Research Article Synthesis, Crystal Structures, and...

Hindawi Publishing CorporationJournal of Inorganic ChemistryVolume 2013 Article ID 206589 10 pageshttpdxdoiorg1011552013206589

Research ArticleSynthesis Crystal Structures and Magnetic Properties ofTernary M(II)-Dicyanamide-hydroxypyridine Complexes

Ling-Ling Zheng

Guangzhou Vocational College of Technology amp Business 511442 China

Correspondence should be addressed to Ling-Ling Zheng zsuzhengllyahoocomcn

Received 29 March 2013 Accepted 30 April 2013

Academic Editor Henryk Kozlowski

Copyright copy 2013 Ling-Ling Zheng This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Three two-dimensional (2D) and 3D supramolecular coordination architectures based on ternary M(II)-dicyanamide-2-hydro-xypyridine systems [Co(hmpH)

2(dca)2] (1) [Cu(hmpH)

2(dca)2] (2) and [Mn(hepH)

2(dca)2] (3) (dca = dicyanamide hmpH =

2-(hydroxymethyl)pyridine hepH = 2-(hydroxyethyl)pyridine) have been synthesized 1 is a mononuclear Co(II) complex Themononuclear units are interlinked into a 2D (44) hydrogen-bonded layer via OndashHsdot sdot sdotN hydrogen bonds between the hydroxylgroups and the noncoordinating nitrile ends These 2D layers are further extended into a 3D supramolecular architecture via theinterlayer pyridyl-pyridyl stacking interaction 2 has a 1D coordination chain structure formed by the double 120583

15-dca bridged

dinuclear [Cu2(12058315-dca)2(hmpH)

2] unit and the 120583

13-dca bridges via weak CundashN coordination and these 1D coordination chains

are further extended into 2D hydrogen-bonded layers via strong OndashHsdot sdot sdotN hydrogen-bonding interaction between the hydroxylgroups and the noncoordinating nitrile ends 3 is a 2D (44) coordination network made of 1D [Mn(hepH)(120583

15-dca)] helical chain

units and interchain double (12058315-dca) bridges Pairs of [Mn(hepH)(120583

15-dca)] helical chains are interlinked by the double (120583

15-

dca) bridges into a racemic coordination layer structure which is further extended into a 3D hydrogen-bonded network Magneticstudies reveal that weak antiferromagnetic exchange occurs in 3

1 Introduction

Since the pioneering reports of Robson and coworkers in1990 [1 2] this realm of crystal engineering is growinginterest and great efforts have been devoted to the assem-bly of supramolecular systems of organic molecular solidsand coordination polymers through hydrogen bonds andor coordination bonds with the resultant crystalline mate-rials having a wide range of potential applications suchas electronic magnetic optical absorbent and catalyticmaterials [3ndash29] In recent years much attention has beendevoted to dicyanamide-anion- (dca-) bridged coordinationpolymers [30ndash42] for the large variety ofmagnetic propertiesespecially the 120572-M(dca)2 series of compounds which haveisomorphous rutile-like structure display ferromagnetism(Co Ni) [43ndash46] spin-canted antiferromagnetism (Cr MnFe) [47 48] and paramagnetism (Cu) [45 46] Of furtherimportance from a structural perspective when auxiliaryL ligands are introduced to the ternary MII-dca-L systemsdifferent coordination architectures such as mononuclear

and dinuclear compounds [49] 1D chains [50ndash58] 2D (44)or (63) [59ndash63] sheets and 3D network topologies [64ndash67] could be constructed (Scheme 1) Interestingly inter-esting in situ nucleophilic addition reactions were observedbetween dca and the auxiliary ligands [68ndash73] On the otherhand weak interactions such as hydrogen bonding and 120587-120587 interactions play an important role for construction ofhigh-dimensional supramolecular systems [74ndash76] From theviewpoint of rational network design if the coligand cancombine multifunctions such as coordination hydrogen-bond donor or acceptor and aromaticity many interestingsupramolecular architectures will be constructed

In this work two 2-hydroxypyridines 2-(hydroxymethyl)pyridine (hmpH) and 2-(hydroxyethyl) pyridine (hepH)were chosen as the auxiliary ligands to the M(II)-dca-Lsystems to realize this rational crystal engineering for thefollowing reasons (1) hmpH and hepH can act as chelatingligand (2) the hydroxyl groups of hmpH and hepH mayact as the hydrogen bond donors which generate stronghydrogen bond with the amide nitrogen atom of the dca

2 Journal of Inorganic Chemistry

N

NN

N

NN

N

NN

N

NN

N

NN

N

NN

N

NNN

NN

1205831 1205833

12058315 12058313

120583135 120583115

1205831135 12058311355

Scheme 1 Schematic showing the coordination modes of dca

ligand We report herein three ternary supramolecular archi-tectures [Co(dca)

2(hmpH)

2] (1) [Cu(dca)

2(hmpH)

2] (2)

and [Mn(dca)2(hepH)]

119899(3) obtained by this strategy

2 Experimental

21 Materials and General Methods The reagents and sol-vents employed were commercially available and used asreceived without further purification The C H and Nmicroanalyses were carried out with an Elementar Vario-ELCHNS elemental analyzer The FT-IR spectra were recordedfrom KBr pellets in the range 4000ndash400 cmminus1 on a BrukerTENSOR27 spectrometer Variable-temperature magneticsusceptibility measurements were made using a SQUIDmagnetometer MPMS XL-7 (QuantumDesign) at 01 T for 3The diamagnetic correction for each sample was determinedfrom Pascalrsquos constants

22 Synthesis

221 Synthesis of [Co(hmpH)2(dca)2] (1) Amethanol solu-

tion (10mL) of Co(NO3)2sdot6H2O (145mg 05mmol) was

added dropwise to a CH3OHH

2O solution (20mL)

containing sodium dicyanamide (89mg 10mmol) andhmpH(109mg 10mmol) A red solution formed onaddition of metal salt to the ligands The mixture solutionwas filtered and solvent evaporated at room temperatureWell-shaped red block crystals of 1 were obtained within 1week in 62 yield Anal calcd for C

16H14CoN8O2 C 4695

H 345 N 2738 Found C 4653 H 352 N 2721 IR3081m 2215vs 1602m 1561m 1483s 1432m 1385w 1347w1298vs 1250s 1142vs 1081m 988w 861m 754m 675m 646w612w 450vw

222 Synthesis of [Cu(hmpH)2(dca)2] (2) Amethanol solu-

tion (10mL) of Cu(NO3)2sdot3H2O (121mg 05mmol) was


2O solution (20mL) con-

taining sodium dicyanamide (89mg 10mmol) and hmpH(109mg 10mmol) A blue solution formed on addition ofmetal salt to the ligandsThemixture was filtered and solventevaporated at room temperature Well-shaped blue blockcrystals of 2 were obtained within 1 week in 83 yield Analcalcd for C

10H7CuN7O C 3941 H 232 N 3217 Found

C 3932 H 241 N 3203 IR 3706w 3429m 3074w 2855m2378s 2214vs 1613s 1571m 1485m 1440s 1366m 1292m1223vw 1159vw 1092vs 931vw 821vw 762s 722m 673s 623s533m 483w 438m

223 Synthesis of [119872119899(ℎ119890119901119867)2(119889119888119886)

2]

119899(3) hepH (123mg

10mmol) dissolved in a minimum amount of methanolwas added to an aqueous solution containing MnCl

2sdot4H2O

(99mg 05mmol) and sodium dicyanamide (89mg10mmol) Block colorless crystals of 3 were grown after5 days Yield ca 74 Anal Calcd for C

