Crystal structures of triorganophosphinegold(I) O-cyclohexyldithiocarbonates: R3PAu(S2CO-c-C6H11), R = Et, Ph and c-hexyl

George Siasios and Edward R. T. Tiekink


The crystal structures of the title compounds R3PAu(S2CO-c-C6H11), R = Et, Ph and c-hexyl, have been determined at room temperature. Monoclinic crystals of the R = Et compound have space group C2/c with unit cell dimensions a = 26.754(4) Å, b = 7.264(1) Å, c = 18.928(3) Å, β = 102.04(1)°, Z = 8 and Dx = 1.811 Mg m−3. Crystals of the R = Ph structure are triclinic with space group P[unk] and unit cell dimensions a = 11.372(2) Å, b = 13.053(6) Å, c = 9.488(3) Å; α = 109.45(3)°, β = 99.19(2)°, γ = 106.28(3)°, Z = 2 and Dx = 1.722 Mg m−3. The R = c-hexyl compound crystallizes in the orthorhombic space group P212121 with unit cell dimensions a = 8.121(1) Å, b = 11.108(4) Å, c = 30.212(5) Å,Z = 4 and Dx = 1.591 Mg m−3. The structures were refined by a full-matrix least-squares procedure on 1908 reflections to final R = 0.039 for the R = Et compound, 3664 reflections and R = 0.055 for R = Ph and 1501 reflections and R = 0.040 for R = c-hexyl. The Au atom in each of the structures is linearly coordinated by the S atom, derived from a monodentate xanthate ligand, and the P atom. Different orientations of the xanthate ligands results in two structural forms. For the R = Et and Ph compounds the O atom is in close proximity of the Au atom whereas for the R = c-hexyl compound the S atom is orientated towards the Au atom. The different structures are rationalized in terms of the steric demands of the phosphine ligands. A close Au … Au interaction of 3.120(1) Å is found in the R = Et compound; no such contacts are observed in the R = Ph and c-hexyl structures.

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