complex wasfirst obtained from the X-ray coordinates The molecularstructure of the title complex in the ground state (in vacuo) isoptimized by UB3LYPmethods with 6-31G(d) and LanL2DZbasis sets Besides the nonlinear optical effects themolecularelectrostatic potential (MEP) frontier molecular orbitals(FMO) and the Mulliken population analysis of the titlecomplex were determined by theoretical calculation results
3 Results and Discussion
31 Structural Description of the Complex The title complexa ORTEP-3 [32] view of which is shown in Figure 1 iscrystallizing in the monoclinic space group P21n with fourmolecules in unit cell The asymmetric unit in the crystalstructure contains the Ni(II) that is a cation perchlorateanions and six 1-vinylimidazole molecules The Ni(II) atomdisplays a Jahn-Teller distorted octahedral coordinationgeometry with six N atoms from six 1-vinylimidazole ligandsin the equatorial plane and in axial positions NindashN1 NindashN3 and NindashN5 bond lengths are 2110(3) A 2129(3) Aand 2125(3) A respectively These NindashN bond lengths are
Journal of Crystallography 3
C1
N1
Ni1
C2C3
C4
C5C6C7
C8C9
C10
C11
C12
C13
C14C15
N2 N3
N4
N5
N6
Figure 1 An ORTEP view of the title complex with the atomicnumbering scheme Displacement ellipsoids are shown at the 30probability level
minus119909 minus119910 + 1 minus119911 + 1Cg1 is the centroid of the imidazole (N5 N6 C11ndashC13) ring
comparable with those reported by [33 34] When the bondlengths and angles of the imidazole rings in the title complexare compared with literature [35] it is seen that there are nosignificant differences
The crystal packing is stabilized by a single intermolecularCndashHsdot sdot sdotO hydrogen-bonding interaction (Table 2 Figure 2)giving a view of the crystal structure of complex approxi-mately along the a axis Also in the structure there is a C2ndashH2sdot sdot sdot 120587 interaction between the C2 atom and imidazole (N5N6 C11ndashC13) ring (symmetry code (b)minus119909minus119910+1 andminus119911+1)The distance of atom C2 between the centroids of these ringsis 346A
32 Magnetic Properties and Thermal Analysis Magneticmoment determined for the hexa(1-vinylimidazole)Ni(II)perchlorate complex at room temperature is 290 BM Thesevalues are characteristic of high-spin octahedral complexes ofmetals [36]
The thermal decomposition behavior of the complex wasfollowed up to 750∘C in a static air atmosphere The complexis thermally stable up to 178∘C The results of TGADTAcurves of complex are illustrated in Figure 3 The TG curvesexhibit a continuous mass loss Therefore it was almostimpossible to calculate mass loss value for each step Thestages of the temperature range of 178ndash590∘C are relatedto the repeatedly decomposition of the six 1-vinylimidazole
Ni
N
N
NN
N
NN
N
N
N
N
N
2+
2 middot [ClO4minus]
Scheme 1 The chemical diagram of the title complex
ligands by giving both endo- and exothermic effects Themass loss calculations suggest that the remainder is left asa final product NiO is the end product (Teo 111 exp122)
33 Quantum Chemical Computational Studies
331 Theoretical Structures The molecular structure ofthe title complex was also investigated theoretically seeScheme 1The starting coordinates were those obtained fromthe X-ray structure determination and in the ground state(in vacuo) was optimized using DFT(UB3LYP) with the 6-31G(d) and LanL2DZ basis sets However it should not beforgotten in here that the experimental results belong to solidphase and theoretical calculations belong to gaseous phaseThe optimized molecular structure of the title molecule wasobtained from Gaussian 03 program as shown in Figure 4The molecular structure of the complex belongs to C1 pointgroup symmetry with 89 atoms composing the structureRandomly selected geometric parameters (bond length bondangle and torsion angles) were experimentally obtained andtheoretically calculated by UB3LYP methods with basis setslisted in Table 3 And these selected parameters are comparedwith their experimental data Correlation values (1198772) are09949 and 09881 for bond lengths 09522 and 09994for bond angles and 01988 and 01043 for torsion anglesrespectively Consequently according to correlations valuesfor the bond length and torsion angle the 6-31G(d) basis setmethod is more useful than the LanL2DZ basis set methodConversely for bond angles the LanL2DZ basis set methodis more useful than the 6-31G(d) basis set method
A logical method for globally comparing the structuresobtained with the theoretical calculations is by superimpos-ing the molecular skeleton with that obtained from X-raydiffraction giving RMSEs of 0084 and 0071 A for the samemethods respectively As a result 6-31G(d) correlates a littlewell with the geometrical parameters when compared withLANL2Z method (Figure 5)
4 Journal of Crystallography
Table 3 Randomly selected geometric parameters (A ∘)
332 Nonlinear Optical Effects Nonlinear optical (NLO)effects arise from the interactions of electromagnetic fieldsin various media to produce new fields altered in phasefrequency amplitude or other propagation characteristicsfrom the incident fields [37] In the recent years because ofpotential applications inmodern communication technologydata storage telecommunication and optical signal process-ing a large number of research papers in new materialsexhibiting efficient nonlinear optical (NLO) properties havebeen of great interest [38ndash42]
The calculations of the mean linear polarizability (120572tot)and the mean first hyperpolarizability (120573tot) from the Gaus-sian output have been explained in detail previously andDFT has been extensively used as an effective method toinvestigate the organic NLO materials [43] The values of thepolarizability120572 and the first hyperpolarizability120573 ofGaussian
03 output are reported in atomic units (au) so the calculatedvalues have been converted into electrostatic units (esu) (1205721 au = 01482 times 10minus24 esu 120573 1 au = 86393 times 10minus33 esu)
The total molecular dipole moment (120583tot) linear polar-izability (120572tot) and first-order hyperpolarizability (120573tot) ofthe title compound were calculated with the UB3LYP6-31G(d) and UB3LYPLanL2DZ methods The calculated val-ues of 120583tot 120572tot and 120573tot are 2939D 5995A3 and 698610minus30 cm5esu for UB3LYP6-31G(d) and 3958D 6552A3and 2781 10minus30 cm5esu for UB3LYPLanL2DZ respectivelyUrea is one of the prototypical molecules used in the studyof the NLO properties of molecular systems Therefore itwas used frequently as a threshold value for comparativepurposes Theoretically the first-order hyperpolarizabilityof the title compound is of 12 and 144 times magnitudeof urea at the same levels respectively According to theseresults the title compound is a good candidate of NLOmaterial
333 Molecular Electrostatic Potential The molecular elec-trostatic potential (MEP) is related to the electronic densityand is a very useful descriptor in understanding sites forelectrophilic attack and nucleophilic reactions as well ashydrogen-bonding interactions [44ndash46]