11H9MnN7O C

4259 H 292 N 3161 Found C 4184 H 307 N 3123IR 3597w 3541w 3286m 3081w 2954vw 2901vw 2310m2273m 2242m 2177s 1606s 1571m 1488s 1440s 1419w1369s 1308vs 1249vw 1155w 1107m 1075m 1029s 940m890vw 866w 759m 658w 640vw 579w 515m 451vw 416vw

23 X-Ray Crystallographic Study Single-crystal data of 1ndash3 were collected at 293(2) K on a Bruker Smart 1000 CCDdiffractometer with Mo Ka radiation (120582 = 071073 A)All empirical absorption corrections were applied using theSADABS program [77] The structure was solved usingdirect method which yielded the positions of all nonhydro-gen atoms These were refined first isotropically and thenanisotropically All calculations were performed using theSHELXTL programs [78] The crystallographic data for 1ndash3 are summarized in Table 1 The selected bond lengths andangles are listed in Table 2

CCDC 711609ndash711611 contain the supplementary crystal-lographic data for this paper These data can be obtained freeof charge from the Cambridge Crystallographic Data Centre

3 Results and Discussion

31 Synthesis and Characterization Air-stable complexes 1ndash3were obtained from the reactions of metal(II) salts Na(dca)and 2-hydroxypyridine-type ligands (Scheme 2) in whichthe hydroxypyridines act as chelating ligands Moreover theproducts are independent of the ligand-to-metal ratios

In contrary under base condition 2-hydroxypyridine-type ligands such as hmpH hepH and 26-pyridinedim-ethanol have been found to act as bridging ligands togenerate some fascinating polynuclearmetal-clusters [79ndash82]and the extended 1D or 2D metal cluster-based coordinationpolymers with dca as bridges in recent years [83ndash85]

The IR spectra of 1ndash3 are quite similar They all showstrong absorptions in the range of 2310ndash2100 cmminus1 whichcorrespond to the ]s+]as (C equiv N) ]as (C equiv N) and ]s (C equiv N)modes of the dca ligand [86]

Journal of Inorganic Chemistry 3

NO H

NO H

NO H

M(II)+

dca

Coligand

0-D complex

1-D chain

2-D (6 3) layer

2-D H-bonded (4 4) layer


3-D H-bonded network

Scheme 2 Schematic showing the synthesis of complexes 1ndash3

Table 1 Crystal and structure refinement for compounds 1ndash3

Compound 1 2 3Formula C16H14CoN8O2 C10H7CuN7O C11H9MnN7OFormula mass 40928 30477 31019Cryst syst Monoclinic Triclinic MonoclinicSpace group C2c P-1 P21c119886 (A) 185091 (19) 74025 (10) 12828 (3)119887 (A) 78876 (8) 75004 (9) 80561 (18)119888 (A) 140965 (15) 114982 (15) 12982 (3)120572 (∘) 9000 78557 (2) 9000120573 (∘) 118124 (2) 89574 (2) 103162 (5)120574 (∘) 9000 72701 (2) 9000119881 (A3) 18150 (3) 59650 (13) 13064 (5)119885 4 2 4119879(K) 293 (2) 293 (2) 293 (2)119865 (000) 836 306 628Dc (g cmminus3) 1498 1697 1577120583 (mmminus1) 0975 1834 1017Final 119877 indexes[119868 gt 2120590(119868)] 00319 00832 00391 00926 00488 01032

Final R indexes[all data] 00345 00847 00449 00963 00955 01219

1198771 = sum ||119865119900| minus |119865119888|| sum |119865119900| 1199081198772 = [sum119908(1198652

119900minus 1198652

119888)2

sum119908(1198652

119900)2

]

12

32 Structure Description Compound 1 crystallizes in mon-oclinic space group C2cwith the asymmetric unit consistingof half formula unit The Co1 ion lies on a special posi-tion and adopts a greatly distorted octahedral environment(Figure 1(a)) ligated by two N atoms (CondashN = 2114(2) A) andtwo O atoms (CondashO = 2165(7) A) from two chelate hmpHligands and two nitrile N (CondashN = 2077(2) A) atoms fromtwo trans-dca ligands The dca ligand is in 120583

1coordination

mode and acts as a terminal ligand The dca anions adoptnonlinear bonding configurations about the Co ions with C1ndashN1ndashCo1 = 16208(3)∘

These mononuclear units are further cross-linked bystrongNsdot sdot sdotHndashO[87] hydrogen-bonding interaction between

hydroxyl groups and uncoordinated nitrile ends of the dcaligands (O1sdot sdot sdotN3b = 2728(2) A O1ndashH1Osdot sdot sdotN3b = 1690∘) toform a 2D sheet with (44) topology as shown in Figure 1(b)

Analysis of the crystal packing of 1 shows that these sheetsagain interdigitate to form 3D supramolecular architecture(Figure 1(c)) with the average interplanar distance betweenpyridine rings being ca 355 A

Compound 2 crystallizes in triclinic P-1 space groupwith the asymmetric unit containing half formula unitThe copper atoms are coordinated to one chelating hmpHligand coordinating via the pyridyl nitrogen atom donor(CundashN = 1988(2) A) and hydroxyl oxygen atom (CundashO = 1986(2) A) two bridging 120583

15-dca anions (CundashN =

1968(3) and 2323(3) A) and one ldquoterminalrdquo dca anion (CundashN = 1965(3) A) The coordination geometry of CuII center(CuN

4O) can be described as a square pyramid The N3

atom occupied the apical position Similar to 1 the dcaanions adopt nonlinear bonding configurations about Cuion with C2ndashN3ndashCu = 1515(2)∘ C2ndashN1ndashCu = 1617(2)∘ andC3ndashN4ndashCu = 1654(2)∘ The bridging dca anions extend theCuII centers to generate a dinuclear with double dca bridges(Figure 2(a)) The Cusdot sdot sdotCu separation is 7311(2) A Thesedinuclear units are further linked by weak CundashN interactions(2866 (3) A) between the copper atoms and ldquouncoordinatedrdquoamide nitrogen atoms of the terminal dca anions to formdouble dca bridges (Cusdot sdot sdotCu = 5827(6) A) The Cusdot sdot sdotCuseparations through 13-120583

2-dca are significantly shorter than

those through 15-1205832-dca These weak interactions generated

1D chains as shown in Figure 2(b) These 1D chains arelinked by alternative 120583

15- and 120583

13-dca bridges which are

less common for the dca ligand [88ndash95] The weak copper(II) coordination leads to a pseudo-Jahn-Teller elongatedoctahedral geometry

Adjacent coordination chains are extended into 2D hyd-rogen-bonded layers by theO1ndashH1sdot sdot sdotN6b hydrogen-bondinginteraction between the hydroxyl groups and the uncoordi-nated nitrile ends of the dca ligands (O1sdot sdot sdotN6b = 2661(4) AO1ndashH1Osdot sdot sdotN6b = 1725∘) as shown in Figure 2(c)

Compound 3 crystallizes in monoclinic space groupP21c with the asymmetric unit consisting of half formula

unitThemanganese ion is coordinated to one chelating hepHligand coordinating via the pyridyl nitrogen atom donor


Table 2 Selected bond distances (A) and angles (deg) for 1ndash3

1Co(1)-N(1) 20767 (18) Co(1)-O(1) 21653 (15)Co(1)-N(4) 21136 (16) O(1)-H(1O)sdot sdot sdotN(3b) 2728 (2)

N(1)-Co(1)-N(1a) 9573 (10) N(4)-Co(1)-O(1) 7541 (6)N(1)-Co(1)-N(4) 9551 (7) N(1)-Co(1)-O(1a) 8687 (7)N(1)-Co(1)-N(4a) 9688 (7) N(4)-Co(1)-O(1a) 9163 (6)N(4)-Co(1)-N(4a) 16149 (10) O(1)-Co(1)-O(1a) 9194 (8)N(1)-Co(1)-O(1) 17081 (6) O(1)-H(1O)sdot sdot sdotN(3b) 1690

