Magnetic Properties and Crystal Structures of Binuclear Copper(II) Complexes with Heterocyclic Thione Donors of 1,3-Bis(hydroxymethyl)-2-imidazolidinethione and 1-Hydroxymethyl-3-methyl-2-imidazolidinethione

Article abstract of DOI:10.1246/bcsj.68.2533

A new series of binuclear copper(II) complexes with 1,3-bis(hydroxymethyl)-2-imidazolidinethione, 1)>2 (where R=CH3 (1), C6H5 (2), 2-CH3C6H4 (3), 4-CH3C6H4 (4), 2-ClC6H4 (5), and 2-BrC6H4 (6)), and with 1-hydroxymethyl-3-methyl-2-imidazolidinethione, 2)>2 (where R=CH3 (7), 2-CH3C6H4 (8), and 4-CH3C6H4 (9)), have been prepared.The magnetic susceptibility data of complexes 1-9 conform to the usual dimer equation with the -2J values ranging from 227 to 992 cm^-1.Crystal structure analyses of 3, 4, 7, and 9 revealed that two copper atoms are linked by two alkoxo-bridges with separations of 3.015(3)-3.069(3) Angstroem in each complex.The coordination around each copper atom of the complexes is essentially a square planar configuration with one sulfur and two alkoxo-oxygen atoms of HL¹ or L² and one oxygen atom of carboxylates.Each alkoxo-group asymmetrically bridges with the Cu1-O1 bonds (1.90-1.92 Angstroem), which are shorter than the Cu1'-O1 bonds (1.93-1.97 Angstroem).The -2J values for complexes 3, 4, 7, and 9 are much better correlated with the Cu1'-O1 bond distances than with the alkoxo-bridging Cu1-O1-Cu1' angles.