Investigation of the Coordination Behavior of P4S3 towards 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.