Bismuth Carboxylates with Brucite- and Fluorite-Related Structures: Synthesis Structure and...

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Article

Bismuth Carboxylates with brucite and fluorite-related structures: Synthesis Structure and Properties

Shiv R. Sushrutha, and Srinivasan NatarajanCryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg4000654 • Publication Date (Web): 27 Feb 2013

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Bismuth Carboxylates with brucite and fluorite-related structures:

Synthesis Structure and Properties

S R Sushrutha, Srinivasan Natarajan*

Framework solids Laboratory, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-

560012, India.

* Corresponding author, Email: [email protected]

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Abstract

Three new compounds of bismuth, [C4N2H10][Bi(C7H4NO4)(C7H3NO4)].H2O, I, [Bi(C5H3N2O4)

(C5H2N2O4)], II and [Bi(µ2-OH)(C7H3NO4)], III have been prepared by the reaction between bismuth nitrate and

heterocyclic aromatic dicarboxylic acids, 2,6-pyridinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 3,4-

pyridinedicarboxylic acid, respectively, under hydrothermal conditions. The structures of all the compounds have

linkages between Bi2O2 and the corresponding dicarboxylate forming a simple molecular unit in I, a bilayer

arrangement in II and a three-dimensional extended structure in III. The topological arrangement of the nodal

building units in the structures indicates that a brucite related layer (II) and fluorite related arrangement (III) can be

realized in these structures. By utilizing the secondary interactions, one can correlate the structure of III to a

Kagome related one. The observation of such classical inorganic related structures in the bismuth carboxylates is

noteworthy. Lewis acid catalytic studies on the formation of ketal suggest the possible participatory role of the lone

pair of electrons. All the compounds are characterized employing, elemental analysis, IR, UV-vis, thermal studies.

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Introduction

Inorganic coordination polymers or metal-organic frameworks are an important family of compounds in the

area of materials chemistry.1 The compounds have interesting structures formed by the clever combination of

inorganic coordination chemistry and organic functional groups. It is known that the rigid organic backbone in these

compounds is crucial for many of its interesting physical and chemical properties such as catalysis, sorption and

separation.2 The large number as well as the diversity observed in the structures of inorganic coordination polymers

is a testimony for the continuing interest.1 The majority of the compounds have been prepared employing either the

transition metals or the lanthanides.3 It is to be noted that the main group elements have not received much

attention. Of the main group elements, Al,4 Ga,5 In,6 Pb,7 Sn8 have been investigated and appear to form interesting

structures.

Bismuth, though part of the main group element, has not been studied in sufficient detail. Bi3+ ions may be

of interest due to the presence of its stereo active lone pair of electrons.9 The earlier studies of Sn2+ compounds in

open-framework phosphates suggest the possible structure directing role for the lone pair of electrons.10 Similar lone

pair effects have also been observed in Sn2+ oxalates11 and Pb2+ compounds as well.12

From the available structures of Bi3+ carboxylates,13 one finds reasonable evidence for the structure

directing role for the lone pair of electrons. The lone pair of electrons appears to participate in structure-direction

role, depending on the coordination environment around the Bi3+ cation.14 One can rationalize this observation,

rather naively, that low coordination would lead to non-spherical charge distribution around the Bi3+ cation resulting

in the lone pair to actively participate in a structure-directing role (hemi-directed).15 Higher coordination, on the

other hand, would result in steric hindrance as well as to a more uniform charge distribution around the Bi3+ cation

leading to an inactive role for the lone pair of electrons (holo-directed).16a It is clear that the nature and the role of

the lone pair of electrons in Bi3+ carboxylates is interesting and there is considerable scope to investigate this further

in other Bi3+ carboxylates.

One of the advantages in inorganic coordination polymers is the formations of more open and porous

structures, by employing subtle crystal engineering principles. The impetus to study the bismuth based compounds

would be to exploit the lone pair of electrons not only in structure direction but also in related properties such as

catalysis. It would be preferable to have open structures in which the lone pair of electrons are freely accessible and

available for manipulations. From the Pearson’s theory of hard-soft acids and bases, Bi3+ ions can be considered to

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be a borderline acid.17 From the available structures in the literature, it appears that Bi3+ ion can bind fairly well

with ligands possessing O and N donor atoms. Thus, one can expect to find the anions of amino polycarboxylic acid

and polyamino carboxylic acids to form stable compounds with Bi3+ ions. The recent findings on the formation of

coordination polymeric structure of Bi3+ ions support this view.13 In addition, the larger size of the Bi3+ ions would

give coordination number higher than six in most of the compounds, which is also the observed behavior.18 As part

of a program to prepare new inorganic coordination polymers, we are interested in the reaction between heterocyclic

aromatic carboxylic acids and Bi3+ ions.