The molecular electrostatic potential 119881(119903) at a givenpoint 119903(119909 119910 119911) in the vicinity of a molecule is definedin terms of the interaction energy between the electricalcharge generated from the molecule electrons and nucleiand a positive test charge (a proton) located at 119903 For thesystem studied the 119881(119903) values were calculated as describedpreviously using the following [47]
where 119885119860is the charge of nucleus A located at 119877
119860 120588(1199031015840) is
the electronic density function of the molecule and 1199031015840 is thedummy integration variable Being a real physical property119881(119903) can be determined experimentally by diffraction or bycomputational methods [48] To predict reactive sites forelectrophilic and nucleophilic attack for the title moleculeMEP was calculated at the 6-31G(d) and LanL2DZ optimizedgeometries The negative (red) regions of MEP were relatedto electrophilic reactivity and the positive (blue) regions tonucleophilic reactivity shown in Figure 6 As can be seenfrom the figure there is one possible site on the title complexfor electrophilic attack The negative region is localised onthe carbon atom of the imidazole ring C13 with a maximumvalue of minus0049 and minus0064 au for UB3LYP6-31G(d) andUB3LYPLanL2DZ basis sets These results provide informa-tion concerning the region where the complex can interactintermolecularly and bond metallically Therefore Figure 6confirms the existence of an intermolecular C13ndashH13sdot sdot sdotO2interaction between theO atoms perchlorate ion andC atomsof the imidazole ring
Journal of Crystallography 5
0
a
b
c
Figure 2 Part of the crystal packing of the title complex For clarity hydrogen atoms and hydrogen bonds are not shown
334 HOMO-LUMO Analysis The highest occupied molec-ular orbital (HOMO) and the lowest lying unoccupiedmolec-ular orbital (LUMO) are named as frontier molecular orbitals(FMO)
The distributions and energy levels of the HOMO andLUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ level for the title complex are shown inFigure 7 The calculations indicate that the title complex has89 and 84 occupied molecular orbitals and the value of the
energy separation between the HOMO and LUMO are minus15and minus114 eV for at the same levels respectively
A molecule with a small frontier orbital gap is morepolarizable and is generally associated with a high chemicalreactivity and low kinetic stability and is also termed as softmolecule [49] The HOMO and LUMO energies the energygap (Δ119864) the ionization potential (119868) the electron affinity(119860) the absolute electronegativity (120594) the absolute hardness(120578) and softness (119878) for molecule have been calculated at
6 Journal of Crystallography
1000
900
800
700
600
500
400
300
200
100
4000
3500
3000
2500
2000
1500
1000
500
000
minus500
minus1000
minus1500
1000 2000 3000 4000 5000 6000 7000
7000
6000
5000
4000
3000
2000
1000
0000
minus1000
minus2000
DD
TA (120583
V∘
C)
Temperature (∘C)
TG (
)
DTG
(120583g
∘ C)
Figure 3 TGADTA curves of complex
Ni
(a)
Ni
(b)
Figure 4 The theoretical geometric structures of the title compound ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ)
(a) (b)
Figure 5 Atom-by-atom superimposition of the structures calculated (red) ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ) on the X-raystructure (yellow) of the title complex Hydrogen atoms have been omitted for clarity
Journal of Crystallography 7
UB3LYPLanL2DZ
UB3LYP6-31G(d)minus0049
minus0064
0049
0064
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
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[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
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[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
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[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
In this present study hexa(1-vinylimidazole)Ni(II) per-chlorate has been investigated both experimentally and the-oretically In experimental study the complex was synthe-sized and characterized by single-crystal X-ray diffractionmethods In theoretical study the geometric parameters ofthe title complex in the ground state have been calculatedusing the density functional method (DFT) (UB3LYP) with6-31G(d) and LanL2DZ basis sets The calculated optimizedstructures were compared with their X-ray structure Itwas noted here that the experimental results belong tosolid phase and theoretical calculations belong to gaseousphase In the solid state the existence of the crystal fieldalong with the intermolecular interactions has connected themolecules together which result in the differences of bondparameters between the calculated and experimental values[23]
(ClO4)2 1-vinylimidazole and ethanol were purchased from
commercial sources and used without further purificationPerkin Elmer Diamond TGDTA thermal analyzer was usedto record simultaneous TG DTG and DTA curves in thestatic air atmosphere at a heating rate of 10 Kmin 21 in thetemperature range 30ndash750∘C using platinum crucibles
22 Synthesis Nickel(II) perchlorate hexahydrate (036 g10mmol) was dissolved in 20mL ethanol and 1-vinylimida-zole (056 g 60mmol) was added slowly The mixturewas stirred for 1 h filtered and left for crystallizationSingle crystals of hexa(1-vinylimidazole)Ni(II) perchloratesuitable for X-ray analysis were obtained after one week(yield 56)
23 Crystal Structure Analysis Diffraction data for com-plex was collected on Agilent Diffraction SuperNova (sin-gle source at offset) Eos diffractometer using graphitemonochromated Mo Ka radiation (120582 = 071073 A) at 296KThe structure was solved by direct methods using SHELXS-97 [24] and implemented in the WinGX [25] programsuite The refinement was carried out by full-matrix least-squares method on the positional and anisotropic tempera-ture parameters of the nonhydrogen atoms or equivalentlycorresponding to 241 crystallographic parameters usingSHELXL-97 [26] All H atoms were positioned geometricallyand treated using a riding model fixing the bond lengthsat 086 093 097 and 096 A for NH CH and CH
2atoms
respectively All otherH atomswere positioned geometricallyand refined with a riding model with Uiso 12 times that ofattached atoms Data collection is by CrysAlis PRO [27]cell refinement by CrysAlis RED [28] and data reductionby CrysAlis RED [28] The general-purpose crystallographictool PLATON [29] was used for the structure analysis andpresentation of the results Details of the data collectionconditions and the parameters of the refinement process aregiven in Table 1
Table 1 Crystal data and structure refinement parameters for thetitle complex
