Constructions of a set of novel hydrogen-bonded supramolecules from reactions of cobalt(II) salt with bis(3,5-dimethylpyrazolyl)methane and different carboxylic acids

Reactions of CoX2·6H2O (X = Cl−, ClO4−) with bis(3,5-dimethylpyrazolyl)methane (dmpzm) and formic acid, acetic acid, benzoic acid, salicylic acid, maleic acid, or fumaric acid under the presence of KOH solution produced a new family of Co(II)/dmpzm complexes, [Co(dmpzm)2L]X·nH2O (1: L = O2CH, X = Cl, n = 2; 2: L = OAc, X = Cl, n = 3; 3: L = benzoate, X = ClO4, n = 1/3; 4: L = salicylate, X = ClO4, n = 1/3) and [Co2(dmpzm)4L](ClO4)2·nSolv (5: L = maleate, n = 3, Solv = H2O; 6: L = fumarate, n = 2, Solv = MeOH). These compounds were structurally characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Compounds 1-4 are mononuclear while 5-6 are binuclear. Each cobalt atom of 1-6 is hexacoordinate, with a distorted octahedral CoN4O2 coordination geometry incorporating two N,N′-bidentate dmpzm ligands and one O,O′-bidentate carboxylate ligand. There are rich intra- and intermolecular hydrogen bonds in the crystals of 1-6, thereby forming either 2D hydrogen-bonded networks (1 and 2) or 3D hydrogen-bonded networks (3-6). In addition, the thermal behaviors of 1-6 were also investigated.