During the course of this study, we have isolated three new compounds employing 2,6-pyridine

dicarboxylic acid (2,6-PDC), 4,5-imidazoledicarboxylic acid (4,5-IDC) and 3,4-pyridinedicarboxylic acid (3,4-

PDC). The compounds, [C4N2H10][Bi(C7H4NO4)(C7H3NO4)].H2O, I, [Bi(C5H3N2O4) (C5H2N2O4)], II and [Bi(µ2-

OH)(C7H3NO4)], III have one-, two- and three-dimensional structure. In this paper, the synthesis, structure and

properties of the three compounds are presented.

Experimental Section

Synthesis and Characterization

Reagents needed for the synthesis were used as received; Bi(NO3)3.5H2O [Fluka, 99%], 2,6-pyridine

dicarboxylic acid (2,6-PDC) [Lancaster (U.K), 98%], 4,5-imidazoledicarboxylic acid (4,5-IDC) [Lancaster (U.K),

97%], 3,4-pyridinedicarboxylic acid (3,4-PDC) [Aldrich, 97%], imidazole [Merck, 99%], piperazine (pip) [CDH

(India), 98%]. All the compounds were synthesized employing the hydrothermal method. For the preparation of

compound I, Bi(NO3)3. 5H2O (0.243 g, 0.5 mM), 2,6-PDC (0.142 g, 0.85 mM), pip (0.044 g, 0.5 mM) and 7 ml

water were mixed at room temperature for 30 mins. The reaction mixture with the composition, 1 Bi(NO3)3.5H2O :

1.7 2,6-PDC : 1 pip : 777 H2O, was carefully transferred to a 23 ml PTFE stainless steel autoclave and heated at

180oC for 72hrs. The resulting product containing large quantities of light brown block-like crystals was filtered

under vacuum, washed with deionized water and dried at ambient conditions. A similar synthesis procedure was

employed for the preparation of compounds II and III, but by using 4,5-IDC and 3,4-PDC, respectively in place of

2,6-PDC. The synthesis composition and the conditions employed is listed in Table 1.

The powder X-ray diffraction (PXRD) patterns for all the synthesized compounds were recorded in the 2θ

range 5-50o using Cu Kα radiation (Philips X’pert). The observed PXRD pattern was found to be entirely consistent

with the simulated pattern generated using the single crystal X-ray structure (ESI, Figure S1-S3), indicating the

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phase purity of the products. The infrared (IR) spectroscopic studies were carried out using KBr pellets (Perkin-

Elmer, SPECTRUM 1000). The IR spectra for all the compounds exhibited characteristic bands (ESI, Table S1).19

The observation of bands at 3459 cm-1 and 3071 cm-1 in I confirms the presence of lattice water molecules and the

carboxylic acid group, respectively. The band at 3603 cm-1 observed in III suggests the presence of a µ2-hydroxyl

group (ESI, Figure S4).

Thermogravimetric analysis (TGA) (Metler-Toledo) was carried out in an oxygen atmosphere (flow rate =

50 ml/min) in the temperature range 30oC – 950oC (heating rate = 5oC/min) (ESI, Figure S5). In the case of

compound I, a small weight loss of 3.6% observed around 140oC corresponds to the loss of water molecule (calc. 3

%). The second weight loss of 57.4% observed around 400oC could be due to the loss of piperazine and the

carboxylate moieties (calc. 59.4%). The total observed weight loss of 61% corresponds well with the loss of lattice

water molecules and all the organic species (calc. 62.4%). For compound II, a single step weight loss of 53.3%

observed around 380oC corresponds to the loss of the organic carboxylate moieties (calc. 56.4%), similar behavior

was also observed for compound III, with a weight loss of 42.3% around 380oC, which corresponds with the loss of

the organic carboxylate moieties (calc. 42.2%). The final calcined products were found to be crystalline in all the

cases by PXRD and correspond to Bi2O3 (JCPDS: 41-1449).

