Single-crystal and high-resolution X-ray diffraction studies and Raman spectrum of a phosphorus(V) chloride complex containing a single bromide ion, P3Cl14Br

Abstract

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)Å, 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 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.