Structural characterization of some novel oxidation products of triphenylstibine

Room-temperature single-crystal X-ray structural characterizations of two oxidation products of triphenylstibine of the form XPh₃SbOSbPh₃X are recorded for X = Cl, NO₃. ClPh₃SbOSbPh₃Cl is monoclinic, P2₁/c, Z = 4 f.u., a 9.109(4), b 19.809(8), c 19.30(2) A, β 109.27(5)°, conventional R on |F| being 0.038 for N_o 4431 'observed' (I > 3σ(I)) independent reflections. In this complex, Sb-O-Sb is quasi-linear, 173.1(3)°, in contrast to the previously recorded benzene solvate, in which it is 139.0(3)°; in the nitrate, [(O₂NO)Ph₃SbOSbPh₃(ONO₂)], triclinic, P1̄, Z = 2 f.u., a 15.609(5), b 13.238(4), c 10.140(2) Å, α 87.11(2), β 88.46(7), γ 72.93(2)°, R 0.036 for N_o 5275, it is also bent (137.0(2)°). The anionic substituent is opposed to the oxo bridge in the trigonal bipyramidal five-coordinate array about the metal in both complexes. A redetermination of the structure of Ph₈Sb₄O₆ is recorded, presenting a non-disordered model in a triclinic P1̄ cell, a 19.698(3), b 11.635(2), c 9.739(2) Å, α 92.28(1), β 98.98(1), γ 99.74(1)°, Z = 2 f.u., R 0.046 for N_o 3578. A new ('β') phase of triphenylstibine, crystallized from hexane/toluene is also recorded: monoclinic, P2₁/c, a 15.386(8), b 11.304(5), c 19.078(8) Å, β 111.64(4)°, Z = 8, R 0.045 for N_o 3393.