2Cu(1)-N(4) 1965 (3) Cu(1)-N(7) 1988 (2)Cu(1)-N(1) 1968 (3) Cu(1)-N(3a) 2323 (3)Cu(1)-O(1) 1985 (2) O(1)sdot sdot sdotN(6b) 2661 (4)

N(4)-Cu(1)-N(1) 9442 (13) O(1)-Cu(1)-N(7) 8068 (10)N(4)-Cu(1)-O(1) 8938 (11) N(4)-Cu(1)-N(3a) 9962 (12)N(1)-Cu(1)-O(1) 17608 (10) N(1)-Cu(1)-N(3a) 9043 (12)N(4)-Cu(1)-N(7) 16111 (11) O(1)-Cu(1)-N(3a) 8990 (11)N(1)-Cu(1)-N(7) 9541 (11) N(7)-Cu(1)-N(3a) 9641 (11)O(1)-H(1O)sdot sdot sdotN(6b) 1725

3Mn(1)-N(3a) 2175 (4) Mn(1)-N(6b) 2227 (4)Mn(1)-O(1) 2187 (3) Mn(1)-N(4) 2238 (4)Mn(1)-N(1) 2224 (4) Mn(1)-N(7) 2290 (3)O(1) sdot sdot sdotN(5d) 2859 (4)

N(3a)-Mn(1)-O(1) 17477 (14) N(1)-Mn(1)-N(4) 17438 (14)N(3a)-Mn(1)-N(1) 8676 (15) N(6b)-Mn(1)-N(4) 8705 (14)O(1)-Mn(1)-N(1) 8834 (13) N(3a)-Mn(1)-N(7) 9925 (13)N(3a)-Mn(1)-N(6b) 9657 (14) O(1)-Mn(1)-N(7) 8267 (11)O(1)-Mn(1)-N(6b) 8221 (12) N(1)-Mn(1)-N(7) 9121 (13)N(1)-Mn(1)-N(6b) 9692 (14) N(6b)-Mn(1)-N(7) 16259 (13)N(3a)-Mn(1)-N(4) 8884 (15) N(4)-Mn(1)-N(7) 8605 (13)O(1)-Mn(1)-N(4) 9615 (13) O(1)-H(1O)sdot sdot sdotN(5d) 1652Symmetry codes (a) minus119909 119910 minus119911 + 32 (b) 119909 minus 12 119910 minus 12 119911 for 1 (a) minus119909 + 1 minus119910 + 2 minus119911 + 2 (b) minus119909 + 1 minus119910 + 3 minus119911 + 1 for 2 (a) minus119909 119910 + 12 minus119911 + 12 (b)minus119909 + 1 minus119910 minus 1 minus119911 + 1 (d) 119909 minus119910 minus 32 119911 minus 12 for 3

(MnndashN = 2291(3) A) and hydroxyl oxygen atom (MnndashO =2188(3) A) and four nitrile nitrogen atoms from four 120583

15-

dca anions (MnndashN = 2175(4)ndash2271(4) A) featuring a dis-torted MnN

5O octahedron environment The surrounding

of manganese ion is shown in Figure 3(a) Each manganeseion is connected to another three manganese ions by meansof two single (Mnsdot sdot sdotMn = 8192(1) A) and one double dcabridges (Mnsdot sdot sdotMn = 7467(1) A) in an end-to-end (120583

15)

coordination mode leading to 2D (63) coordination layers(Figure 3(b)) which have been found in dca chemistry [30]As expected the dca anions do not coordinate linearly tothe metal centers with CndashNndashMn angles of 1534(1)∘ndash1697(1)∘As a result the topology of the coordination network is thatof a herringbone-waved grid since the rings have a slightchair conformation The bidentate hepH ligands are locatedon both sides of each layer

The 2D coordination layers are cross-linked by strongOndashHsdot sdot sdotN hydrogen-bonding interactions between hydroxylgroup and amido nitrogen atoms of dca anions (O1sdot sdot sdotN5d =2859(4) A O1ndashH1Osdot sdot sdotN5d = 1652∘) These hydrogen-bonding interactions extend these 2D layers into a 3Dsupramolecular architecture which is further consolidated bythe nonclassical CndashHsdot sdot sdotN hydrogen-bonding interaction asshown in Figure 3(c)

33 Magnetic Properties The magnetic properties of 3 areshown in Figure 4 as 120594

119872(inset) and 120594

119872119879 versus 119879 plots

(120594119872

is the molar magnetic susceptibility for one MnII ion)Taking into consideration the two-dimensional structuremagnetic data are taken for one manganese ion The valueof 120594119872119879 product at 300K is 419 cm3molminus1 K which is the

typical value for one isolated Mn(II) ion (119892 = 20) This


C1

C2

C3C4

C5

C6C7

C8

01

N1

N2N3

N4A

N1AN4

01A

Co1O

O

OO

OO

OO

O

OO

OO

O

(a)

(b)

(c)

Figure 1 Coordination environments of the metal ions in 1 (a) andthe hydrogen-bonded 2D layer (b) 3D molecular architecture withinterbilayer 120587-120587 interaction (c)

value remains unchanged up to 50K and then decreasesrapidly from 398 cm3molminus1 K at ca 50K to 163 cm3molminus1 Kat 20 K This feature is indicative of weak antiferromagneticcoupling interaction among the Mn(II) ions Because of thelong Mnsdot sdot sdotMn separation of 8192(1) A by single 120583-15-dcabridge in 3 a simplified dinuclear Mn(II) model was used toanalyze the magnetic exchange interaction via the two singleand one double 120583-15-dca bridges (119867 = minus119869119878Mn(1) sdot119878Mn(2)) [96]similar to the reported method in [97] The best-fit parame-ters are obtained to be 119892 = 199 119869 = minus0011 cmminus1 and 119877 =1times10

minus5 119869 is the exchange interaction through double 12058315-dca

01AO

OO

O

OO

O

O

OO

O

O O

O

N4A

N7AN1A

N3C2N2

C1N1Cu1

N3A01

N4C3

N5C4

N6

N7

Cu1A

(a)

CuO

NC

(b)

CuOH

NC

(c)

Figure 2 Coordination environments of the metal ions in 2 (a) andthe 1D chain extended by CundashN weak interaction (b) 2D layer builtby Nsdot sdot sdotHndashO hydrogen bond (c)

bridges 119892 is the Lande factor and 119877 is the agreement factorfor defined as 119877 = [sum (120594obs minus 120594calc)

2sum120594obs

2]

12

This fittingresult is in accordance with the very weak antiferromagneticcoupling existing in the reported Mn(II)-120583

15-dca-coligand

systems [97]


Mn1B

Mn1A

N3A

N6BMn1

N4C3

N5

C4

N6

01O

OO

O

O

O

O

OO N1

C1

N2

C2N3

Mn1C

N7

(a)

MnO

NC

(b)

a

b

c

MnO

NC

(c)

Figure 3 Coordination environments of the metal ions in 3 (a) and 2D layer (b) Hydrogen-bonded 3D network (c) (the uncoordinatedatoms are deleted for clarity)

0 50 100 150 200 250 300

0

02

04

06

08

1

2

3

4

5

119879 (K)

120594MT

(cm3

K m

olminus1)

120594M

(cm3

molminus1)

