The unexpected versatility of P(4)S(3) as a building block in polymeric copper halide networks: 2,3-P, 1,2,3-P and all-P coordination.

Layering solutions of P(4)S(3) in CH(2)Cl(2) with solutions of CuCl or CuI in CH(3)CN gives the coordination polymers (P(4)S(3))(3)(CuCl)(7) (1), (P(4)S(3))(2)(CuCl)(3) (2), (P(4)S(3))(CuI) (3) and (P(4)S(3))(CuI)(3) (4), respectively, after slow diffusion. The yellow compounds were characterised by elemental analysis, (31)P magic-angle spinning (MAS) NMR spectroscopy and single-crystal X-ray crystallography. The solid-state structures demonstrate the unexpected ligand versatility of the P(4)S(3) molecule, which interacts through two, three, or even all of the phosphorus atoms with copper according to the nature of the copper halide. Compound 1 has a three-dimensional network in which linear and cylindrical infinite CuCl subunits coexist with diatomic CuCl building blocks. For the first time, all four P atoms of the P(4)S(3) cage are involved in coordination with metal atoms. The 3D structure of 2 contains stacks of P(4)S(3) that are interconnected by slightly undulated and planar [CuCl](n) ribbons. Compound 3 is a one-dimensional polymer composed of alternating (CuI)(2) rings and P(4)S(3) bridges. The structure of 4 consists of undulated [CuI](n) layers in which the P(4)S(3) cage functions as a bridge within the layer, as well as a spacer between the layers. The (31)P MAS NMR spectra obtained are in good agreement with the solid-state structures obtained crystallographically. Thus, analytically pure 3 and 4 show singlet peaks that correspond to uncoordinated P and quartets owing to coupling with (63)Cu and (65)Cu, respectively, whereas that of 1 contains quartets according to all-P coordination. The spectrum of 2 was obtained from a sample that still contained 40 % of 1.