Chemical formula C30H36N12Ni 2(ClO4)Formula weight 82232Temperature (K) 296Wavelength (A) 071073MoK120572Crystal system MonoclinicSpace group P 21nUnit cell parameters119886 = 119887 = 119888 (A) 8442(5) 13686(8) 16041(9)120573 (∘) 96638(5)Volume (A3) 184085(18)119885 1Calculated density (Mgm3) 1484120583 (mmminus1) 074119879min 119879max 0882 1119865000
852Crystal size (mm) 01 times 01 times 01
ℎmin ℎmax minus6 10119896min 119896max minus16 14119897min 119897max minus19 19Theta range for data collection (∘) 32 le 120579 le 26
Measured reflections 7193Independentobserved reflections 3525Refinement method Full-matrix least-squares on 1198652
119908119877(1198652) 0119
119877int 0036Δ120588max Δ120588min (eA
3) 051 minus028
24 Computational Procedures All the calculations wereperformed by using Gaussian 03 package [30] and Gauss-View molecular visualization programs [31] on the personalcomputer without restricting any symmetry for the titlecomplex For modeling the initial guess of the complex wasfirst obtained from the X-ray coordinates The molecularstructure of the title complex in the ground state (in vacuo) isoptimized by UB3LYPmethods with 6-31G(d) and LanL2DZbasis sets Besides the nonlinear optical effects themolecularelectrostatic potential (MEP) frontier molecular orbitals(FMO) and the Mulliken population analysis of the titlecomplex were determined by theoretical calculation results
3 Results and Discussion
31 Structural Description of the Complex The title complexa ORTEP-3 [32] view of which is shown in Figure 1 iscrystallizing in the monoclinic space group P21n with fourmolecules in unit cell The asymmetric unit in the crystalstructure contains the Ni(II) that is a cation perchlorateanions and six 1-vinylimidazole molecules The Ni(II) atomdisplays a Jahn-Teller distorted octahedral coordinationgeometry with six N atoms from six 1-vinylimidazole ligandsin the equatorial plane and in axial positions NindashN1 NindashN3 and NindashN5 bond lengths are 2110(3) A 2129(3) Aand 2125(3) A respectively These NindashN bond lengths are
Journal of Crystallography 3
C1
N1
Ni1
C2C3
C4
C5C6C7
C8C9
C10
C11
C12
C13
C14C15
N2 N3
N4
N5
N6
Figure 1 An ORTEP view of the title complex with the atomicnumbering scheme Displacement ellipsoids are shown at the 30probability level
minus119909 minus119910 + 1 minus119911 + 1Cg1 is the centroid of the imidazole (N5 N6 C11ndashC13) ring
comparable with those reported by [33 34] When the bondlengths and angles of the imidazole rings in the title complexare compared with literature [35] it is seen that there are nosignificant differences
The crystal packing is stabilized by a single intermolecularCndashHsdot sdot sdotO hydrogen-bonding interaction (Table 2 Figure 2)giving a view of the crystal structure of complex approxi-mately along the a axis Also in the structure there is a C2ndashH2sdot sdot sdot 120587 interaction between the C2 atom and imidazole (N5N6 C11ndashC13) ring (symmetry code (b)minus119909minus119910+1 andminus119911+1)The distance of atom C2 between the centroids of these ringsis 346A
32 Magnetic Properties and Thermal Analysis Magneticmoment determined for the hexa(1-vinylimidazole)Ni(II)perchlorate complex at room temperature is 290 BM Thesevalues are characteristic of high-spin octahedral complexes ofmetals [36]
The thermal decomposition behavior of the complex wasfollowed up to 750∘C in a static air atmosphere The complexis thermally stable up to 178∘C The results of TGADTAcurves of complex are illustrated in Figure 3 The TG curvesexhibit a continuous mass loss Therefore it was almostimpossible to calculate mass loss value for each step Thestages of the temperature range of 178ndash590∘C are relatedto the repeatedly decomposition of the six 1-vinylimidazole
Ni
N
N
NN
N
NN
N
N
N
N
N
2+
2 middot [ClO4minus]
Scheme 1 The chemical diagram of the title complex
ligands by giving both endo- and exothermic effects Themass loss calculations suggest that the remainder is left asa final product NiO is the end product (Teo 111 exp122)
33 Quantum Chemical Computational Studies
331 Theoretical Structures The molecular structure ofthe title complex was also investigated theoretically seeScheme 1The starting coordinates were those obtained fromthe X-ray structure determination and in the ground state(in vacuo) was optimized using DFT(UB3LYP) with the 6-31G(d) and LanL2DZ basis sets However it should not beforgotten in here that the experimental results belong to solidphase and theoretical calculations belong to gaseous phaseThe optimized molecular structure of the title molecule wasobtained from Gaussian 03 program as shown in Figure 4The molecular structure of the complex belongs to C1 pointgroup symmetry with 89 atoms composing the structureRandomly selected geometric parameters (bond length bondangle and torsion angles) were experimentally obtained andtheoretically calculated by UB3LYP methods with basis setslisted in Table 3 And these selected parameters are comparedwith their experimental data Correlation values (1198772) are09949 and 09881 for bond lengths 09522 and 09994for bond angles and 01988 and 01043 for torsion anglesrespectively Consequently according to correlations valuesfor the bond length and torsion angle the 6-31G(d) basis setmethod is more useful than the LanL2DZ basis set methodConversely for bond angles the LanL2DZ basis set methodis more useful than the 6-31G(d) basis set method
A logical method for globally comparing the structuresobtained with the theoretical calculations is by superimpos-ing the molecular skeleton with that obtained from X-raydiffraction giving RMSEs of 0084 and 0071 A for the samemethods respectively As a result 6-31G(d) correlates a littlewell with the geometrical parameters when compared withLANL2Z method (Figure 5)
4 Journal of Crystallography
Table 3 Randomly selected geometric parameters (A ∘)
332 Nonlinear Optical Effects Nonlinear optical (NLO)effects arise from the interactions of electromagnetic fieldsin various media to produce new fields altered in phasefrequency amplitude or other propagation characteristicsfrom the incident fields [37] In the recent years because ofpotential applications inmodern communication technologydata storage telecommunication and optical signal process-ing a large number of research papers in new materialsexhibiting efficient nonlinear optical (NLO) properties havebeen of great interest [38ndash42]
The calculations of the mean linear polarizability (120572tot)and the mean first hyperpolarizability (120573tot) from the Gaus-sian output have been explained in detail previously andDFT has been extensively used as an effective method toinvestigate the organic NLO materials [43] The values of thepolarizability120572 and the first hyperpolarizability120573 ofGaussian
03 output are reported in atomic units (au) so the calculatedvalues have been converted into electrostatic units (esu) (1205721 au = 01482 times 10minus24 esu 120573 1 au = 86393 times 10minus33 esu)
