Dithiooxalate ligand complexes. Crystal structure and bonding of tetraphenylarsonium and tetraphenylphosphonium salts of the bis(dithiooxalato)nickelate(II) anion

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Abstract
Two new compounds belonging to the family of bis(dithiooxalato)nickelate(II) complex anion with the general formula [(C6H5)4X]2- [Ni(S2C2O2)2], where X = P (NIDTP) and As (NIDTAS), have been synthetized. Crystal structure analyses of these compounds show that both crystallize in the triclinic system, space group is P[unk] with Z = 2. Crystal data for NIDTP are: a = 11.050(5), b = 13.263(7), c = 18.385(8) Å, α = 111.97(5), β = 90.49(5), γ = 106.10(4)°, V = 2382(2) Å3, F(000) = 1012, Dx = 1.364, D0 = 1.37(1) Mg·m−3, R = 0.040 and Rw = 0.046 for 6732 observed reflections; for NIDTAS: a = 10.446(5), b = 17.525(8), c = 14.07(4) Å, α = 91.20(9), β = 100.8(1), γ = 88.28(4)°, V = 2528(7) Å3, F(000) = 1084, Dx = 1.400, D0 = 1.40(1) Mg·m−3, R = 0.112 and Rw = 0.124 for 2174 observed reflections. While the asymmetrical unit of the compound NIDTP contains one discrete complex [Ni(S2C2O2)2]2− anion, in general position, and two [(C6H5)4P]+ cations, the asymmetrical unit of NIDTAS consists of two centrosymmetric [Ni(S2C2O2)2]2− anions and two [(C6H5)4As]+ cations. In both cases the organic cations and anions are linked by electrostatic interactions and hydrogen contacts of type C – H … O.

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