Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P4Se3 and CuX (X=Cl, Br, I)

The formation of coordination polymers (CuCl)P4Se3 (1), (CuBr)(3)(P4Se3)(2) (2), (CuI)(3)(P4Se3)(2) (3) and (CuI)P4Se3 (4), from solutions of copper(I) halides and P4Se3 by diffusion methods has been studied. The new compounds were characterized by X-ray crystallography, solid-state P-31 MAS NMR and Raman spectroscopy. Theoretical studies on the DFT level in the crystalline phase allowed the unequivocal assignment of the recorded Raman shifts between 200 and 480 cm(-1). The structure of 1 consists of a 2D network of castellated [CuCl](n) chains and bidentate P4Se3 molecules. The 3D network of 2 comprises [CuBr](n) chains, which are linked by tridentate P4Se3 molecules. Compound 3 is a three-dimensional polymer composed of four-membered (CuI)(2) rings and castellated [CuI](n) chains, which are linked by tridentate P4Se3 molecules involving two basal and the apical P atoms. Thermal conversion of 1 at 230 degrees C gives (CuCl)(3)(P4Se3)(2) (5), which is isostructural with 2. The thermal conversion of (CuI)(3)P4S3, which was studied for comparison gave at 371 degrees C (CuI)(3)P4S4, Cu3PS4 and small amounts of Cu6PS5I. (C) 2011 Elsevier Inc. All rights reserved.