IONIC PHOSPHORANE IMINATO COMPLEXES OF SU LFUR(IV) AND SELENIUM(IV) -CRYSTAL-STRUCTURES OF [S(NPME(3))(3)]CL-CENTER-DOT-CH2CL2, [S(NPPH(3))(3)]S4N5 AND [SE(NPME(3))(3)]CL-CENTER-DOT-C7H8

[S(NPMe(3))(3)]Cl . CH2Cl2 and [S(NPPh(3))(3)]S4N5 were prepared by th e reaction of Me(3)SiNPMe(3) or Me(3)SiNPPh(3) with sulfur dichloride and S3N2Cl2, respectively, in CH2Cl2 solutions as colourless, moisture sensitive crystals. The corresponding selenium compound was prepared from SeCl4 and Me(3)SiNPMe(3) in acetonitrile solution; it crystallize s from toluene solutions with one mole of toluene per formula unit. Al l complexes have been characterized by IR spectroscopy and by crystal structure determinations. [S(NPMe(3))(3)]Cl . CH2Cl2: Space group Pna2 (1), Z = 8, 3930 observed unique reflections, R = 0.033. Lattice dimen sions at -120 degrees C: a = 1200.9(1), b = 1020.2(1), c = 1790.5(1) p m. [S(NPPh(3))(3)]S4N5: Space group P6(3), Z = 2, 2586 observed unique reflections, R = 0.054. Lattice dimensions at -100 degrees C: a = b = 1334.7(2), c = 1652.6(2) pm. [Se(NPMe(3))(3)]Cl . C7H8: Space group C 2/c, Z = 8, 1475 observed unique reflections: R = 0.059. Lattice dimen sions at -40 degrees C: a = 1853.6(8), b = 1159.2(4), c = 2053.2(4) pm , beta = 101.92(3)degrees. All compounds contain cations [E(NPR(3))(3) ](+) (E = S: Se) with pyramidal structures. Bond lengths and bond angl es are in average: S-N 162.5 pm, S-N-P 120.5 degrees (R = Me), S-N 161 .8 pm, S-N-P 119.2 degrees (R = Ph), Se-N 177.8 pm, Se-N-P 120.3 degre es.