The total molecular dipole moment (120583tot) linear polar-izability (120572tot) and first-order hyperpolarizability (120573tot) ofthe title compound were calculated with the UB3LYP6-31G(d) and UB3LYPLanL2DZ methods The calculated val-ues of 120583tot 120572tot and 120573tot are 2939D 5995A3 and 698610minus30 cm5esu for UB3LYP6-31G(d) and 3958D 6552A3and 2781 10minus30 cm5esu for UB3LYPLanL2DZ respectivelyUrea is one of the prototypical molecules used in the studyof the NLO properties of molecular systems Therefore itwas used frequently as a threshold value for comparativepurposes Theoretically the first-order hyperpolarizabilityof the title compound is of 12 and 144 times magnitudeof urea at the same levels respectively According to theseresults the title compound is a good candidate of NLOmaterial
333 Molecular Electrostatic Potential The molecular elec-trostatic potential (MEP) is related to the electronic densityand is a very useful descriptor in understanding sites forelectrophilic attack and nucleophilic reactions as well ashydrogen-bonding interactions [44ndash46]
The molecular electrostatic potential 119881(119903) at a givenpoint 119903(119909 119910 119911) in the vicinity of a molecule is definedin terms of the interaction energy between the electricalcharge generated from the molecule electrons and nucleiand a positive test charge (a proton) located at 119903 For thesystem studied the 119881(119903) values were calculated as describedpreviously using the following [47]
where 119885119860is the charge of nucleus A located at 119877
119860 120588(1199031015840) is
the electronic density function of the molecule and 1199031015840 is thedummy integration variable Being a real physical property119881(119903) can be determined experimentally by diffraction or bycomputational methods [48] To predict reactive sites forelectrophilic and nucleophilic attack for the title moleculeMEP was calculated at the 6-31G(d) and LanL2DZ optimizedgeometries The negative (red) regions of MEP were relatedto electrophilic reactivity and the positive (blue) regions tonucleophilic reactivity shown in Figure 6 As can be seenfrom the figure there is one possible site on the title complexfor electrophilic attack The negative region is localised onthe carbon atom of the imidazole ring C13 with a maximumvalue of minus0049 and minus0064 au for UB3LYP6-31G(d) andUB3LYPLanL2DZ basis sets These results provide informa-tion concerning the region where the complex can interactintermolecularly and bond metallically Therefore Figure 6confirms the existence of an intermolecular C13ndashH13sdot sdot sdotO2interaction between theO atoms perchlorate ion andC atomsof the imidazole ring
Journal of Crystallography 5
0
a
b
c
Figure 2 Part of the crystal packing of the title complex For clarity hydrogen atoms and hydrogen bonds are not shown
334 HOMO-LUMO Analysis The highest occupied molec-ular orbital (HOMO) and the lowest lying unoccupiedmolec-ular orbital (LUMO) are named as frontier molecular orbitals(FMO)
The distributions and energy levels of the HOMO andLUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ level for the title complex are shown inFigure 7 The calculations indicate that the title complex has89 and 84 occupied molecular orbitals and the value of the
energy separation between the HOMO and LUMO are minus15and minus114 eV for at the same levels respectively
A molecule with a small frontier orbital gap is morepolarizable and is generally associated with a high chemicalreactivity and low kinetic stability and is also termed as softmolecule [49] The HOMO and LUMO energies the energygap (Δ119864) the ionization potential (119868) the electron affinity(119860) the absolute electronegativity (120594) the absolute hardness(120578) and softness (119878) for molecule have been calculated at
6 Journal of Crystallography
1000
900
800
700
600
500
400
300
200
100
4000
3500
3000
2500
2000
1500
1000
500
000
minus500
minus1000
minus1500
1000 2000 3000 4000 5000 6000 7000
7000
6000
5000
4000
3000
2000
1000
0000
minus1000
minus2000
DD
TA (120583
V∘
C)
Temperature (∘C)
TG (
)
DTG
(120583g
∘ C)
Figure 3 TGADTA curves of complex
Ni
(a)
Ni
(b)
Figure 4 The theoretical geometric structures of the title compound ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ)
(a) (b)
Figure 5 Atom-by-atom superimposition of the structures calculated (red) ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ) on the X-raystructure (yellow) of the title complex Hydrogen atoms have been omitted for clarity
Journal of Crystallography 7
UB3LYPLanL2DZ
UB3LYP6-31G(d)minus0049
minus0064
0049
0064
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
minus119909 minus119910 + 1 minus119911 + 1Cg1 is the centroid of the imidazole (N5 N6 C11ndashC13) ring
comparable with those reported by [33 34] When the bondlengths and angles of the imidazole rings in the title complexare compared with literature [35] it is seen that there are nosignificant differences
The crystal packing is stabilized by a single intermolecularCndashHsdot sdot sdotO hydrogen-bonding interaction (Table 2 Figure 2)giving a view of the crystal structure of complex approxi-mately along the a axis Also in the structure there is a C2ndashH2sdot sdot sdot 120587 interaction between the C2 atom and imidazole (N5N6 C11ndashC13) ring (symmetry code (b)minus119909minus119910+1 andminus119911+1)The distance of atom C2 between the centroids of these ringsis 346A
32 Magnetic Properties and Thermal Analysis Magneticmoment determined for the hexa(1-vinylimidazole)Ni(II)perchlorate complex at room temperature is 290 BM Thesevalues are characteristic of high-spin octahedral complexes ofmetals [36]
The thermal decomposition behavior of the complex wasfollowed up to 750∘C in a static air atmosphere The complexis thermally stable up to 178∘C The results of TGADTAcurves of complex are illustrated in Figure 3 The TG curvesexhibit a continuous mass loss Therefore it was almostimpossible to calculate mass loss value for each step Thestages of the temperature range of 178ndash590∘C are relatedto the repeatedly decomposition of the six 1-vinylimidazole
Ni
N
N
NN
N
NN
N
N
N
N
N
2+
2 middot [ClO4minus]
Scheme 1 The chemical diagram of the title complex
ligands by giving both endo- and exothermic effects Themass loss calculations suggest that the remainder is left asa final product NiO is the end product (Teo 111 exp122)
33 Quantum Chemical Computational Studies
