A new route for preparing coordination polymers from hydrothermal reactions involving in situ ligand synthesis.

Abstract

The coordination chemistry of inorganic cobalt salt and the organic ligands H(4)bbh (=benzene-1,2,4,5-bihydrazide) and H(3)bcbh (=benzene-4-carboxylate-1,2-bihydrazide) generated through the in situ hydrothermal acylate reaction of H(4)bta (=benzene-1,2,4,5-tetracarboxylic acid) and H(3)btc (=benzene-1,2,4-tricarboxylic acid) with hydrazine hydrate, respectively, has been investigated. Three new coordination polymers were prepared and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The compound [Co(micro(3)-H(2)bbh)(phen)](n)() (1) (triclinic space group P with a = 9.762(4) A, b = 10.169(4) A, c = 11.143(4) A, alpha = 80.96(3) degrees, beta = 64.49(3) degrees, gamma = 71.88(3) degrees, Z = 2) was synthesized from the reaction of CoCl(2).6H(2)O, H(4)bta (=benzene-1,2,4,5-tetracarboxylic acid), N(2)H(4).H(2)O, phen (=1,10-phenanthroline) and H(2)O, and consists of one-dimensional double-chains. [Co(micro(4)-H(2)bbh)(H(2)O)(2)](n)() (2) (monoclinic space group P2(1)/c with a = 6.8687(5) A, b = 7.5943(6) A, c = 10.0401(6) A, beta = 95.250(4) degrees, Z = 2) was generated by the combination of CoCl(2).6H(2)O, H(4)bta, N(2)H(4).H(2)O, and H(2)O. It adopts a three-dimensional structural motif in the solid state with channels consisting of 20-numbered rings. [Co(micro(3)-Hbcbh)(bpy)](n)() (3) (monoclinic space group Cc with a = 9.9464(13) A, b = 23.685(5) A, c = 7.9491 (16) A, beta = 117.677(13) degrees, Z = 4) was obtained from the mixture of CoCl(2).6H(2)O, N(2)H(4).H(2)O, H(3)btc (=benzene-1,2,4-tricarboxylic acid), bpy (=2,2'-dipyridyl), and H(2)O, and features a two-dimensional plane. The results of magnetic research indicate that there exist antiferromagnetic interactions between Co centers in both compounds 1 and 2.