Optical Studies

The UV-vis spectroscopic studies were recorded in the solid state at room temperature (Perkin-Elmer

model Lambda 35). The observed optical spectra of the compounds were compared with the spectra obtained for the

sodium salts of 2,6-pyridinedicarboxylic acid, 4,5-imidazoledicarboxylic acid and 3,4-pyridinedicarboxylic acid.

While compound I exhibited an absorption maxima at around 315 nm, for II at 300 nm and for III the absorption

maxima was observed at 310 nm and with a shoulder at 270 nm, respectively. The absorption peaks may be

assigned to the intraligand π � π* transition.20 In addition to the band at 315 nm for I, the spectra has a broad

feature at ~510 nm, which may be due to the metal to ligand charge-transfer involving the possible promotion of the

lone pair of electrons of the metal to the π* orbital of the ligand (ESI, Figure S6-S7). Similar optical absorption

behavior has been observed before in bismuth bipyridyl and bismuth corrole complexes.21

The photoluminescence spectra for all the compounds were recorded on solid samples at room temperature

(Perkin-Elmer, LS 55) (ESI, Figure S8). Compound I, when excited at 315 nm, emits band centered around 405 nm

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and 420 nm, which could be tentatively assigned to the π* � π and π* � n transitions of the ligand. 22a, b In

addition, a band centered around 485 nm was also observed, which could be blue emission seen earlier in

[Bi(C7H3NO4)2]. H3O+.(H2O)0.83.

13b This transition could be due to MLCT or 1P1 � 1S0 and 3P1 � 1S0 transition of s2

electrons of the Bi3+.23 Compound II, when excited at 300 nm, exhibits emission bands at around 390 nm and 425

nm. The emissions could be due the intraligand π* � π and π* � n transitions. 22c, d Compound III exhibits

emission bands at 410 nm and 423 nm, when excited using a wavelength of 310 nm. These bands could be due to

π* � π and π* � n transitions of the ligand respectively. 22a, b In all the three compounds, a weak emission in the

blue region is also observed, which could be due to MLCT or s2 electrons of the bismuth center.23, 13b

Single-Crystal Structure Determination

A suitable single crystal of each compound was selected under a polarizing optical microscope and glued to

a thin glass fiber. The single crystal data were collected at 293(2) K on a Oxford Xcalibur (Mova) diffractometer

equipped with an EOS CCD detector. The X-ray generator was operated at 50 kV and 0.8 mA using Mo Kα

(λ=0.71073 Å) radiation. The cell refinement and data reduction were accomplished using CrysAlis RED.24 The

structure was solved by direct methods and refined using SHELX97 present in the WinGX suit of programs (version

1.63.04a).25 The oxygen atom of the lattice water molecule in I was found to be disordered over two positions with

occupancies of 0.53(2) and 0.47(2), respectively . The disorder of the lattice water molecules precluded the location

of the hydrogen atoms in I. The positions of all other hydrogen atoms were initially located from the difference

Fourier map and for the final refinement, were placed in geometrically ideal positions and refined in the riding

mode. The full matrix least square refinement against |F2| was carried out using WinGx package of programs.26 The

final refinements included atomic positions for all the atoms, anisotropic thermal parameters for all the non-

hydrogen atoms, and isotropic thermal parameters for all the hydrogen atoms. The details of the structure solution

and final refinement parameters are given in Table 2. The CCDC numbers for the compounds are: 918444 for I,

918445 for II, and 918446for III.

Results and Discussion

Structure of [C4N2H10][Bi(C7H4NO4)(C7H3NO4)].H2O, I

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The asymmetric unit of I has 29 non-hydrogen atoms, that includes one Bi3+ ion, one 2,6-PDC anion, one

mono protonated 2,6-PDC anion, half piperazine molecule and one lattice water molecule (ESI, Figure S9). The

Bi3+ ion is seven coordinated with two nitrogen and five oxygen atoms to form a BiO5N2 distorted mono-capped

trigonal prismatic geometry (ESI, Figure S9). The Bi – O bond distances are in the range 2.282(4) – 2.612(5) Å (av.