331 Theoretical Structures The molecular structure ofthe title complex was also investigated theoretically seeScheme 1The starting coordinates were those obtained fromthe X-ray structure determination and in the ground state(in vacuo) was optimized using DFT(UB3LYP) with the 6-31G(d) and LanL2DZ basis sets However it should not beforgotten in here that the experimental results belong to solidphase and theoretical calculations belong to gaseous phaseThe optimized molecular structure of the title molecule wasobtained from Gaussian 03 program as shown in Figure 4The molecular structure of the complex belongs to C1 pointgroup symmetry with 89 atoms composing the structureRandomly selected geometric parameters (bond length bondangle and torsion angles) were experimentally obtained andtheoretically calculated by UB3LYP methods with basis setslisted in Table 3 And these selected parameters are comparedwith their experimental data Correlation values (1198772) are09949 and 09881 for bond lengths 09522 and 09994for bond angles and 01988 and 01043 for torsion anglesrespectively Consequently according to correlations valuesfor the bond length and torsion angle the 6-31G(d) basis setmethod is more useful than the LanL2DZ basis set methodConversely for bond angles the LanL2DZ basis set methodis more useful than the 6-31G(d) basis set method
A logical method for globally comparing the structuresobtained with the theoretical calculations is by superimpos-ing the molecular skeleton with that obtained from X-raydiffraction giving RMSEs of 0084 and 0071 A for the samemethods respectively As a result 6-31G(d) correlates a littlewell with the geometrical parameters when compared withLANL2Z method (Figure 5)
4 Journal of Crystallography
Table 3 Randomly selected geometric parameters (A ∘)
332 Nonlinear Optical Effects Nonlinear optical (NLO)effects arise from the interactions of electromagnetic fieldsin various media to produce new fields altered in phasefrequency amplitude or other propagation characteristicsfrom the incident fields [37] In the recent years because ofpotential applications inmodern communication technologydata storage telecommunication and optical signal process-ing a large number of research papers in new materialsexhibiting efficient nonlinear optical (NLO) properties havebeen of great interest [38ndash42]
The calculations of the mean linear polarizability (120572tot)and the mean first hyperpolarizability (120573tot) from the Gaus-sian output have been explained in detail previously andDFT has been extensively used as an effective method toinvestigate the organic NLO materials [43] The values of thepolarizability120572 and the first hyperpolarizability120573 ofGaussian
03 output are reported in atomic units (au) so the calculatedvalues have been converted into electrostatic units (esu) (1205721 au = 01482 times 10minus24 esu 120573 1 au = 86393 times 10minus33 esu)
The total molecular dipole moment (120583tot) linear polar-izability (120572tot) and first-order hyperpolarizability (120573tot) ofthe title compound were calculated with the UB3LYP6-31G(d) and UB3LYPLanL2DZ methods The calculated val-ues of 120583tot 120572tot and 120573tot are 2939D 5995A3 and 698610minus30 cm5esu for UB3LYP6-31G(d) and 3958D 6552A3and 2781 10minus30 cm5esu for UB3LYPLanL2DZ respectivelyUrea is one of the prototypical molecules used in the studyof the NLO properties of molecular systems Therefore itwas used frequently as a threshold value for comparativepurposes Theoretically the first-order hyperpolarizabilityof the title compound is of 12 and 144 times magnitudeof urea at the same levels respectively According to theseresults the title compound is a good candidate of NLOmaterial
333 Molecular Electrostatic Potential The molecular elec-trostatic potential (MEP) is related to the electronic densityand is a very useful descriptor in understanding sites forelectrophilic attack and nucleophilic reactions as well ashydrogen-bonding interactions [44ndash46]
The molecular electrostatic potential 119881(119903) at a givenpoint 119903(119909 119910 119911) in the vicinity of a molecule is definedin terms of the interaction energy between the electricalcharge generated from the molecule electrons and nucleiand a positive test charge (a proton) located at 119903 For thesystem studied the 119881(119903) values were calculated as describedpreviously using the following [47]
where 119885119860is the charge of nucleus A located at 119877
119860 120588(1199031015840) is
the electronic density function of the molecule and 1199031015840 is thedummy integration variable Being a real physical property119881(119903) can be determined experimentally by diffraction or bycomputational methods [48] To predict reactive sites forelectrophilic and nucleophilic attack for the title moleculeMEP was calculated at the 6-31G(d) and LanL2DZ optimizedgeometries The negative (red) regions of MEP were relatedto electrophilic reactivity and the positive (blue) regions tonucleophilic reactivity shown in Figure 6 As can be seenfrom the figure there is one possible site on the title complexfor electrophilic attack The negative region is localised onthe carbon atom of the imidazole ring C13 with a maximumvalue of minus0049 and minus0064 au for UB3LYP6-31G(d) andUB3LYPLanL2DZ basis sets These results provide informa-tion concerning the region where the complex can interactintermolecularly and bond metallically Therefore Figure 6confirms the existence of an intermolecular C13ndashH13sdot sdot sdotO2interaction between theO atoms perchlorate ion andC atomsof the imidazole ring
Journal of Crystallography 5
0
a
b
c
Figure 2 Part of the crystal packing of the title complex For clarity hydrogen atoms and hydrogen bonds are not shown
334 HOMO-LUMO Analysis The highest occupied molec-ular orbital (HOMO) and the lowest lying unoccupiedmolec-ular orbital (LUMO) are named as frontier molecular orbitals(FMO)
The distributions and energy levels of the HOMO andLUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ level for the title complex are shown inFigure 7 The calculations indicate that the title complex has89 and 84 occupied molecular orbitals and the value of the
energy separation between the HOMO and LUMO are minus15and minus114 eV for at the same levels respectively
A molecule with a small frontier orbital gap is morepolarizable and is generally associated with a high chemicalreactivity and low kinetic stability and is also termed as softmolecule [49] The HOMO and LUMO energies the energygap (Δ119864) the ionization potential (119868) the electron affinity(119860) the absolute electronegativity (120594) the absolute hardness(120578) and softness (119878) for molecule have been calculated at
6 Journal of Crystallography
1000
900
800
700
600
500
400
300
200
100
4000
3500
3000
2500
2000
1500
1000
500
000
minus500
minus1000
minus1500
1000 2000 3000 4000 5000 6000 7000
7000
6000
5000
4000
3000
2000
1000
0000
minus1000
minus2000
DD
TA (120583
V∘
C)
Temperature (∘C)
TG (
)
DTG
(120583g
∘ C)
Figure 3 TGADTA curves of complex
Ni
(a)
Ni
(b)
Figure 4 The theoretical geometric structures of the title compound ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ)
(a) (b)
Figure 5 Atom-by-atom superimposition of the structures calculated (red) ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ) on the X-raystructure (yellow) of the title complex Hydrogen atoms have been omitted for clarity
Journal of Crystallography 7
UB3LYPLanL2DZ
UB3LYP6-31G(d)minus0049
minus0064
0049
0064
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
