Investigation of the Coordination Behavior of P4S3towards CuBr

The formation of coordination polymers from copper(I) bromide and P4S3, a potentially tetradentate P-donor bridging ligand, was studied. Whereas (P4S3)3(CuBr)7 (1) formed in excellent yield, (P4S3)(CuBr)3 (2) and (P4S3)(CuBr) (3) crystallized as mixtures. The new compounds were characterized by X-ray crystallography and solid-state 31P MAS NMR spectroscopy. The structure of 1 consists of a 3D network of cylindrical (CuBr)n columns, castellated (CuBr)n chains and diatomic CuBr units. These building blocks are linked by tetradentate P4S3 molecules. The structure of 2 comprises undulated (CuBr)n layers, which are intra- and interlayer linked by tridentate P4S3 molecules. Compound 3 is a one-dimensional polymer composed of four-membered Cu2Br2 rings, which are bridged by the P3 bases of two P4S3 molecules.