SINGLE-CRYSTAL AND HIGH-RESOLUTION X-RAY-DIFFRACTION STUDIES AND RAMAN-SPECTRUM OF A PHOSPHORUS(V) CHLORIDE COMPLEX CONTAINING A SINGLE BROMIDE ION, P3CL14BR

The solid-state structure of the compound of empirical formula P3Cl14Br, has been investigated hy single-crystal and high-resolution powder diffraction techniques. The results of the structural study are correlated with the Raman spectra of P3Cl14Br and metastable PCl5, Refinement in tetragonal space group 14, with a = 8.739(2), c = 12.320(1) Angstrom, Z = 2 and R = 0.058 yielded a structure composed of two PCl4+ tetrahedra of C-s symmetry, one PCl6- octahedron of C-4v symmetry. and one Br-. Rietveld refinement of powder data was carried out in 14 and 14/m. The Raman spectrum of the same crystal used for single crystal X-ray analysis was found to be strikingly similar to that of metastable PCl5 with vibrational degeneracies lifted. Metastable PCl5 and P3Cl14Br are structurally very similar.