Auriphilic Interactions in Gold(I) Thiolate Complexes: Crystal Structures of Complexes [C6H5SAuPPh3]2 and [C6H5S(AuPPh3)2]2(BF4)2

The structures of C(6)H(5)SAuPPh(3) (I) and [C(6)H(5)S(AuPPh(3))(2)]BF(4) (II) are determined from an X-ray diffraction experiment (Enraf-Nonius CAD-4 diffractometer, MoK(alpha) radiation, graphite monochromator, R = 0.0306 and 0.0855, respectively). Crystals I are triclinic, a = 11.027(9), b = 11.545(9), c = 16.752(10) angstrom, alpha = 97.05(5)degrees, beta = 93.50(4)degrees, gamma = 93.17(4)degrees, V = 2108(3) angstrom(3), Z = 4, space group P (1) over bar. Crystals II are triclinic, a = 19.143(9), b = 19.443(9), c = 21.093(9) angstrom, alpha = 84.24(4)degrees, beta = 83.69(4)degrees, gamma = 87.79(4)degrees, V = 7761(6) angstrom(3), Z = 8, space group P (1) over bar. The unit cells of I and II comprise two and four independent formula units, respectively. The independent molecules in I are combined into dimers by virtue of the Au center dot center dot center dot Au interaction [3.142(2) angstrom]. Compound II is a salt containing two BF(4)(-) anions per one centrosymmetric doubly charged dimeric cation [C(6)H(5)S(AuPPh(3))(2)](2)(2+) formed owing to a pair of Au center dot center dot center dot Au interactions [3.118(3)-3.150(3) angstrom]. In each of the monomeric fragments of this cation, the interaction also occurs between the two gold atoms linked to a common sulfur atom of the phenylthiolate ligand [Au center dot center dot center dot Au 2.984(3)-3.142(3) angstrom]. Molecule I and cation II exhibit the usual geometry. The auriphilic interactions in the related compounds are discussed.