2.447 Å) and Bi – N distances are 2.412(5) and 2.473(5) Å, respectively, (Table 3) which are comparable to other

observed distances.13 The O/N – Bi – O/N bond angles are in the range of 63.4(2)o – 154.4(2)o (ESI, Table S2).

Though most of the Bi – O/N distances are found to be around 2.4 – 2.6 Å range, one distance was observed to be

short (2.282(4) Å). A closer look at the geometry around the central Bi3+ ion suggest that this distance could be

opposite to the possible position of the lone pair of electrons of the Bi3+ ion. Thus the lone pair of electron in I

appears to be active and distorts the geometry of the polyhedra around the Bi3+ ion. Similar distortions and

shortening of bond opposite to the lone pair have been observed earlier in Pb2+ containing compounds.27 All the

carboxylate group in I exhibits a monodentate η1 – binding mode (ESI, Figure S9c).

In compound I, the bismuth centers are connected through a µ3 – oxygen [O(1)] of the carboxylate unit

forming a simple dimeric molecular complex. As can be noted from Table 3, the longest Bi – O distance was

observed to be 2.612(5) Å, which is comparable to the Bi – O distances observed in other bismuth containing

compounds.13

In I, we also observed that the free oxygen of the carboxylate ion [O(8)] is 3.018 Å away from the nearest

Bi-dimer units. This oxygen can exert weak secondary interactions with the Bi3+ ion, which would result in an

extended one-dimensional linkage of the Bi-dimers through the 2,6-PDC units (Figure 1a,b). The one-dimensional

chain units resemble a ladder, commonly observed in many open-framework phosphate structures.28 Weak

secondary interactions of this nature have been observed in many inorganic coordination polymers.29 Careful

observation of the structure of I reveals that the structure may be closely related to the structure of

[Bi(C7H4NO4)(C7H3NO4)H2O]2.5H2O.29a The molecular structure of [Bi(C7H4NO4)(C7H3NO4)H2O]2.5H2O consists

of dimeric units, which are similar to that observed in I. In addition, the secondary interactions of the type observed

in I are also found in this structure, which would give extended one-dimensional ladder-like structure.

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Structure of [Bi(C5H3N2O4) (C5H2N2O4)], II

The asymmetric unit of II has 23 non-hydrogen atoms that includes one Bi3+ ion, one 4,5-IDC anion and

one 4,5-IDCH (mono protonated 4,5-imidazoledicarboxylic acid) anion (ESI, Figure S10). The Bi3+ ion is eight

coordinated with six oxygen and two nitrogen atoms, which forms BiO6N2 distorted bicapped-trigonal prismatic

geometry (ESI, Figure S10). The Bi – O distances are in the range 2.323(5) – 2.855(5) Å (av. 2.589 Å) and Bi – N

distances are 2.323(5) and 2.425(5) Å, which are in agreement with those observed in other structures (Table 3).13

The O/N – Bi – O/N bond angles are in the range of 67.6(15)o – 148.5(15)o (ESI, Table S2). Unlike in I, the Bi – O

distances does not exhibit much variations, suggesting that the lone pair of electron may not be active in II.

Structure of II has two crystallographically independent imidazole dicrboxylate units. One of the

imidazole carboxylate unit has the carboxylic acid group intact (4,5-IDCH) and is terminal. The other dicaboxylate

anion (4,5-IDC) participates in the formation of the two dimensional layer. The carboxylate group of the terminal

4,5-IDCH unit binds Bi center in a monodentate η1 – mode and the protonated –COOH group is free. Of the two

carboxylate groups of 4,5-IDC, one binds two bismuth centers in bridging bidentate µ2-η1:η1 mode, while the other

links three bismuth centers in bridging tridentate µ3-η2:η1 mode (ESI Figure S10c). The bismuth centers are

connected through a µ3-oxygen [O(3)] forming a Bi2O2 dimers, which gives rise to the bilayer arrangement. The

mono-protonated imidazole carboxylates projects out of the plane and occupy the inter-layer spaces (Figure 2a).

Another way to describe this structure is to view the connectivity between the Bi and 4,5-IDC. Thus, the

Bi3+ ions are connected with 4,5-IDC forming a simple layer (Figure 2b), which are connected through the µ3-

oxygen [O(3)] giving rise to the bilayer structure (Figure 2a). If we consider the Bi2O2 dimer and 4,5-IDC as single

nodes, then this structural arrangement can be simplified further. Structurally, each 4,5-IDC anions are connected

with three Bi2O2 centers, whereas each Bi2O2 centers are connected with six 4,5-IDC anions (three in each layer).

