Crystal structures of a series of compounds with cations of the type [R3PNH2](+), [R3PN(H)SiMe3](+), and [R3PN(SiMe3)(2)](+)

The crystal structures of a series of compounds with cations of the type [R 3PNH2](+), [R3PN(H)SiMe3](+), and [R3PN(SiMe3)(2)](+), in which R represent s various organic residues, are determined by means of X-ray structure anal yses at single crystals. The disilylated compounds [Me3PN(SiMe3)(2)](+) I-, [Et3PN(SiMe3)(2)]I-+(-), and [Ph3PN(SiMe3)(2)]I-+(3)- are prepared from the corresponding silylated phos phaneimines R3PNSiMe3 with Me3SiI. [Me3PNH2]Cl (1): Space group P2(1)/n, Z = 4, lattice dimensions at -71 degr ees C: a = 686.6(1), b = 938.8(1), c = 1124.3(1) pm; beta = 103.31(1)degree s; R = 0.0239. [Et3PNH2]Cl (2): Space group Pbca, Z = 8, lattice dimensions at -50 degrees C: a = 1272.0(2), b = 1147.2(2), c = 1302.0(3) pm; R = 0.0419. [Et3PNH2]I (3): Space group P2(1)2(1)2(1), Z = 4, lattice dimensions at -50 degrees C: a = 712.1(1), b = 1233.3(2), c = 1257.1(2) pm; R = 0.0576. [Et3PNH2](2)[B10H10] (4): Space group P2(1)/n, Z = 4, lattice dimensions at -50 degrees C: a = 809.3(1), b = 1703.6(1), c = 1800.1(1) pm; beta = 96.34 (1)degrees; R = 0.0533. [Ph3PNH2]ICI2 (5): Space group <P(1)over bar>, Z = 2, lattice dimensions at -60 degrees C: a = 825.3(3), b = 1086.4(3), c = 1241.2(4) pm; a = 114.12(2 )degrees, beta = 104.50(2)degrees, gamma = 93.21(2)degrees; R = 0.0644. In the compounds 1-5 the cations are connected with their anions via hydrog en bonds of the NH2 groups with 1-3 forming zigzag chains. [Me3PN(H)SiMe3][O3S-CF3] (6): Space group P2(1)/c, Z = 8, lattice dimension s at -83 degrees C: a = 1777.1(1), b = 1173.6(1), c = 1611.4(1) pm; beta = 115.389(6)degrees; R = 0.0332. [Et3PN(H)SiMe3]I (7): Space group P2(1)/n, Z = 4, lattice dimensions at -70 degrees C: a = 1360.2(1), b = 874.2(1), c = 1462.1(1) pm; beta = 115.19(1) degrees; R = 0.066. In 6 and 7 the cations form ion pairs with their anions via NH ... X hydrog en bonds. [Me3PN(SiMe3)(2)]I (8): Space group P2(1)/c, Z = 8, lattice dimensions at - 60 degrees C: a = 1925.4(9), b = 1269.1(1), c = 1507.3(4); beta = 111.79(3) degrees; R = 0.0581. [Et3PN(SiMe3)(2)]I (9): Space group Pbcn, Z = 8, latti ce dimensions at -50 degrees C: a = 2554.0(2), b = 1322.3(1), c = 1165.3(2) pm; R = 0.037. [Ph3PN(SiMe3)(2)]I-3 (10): Space group P2(1), Z = 2, lattic e dimensions at -50 degrees C: a = 947.7(1), b = 1047.6(1), c = 1601.6(4) p m; beta = 105.96(1)degrees; R = 0.0334. 8 to 10 are built up from separated ions.