One-Dimensional Coordination Polymers from the Self-Assembly of Copper(II) Carboxylates and 4,4′-Dithiobis(pyridine)

A twisted ligand, 4,4′-dithiobis(pyridine), 4pds, was reacted with copper(II) carboxylates to synthesize one-dimensional coordination polymers: [Cu4(CH3COO)6(μ3-OH)2(4pds)2]n (1), [Cu(CH3COO)2(4pds)·6H2O]n (2), [{Cu2(C6H5COO)4}2(4pds)2]n (3), and [{Cu2[CH3(CH2)4COO]4}2(4pds)2]n (4). The crystal structure of 1 reveals a repeated rhomboid structure in which the Cu4(CH3COO)6(OH)2 core is linked by two 4pds ligands. The 4 : 2 (Cu : 4pds) stoichiometry of 1 transforms into the 1 : 1 (Cu : 4pds) one of 2 in aqueous solution. Compound 2 has a porous honeycomb-like structure, which is occupied by carboxylate ions and water molecules. Compounds 3 and 4 are zigzag chains consisting of alternate linking of the Cu2(RCOO)4 unit and 4pds ligand. The variable-temperature magnetic susceptibility data of 1 and 3 are consistent with the net antiferromagnetic interaction within the tetranuclear or dinuclear core.