332 Nonlinear Optical Effects Nonlinear optical (NLO)effects arise from the interactions of electromagnetic fieldsin various media to produce new fields altered in phasefrequency amplitude or other propagation characteristicsfrom the incident fields [37] In the recent years because ofpotential applications inmodern communication technologydata storage telecommunication and optical signal process-ing a large number of research papers in new materialsexhibiting efficient nonlinear optical (NLO) properties havebeen of great interest [38ndash42]
The calculations of the mean linear polarizability (120572tot)and the mean first hyperpolarizability (120573tot) from the Gaus-sian output have been explained in detail previously andDFT has been extensively used as an effective method toinvestigate the organic NLO materials [43] The values of thepolarizability120572 and the first hyperpolarizability120573 ofGaussian
03 output are reported in atomic units (au) so the calculatedvalues have been converted into electrostatic units (esu) (1205721 au = 01482 times 10minus24 esu 120573 1 au = 86393 times 10minus33 esu)
The total molecular dipole moment (120583tot) linear polar-izability (120572tot) and first-order hyperpolarizability (120573tot) ofthe title compound were calculated with the UB3LYP6-31G(d) and UB3LYPLanL2DZ methods The calculated val-ues of 120583tot 120572tot and 120573tot are 2939D 5995A3 and 698610minus30 cm5esu for UB3LYP6-31G(d) and 3958D 6552A3and 2781 10minus30 cm5esu for UB3LYPLanL2DZ respectivelyUrea is one of the prototypical molecules used in the studyof the NLO properties of molecular systems Therefore itwas used frequently as a threshold value for comparativepurposes Theoretically the first-order hyperpolarizabilityof the title compound is of 12 and 144 times magnitudeof urea at the same levels respectively According to theseresults the title compound is a good candidate of NLOmaterial
333 Molecular Electrostatic Potential The molecular elec-trostatic potential (MEP) is related to the electronic densityand is a very useful descriptor in understanding sites forelectrophilic attack and nucleophilic reactions as well ashydrogen-bonding interactions [44ndash46]
The molecular electrostatic potential 119881(119903) at a givenpoint 119903(119909 119910 119911) in the vicinity of a molecule is definedin terms of the interaction energy between the electricalcharge generated from the molecule electrons and nucleiand a positive test charge (a proton) located at 119903 For thesystem studied the 119881(119903) values were calculated as describedpreviously using the following [47]
where 119885119860is the charge of nucleus A located at 119877
119860 120588(1199031015840) is
the electronic density function of the molecule and 1199031015840 is thedummy integration variable Being a real physical property119881(119903) can be determined experimentally by diffraction or bycomputational methods [48] To predict reactive sites forelectrophilic and nucleophilic attack for the title moleculeMEP was calculated at the 6-31G(d) and LanL2DZ optimizedgeometries The negative (red) regions of MEP were relatedto electrophilic reactivity and the positive (blue) regions tonucleophilic reactivity shown in Figure 6 As can be seenfrom the figure there is one possible site on the title complexfor electrophilic attack The negative region is localised onthe carbon atom of the imidazole ring C13 with a maximumvalue of minus0049 and minus0064 au for UB3LYP6-31G(d) andUB3LYPLanL2DZ basis sets These results provide informa-tion concerning the region where the complex can interactintermolecularly and bond metallically Therefore Figure 6confirms the existence of an intermolecular C13ndashH13sdot sdot sdotO2interaction between theO atoms perchlorate ion andC atomsof the imidazole ring
Journal of Crystallography 5
0
a
b
c
Figure 2 Part of the crystal packing of the title complex For clarity hydrogen atoms and hydrogen bonds are not shown
334 HOMO-LUMO Analysis The highest occupied molec-ular orbital (HOMO) and the lowest lying unoccupiedmolec-ular orbital (LUMO) are named as frontier molecular orbitals(FMO)
The distributions and energy levels of the HOMO andLUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ level for the title complex are shown inFigure 7 The calculations indicate that the title complex has89 and 84 occupied molecular orbitals and the value of the
energy separation between the HOMO and LUMO are minus15and minus114 eV for at the same levels respectively
A molecule with a small frontier orbital gap is morepolarizable and is generally associated with a high chemicalreactivity and low kinetic stability and is also termed as softmolecule [49] The HOMO and LUMO energies the energygap (Δ119864) the ionization potential (119868) the electron affinity(119860) the absolute electronegativity (120594) the absolute hardness(120578) and softness (119878) for molecule have been calculated at
6 Journal of Crystallography
1000
900
800
700
600
500
400
300
200
100
4000
3500
3000
2500
2000
1500
1000
500
000
minus500
minus1000
minus1500
1000 2000 3000 4000 5000 6000 7000
7000
6000
5000
4000
3000
2000
1000
0000
minus1000
minus2000
DD
TA (120583
V∘
C)
Temperature (∘C)
TG (
)
DTG
(120583g
∘ C)
Figure 3 TGADTA curves of complex
Ni
(a)
Ni
(b)
Figure 4 The theoretical geometric structures of the title compound ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ)
(a) (b)
Figure 5 Atom-by-atom superimposition of the structures calculated (red) ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ) on the X-raystructure (yellow) of the title complex Hydrogen atoms have been omitted for clarity
Journal of Crystallography 7
UB3LYPLanL2DZ
UB3LYP6-31G(d)minus0049
minus0064
0049
0064
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
Figure 2 Part of the crystal packing of the title complex For clarity hydrogen atoms and hydrogen bonds are not shown
334 HOMO-LUMO Analysis The highest occupied molec-ular orbital (HOMO) and the lowest lying unoccupiedmolec-ular orbital (LUMO) are named as frontier molecular orbitals(FMO)
The distributions and energy levels of the HOMO andLUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ level for the title complex are shown inFigure 7 The calculations indicate that the title complex has89 and 84 occupied molecular orbitals and the value of the
energy separation between the HOMO and LUMO are minus15and minus114 eV for at the same levels respectively
A molecule with a small frontier orbital gap is morepolarizable and is generally associated with a high chemicalreactivity and low kinetic stability and is also termed as softmolecule [49] The HOMO and LUMO energies the energygap (Δ119864) the ionization potential (119868) the electron affinity(119860) the absolute electronegativity (120594) the absolute hardness(120578) and softness (119878) for molecule have been calculated at
6 Journal of Crystallography
1000
900
800
700
600
500
400
300
200
100
4000
3500
3000
2500
2000