Figure 4 Plot of the 120594119872119879 versus 119879 Solid lines represent the best fit

with the parameters given in the text for 3

4 ConclusionIn this study we have demonstrated the constructionof ternary M(II)-dca-2-hydroxypyridine supramolecular

architectures from low to high dimensionality via bothmetal coordination and hydrogen-bonding interactionsThe dca ligand displays quite different coordination modesof monodentate in 1 double-bridge in 2 and single- anddouble-bridge fashion in 3 We are extending this strategy toconstruct new supramolecular architectures by using otherfunctional coligands

References

[1] B F Hoskins and R Robson ldquoDesign and construction ofa new class of scaffolding-like materials comprising infinitepolymeric frameworks of 3D-linked molecular rods A reap-praisal of the zinc cyanide and cadmium cyanide struc-tures and the synthesis and structure of the diamond-relatedframeworks [N(CH3)4][CuIZnII(CN)4] and CuI[4410158404

10158401015840

4101584010158401015840

-tetracyanotetraphenylmethane]BF4xC6H5NO2rdquo Journal of theAmerican Chemical Society vol 112 pp 1545ndash1554 1990

[2] K R Seddon and M Zaworotko Eds Crystal Engineering TheDesign and Application of Functional Solids Kluwer AcademicDodrecht The Netherlands 1996


[3] G R Desiraju ldquoSupramolecular synthons in crystal enginee-ringmdasha new organic synthesisrdquo Angewandte Chemie Interna-tional Edition vol 34 no 21 pp 2311ndash2327 1995

[4] C B Aakeroy and A M Beatty ldquoReview crystal engineeringof hydrogen-bonded assembliesmdasha progress reportrdquoAustralianJournal of Chemistry vol 54 no 7 pp 409ndash421 2001

[5] K T Holman A M Pivovar J A Swift andM DWard ldquoMet-ric engineering of soft molecular host frameworksrdquo Accounts ofChemical Research vol 34 no 2 pp 107ndash118 2001

[6] A D Burrows ldquoCrystal engineering using multiple hydrogenbondsrdquo Structure and Bonding vol 108 pp 55ndash96 2004

[7] D Braga L Maini M Polito and F Grepioni ldquoHydrogenbonding interactions between ions a powerful tool inmolecularcrystal engineeringrdquo Structure and Bonding vol 111 pp 1ndash322004

[8] A J Blake N R Champness P Hubberstey W S Li M AWithersby and M Schroder ldquoInorganic crystal engineeringusing self-assembly of tailored building-blocksrdquo CoordinationChemistry Reviews vol 183 no 1 pp 117ndash138 1999

[9] B Moulton and M J Zaworotko ldquoFrom molecules to crystalengineering supramolecular isomerism and polymorphism innetwork solidsrdquoChemical Reviews vol 101 no 6 pp 1629ndash16582001

[10] L Carlucci G Ciani and D M Proserpio ldquoPolycatenationpolythreading and polyknotting in coordination network che-mistryrdquo Coordination Chemistry Reviews vol 246 no 1-2 pp247ndash289 2003

[11] C Janiak ldquoEngineering coordination polymers towards appli-cationsrdquo Dalton Transactions no 14 pp 2781ndash2804 2003

[12] R Robson ldquoA net-based approach to coordination polymersrdquoJournal of the Chemical Society Dalton Transactions vol 2000no 21 pp 3735ndash3744 2000

[13] S Kitagawa and SMasaoka ldquoMetal complexes of hexaazatriph-enylene (hat) and its derivatives-from oligonuclear complexesto coordination polymersrdquo Coordination Chemistry Reviewsvol 246 pp 73ndash88 2003

[14] K Biradha ldquoCrystal engineering from weak hydrogen bondsto co-ordination bondsrdquo CrystEngComm vol 5 pp 374ndash3842003

[15] A M Beatty ldquoOpen-framework coordination complexes fromhydrogen-bonded networks toward hostguest complexesrdquoCoordination Chemistry Reviews vol 246 pp 131ndash143 2003

[16] C N R Rao S Natarajan and R Vaidhyanathan ldquoMetalcarboxylates with open architecturesrdquo Angewandte ChemieInternational Edition vol 43 no 12 pp 1466ndash1496 2004

[17] P J Hagrman D Hagrman and J Zubieta ldquoOrganic-inorganichybrid materials from ldquoSimplerdquo coordination polymers toorganodiamine-templated molybdenum oxidesrdquo AngewandteChemie International Edition vol 38 pp 2638ndash2684 1999

[18] O Kahn ldquoChemistry and physics of supramolecular magneticmaterialsrdquo Accounts of Chemical Research vol 33 no 10 pp647ndash657 2000

[19] O R Evans andW Lin ldquoCrystal engineering of NLO materialsbased on metal-organic coordination networksrdquo Accounts ofChemical Research vol 35 pp 511ndash522 2002

[20] O M Yaghi M OrsquoKeeffe N W Ockwig H K Chae MEddaoudi and J Kim ldquoReticular synthesis and the design ofnew materialsrdquo Nature vol 423 no 6941 pp 705ndash714 2003

[21] B Kesanli and W Lin ldquoChiral porous coordination networksrational design and applications in enantioselective processesrdquoCoordination Chemistry Reviews vol 246 no 1-2 pp 305ndash3262003

[22] S Kitagawa R Kitaura and S I Noro ldquoFunctional porous coor-dination polymersrdquo Angewandte Chemie International Editionvol 43 no 18 pp 2334ndash2375 2004

[23] S R Batten and R Robson ldquoInterpenetrating nets orderedperiodic entanglementrdquo Angewandte Chemie International Edi-tion vol 37 pp 1460ndash1494 1998

[24] S Leininger B Olenyuk and P J Stang ldquoSelf-assembly ofdiscrete cyclic nanostructures mediated by transition metalsrdquoChemical Reviews vol 100 no 3 pp 853ndash908 2000

[25] G F Swiegers and T J Malefetse ldquoNew self-assembled struc-tural motifs in coordination chemistryrdquo Chemical Reviews vol100 no 9 pp 3483ndash3537 2000

[26] B J Holliday and C A Mirkin ldquoStrategies for the constructionof supramolecular compounds through coordination chem-istryrdquo Angewandte Chemie International Edition vol 40 pp2022ndash2043 2001

[27] M Eddaoudi D B Moler H Li et al ldquoModular chemistrysecondary building units as a basis for the design of highlyporous and robust metal-organic carboxylate frameworksrdquoAccounts of Chemical Research vol 34 no 4 pp 319ndash330 2001

[28] D L Caulder and K N Raymond ldquoSupermolecules by designrdquoAccounts of Chemical Research vol 32 no 11 pp 975ndash982 1999

[29] Y Rodıguez-Martın M Hernandez-Molina F S Delgado etal ldquoStructural versatility of the malonate ligand as a toolfor crystal engineering in the design of molecular magnetsrdquoCrystEngComm vol 4 pp 522ndash535 2002

[30] S R Batten and K S Murray ldquoStructure and magnetismof coordination polymers containing dicyanamide and tri-cyanomethaniderdquo Coordination Chemistry Reviews vol 246no 1-2 pp 103ndash130 2003

[31] S R Batten P Jensen C J Kepert et al ldquoSyntheses structuresand magnetism of 120572-Mn(dca)

2 [Mn(dca)

2(H2O)2]sdotH2O [Mn

(dca)2(C2H5OH)2]sdot(CH

3)2CO [Fe(dca)

2(CH3OH)2]rdquo Journal

of the Chemical Society no 17 pp 2987ndash2997 1999[32] I Dasna S Golhen LOuahabO Pena J Guillevic andM Fet-

touhi ldquo1-Dmixed stack of coordinated and uncoordinated radi-cals in MnII(NITpPy)

4[N(CN)

2]2(NITpPy = nitronyl nitroxide

radical)rdquo Journal of the Chemical Society Dalton Transactionsno 2 pp 129ndash132 2000

