Crystal structures of three complexes of zinc chloride with tri-tert-butylphosphane

Under anhydrous conditions and in the absence of a Lewis-base solvent, a zinc chloride complex with tri-tert-butylphosphane as the μ-bridged dimer is formed, viz. di-μ-chlorido-bis[chloridobis(tri-tert-butylphosphane)zinc], [ZnCl4(C12H27P)2], (1), which features a nearly square-shaped (ZnCl)2 cyclic core and whose Cl atoms interact weakly with C - H groups on the phosphane ligand. In the presence of THF, monomeric dichlorido(tetrahydrofuran-κO)(tri-tert-butylphosphane-κP)zinc, [ZnCl2(C4H8O)(C12H27P)] or [P(tBu3)(THF)ZnCl2], (2), is formed. This slightly distorted tetrahedral Zn complex has weak C - H⋯Cl interactions between the Cl atoms and phosphane and THF C - H groups. Under ambient conditions, the hydrolysed complex tri-tert-butylphosphonium aquatrichloridozincate 1,2-dichloroethane monosolvate, (C12H28P)[ZnCl3(H2O)]·C2H4Cl2 or [HPtBu3]⁺ [(H2O)ZnCl3]^-·C2H4Cl2, (3), is formed. This complex forms chains of [(H2O)ZnCl3]^- anions from hydrogen-bonding interactions between the water H atoms and Cl atoms that propagate along the b axis.