PHOSPHORANE IMINATO COMPLEXES OF SULFUR - SYNTHESES AND CRYSTAL-STRUCTURES OF [O3SS(NPPH(3))(2)]CENTER-DOT(CH3CN, [SO(NPPH(3))(2)], AND [SCL(NPME(3))(2)]CL

The title compounds have been prepared by the reaction of Me(3)SiNPPh(3) with SO2 and SOCl2 respectively, and by the reaction of Me(3)SiNPMe(3) with S2Cl2. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O3SS(NPPh(3))(2))] . CH3CN: Space group Pca2(1), Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at -60 degrees C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S-S bond length of 218.2 pm and bond lengths S-N of 161.2 and P-N of 160.1 pm. [SO(NPPh(3))(2)]: Space group P2(1)/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at -50 degrees C: a = 1173.1, b = 1585.6, c = 1619.2 pm, beta = 98.13 degrees. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S-N 166 pm and P-N 163 pm in average. [SCI(NPMe(3))(2)]Cl: Space group P $($) over bar$$ 1, Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20 degrees C: a = 613.2, b = 1030.3, c = 1111.4 pm, alpha = 88.48 degrees, beta = 88.01 degrees, gamma = 83.10 degrees. The compound forms ions [SCI(NPMe(3))(2)](+) and Cl-. In the cation the sulfur atom is phi-tetrahedrally coordinated with a long S-Cl distance of 246.9 pm and bond lengths S-N of 155.3 pm and P-N of 164.3 pm in average.