Mo(W)/Cu/S coordination polymers based on tetranuclear cubane-like cluster nodes and 1,4-bis(3,5-dimethypyrazol-1-yl)butane flexible ligand

Abstract

Three new coordination compounds {[MoOS3Cu3I(bbd)1.5]·2DMF}n (1), {[MoS4Cu3Br(bbd)1.5]·MeOH·2H2O}n (2) and {[WS4Cu3Br(bbd)1.5]·DMF}n (3), incorporating tetranuclear cubane-like cluster units, have been prepared under ambient conditions in DMF by the reaction of CuX (X = Br, I) and (NH4)2[MXS3] (M = Mo, W; X = S, O) with a flexible linker ligand, 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd). The complexes have been characterized by elemental analyses, IR and UV-Vis spectroscopy. Single-crystal X-ray structure determinations of 1 and 2 have also been undertaken. In the polymeric structures of 1 and 2, two inorganic tetranuclearcubane-like fragments [MoOS3Cu3I] (in 1) and [MoS4Cu3Br] (in 2) are linked by a pair of μ-bbd ligands to form 22-membered rings. In both polymers, the double-cluster/double-bridge units are further linked by a single μ-bbd ligand to generate polymeric chains. In 1 and 2 the Cu atoms possess a distorted tetrahedral geometry formed by an S2NX donor atom set (X = I in 1 and X = Br in 2). In 1, adjacent chains are stabilized by intermolecular C-Ha⋯π interactions. © 2015 Elsevier B.V.