1500
1000
500
000
minus500
minus1000
minus1500
1000 2000 3000 4000 5000 6000 7000
7000
6000
5000
4000
3000
2000
1000
0000
minus1000
minus2000
DD
TA (120583
V∘
C)
Temperature (∘C)
TG (
)
DTG
(120583g
∘ C)
Figure 3 TGADTA curves of complex
Ni
(a)
Ni
(b)
Figure 4 The theoretical geometric structures of the title compound ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ)
(a) (b)
Figure 5 Atom-by-atom superimposition of the structures calculated (red) ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ) on the X-raystructure (yellow) of the title complex Hydrogen atoms have been omitted for clarity
Journal of Crystallography 7
UB3LYPLanL2DZ
UB3LYP6-31G(d)minus0049
minus0064
0049
0064
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
Figure 4 The theoretical geometric structures of the title compound ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ)
(a) (b)
Figure 5 Atom-by-atom superimposition of the structures calculated (red) ((a) = UB3LYP6-31G(d) (b) = UB3LYPLanL2DZ) on the X-raystructure (yellow) of the title complex Hydrogen atoms have been omitted for clarity
Journal of Crystallography 7
UB3LYPLanL2DZ
UB3LYP6-31G(d)minus0049
minus0064
0049
0064
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
Figure 6 Molecular electrostatic potential map (MEP) (in au) cal-culated at UB3LYP6-31G(d) and UB3LYPLanL2DZ level frontiermolecular orbitals analysis
the same levels and the results are given in Table 4 Byusing HOMO and LUMO energy values for a moleculeelectronegativity and chemical hardness can be calculatedas follows 120594 = (119868 + 119860)2 (electronegativity) 120578 = (119868 minus119860)2 (chemical hardness) and 119878 = 12120578 (chemical softness)where 119868 and 119860 are ionization potential and electron affinity119868 = minus119864HOMO and 119860 = minus119864LUMO respectively [50]
335 The Mulliken Charge Population TheMulliken atomiccharge calculation has an important role in the applica-tion of quantum chemical calculation to molecular systembecause of atomic charges effect dipole moment molecularpolarizability electronic structure and a lot of properties ofmolecular systemsThe charge distributions calculated by theMullikenmethod [51ndash54] for the equilibrium geometry of thecomplex is given in Figure 8The calculatedMulliken chargesof C13 and H13 atoms are determined as minus012 and 016 e andminus021 and 026 e for the 6-31G(d) and LanL2DZ methodsrespectively These values confirm intermolecular hydrogenbond C13ndashH13sdot sdot sdotO2
4 Conclusions
In this present investigation molecular structure nonlinearoptical effects molecular electrostatic potential HOMO-LUMO analysis and the Mulliken charge populations ofhexa(1-vinylimidazole)Ni(II) perchlorate have been studied
EHOMO = minus198 eV
ΔE = minus15 eV
minus048 eVELUMO =
EHOMO = minus216 eV
ΔE = minus114 eV
ELUMO = minus102 eV
UB3LYPLanL2DZUB3LYP6-31G(d)
Figure 7 The distributions and energy levels of the HOMOand LUMO orbitals computed at the UB3LYP6-31G(d) andUB3LYPLanL2DZ levels for the title complex
Table 4 The calculated frontier orbital energies electronegativityhardness and softness of complex using UB3LYP6-31G(d) andUB3LYPLanL2DZ levels
using DFT (UB3LYP6-31G(d) and UB3LYPLanL2DZ) cal-culations They are compared with the calculated geometricparameters (bond lenght bond angle and torsion angle)with their experimental data It is seen that there are nosignificant differences when the experimental structure iscompared with theoretical structures It was noted here thatthe experimental results belong to solid phase and theoreticalcalculations belong to gaseous phaseThepredicted nonlinearoptical (NLO) properties of the complex are much greaterthan those of urea The complex is a good candidate assecond-order nonlinear optical material Besides The MEPmap shows that the negative potential sites are on electroneg-ative atoms and the positive potential sites are around thehydrogen atomsThese sites provide information concerningthe region fromwhere the compound can undergo intra- andintermolecular interactions Similarly the Mulliken chargesconfirm the intermolecular hydrogen bonds in the crystal
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
Figure 8 The charge distribution calculated by the Mullikenmethod for complex
Disclosure
Supplementary file (crystallographic data) for the structurereported in this paper has been depositedwith theCambridgeCrystallographic Data Center as Supplementary Publicationno CCDCndash940965 Copies of the data can be obtainedfree of charge on application to CCDC 12 Union RoadCambridge CB2 1EZ UK (fax (+44)1223 336-033 e-maildepositccdccamacuk)
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work was supported by TUBITAK-The Scientific andTechnologıcal Research Council of Turkey (Project no110T131 )
References
[1] httpenwikipediaorgwikiImidazole[2] K Kurdziel and T Glowiak ldquoPalladium(II) complexes of 1-
[3] S Yoshida and H Ishida ldquoA study on the orientation of imi-dazoles on copper as corrosion inhibitor and possible adhesion
promoter for electric devicesrdquo The Journal of Chemical Physicsvol 78 no 11 pp 6960ndash6969 1983
[4] S Yoshida and H Ishida ldquoA FT-IR reflection-absorptionspectroscopic study of an epoxy coating on imidazole-treatedcopperrdquo Journal of Adhesion vol 16 no 3 pp 217ndash232 1984
[5] N K Tatel J Franco and I S Patel ldquoCorrosion of 6337 brass incitric acid solution and its inhibition by azole-type compoundsrdquoJournal of the Indian Chemical Society vol 54 pp 815ndash816 1977
[6] L Shargel AHMutnick P F Souney and LN SwansonCom-prehensive Pharmacy Review Lippincott Williams amp Wilkins6th edition 2006
[7] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974
[8] G Challa J Reedijk and P W N M van Leeuwen ldquoMacro-molecularmetal complexes as catalysts with improved stabilityrdquoPolymers for Advanced Technologies vol 7 no 8 pp 625ndash6331996
[9] C G Overberger and R Tomko ldquoCatalysis by water-solubleimidazole-containing polymersrdquo ACS Symposium Series vol212 pp 13ndash21 1983
[10] M Suzuki S Kobayashi T Koyama et al ldquoKinetics of intra-polymer electron-transfer reactions in macromolecule-metalcomplexesrdquo Journal of the Chemical Society Faraday Transac-tions vol 91 no 17 pp 2877ndash2880 1995
[11] G Manecke and R Schlegel ldquoPolymere imidazolcarbonsauren2 Uber das schwermetallionenbindungsvermogen von chela-tharzen mit 45-sicarboxyimidazolyl-gruppenrdquo Macromolecu-lar Chemistry vol 179 pp 19ndash27 1978
[12] J Wang and C Chen ldquoBiosorbents for heavy metals removaland their futurerdquo Biotechnology Advances vol 27 no 2 pp 195ndash226 2009
[13] S Pramanik S Dhara S S Bhattacharyya and P Chattopad-hyay ldquoSeparation and determination of somemetal ions on newchelating resins containing N N donor setsrdquo Analytica ChimicaActa vol 556 no 2 pp 430ndash437 2006
[14] B L Rivas M Jara and E D Pereira ldquoPreparation and adsorp-tion properties of the chelating resins containing carboxylicsulfonic and imidazole groupsrdquo Journal of Applied PolymerScience vol 89 no 10 pp 2852ndash2856 2003
