Formation of a four-bladed waterwheel-type chloro-bridged dicopper(II) complex with dithiamacrocycle via double exo-coordination

Abstract

A combination of O3S2-macrocycles incorporating different sulfur-to-sulfur separations (S-(CH2)(n)-S, L-1: n = 2, L-2: n = 3) and copper(II) nitrate afforded new types of both monocopper(II) and dicopper(II) complexes, respectively. L-1 gave a 1D coordination polymer [Cu-2(L-1)(2)(NO3)(4)](n) (1) based on a convergent exo-coordination mode while L-2 resulted in the formation of a divergent exo/exo-coordinated dicopper(II) complex, [Cu-2(L(ox))(2)4(mu-Cl)](NO3)(4) (2), whose shape resembles a four-bladed waterwheel in which in situ oxidized macrocycles (L-ox(2)) act as the blades and a Cu-II-(mu-Cl)-Cu-II entity corresponds to the axle shaft. The chloro-bridging ligand is derived from the dichloromethane solvent and its arrangement is held together by C-H center dot center dot center dot Cl- H-bonds. Compound 2 shows a weak antiferromagnetic property via the Cu-II-(mu-Cl)-Cu-II entity.