THE SYNTHESIS, CRYSTAL AND MOLECULAR-STRUCTURES OF TRIPHENYL(PHENYLTHIO)SILANE, PH3SISPH, AND OF BIS(MU-THIOPHENOLATO)BIS(TETRACARBONYLTUNGSTEN(I)],[W(CO)4(SPH)]2

Preparations and X-ray structure determinations are described for Ph3SiSPh and [W(CO)4(μ-SPh)]2. The compound Ph3SiSPh crystallizes in space group Pcab with a = 15.260 Å, b = 15.968 Å, c = 16.757 Å, Z = 8, dcalc = 1.20 g cm-3 (MoKaα1, = 0.70930 Å). The structure was solved with MULTAN and refined to the final R = 0.050 for 1933 significant reflections. The molecule has an unusual C-S-Si angle of 99.5° and a short Si-S bond length of 2.156 A. The compound [W(CO)4(μ-SPh)]2 crystallizes in the space group P21/c with a = 9.164 Å, b = 12.054 Å, c = 11.163 Å, β = 111.63°, Z = 2, dcalc = 2.35 g cm-3 (MoKα1, = 0.70930 Å). The structure was solved with MULTAN and refined to the final R = 0.062 for 2748 significant reflections. The molecule is a dimer with a cry stallographic center of symmetry. There is a short W-W distance (2.972 Å), a wide S-W-S′ angle (106.3°), a compressed W- S-W′ angle (73.67°) and there is distortion of a CO on each W due to the close approach of an ortho-H in a phenyl ring.