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

Reaction of solutions of [ Cp 2 ∗ Mo2P2S3] (1; Cp ∗ = η5-C5Me5) in CH2Cl2 with solutions of CuHal (Hal = Cl, Br, I) in CH3CN gave after slow diffusion the novel coordination polymers [ Cp 2 ∗ Mo2P2S3(CuCl)4] (2), [ Cp 2 ∗ Mo2P2S3(CuBr)3] (3) and [ Cp 2 ∗ Mo2P2S3(CuI)3] (4). The products were characterized by elemental analysis, 31P magic angle spinning (MAS) NMR spectroscopy and single-crystal X-ray crystallography. The solid-state structures of 2 and 3 are composed of two-dimensional polymeric networks, whereas that of 4 contains parallel stacks of one-dimensional ribbons. In all cases the planar cyclo-P2S3 middle deck of the organometallic building block 1 provides one or two P atoms of the PS dumbbells along with the singly bridging sulfur atom as coordination sites for the various copper halide subunits. The assignment of P atoms follows from the correlation of 31P MAS NMR spectra with X-ray crystallographic data. In all compounds the distribution of main group atoms in the cyclo-P2S3 middle deck is different from that previously found in the starting material 1.