Investigation of the Coordination Behavior of P 4 S 3 towards CuBr

The formation of coordination polymers from copper(I) bromide and P 4 S 3 , a potentially tetradentate P‐donor bridging ligand, was studied. Whereas (P 4 S 3 ) 3 (CuBr) 7 ( 1 ) formed in excellent yield, (P 4 S 3 )(CuBr) 3 ( 2 ) and (P 4 S 3 )(CuBr) ( 3 ) crystallized as mixtures. The new compounds were characterized by X‐ray crystallography and solid‐state 31 P 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 P 4 S 3 molecules. The structure of 2 comprises undulated (CuBr) n layers, which are intra‐ and interlayer linked by tridentate P 4 S 3 molecules. Compound 3 is a one‐dimensional polymer composed of four‐membered Cu 2 Br 2 rings, which are bridged by the P 3 bases of two P 4 S 3 molecules.