This type of visualization would give a binodal (6, 3)- net with the Schlafli symbol (43)2(46.66.83) (Figure 2c). The

(6, 3) net is one of the commonly observed nets in inorganic coordination polymers and many classical inorganic

structures such as CdCl2, CdI2, TiS2, Mg(OH)2 (brucite) possess similar type of cation and anion connectivity (ESI

Figure S11,12). 30 The structural arrangement in II closely resembles the brucite structure.

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The bilayer arrangement, observed in II, have been encountered in other metal carboxylate systems.31 To

the best of our knowledge, this is the first observation of a bilayer arrangement in a bismuth carboxylate system.

The structure of II has some similarity with the structure of [Bi3(µ3-O)2(C7H4NO4)(C7H3NO4)2(H2O)2].13c In this

structure, the Bi6O4 cluster units are connected through the 2,5-PDC anions forming a two-dimensional layer with

terminal carboxylic acid units (ESI Figure S13). The layer arrangement as well as the overall topology however, is

different in both the structures.

Structure of [Bi(µ2-OH)(C7H3NO4)], III

The asymmetric unit of III has 14 non-hydrogen atoms that includes one Bi3+ ion, one 3,4-PDC anion and

one µ2-hydroxyl ion (ESI, Figure S14). The Bi3+ ion is seven coordinated with four carboxylate oxygens, two

hydroxyl oxygens and one nitrogen atom and forms a Bi(OH)2O4N distorted monocapped octahedral geometry (ESI,

Figure S14). The Bi – O bond distances are in the range 2.181(6) – 2.782 (2) Å (av. 2.481 Å) and the Bi – N

distance is 2.653 (9) Å (Table 3). The O/N – Bi – O/N bond angles are in the range of 67.8(3)o – 154.1(3)o (ESI,

Table S2). One relatively shorter Bi – O distances is observed [Bi – O(1) 2.181(6) Å]. A closer look at the

geometry around the central Bi3+ ion suggest that this distance could be opposite to the possible position of the lone

pair of electrons of the Bi3+ ion. Thus, the lone pair of electron in III appears to be active which also distorts the

coordination geometry around the Bi centers.

The carboxylate groups of the 3,4-PDC ligand exhibits two different binding modes. While one of the

carboxylate groups bridge in the µ2-η1:η1 mode, the other one binds in the η1:η1 chelating mode (ESI, Figure S14c).

The Bi centers are connected through the µ2-hydroxyl oxygen [O(1)] atoms forming a Bi2O2 dimer units. The dimer

units are connected by the carboxylate groups forming one-dimensional chains (Figure 3a). The 1D chains are

connected through the nitrogen of the pyridine group as well as by the other carboxylate group forming the three-

dimensional structure (Figure 3b). The another way to visualize the structure is to consider the Bi2O2 dimer cations

and the 3,4-PDC anions as the nodes. Thus, each Bi2O2 dimer cation is connected to eight 3,4-PDC anions and each

3,4-PDC anion is connected to four different bismuth dimers cations. This cation-anion connectivity (8:4) is exactly

similar to that observed in the fluorite (CaF2) structure. In order to visualize the formation of the fluorite type lattice

in III, the Bi2O2 dimer and the 3,4-PDC anion can be considered as individual spheres of differing sizes, which

results in a structure that closely resembles the fluorite structure (Figure 4a and 4b).

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In this structure also secondary Bi – O interactions have been observed with distances of 3.008 Å [Bi(1) –

O(4)] and 3.128 Å [Bi(1) – O(5)]. The secondary interactions would lead to a change in coordination around the

Bi3+ ions from seven to nine (ESI Figure S15). The increase in coordination around the Bi3+ ions gives rise to an

infinite Bi – O – Bi linkage in the two-dimensions (ESI, Figure S16). A closer look at the connectivity between the

Bi-dimers with the increased coordination due to the secondary interactions reveals that the layer arrangement

resembles a Kagome related layer (Figure 5a-c). The 3,4-PDC unit connects the Kagome related layers to form the

three-dimensional structure (Figure 5d). It may be noted that Kagome related layers have been observed before in

inorganic coordination polymers, though not frequently.32, 13b This is the second such observation in the family of

bismuth carboxylates.

