Supramolecular copper halide networks using the coordinative flexibility of the cyclo-P2S3 middle deck in (C5Me5)2Mo2P2S3: Phosphorus versus sulfur coordination

► We describe a new type of copper(I) halide coordination polymers. ► The tripledecker complex (C5Me5)2Mo2P2S3 reveals new coordination patterns. ► Competitive coordination behavior of P and S sites in the P2S3 middle deck. ► The coordinative flexibility opens new perspectives in coordination chemistry. ► Straight-forward application of 31P MAS NMR spectroscopy.