[15] M D Green and T E Long ldquoDesigning imidazole-based ionicliquids and ionic liquid monomers for emerging technologiesrdquoPolymer Reviews vol 49 pp 291ndash314 2009
[16] M R Grimmett ldquoImidazolesrdquo in Comprehensive HeterocyclicChemistry II A R Katritzky C W Ress and E F V ScrivenEds vol 3 pp 77ndash220 Pergamon Press Oxford UK 1996
[17] M R Grimmett Imidazoleand Benzimidazole Synthesis Aca-demic Press New York NY USA 1997
[18] M R Grimmett ldquoAdvances in imidazole chemistryrdquo Advancesin Heterocyclic Chemistry vol 12 pp 103ndash183 1970
[19] A Novelli and A de Santis ldquoGeneral synthesis of C substitutedimidazolesrdquo Tetrahedron Letters vol 8 no 3 pp 265ndash269 1967
[20] Y Kurimura T Abe Y Usui E Tsuchida H Nishide and GChalla ldquoCharacteristic behaviour of the complexation of cop-per(II) with polymer-bound vinylimidazole ligandsrdquo Journal ofthe Chemical Society Faraday Transactions vol 90 no 23 pp3563ndash3566 1994
[21] T Ziegler ldquoDensity functional theory as a practical tool for thestudy of elementary reaction steps in organometallic chemistryrdquoPure and Applied Chemistry vol 63 pp 873ndash878 1991
Journal of Crystallography 9
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
[22] P M W Gill B G Johnson J A Pople and M J FrischldquoThe performance of the Becke-Lee-Yang-Parr (B-LYP) densityfunctional theory with various basis setsrdquo Chemical PhysicsLetters vol 197 no 4-5 pp 499ndash505 1992
[23] F F Jian P S Zhao Z S Bai and L Zhang ldquoQuantumchemical calculation studies on 4-phenyl-1-(propan-2- yli-dene)thiosemicarbaziderdquo Structural Chemistry vol 16 no 6pp 635ndash639 2005
[24] GM Sheldrick SHELXL 97 Program for the Solution of CrystalStructures University of Gottingen Gottingen Germany 1997
[25] L J Farrugia ldquoWinGX suite for small-molecule single-crystalcrystallographyrdquo Journal of Applied Crystallography vol 32 no4 pp 837ndash838 1999
[26] G M Sheldrick SHELXL-97 Program for Crystal StructuresRefinement University of Gottingen Gottingen Germany 1997
[29] A L Spek ldquoStructure validation in chemical crystallographyrdquoActa Crystallographica D vol 65 no 2 pp 148ndash155 2009
[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 03Revision E01 Gaussian Inc Wallingford Conn USA 2004
[31] R Dennington II T Keith and J Millam Gauss View Version412 Semichem Inc Shawnee Mission Kan USA 2007
[32] L J Farrugia ldquoORTEP-3 for Windowsmdasha version of ORTEP-III with a Graphical User Interface (GUI)rdquo Journal of AppliedCrystallography vol 30 p 565 1997
[33] N Sireci U Yılmaz H Kucukbay et al ldquoSynthesis of 1-substituted benzimidazole metal complexes and structuralcharacterization of dichlorobis(1-phenyl-1 H -benzimidazole-120581N3)cobalt(II) and dichlorobis (1-phenyl-1 H -benzimidazole-120581N3)zinc(II)rdquo Journal of Coordination Chemistry vol 64 no 11pp 1894ndash1902 2011
[34] M Akkurt S Karaca H Kucukbay E Orhan and OBuyukgungor ldquoDichlorobis[1-(2-ethoxyethyl)-1H-benzimida-zole-120581N3]nickel(II)rdquo Acta Crystallographica E vol 61 pp m41ndashm43 2005
[35] F Sen R Sahin O Andac and M Tas ldquotrans-Bis(nitrato-120581O)tetrakis(1-vinyl-1H-imidazole-120581N3)copper(II)rdquo Acta Crys-tallographica E vol 68 p m1045 2012
[36] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1984
[37] Y-X Sun Q-L Hao W-X Wei et al ldquoExperimental and den-sity functional studies on 4-(34-dihydroxybenzylideneamino)antipyrine and 4-(234-trihydroxybenzylideneamino)antipy-rinerdquo Journal ofMolecular Structure THEOCHEM vol 904 no1ndash3 pp 74ndash82 2009
[38] R Zhang B Du G Sun and Y Sun ldquoExperimental and the-oretical studies on o- m- and p-chlorobenzylideneaminoanti-pyrinesrdquo Spectrochimica Acta A vol 75 no 3 pp 1115ndash11242010
[39] S Yazıcı C Albayrak I Gumrukcuoglu I Senel and OBuyukgungor ldquoExperimental and density functional theory(DFT) studies on (E)-2-acetyl-4-(4-nitrophenyldiazenyl) phe-nolrdquo Journal of Molecular Structure vol 985 no 2-3 pp 292ndash298 2011
[40] D S Chemia and J ZyssNonLinearOptical Properties ofOrgan-ic Molecules and Crystal Academic Press New York NY USA1987
[41] J Zyss Molecular Non Linear Optics Academic Press BostonMass USA 1994
[42] A Ben Ahmed H Feki Y Abid and C Minot ldquoMolecularstructure vibrational spectra and nonlinear optical proper-ties of orthoarsenic acid-tris-(hydroxymethyl)-aminomethaneDFT studyrdquo Spectrochimica Acta A vol 75 no 4 pp 1315ndash13202010
[43] G A Babu and P Ramasamy ldquoGrowth and characterization ofan organic NLO material ammonium malaterdquo Current AppliedPhysics vol 10 no 1 pp 214ndash220 2010
[44] E Scrocco and J Tomasi ldquoElectronic molecular structurereactivity and intermolecular forces an euristic interpretationby means of electrostatic molecular potentialsrdquo Advances inQuantum Chemistry vol 11 pp 115ndash193 1979
[45] F J Luque J M Lopez and M Orozco ldquoPerspective onldquoElectrostatic interactions of a solutewith a continuumAdirectutilization of ab initio molecular potentials for the prevision ofsolvent effectsrdquordquoTheoretical Chemistry Accounts vol 103 no 3-4 pp 343ndash345 2000
[46] N Okulik and A H Jubert ldquoTheoretical analysis of the reactivesites of non-steroidal anti-inflammatory drugsrdquo Internet Elec-tronic Journal of Molecular Design vol 4 pp 17ndash30 2005
[47] P Politzer and J SMurray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 no 3 pp 134ndash142 2002
[48] P Politzer and D G Truhlar Chemical Applications of Atomicand Molecular Electrostatic Potentials Plenum New York NYUSA 1981
[49] I Fleming Frontier Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons London UK 1976
[50] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the United States of America vol 83 no22 pp 8440ndash8841 1986
[51] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions Irdquo The Journal of Chemical Physicsvol 23 no 10 pp 1833ndash1840 1955
[52] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions II Overlap populations bondorders and covalent bond energiesrdquo The Journal of ChemicalPhysics vol 23 no 10 pp 1841ndash1846 1955
[53] R S Mulliken ldquoElectronic population analysis on LCAO-MO molecular wave functions III effects of hybridization onoverlap and gross AO populationsrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2338ndash2342 1955
[54] R S Mulliken ldquoElectronic population analysis on LCAO-MOmolecular wave functions IV bonding and antibonding inLCAO and valence-bond theoriesrdquo The Journal of ChemicalPhysics vol 23 no 12 pp 2343ndash2346 1955
![Latest Advances in the Development of Eukaryotic …...the previous low resolution structure prediction [36]. Vault structure analysis by X-ray di raction at 3.5 Å resolution [25]](https://static.documents.pub/doc/80x56/5f9f9829d7715432f15a1902/latest-advances-in-the-development-of-eukaryotic-the-previous-low-resolution.jpg)