A closer examination of the connectivity of the Bi2O2 dimer units in III reveals that each Bi2O2 dimer units

are linked to twelve other Bi2O2 units through the 3,4-PDC linkers. Here the secondary interactions are not

considered. This arrangement would give rise to a fcu topology (12-c net) (Figure 6a). The structure of III has

some similarity with that observed in the bismuth carbaxylate, reported earlier, [C4H16N2][Bi4(C8H4O4)7

(C3H5N2)].(C6H14N2O2),16a but the overall structural arrangement is different. In the structure of [C4H16N2]

[Bi4(C8H4O4)7 (C3H5N2)].(C6H14N2O2), each Bi2O2 dimer units are connected to four other Bi2O2 units through 1,4-

BDC linkers. This arrangement would result in a diamond topology (4, 4-net). This structure also has a twofold

interpenetration (Figure 6b).

Thus, the structure of III can be viewed either as a fluorite-related structure (considering both the anion and

cation connectivity) or as a fcu topology (from the Bi2O2 dimer connectivity alone). A Kagome related structure

would result by invoking the weak secondary interaction between the Bi and the oxygen atoms. These observations

suggest the rich diversity in the structures of the coordination polymers of bismuth.

Heterogeneous Catalytic Studies

Many inorganic coordination polymers have been investigated for their catalytic properties, as they exhibit

Lewis acid behavior. One of the earliest work in this area is due to Fujitha and co-workers,33 who established that

the cadmium centers in [(Cd(4,4’-bpy)2)(NO3)2]∞ were conducive for the cyanosilylation of imines. There are

reports of similar Lewis acid behavior in some of the bismuth containing compounds as well.34 As mentioned

before, Bi3+ ion can be considered to be a borderline acid, according to Pearson’s theory of hard and soft acids and

bases.16 In addition, we wanted to explore the possible impact of the holo or hemi-direction of the lone-pair of

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electrons in heterogeneous catalysis. To this end, we examined the acetal formation as well as the esterification

reactions employing the present compounds as Lewis acid catalysts (Scheme-1). The experimental protocols

employed for the acetal formation reaction is similar to that employed in the literature.35a In a typical experiment,

0.05 mM of the bismuth carboxylate (catalyst) was suspended in a 10 ml of toluene. Acetone (0.58 g 10 mM) was

added with ethylene glycol (0.62 g 10 mM) and the entire mixture was stirred and heated at 60oC for 24 hrs. The

formation of the corresponding ketal was analyzed using 1H NMR. From the studies, it became clear that the hemi-

directed compound (II) exhibits considerably more catalytic activity compared to the holo-directed compounds

(I and III) with conversions of 67%, 13% and 37 % for II, I and III, respectively. The control experiments were

carried out in the absence of the catalyst, which produced only 5- 6 % of the ketal. The esterification reaction was

carried out by reacting equimolar quantities of ethanol, and acetic acid at 60oC for one day.35b The yields for this

reaction was considerably less, but the reactivity trend appears to be the same as observed in the ketal formation

reaction. The yield of the ester is as follows: 44 % (II) 15 % (I) 19 % (III). The yields of the products were

calculated from the 1H-NMR spectra. The catalytic studies carried out in the present studies are exploratory

reactions, which establish the Lewis acid character of the bismuth carboxylates.

Scheme - 1

Conclusions

The synthesis, structure and characterization of bismuth carboxylates of varying dimensionalities have been

accomplished. The stabilization of brucite-related (II) and fluorite-related (III) structures in the present compounds

are the first such observation in bismuth carboxylates. The importance of secondary interactions is revealing in the

+

60o C Catalyst,

O

H2C

CH2

OH

HO

O O

Toluene

H3C

H2C OH + H3C + H2OH3C COOH COOC2H5

Catalyst, 60oC

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visualization of a pillared Kagome structure in III. The present studies also suggests that the stereo active lone pair

of electrons of Bi3+ ions have some effect in the Lewis acid catalytic behavior of the present compounds. The

coordination flexibility of the central Bi ions, observed in the present compounds, suggests the possibility of

forming many related phases under suitable experimental conditions.

