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, P 2(1)/c, Z = 4 f.u., a 9.109(4), b 19.809(8), c 19.30(2) Angstrom, beta 109.27(5)degrees, conventional R on \F\ being 0.038 for N-0 4431 'observed' (I > 3 sigma(I)) independent reflections. In this complex, Sb-O-Sb is quasi-linear, 173.1(3)degrees, in contrast to the previously recorded benzene solvate, in which it is 139.0(3)degrees; in the nitrate, [(O2NO)Ph3SbOSbPh3(ONO2)], triclinic, , Z = 2 f.u., a 15.609(5), b 13.238(4), c 10.140(2) Angstrom, alpha 87.11(2), beta 88.46(7), gamma 72.93(2)degrees, R 0.036 for N-0 5275, it is also bent (137.0(2)degrees). 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 cell, a 19.698(3), b 11.635(2), c 9739(2) Angstrom, alpha 92.28(1), beta 98.98(1), gamma 99.74(1)degrees, Z = 2 f.u., R 0.046 for N-0 3578. A new ('beta') phase of triphenylstibine, crystallized from hexane/toluene is also recorded: monoclinic, P 2(1)/c, a 15.386(8), b 11.304(5), c 19.078(8) Angstrom, beta 111.64(4)degrees, Z = 8, R 0.045 for N-0 3393.