Crystal structures of [TiF3(NPPh(3))(HNPPh(3))](2) and of HNPPh(3)

The phosphoraneiminato-phosphaneimine complex [TiF3(NPPh(3)) (HNPPh(3))](2) was obtained by the reaction of TiF4 with Me(3)SiNPPh(3) in boiling dichloromethane. It crystallizes from 1,2-dichloroethane as yellow crystals which include four molecules C2H4Cl2 per dimeric formula unit. Space group P2(1)/n, Z = 2, structure solution with 7270 independent reflections, R = 0.060 for reflections with I > 2 sigma(I). Lattice dimensions at -50 degrees C: a = 1417.5, b = 1896.9, c = 1586.6 pm, beta = 101.22 degrees. The compound forms centrosymmetric dimeric molecules via mu(2)-F bridges with TiF distances of 194.6 and 223.3 pm, the longer one being in trans-position to the N atom of the (NPPh(3))(-) ligand. Its TiN bond length of 177.7 pm corresponds with a double bond. The TiN bond length of the HNPPh(3) donor molecule of 213.4 pm is typical for a donor acceptor bond. According to the crystal structure determination the phosphaneimine HNPPh(3) forms monomeric molecules without intermolecular hydrogen bridges with a PN bond length of 152.4 pm. Space group P2(1)/c, Z = 4, structure solution with 3229 independent reflections, R = 0.062 for reflections with I > 2 sigma(I). Lattice dimensions at -70 degrees C: a = 1460.4, b = 928.9, c = 1096.6 pm, beta = 93.35 degrees.