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, L¹: n = 2, L²: n = 3) and copper(II) nitrate afforded new types of both monocopper(II) and dicopper(II) complexes, respectively. L¹ gave a 1D coordination polymer [Cu₂(L¹)₂(NO₃)₄]_n (1) based on a convergent exo-coordination mode while L² resulted in the formation of a divergent exo/exo-coordinated dicopper(II) complex, [Cu₂(L²_ox)₄(μ-Cl)](NO₃)₄ (2), whose shape resembles a four-bladed waterwheel in which in situ oxidized macrocycles (L²_ox) act as the blades and a Cu^II-(μ-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⋯Cl⁻ H-bonds. Compound 2 shows a weak antiferromagnetic property via the Cu^II-(μ-Cl)-Cu^II entity.