SOME STRUCTURAL CHEMISTRY OF ORGANOLEAD(IV) COMPOUNDS CONTAINING LEAD-SULPHUR BONDS. THE CRYSTAL AND MOLECULAR STRUCTURES OF TRIPHENYLLEAD BENZENETHIOLATE, Ph3PbSPh, TRIPHENYLLEAD O,O'-DIETHYLDITHIOPHOSPHATE, Ph3PbS2P(OEt)2, AND DIPHENYLLEAD BIS(O,O'-DIBENZYLDITHIOPHOSPHATE), Ph2Pb<S2...

Article abstract of DOI:10.1016/0022-328X(85)87406-4

The crystal and molecular structures of three organolead compounds containing lead-sulphur bonds are described.Crystals of triphenyllead benzenethiolate (I, C24H20Pbs) are in the monoclinic space group P2₁/c, with a 7.657, b 16.427, c 16.239 Angstroem, β 93.781 deg, Z=4; crystals of triphenyllead O,O'-diethyldithiophosphate (II, C22H25O2PPbS2), and diphenyllead bis(O,O'-dibenzyldithiophosphate) (III, C40H38O4PbS4) are both in triclinic space group P<*>, with a 9.579, b 10.602, c 12.710 Angstroem, α 101.623, β 99.554, γ 100.719 deg, Z=2, and a 11.760, b 12.532, c 16.263 Angstroem, α 80.14, β 111.46, γ 112.41 deg, Z=2, respectively.Structures were determined by the heavy atom method using 2820, 2752, and 3084 independent, non-zero reflections with I>3?(I) for compounds I, II and III, respectively, collected using an automated four-circle diffractometer using Mo-K_α radiation (λ 0.71069 Angstroem).The refinements converged at conventional R-values of 3.44percent, 7.40percent and 7.68percent for I, II, and III, respectively.Both Ph3PbSPh and Ph3PbS2(OEt)2 form lattices comprising non-interacting molecules with geometries at lead only slightly distorted from tetrahedral.The distortion in the dithiophosphate is somewhat greater than in the benzenethiolate, and is accompanied by a marginally longer lead-sulphur distance (2.554(6) Angstroem vs. 2.515(2) Angstroem).The lead in Ph2Pb2 are coordinated in a distorted octahedral fashion by two mutually trans phenyl groups (angle CPbC 165.0(9) deg) and two anisobidentate dithiophosphate ligands, each forming one short bond (2.723(6), 2.679(6) Angstroem) and one long bond (2.940(7), 2.957(6) Angstroem) to lead.In the crystal lattice, adjacent pairs of molecules are linked by long (3.69(2) Angstroem) lead-sulphur contacts to give an overall equatorial arrangement.