.Acknowledgement

The author thanks Dr. Debajit Sarma for help with the work. SN thanks Department of Science and

Technology (DST), Government of India, for the award of a research grant. SN also thanks DST, Government of

India, for the award of RAMANNA fellowship. SR and SN thank the Council of Scientific and Industrial Research

(CSIR), Government of India for award of a research fellowship and a research grant.

Supporting Information Available: Simulated and experimental PXRD patterns, TGA curves, IR spectra, UV-vis

spectra, photoluminescence spectra, bond angles of the compounds, asymmetric unit, bismuth and carboxylate

connectivity diagram and other structural figures. This information is available free of charge via the internet at

http://pubs.acs.org/.

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Figure captions

Fig 1. (a) The one-dimensional chain formed by the connectivity between Bi2O2 dimers and 2,6-PDC through

Bi – O secondary interactions (shown in green).

(b) The arrangement of the one-dimensional ladders. Note that the piperazine molecule occupies the spaces

in between the chain units.

Fig 2. (a) The two-dimensional bilayer formed by the connectivity between Bi2O2 and 4,5-IDC. Note that the

other 4,5-IDCH project in a direction perpendicular to the bilayers.

(b) View of the single layer in II. Two such layers are connected through the Bi – O – Bi dimer linkages.

(c) View of the (6, 3) net in II. Note that the Bi2O2 units and 4,5-IDC units are considered as single

nodes. The other hanging 4,5-IDCH is not shown for clarity.

Fig 3. (a) The view of the one-dimensional chain in III formed by the connectivity between Bi2O2 dimer units and

the carboxylate oxygens.

(b) View of the three dimensional structure of III.

Fig 4. (a) Figure shows the connectivity between the Bi2O2 dimers and the 3,4-PDC units by considering each as

the node. (b) The CaF2, fluorite, structure. Note the close similarity between both the structures.

Fig 5. (a) The view of the Kagome layer in III formed by infinite Bi – O – Bi connectivity through Bi – O

secondary coordination (oxygens involved in secondary coordination shown in green).

(b) The connectivity between the Bi2-dimers showing the Kagome layered arrangement (secondary

coordination is represented by dotted lines). The red-line is a guide to the eye to visualize the Kagome

arrangement. The blue spheres represent the center point of the Bi2-dimer units.

(c) View of the Kagome layer in III.

(d) The view of the structure of III showing the pillared Kagome layer arrangement.

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Fig 6. Connectivity between the dimer units through the carboxylate linkers forming the different nets. (a) fcu net

observed in III and (b) the dia net observed in [C4H16N2][Bi4(C8H4O4)7 (C3H5N2)].(C6H14N2O2).15a See

text.

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Table 1: Synthesis composition and conditions employed for the preparation of compounds I – III.

S. no. Composition (mM) Temp(oC) Time(hrs) Product Yield (%)a

1 0.5 mM Bi(NO3)3 .5H2O + 0.85 mM 2,6-

pyridinedicarboxylic acid + 0.85 mM

piperazine + 389 mM H2O

180 72 [C4N2H10][Bi(C7H4NO4)(C7H3NO4)]

.H2O, I

85

2 0.5mM Bi(NO3)3 .5H2O + 1 mM 4,5-

imidazoledicarboxylic acid + 0.5 mM

piperazine + 389 mM H2O

150 72 [Bi(C5H3N2O4) (C5H2N2O4)], II 77

3 0.5 mM Bi(NO3)3 .5H2O + 0.85 mM 3,4-

pyridinedicarboxylic acid + 0.85 mM

imidazole + 389 mM H2O

150 72 [Bi(µ2-OH)(C7H3NO4)], III 70

aYields are calculated based on the respective metals. Compositions given are millmolar composition

CHN analysis: anal. calcd for I: Calc(%) C 34%, H 2%, N 7.02%; Found: C 33.03, H 2.50%, N 7.23%; anal. calc for II:

Calc(%) C 23.22, H 0.96, N 10.26%, Found : C 24.34, H1.07, N 2.33; anal. calc for III: Calc(%) C 21.58%, H 1.02%, N

3.82%; Found: C 22.31%, H 1.81%, N 4.41%.

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Table: 2. Crystal data and structure refinement parameters for compounds I – III.

