Templated coordination polymers [Ni(H2O)4(bipy)](BTA)0.5·H2O (1) and [Co(H2O)4(bipy)](BTA)0.5·H2O (2) (bipy？=？4,4′-Bipyridine, H4BTA？=？1,2,4,5-Benzenetetracarboxylic Acid) were synthesized and characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and thermogravimetric analysis. Both of complexes 1 and 2 are monoclinic crystal system, C2/c space group, and isostructural. The unit of the structure, the metal ion is coordinated by four water molecules and two bipy molecules, is a slightly distorted octahedral configuration, and the carboxyl group from BTA4- ion doesn't coordinate with the metal ion, the H-bonding interactions further connect the mononuclear molecules to generate a 3D supramolecular complex. 1. Introduction Coordination polymers are currently of considerable interest and importance because of the scope they offer for the generation by design of new materials with a range of potentially useful properties, such as magnetism, adsorption, ion exchange, and catalysis [1]. Self-assembly by intermolecular H-bonding and/or aromatic stacking interactions is an effective way on constructing functional supramolecular complex [2, 3]. Therefore, we have constructed coordination polymers based on the H4BTA ligand and transition metal ions by self-assembly method. So far, a mass of coordination polymers constructed by 1,2,4,5-benzenetetracarboxylic acid (H4BTA) have been reported, but studies on H4BTA as a guest molecule are less reported [4]. The results of previous research show that auxiliary ligands such as 4,4′-bipyridine, 2,2′-bipyridine play important role in constructing the complexes with unexpected architectures [5–12]. So, in this paper, we have constructed two supramolecular complexes with H4BTA as a templating agent and bipy as the auxiliary ligand: [Ni(H2O)4(bipy)](BTA)0.5·H2O (1) and [Co(H2O)4(bipy)](BTA)0.5·H2O (2), and the phase purity of the crystalline products was confirmed by powder X-ray diffraction (PXRD, shown in？？Figures 5s and 6s Supplementary Material available online at http://dx.doi.org/10.1155/2012/291682). 2. Experimental 2.1. Materials and General Methods All the reagents were commercially available and used without further purification. Distilled water was used throughout. Elemental (C, H, and N) analyses were performed on a CE-440 (Leeman labs) analyzer. Thermal gravimetric analysis (TGA) was performed on a PerkinElmer TGA 7 instrument in the temperature range of 25–700°C at a heating rate of 10°C/min under air atmosphere. IR spectra were recorded as KBr pellets on a FTIR-8400
References
[1]
V. N. Khrustalev, I. V. Borisova, N. N. Zemlyansky, and M. Y. Antipin, “A new polymorph of triphenyl-methyl-amine: The effect of hydrogen bonding,” Acta Crystallographica C, vol. 65, no. 2, pp. o31–o34, 2009.
[2]
J. C. MacDonald, P. C. Dorrestein, M. M. Pilley et al., “Design of layered crystalline materials using coordination chemistry and hydrogen bonds,” Journal of the American Chemical Society, vol. 122, no. 47, pp. 11692–11702, 2000.
[3]
Y. Cui, H. L. Ngo, P. S. White, and W. Lin, “Hierarchical assembly of homochiral porous solids using coordination and hydrogen bonds,” Inorganic Chemistry, vol. 42, no. 3, pp. 652–654, 2003.
[4]
R. Cao, Q. Shi, D. Sun, M. Hong, W. Bi, and Y. Zhao, “Syntheses and characterizations of copper(II) polymeric complexes constructed from 1,2,4,5-benzenetetracarboxylic acid,” Inorganic Chemistry, vol. 41, no. 23, pp. 6161–6168, 2002.
[5]
S. L. Li, Y. Q. Lan, J. F. Ma et al., “Structures and luminescent properties of seven coordination polymers of zinc(II) and cadmium(II) with 3,3',4,4'-benzophenone tetracarboxylate anion and bis(imidazole),” Crystal Growth and Design, vol. 8, no. 2, pp. 675–684, 2008.
[6]
J. Y. Lu and Z. Ge, “Synthesis and structures of two new metal-organic polymers containing imidazoldicarboxylate ligands for hydrogen bonding networks, one with a covalent pleated sheet conformation,” Inorganica Chimica Acta, vol. 358, no. 3, pp. 828–833, 2005.
[7]
Y. L. Wang, D. Q. Yuan, W. H. Bi et al., “Syntheses and characterizations of two 3D cobalt-organic frameworks from 2D honeycomb building blocks,” Crystal Growth and Design, vol. 5, no. 5, pp. 1849–1855, 2005.
