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 by 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 l4, with a= 8.739(2), c= 12.320(1)A, Z= 2 and R= 0.058 yielded a structure composed of two PCl4+ tetrahedra of Cs symmetry, one PCl6– octahedron of C4v symmetry, and one Br–. Rietveld refinement of powder data was carried out in l4 and l4/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.