[33] G A van Albada M E Quiroz-Castro I Mutikainen UTurpeinen and J Reedijk ldquoThe first structural evidence ofa polymeric Cu(II) compound with a bridging dicyanam-ide anion X-ray structure spectroscopy and magnetism ofcatena-[polybis(2-aminopyrimidine)copper(II)-bis(120583-dicyan-amido)]rdquo Inorganica Chimica Acta vol 298 no 2 pp 221ndash2252000

[34] A Escuer F A Mautner N Sanz and R Vicente ldquoTwo newone-dimensional compounds with end-to-end dicyanamideas a bridging ligand syntheses and structural characteriza-tion of trans-[Mn(4-bzpy)

2(N(CN)

2)2]119899

and cis-[Mn(Bpy)(N(CN)

2)2]119899 (4-bzpy = 4-benzoylpyridine bp = 221015840-bipyri-

dyl)rdquo Inorganic Chemistry vol 39 no 8 pp 1668ndash1673 2000[35] J H Luo M C Hong R Cao et al ldquoSyntheses and crystal

structures of cadmium(II) coordination polymers with end-to-end dicyanamide bridgesrdquo Polyhedron vol 21 no 8 pp 893ndash898 2002

[36] S Martın M G Barandika J I R de Larramendi et al ldquoStruc-tural analysis and magnetic properties of the 1D and 3D com-pounds [M

119899(dca)2119899bipym] (M =Mn Cu dca = dicyanamide

bipym=bipyrimidine n= 1 2)rdquo Inorganic Chemistry vol 40no 15 pp 3687ndash3692 2001


[37] I Dasna S Golhen L Ouahab N Daro and J P SutterldquoSynthesis X-ray crystal structures and magnetic properties ofCuII and MnII complexes containing imino nitroxide radicalsand a dicyanamide anionrdquoNew Journal of Chemistry vol 25 no12 pp 1572ndash1576 2001

[38] B Vangdal J Carranza F Lloret M Julve and J SlettenldquoSyntheses crystal structures and magnetic properties of cop-per(II) dicyanamide complexes dinuclear chain and laddercompoundsrdquo Journal of the Chemical Society Dalton Transac-tions no 4 pp 566ndash574 2002

[39] J Carranza C Brennan J Sletten F Lloret and M JulveldquoThree one-dimensional systems with end-to-end dicyanamidebridges between copper(II) centres structural and magneticpropertiesrdquo Journal of theChemical Society DaltonTransactionsno 16 pp 3164ndash3170 2002

[40] S Dalai P S Mukherjee E Zangrando and N Ray ChaudhurildquoSynthesis crystal structure and magnetic properties of twonew dicyanamide bridged 2D and 1D complexes of Mn(II)rdquoNew Journal of Chemistry vol 26 no 9 pp 1185ndash1189 2002

[41] M Du X J Zhao S R Batten and J Ribas ldquoFrom 1-D coor-dination polymers to 3-D hydrogen-bonding networks crystalengineering and magnetism of CuIIminusdcaminuscyanopyridine sup-ramolecular systems (dca = dicyanamide N(CN)

2

minus)rdquo CrystalGrowth and Design vol 5 pp 901ndash909 2005

[42] M Du XG Wang Z H Zhang L F Tang and X J ZhangldquoSolvent-directed layered Co(II) coordination polymers withunusual solid-state properties from a nanoporous frameworkto the dense polythreading 3-D aggregation rdquo CrystEngCommvol 8 pp 788ndash793 2006

[43] C R Kmety J L Manson Q Z Huang et al ldquoMagnetic PhaseTransitions in MnII[N(CN)

2]2rdquo Molecular Crystals and Liquid

Crystals Science and Technology A vol 334 pp 631ndash640 1999[44] J L Manson C R Kmety Q Z Huang et al ldquoStructure and

magnetic ordering of MnII[N(CN)2]2(M =Co Ni)rdquo Chemistry

of Materials vol 10 no 9 pp 2552ndash2560 1998[45] S R Batten P Jensen B Moubaraki K S Murray and R Rob-

son ldquoStructure and molecular magnetism of the rutile-relatedcompounds M(dca)

2 M=CoII NiII CuII dca = dicyanamide

N(CN)2

minusrdquo Chemical Communications no 3 pp 439ndash440 1998[46] MKurmoo andC J Kepert ldquoHardmagnets based on transition

metal complexes with the dicyanamide anion N(CN)2

minusrdquoNewJournal of Chemistry vol 22 no 12 pp 1515ndash1524 1998

[47] J L Manson C R Kmety F Palacio A J Epstein and J SMiller ldquoLow-field remanent magnetization in the weak ferro-magnetMn[N(CN)

2]2 Evidence for spin-flop behaviorrdquoChem-

istry of Materials vol 13 no 3 pp 1068ndash1073 2001[48] C R Kmety Q Huang J W Lynn et al ldquoNoncollinear

antiferromagnetic structure of the molecule-based magnetMn[N(CN)

2]2rdquo Physical Review B vol 62 no 9 pp 5576ndash5588

2000[49] C X Zhang Z Q Liu D Z Liao and S P Yan ldquoA novel

ferromagnetic coupling one-dimensional complex Cu(II)(NIT3Py)

2[N(CN)

2]2(H2O)2rdquo Inorganica Chimica Acta vol

357 no 2 pp 376ndash380 2004[50] D Ghoshal A K Ghosh J Ribas et al ldquoSynthesis crystal

structure and magnetic behavior of two dicyanamido-bridgedcomplexes of manganese(II) effect of weak interaction incarving regular geometryrdquo Crystal Growth and Design vol 5no 3 pp 941ndash947 2005

[51] B W Sun S Gao B Q Ma and Z MWang ldquoSyntheses struc-tures and magnetic properties of 1-D coordination polymers

containing both dicyanamide and 2-pyrrolidonerdquo InorganicChemistry Communications vol 4 no 2 pp 72ndash75 2001

[52] J L Manson A M Arif C D Incarvito L M Liable-Sands AL Rheingold and J S Miller ldquoStructures and magnetic prop-erties of novel 1-D coordination polymers containing bothdicyanamide and pyridine-type ligandsrdquo Journal of Solid StateChemistry vol 145 no 2 pp 369ndash378 1999

[53] W Dong M Liang Y Q Sun and Z Q Liu ldquoSyntheses andstructures of two 1-D complexes [Co(dmf)

2NCNCN)

2] and

[Cu(bipy)(NCNCN)]ClO4with bridging dicyanamide ligandsrdquo

Zeitschrift fur Anorganische und Allgemeine Chemie vol 629no 14 pp 2443ndash2445 2003

[54] A Escuer F A Mautner N Sanz and R Vicente ldquoSynthesesstructures and magnetic properties of the dicyanamide (dca)polynuclear compounds [Mn(ac)(terpy)(120583

15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899

and [Mn(dca)(terpy)(MeOH)2(120583-terephthal-

ate)]rdquo Inorganica Chimica Acta vol 340 pp 163ndash169 2002[55] A Escuer F A Mautner N Sanz and R Vicente ldquoTwo new

one-dimensional compounds with end-to-end dicyanamideas a bridging ligand syntheses and structural characteri-zation of trans-[Mn(4-bzpy)

2(N(CN)

2)2]119899and cis-[Mn(Bpy)

(N(CN)2)2]119899 (4-bzpy = 4-benzoylpyridine bpy = 221015840-

bipyridyl)rdquo Inorganic Chemistry vol 39 pp 1668ndash1673 2000[56] S Dalai P S Mukherjee E Zangrando and N Ray Chaudhuri

ldquoSynthesis crystal structure and magnetic properties of twonew dicyanamide bridged 2D and 1D complexes of Mn(II)rdquoNew Journal of Chemistry vol 26 no 9 pp 1185ndash1189 2002