[8]
W. G. Lu, L. Jiang, X. L. Feng, and T. B. Lu, “Three 3D coordination polymers constructed by Cd(II) and Zn(II) with imidazole-4,5-dicarboxylate and 4,4'-bipyridyl building blocks,” Crystal Growth and Design, vol. 6, no. 2, pp. 564–571, 2006.
[9]
W. G. Lu, L. Jiang, X. L. Feng, and T. B. Lu, “Four 3D porous metal-organic frameworks with various layered and pillared motifs,” Crystal Growth and Design, vol. 8, no. 3, pp. 986–994, 2008.
[10]
W. Liu, L. Ye, X. Liu, L. Yuan, X. Lu, and J. Jiang, “Rapid synthesis of a novel cadmium imidazole-4,5-dicarboxylate metal-organic framework under microwave-assisted solvothermal condition,” Inorganic Chemistry Communications, vol. 11, no. 10, pp. 1250–1252, 2008.
[11]
H. W. Liu and W. G. Lu, “A new 2D zinc(II) coordination polymer constructed by imidazole-4,5- dicarboxylic acid (H3IDC) and 1,4-Bis(imidazol-1-ylmethyl)-benzene (bix),” Chinese Journal of Structural Chemistry, vol. 29, no. 9, pp. 1416–1420, 2010.
[12]
Y. Li. and W. G. Lu, “A New 3D Layered-pillared Cobalt(II)-organic Framework Constructed by Imidazole-4,5-dicarboxylic Acid (H3IDC) and 4,4'-Bipyridine (bipy),” Chinese Chinese Journal of Structural Chemistry, vol. 30, no. 8, pp. 1207–1213, 2011.
[13]
T. Glowiak, H. Kozlowski, and L. S. Erre, “POlymeric complexes of 3-hydroxy-4-methoxy- and 3-methoxy-4-hydroxybenzoic acids. Crystal structure of the linear-chain complex of with 3-hydroxy-4-methoxybenzoic acid,” Journal of Coordination Chemistry, vol. 25, no. 1, pp. 75–84, 1992.
[14]
R. J. Hobson, M. F. C. Ladd, and D. C. Povey, “Substituted phenols as ligands III: Crystal and molecular structure of bis(4-formyl-2-methoxyphenolato)bis(pyridine)copper(II) monohydrate,” Journal of Crystal and Molecular Structure, vol. 3, no. 6, pp. 377–388, 1973.
[15]
B. Kozlevcar, D. Odlazek, A. Golobic, A. Pevec, P. Strauch, and P. Segedin, “Complexes with lignin model compound vanillic acid. Two different carboxylate ligands in the same dinuclear tetracarboxylate complex [Cu2(C8H7O4)2(O2CCH3)2(CH3OH)2],” Polyhedron, vol. 25, no. 5, pp. 1161–1166, 2006.
[16]
A. Ro？berg, L. Baraniak, T. Reich, C. Hennig, G. Bernhard, and H. Nitsche, “EXAFS structural analysis of aqueous uranium(VI) complexes with lignin degradation products,” Radiochimica Acta, vol. 88, no. 9–11, pp. 593–597, 2000.
[17]
Y. Y. Yu, J. X. Chen, Z. C. Ke, L. S. Hu, X. P. Lin, and Z. C. Zhang, “Hydrothermal synthesis, crystal structure and haracterization of a new keggin polyoxometalate {[AgI(4,4'-bipy)]3[PW12O40]}·(4,4'-bipy),” Chinese Journal of Structural Chemistry, vol. 30, no. 3, pp. 362–367, 2011.
[18]
C. P. Li, Y. L. Tian, and Y. M. Guo, “Cobalt(II), silver(I), and lead(II) tetrabromoterephthalates exhibiting the 1-D linear chain, 2-D CdCl2-type layer, and 3-D penta-nodal mixed-connecting coordination frameworks,” Polyhedron, vol. 28, no. 3, pp. 505–510, 2009.
[19]
G. M. Sheldrick, SHELXS-97. Program for the Solution of Crystal Structures, University of GOttingen, 1997.
[20]
M. F. Jin, F. N. Dai, and D. F. Sun, “Two zinc architectures: a mononuclear complex and a 2d wave-like organic-inorganic hybrid layer,” Chinese Journal of Structural Chemistry, vol. 29, no. 12, pp. 1834–1840, 2010.