Parameter I II III

Empirical formula C16H12N3O9Bi C10H5N4O8 Bi C7H4NO5Bi

Formula Weight 598.98 517.14 389.09

Crystal System Triclinic Triclinic Triclinic

Space group P-1 (no.2) P-1 (no.2) P-1 (no.2)

a/Å 7.111(11) 6.955(7) 7.262(13)

b/Å 10.902(14) 6.997(7) 7.538(12)

c/Å 12.221(18) 12.890(12) 8.112(18)

α (°) 113.39(4) 81.54(8) 97.69(6)

β (°) 97.04(4) 81.01(8) 101.04(6)

γ (°) 92.82(4) 78.70(8) 113.21(5)

Volume/Å3 858.1(2) 603.2(10) 389.6(12)

Z 2 2 2

T/K 293(± 2) 293(± 2) 293(± 2)

ρcalc (g cm-3) 2.311 2.841 3.307

µ/mm-1 10.334 14.673 22.615

Wavelength (Å) 0.71073 0.71073 0.71073

θ range (deg) 2.05 to 25.07 2.99 to 26 2.63 to 24.98

R index [I> 2σ (I)] R1=0.0292, wR2=0.0661 R1= 0.0282, wR2=0.0660 R1=0.0358, wR2=0.0767

R (all data) R1=0.0367, wR2=0.0691 R1=0.0314, wR2=0.0681 R1=0.0408, wR2=0.0778

R1 =∑ | Fo | - | Fc ||/∑ | Fo |; wR2 = {∑ [w (Fo2 - Fc

2)]/ ∑ [w (Fo2) 2]}1/2. w = 1/[ρ2(Fo)2 + (aP)2 + bP]. P = [max

(Fo, O) + 2(Fc)-2]/3 where a=0.0365 and b=0.5807 for I, a=0.0364 and b=0.0000 for II, a=0.0373 and b=0.0000 for

III.

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Table 3: Selected observed bond distances in the compounds I – III.

Bond Distance (Å) Bond Distance (Å)

Compound I

Bi(1)-O(1) 2.612(5) Bi(1)-O(7) 2.282(4)

Bi(1)-O(1)#1 2.523(5) Bi(1)-N(1) 2.473(5)

Bi(1)-O(3) 2.316(5) Bi(1)-N(2) 2.412(5)

Bi(1)-O(5) 2.562(5)

Compound II

Bi(1)-O(1) 2.349(4) Bi(1)-O(5)#1 2.585(4)

Bi(1)-O(3) 2.494(4) Bi(1)-O(6) 2.855(5)

Bi(1)-O(4) 2.628(1) Bi(1)-N(1) 2.323(5)

Bi(1)-O(5) 2.494(4) Bi(1)-N(2) 2.425(5)

Compound III

Bi(1)-O(1) 2.181(6) Bi(1)-O(4) 2.751(7)

Bi(1)-O(1)#1 2.338(7) Bi(1)-O(5) 2.782(2)

Bi(1)-O(2) 2.306(7) Bi(1)-N(1) 2.653(9)

Bi(1)-O(3) 2.380(8)

Symmetry Transformations used to generate equivalent atoms:

I: #1: -x+1,-y+1,-z+1;

II: #1: x+1,y,z;

III: #1: -x+1,-y+1,-z+2

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(a)

(b)

Sushrutha and Natarajan Fig. 1

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(a)

(b)

Bi2O2 dimer

4,5- IDC

(c)

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(b)

(a)


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(b) (a)

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(c)

(b) (a)

(d)

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(b)

(a)

3,4-PDC

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Bismuth Carboxylates with brucite and fluorite-related structures:

Synthesis Structure and Properties

S R Sushrutha, Srinivasan Natarajan*

Bismuth carboxylates exhibiting brucite-related layer and a fluorite-related structure has

been synthesized and characterized. The possible role of lone pair of electrons of BiIII

in the

structure and properties has been evaluated. The brucite and fluorite structures are shown here.

‘For Table of Contents Use Only

* Corresponding author, Email: [email protected]

Bi dimer

4,5-IDC 3,4-PDC

Bi dimer

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Date post:	30-Nov-2016
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Bismuth Carboxylates with Brucite- and Fluorite-Related Structures: Synthesis Structure and...

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