Synthesis and structures of zirconium complexes [Et2H2N]+2[ZrCl6]2–, [Me3NCH2Ph]+2[ZrCl6]2–•MeCN, [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN, and [Ph4Sb]+2[ZrCl6]2–

The complexes [Et2H2N]+2[ZrCl6]2– (1), [Me3NCH2Ph]+2[ZrCl6]2–•MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN (3), and [Ph4Sb]+2[ZrCl6]2– (4) were synthesized by the reaction of zirconium tetrachloride with tetraorganylammonium, -phosphonium, and -stibonium chlorides in acetonitrile and structurally characterized. The nitrogen, phosphorus, and antimony atoms in the cations have a distorted tetrahedral geometry. The Zr–Cl distances in the centrosymmetric octahedral [ZrCl6]2− anions of complexes 1–4 have similar values, the longest bonds being observed in the anion of complex 4. Acetonitrile molecules are involved in the structural organization of the crystals of complex 3via weak hydrogen bonding with phenyl hydrogen atoms of the organylphosphonium cations. In the crystal of 2, no hydrogen bonds between the cations and solvent molecules are observed; acetonitrile molecules fill the cavities formed by cations and anions.