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], [ZnCl(4)(C(12)H(27)P)(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, [ZnCl(2)(C(4)H(8)O)(C(12)H(27)P)] or [P(tBu(3))(THF)ZnCl(2)], (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, (C(12)H(28)P)[ZnCl(3)(H(2)O)]·C(2)H(4)Cl(2) or [HPtBu(3)](+) [(H(2)O)ZnCl(3)](−)·C(2)H(4)Cl(2), (3), is formed. This complex forms chains of [(H(2)O)ZnCl(3)](−) anions from hydrogen-bonding inter­actions between the water H atoms and Cl atoms that propagate along the b axis.