[57] A J Zhou L L Zheng and M L Tong ldquoCatena-Poly[[dimethanolcobalt(II)]-di-120583-1 5-dicyanamido]rdquo Acta Crystal-lographica vol E60 pp m1254ndashm1255 2004


2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)


of the Chemical Society Dalton Transactions no 17 pp 2987ndash2997 1999

[59] D Armentano G de Munno F Guerra J Faus F Lloret andM Julve ldquo221015840-Bipyrimidine- and 23-bis(2-pyridyl)pyrazine-containingmanganese(II) compounds structural andmagneticpropertiesrdquo Dalton Transactions no 24 pp 4626ndash4634 2003

[60] S Konar S Dalai P S Mukherjee M G B Drew J Ribasand N R Chaudhuri ldquoTwo new NiII complexes with 120583

15-

dicyanamide as bridging ligandrdquo Inorganica Chimica Acta vol358 no 4 pp 957ndash963 2005

[61] J L Manson J A Schlueter and C L Nygren ldquoMn(dca)2

(pym)2and Mn(dca)

2(pym)(H

2O) dca = dicyanamide pym=

pyrimidine new coordination polymers exhibiting 1- and 2-Dtopologiesrdquo Dalton Transactions vol 2007 no 6 pp 646ndash6522007

[62] A Q Wu F K Zheng L Z Cai G C Guo and J SHuang ldquoSyntheses and crystal structures of two novel 1-Dmetal complexes with dicyanamide [Zn(pheen)(dca)

2]119899and

[Cu(quin)2(dca)2]119899rdquo Chinese Journal of Structural Chemistry

vol 23 p 1143 2004[63] J H Luo M C Hong R Cao et al ldquoSyntheses and crystal


[64] H L Sun S Gao B Q Ma G Su and S R Batten ldquoStructuresand magnetism of a series Mn(II) coordination polymerscontaining pyrazine-dioxide derivatives and different anionsrdquoCrystal Growth and Design vol 5 no 1 pp 269ndash277 2005


[65] J L Manson J Y Gu J A Schlueter and H H WangldquoStructures and magnetic behavior of 1- 2- and 3D coordina-tion polymers in the Cu(II)-dicyanamide-pyrimidine familyrdquoInorganic Chemistry vol 42 pp 3950ndash3955 2003

[66] P Jensen S R Batten BMoubaraki and K SMurray ldquoSynthe-ses crystal structures andmagnetic properties of first row tran-sition metal coordination polymers containing dicyanamideand 441015840-bipyridinerdquo Journal of the Chemical Society DaltonTransactions no 19 pp 3712ndash3722 2002

[67] S Triki F Thetiot J R Galan-Mascaros and J S Pala ldquoNewcompounds with bridging dicyanamide and bis-chelating 221015840-bipyrimidine ligands syntheses structural characterisationand magnetic properties of the two-dimensional materials[Fe2(dca)4(bpym)]sdotH

2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New

Journal of Chemistry vol 25 pp 954ndash958 2001[68] M L Tong Y M Wu Y X Tong X M Chen H C Chang

and S Kitagawa ldquoRational design of a ferromagnetic trinuclearcopper(II) complex with a novel in-situ synthesised metalloli-gandrdquo European Journal of Inorganic Chemistry vol 2003 no13 pp 2385ndash2388 2003

[69] L L ZhengW X Zhang L J Qin J D Leng J X Lu andM LTong ldquoIsolation of a pentadentate ligand and stepwise synthesisstructures and magnetic properties of a new family of homo-and heterotrinuclear complexesrdquo Inorganic Chemistry vol 46pp 9548ndash9557 2007

[70] L L Zheng H X Li J D Leng J Wang and M L Tong ldquoTwophotoluminescentmetal-organic frameworks constructed fromCd3(1205833-OH) cluster or 1D Zn

5(1205833-OH)

2(120583-OH)

2chain units

and in situ formed Bis(tetrazole)amine ligandsrdquo EuropeanJournal of Inorganic Chemistry vol 2008 no 2 pp 213ndash2172008

[71] L L Zheng J D Leng W T Liu W X Zhang J X Luand M L Tong ldquoCu2+-mediated nucleophilic addition ofdifferent nucleophiles to dicyanamidemdashsynthesis structuresand magnetic properties of a family of mononuclear trinuclearhexanuclear and polymeric copper(II) complexesrdquo EuropeanJournal of Inorganic Chemistry vol 2008 no 29 pp 4616ndash46242008

[72] L L Zheng C K Tan and M L Tong ldquoSynthesis and crys-tal structures of Mn(II)Co(II)- dicyanamide-4-(1H-imidazol-1-yl)aniline ternary complexsrdquo Chinese Journal of InorganicChemistry vol 22 pp 1426ndash1430 2006

[73] A Igashira-Kamiyama T Kajiwara T Konno and T Ito ldquoFer-romagnetic coupling promoted by 1205813N 1205812N bridging systemrdquoInorganic Chemistry vol 45 no 16 pp 6460ndash6466 2006

[74] I Castro-Rodriguez K Olsen P Gantzel and K MeyerldquoUranium complexes supported by an aryloxide functionalisedtriazacyclononane macrocycle synthesis and characterisationof a six-coordinateU(III) species and insights into its reactivityrdquoChemical communications no 23 pp 2764ndash2765 2002

[75] L Brammer ldquoMetals and hydrogen bondsrdquo Dalton Transac-tions no 16 pp 3145ndash3157 2003

[76] H W Roesky and M Andruh ldquoThe interplay of coordinativehydrogen bonding and 120587-120587 stacking interactions in sustainingsupramolecular solid-state architectures a study case of bis(4-pyridyl)- and bis(4-pyridyl-N-oxide) tectonsrdquo CoordinationChemistry Reviews vol 236 pp 91ndash119 2003

[77] G M Sheldrick SADABS 205 University Gottingen[78] SHELXTL 610 Bruker Analytical Instrumentation Madison

Wis USA 2000[79] T C Stamatatos K A Abboud W Wernsdorfer and G Chris-

tou ldquoHigh-nuclearity high-symmetry high-spin molecules a

mixed-valence Mn10cage possessing rare T symmetry and an

S= 22 ground Staterdquo Angewandte Chemie International Editionvol 45 no 25 pp 4134ndash4137 2006

[80] J Yoo A YamaguchiMNakano et al ldquoMixed-valence tetranu-clear manganese single-molecule magnetsrdquo Inorganic Chem-istry vol 40 no 18 pp 4604ndash4616 2001

[81] D N Hendrickson G Christou H Ishimoto et al ldquoMagneti-zation tunneling in single-molecule magnetsrdquo Polyhedron vol20 no 11ndash14 pp 1479ndash1488 2001

[82] L Lecren O Roubeau C Coulon et al ldquoSlow relaxation ina one-dimensional rational assembly of antiferromagneticallycoupled [Mn

4] single-molecule magnetsrdquo Journal of the Ameri-

can Chemical Society vol 127 no 49 pp 17353ndash17363 2005[83] H Miyasaka K Nakata L Lecren et al ldquoTwo-dimensional

networks based onMn4complex linked by dicyanamide anion

from single-molecule magnet to classical magnet behaviorrdquoJournal of the American Chemical Society vol 128 no 11 pp3770ndash3783 2006

[84] H Miyasaka K Nakata K Sugiura M Yamashita and RClerac ldquoA three-dimensional ferrimagnet composed of mxed-valence Mn

4clusters linked by an Mn[N(CN)

2]6

4minus unitrdquoAngewandte Chemie International Edition vol 43 no 6 pp707ndash711 2004

[85] J Yoo W Wernsdorfer E C Yang M Nakano A L Rhein-gold and D N Hendrickson ldquoOne-dimensional chain oftetranuclear manganese single-molecule magnetsrdquo InorganicChemistry vol 44 no 10 pp 3377ndash3379 2005

[86] H K Kohler A Kolbe and G Lux ldquoMetall-pseudohalogenide27 Zur struktur der dicyanamide zweiwertiger 3d-MetalleM(N(CN)

2)2rdquo Zeitschrift fur Anorganische und Allgemeine

Chemie vol 428 pp 103ndash112 1977[87] G R Desiraju and T Steiner The Weak Hydrogen Bond in

Structural Chemistry and Biology Oxford University PressOxford UK 1999

[88] B W Sun S Gao B Q Ma D Z Niu and Z M Wang ldquoSyn-theses structures andmagnetic properties of three-dimensionalco-ordination polymers constructed by dimer subunits rdquo Jour-nal of the Chemical Society Dalton Transactions no 22 pp4187ndash4191 2000

[89] Z M Wang B W Sun J Luo et al ldquoBimetallic sand-wiches assembled with chelated CuZn cations and manganesedicyanamide polymeric laddersrdquo Polyhedron vol 22 no 3 pp433ndash439 2003

[90] B W Sun S Gao B Q Ma and Z MWang ldquoSyntheses struc-tures and magnetic properties of 1-D coordination polymer-scontaining both dicyanamide and 2-pyrrolidonerdquo InorganicaChimica Acta vol 4 pp 72ndash75 2001

[91] Z M Wang B W Sun J Luo et al ldquoBimetallic sheet and3D threefold interpenetrating diamond-like network const-ructed by chelate Cu cations and Mn dicyanamide polymericchains Synthesis crystal structure and magnetism of [Cu(L)2][Mn(dca)

4] (L = ethylenediamine or 13-diaminopropane

dca = dicyanamide N(CN)2

minus)rdquo Inorganica Chimica Acta vol332 no 1 pp 127ndash134 2002

[92] W F Yeung S Gao W T Wong and T C Lau ldquoAntiferromag-netic ordering in a novel five-connected 3-D polymer Cu

2(25-

Me2pyz)[N(CN)

2]4119899(25-Me

2pyz = 25-dimethylpyrazinerdquoNew

Journal of Chemistry vol 26 pp 523ndash525 2002[93] J L Manson Q Z Huang J W Lynn et al ldquoLong-range

magnetic order inMn[N(CN)2]2(pyz) pyz = pyrazine Suscep-

tibility magnetization specific heat and neutron diffraction


measurements and electronic structure calculationsrdquo Journal ofthe American Chemical Society vol 123 no 1 pp 162ndash172 2001

[94] P M van der Werff S R Batten P Jensen B Moubaraki andK S Murray ldquoCation templation of anionic metal dicyanamidenetworksrdquo Inorganic Chemistry vol 40 pp 1718ndash1722 2001

[95] H L Sun Z M Wang and S Gao ldquoSynthesis crystal struc-tures and magnetism of cobalt coordination polymers basedon dicyanamide and pyrazine-dioxide derivativesrdquo InorganicChemistry vol 44 no 7 pp 2169ndash2176 2005

[96] J Curely F Lloret and M Julve PhysicalReview B vol 58 p1465 1988

[97] D Armentano G de Munno F Guerra M Julve and FLloret ldquoLigand effects on the structures of extended networksof dicyanamide-containing transition-metal ionsrdquo InorganicChemistry vol 45 no 12 pp 4626ndash4636 2006

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


N

NN

N

NN

N

NN

N

NN

N

NN

N

NN

N

NNN

NN

1205831 1205833

12058315 12058313

120583135 120583115

1205831135 12058311355

Scheme 1 Schematic showing the coordination modes of dca

ligand We report herein three ternary supramolecular archi-tectures [Co(dca)

2(hmpH)

2] (1) [Cu(dca)

2(hmpH)

2] (2)

and [Mn(dca)2(hepH)]

119899(3) obtained by this strategy

2 Experimental

21 Materials and General Methods The reagents and sol-vents employed were commercially available and used asreceived without further purification The C H and Nmicroanalyses were carried out with an Elementar Vario-ELCHNS elemental analyzer The FT-IR spectra were recordedfrom KBr pellets in the range 4000ndash400 cmminus1 on a BrukerTENSOR27 spectrometer Variable-temperature magneticsusceptibility measurements were made using a SQUIDmagnetometer MPMS XL-7 (QuantumDesign) at 01 T for 3The diamagnetic correction for each sample was determinedfrom Pascalrsquos constants

22 Synthesis

221 Synthesis of [Co(hmpH)2(dca)2] (1) Amethanol solu-

tion (10mL) of Co(NO3)2sdot6H2O (145mg 05mmol) was


2O solution (20mL)

containing sodium dicyanamide (89mg 10mmol) andhmpH(109mg 10mmol) A red solution formed onaddition of metal salt to the ligands The mixture solutionwas filtered and solvent evaporated at room temperatureWell-shaped red block crystals of 1 were obtained within 1week in 62 yield Anal calcd for C

16H14CoN8O2 C 4695

H 345 N 2738 Found C 4653 H 352 N 2721 IR3081m 2215vs 1602m 1561m 1483s 1432m 1385w 1347w1298vs 1250s 1142vs 1081m 988w 861m 754m 675m 646w612w 450vw

222 Synthesis of [Cu(hmpH)2(dca)2] (2) Amethanol solu-

tion (10mL) of Cu(NO3)2sdot3H2O (121mg 05mmol) was


2O solution (20mL) con-

taining sodium dicyanamide (89mg 10mmol) and hmpH(109mg 10mmol) A blue solution formed on addition ofmetal salt to the ligandsThemixture was filtered and solventevaporated at room temperature Well-shaped blue blockcrystals of 2 were obtained within 1 week in 83 yield Analcalcd for C

10H7CuN7O C 3941 H 232 N 3217 Found

C 3932 H 241 N 3203 IR 3706w 3429m 3074w 2855m2378s 2214vs 1613s 1571m 1485m 1440s 1366m 1292m1223vw 1159vw 1092vs 931vw 821vw 762s 722m 673s 623s533m 483w 438m

223 Synthesis of [119872119899(ℎ119890119901119867)2(119889119888119886)

2]

119899(3) hepH (123mg

10mmol) dissolved in a minimum amount of methanolwas added to an aqueous solution containing MnCl

2sdot4H2O

(99mg 05mmol) and sodium dicyanamide (89mg10mmol) Block colorless crystals of 3 were grown after5 days Yield ca 74 Anal Calcd for C

11H9MnN7O C

4259 H 292 N 3161 Found C 4184 H 307 N 3123IR 3597w 3541w 3286m 3081w 2954vw 2901vw 2310m2273m 2242m 2177s 1606s 1571m 1488s 1440s 1419w1369s 1308vs 1249vw 1155w 1107m 1075m 1029s 940m890vw 866w 759m 658w 640vw 579w 515m 451vw 416vw

23 X-Ray Crystallographic Study Single-crystal data of 1ndash3 were collected at 293(2) K on a Bruker Smart 1000 CCDdiffractometer with Mo Ka radiation (120582 = 071073 A)All empirical absorption corrections were applied using theSADABS program [77] The structure was solved usingdirect method which yielded the positions of all nonhydro-gen atoms These were refined first isotropically and thenanisotropically All calculations were performed using theSHELXTL programs [78] The crystallographic data for 1ndash3 are summarized in Table 1 The selected bond lengths andangles are listed in Table 2

CCDC 711609ndash711611 contain the supplementary crystal-lographic data for this paper These data can be obtained freeof charge from the Cambridge Crystallographic Data Centre

3 Results and Discussion

31 Synthesis and Characterization Air-stable complexes 1ndash3were obtained from the reactions of metal(II) salts Na(dca)and 2-hydroxypyridine-type ligands (Scheme 2) in whichthe hydroxypyridines act as chelating ligands Moreover theproducts are independent of the ligand-to-metal ratios

In contrary under base condition 2-hydroxypyridine-type ligands such as hmpH hepH and 26-pyridinedim-ethanol have been found to act as bridging ligands togenerate some fascinating polynuclearmetal-clusters [79ndash82]and the extended 1D or 2D metal cluster-based coordinationpolymers with dca as bridges in recent years [83ndash85]

The IR spectra of 1ndash3 are quite similar They all showstrong absorptions in the range of 2310ndash2100 cmminus1 whichcorrespond to the ]s+]as (C equiv N) ]as (C equiv N) and ]s (C equiv N)modes of the dca ligand [86]


NO H

NO H

NO H

M(II)+

dca

Coligand

0-D complex

1-D chain

2-D (6 3) layer








1198771 = sum ||119865119900| minus |119865119888|| sum |119865119900| 1199081198772 = [sum119908(1198652

119900minus 1198652

119888)2

sum119908(1198652

119900)2

]

12


1coordination













15- and 120583















15-




15)




119872(inset) and 120594

119872119879 versus 119879 plots

(120594119872




C1

C2

C3C4

C5

C6C7

C8

01

N1

N2N3

N4A

N1AN4

01A

Co1O

O

OO

OO

OO

O

OO

OO

O

(a)

(b)

(c)




01AO

OO

O

OO

O

O

OO

O

O O

O

N4A

N7AN1A

N3C2N2

C1N1Cu1

N3A01

N4C3

N5C4

N6

N7

Cu1A

(a)

CuO

NC

(b)

CuOH

NC

(c)



2sum120594obs

2]

12


15-dca-coligand

systems [97]


Mn1B

Mn1A

N3A

N6BMn1

N4C3

N5

C4

N6

01O

OO

O

O

O

O

OO N1

C1

N2

C2N3

Mn1C

N7

(a)

MnO

NC

(b)

a

b

c

MnO

NC

(c)


0 50 100 150 200 250 300

0

02

04

06

08

1

2

3

4

5

119879 (K)

120594MT

(cm3

K m

olminus1)

120594M

(cm3

molminus1)





References


10158401015840

4101584010158401015840

































2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)




4[N(CN)





2(N(CN)

2)2]119899














2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NO H

NO H

NO H

M(II)+

dca

Coligand

0-D complex

1-D chain

2-D (6 3) layer








1198771 = sum ||119865119900| minus |119865119888|| sum |119865119900| 1199081198772 = [sum119908(1198652

119900minus 1198652

119888)2

sum119908(1198652

119900)2

]

12


1coordination













15- and 120583















15-




15)




119872(inset) and 120594

119872119879 versus 119879 plots

(120594119872




C1

C2

C3C4

C5

C6C7

C8

01

N1

N2N3

N4A

N1AN4

01A

Co1O

O

OO

OO

OO

O

OO

OO

O

(a)

(b)

(c)




01AO

OO

O

OO

O

O

OO

O

O O

O

N4A

N7AN1A

N3C2N2

C1N1Cu1

N3A01

N4C3

N5C4

N6

N7

Cu1A

(a)

CuO

NC

(b)

CuOH

NC

(c)



2sum120594obs

2]

12


15-dca-coligand

systems [97]


Mn1B

Mn1A

N3A

N6BMn1

N4C3

N5

C4

N6

01O

OO

O

O

O

O

OO N1

C1

N2

C2N3

Mn1C

N7

(a)

MnO

NC

(b)

a

b

c

MnO

NC

(c)


0 50 100 150 200 250 300

0

02

04

06

08

1

2

3

4

5

119879 (K)

120594MT

(cm3

K m

olminus1)

120594M

(cm3

molminus1)





References


10158401015840

4101584010158401015840

































2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)




4[N(CN)





2(N(CN)

2)2]119899














2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










15-




15)




119872(inset) and 120594

119872119879 versus 119879 plots

(120594119872




C1

C2

C3C4

C5

C6C7

C8

01

N1

N2N3

N4A

N1AN4

01A

Co1O

O

OO

OO

OO

O

OO

OO

O

(a)

(b)

(c)




01AO

OO

O

OO

O

O

OO

O

O O

O

N4A

N7AN1A

N3C2N2

C1N1Cu1

N3A01

N4C3

N5C4

N6

N7

Cu1A

(a)

CuO

NC

(b)

CuOH

NC

(c)



2sum120594obs

2]

12


15-dca-coligand

systems [97]


Mn1B

Mn1A

N3A

N6BMn1

N4C3

N5

C4

N6

01O

OO

O

O

O

O

OO N1

C1

N2

C2N3

Mn1C

N7

(a)

MnO

NC

(b)

a

b

c

MnO

NC

(c)


0 50 100 150 200 250 300

0

02

04

06

08

1

2

3

4

5

119879 (K)

120594MT

(cm3

K m

olminus1)

120594M

(cm3

molminus1)





References


10158401015840

4101584010158401015840

































2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)




4[N(CN)





2(N(CN)

2)2]119899














2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


C1

C2

C3C4

C5

C6C7

C8

01

N1

N2N3

N4A

N1AN4

01A

Co1O

O

OO

OO

OO

O

OO

OO

O

(a)

(b)

(c)




01AO

OO

O

OO

O

O

OO

O

O O

O

N4A

N7AN1A

N3C2N2

C1N1Cu1

N3A01

N4C3

N5C4

N6

N7

Cu1A

(a)

CuO

NC

(b)

CuOH

NC

(c)



2sum120594obs

2]

12


15-dca-coligand

systems [97]


Mn1B

Mn1A

N3A

N6BMn1

N4C3

N5

C4

N6

01O

OO

O

O

O

O

OO N1

C1

N2

C2N3

Mn1C

N7

(a)

MnO

NC

(b)

a

b

c

MnO

NC

(c)


0 50 100 150 200 250 300

0

02

04

06

08

1

2

3

4

5

119879 (K)

120594MT

(cm3

K m

olminus1)

120594M

(cm3

molminus1)





References


10158401015840

4101584010158401015840

































2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)




4[N(CN)





2(N(CN)

2)2]119899














2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Mn1B

Mn1A

N3A

N6BMn1

N4C3

N5

C4

N6

01O

OO

O

O

O

O

OO N1

C1

N2

C2N3

Mn1C

N7

(a)

MnO

NC

(b)

a

b

c

MnO

NC

(c)


0 50 100 150 200 250 300

0

02

04

06

08

1

2

3

4

5

119879 (K)

120594MT

(cm3

K m

olminus1)

120594M

(cm3

molminus1)





References


10158401015840

4101584010158401015840

































2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)




4[N(CN)





2(N(CN)

2)2]119899














2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of































2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)




4[N(CN)





2(N(CN)

2)2]119899














2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







2










N(CN)2











2[N(CN)








2NCNCN)

2] and




15-dca)]

119899[Mn(pdz)

2

(12058315-dca)2]119899




2(N(CN)







2 [Mn(dca)

2(H2O)2]sdotH2O [Mn


3)2CO [Fe(dca)





15-



(pym)2and Mn(dca)

2(pym)(H




2]119899and









2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





2O and [Fe

2(dca)4(bpym)(H

2O)2]rdquo New





5(1205833-OH)

2(120583-OH)

2chain units






















2]6















2(25-

Me2pyz)[N(CN)

2]4119899(25-Me




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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