Synthese und Kristallstrukturen der ionischen Kronenetherkomplexe [TiCl₃(15-Krone-5)(CH₃CN)][SbCl₆) und [VCI(OH)(18-Krone-6)(CH₃CN)₂][SbCl₆] · ½(18-Krone-6 · CH₃CN) / Synthesis and Crystal Structures of the Ionic Crown Ether Complexes [TiCl₃(15-Crown-5)(CH₃CN)][SbCl₆) und [VCI(OH)(18-Crown-6)(CH₃CN)₂][SbCl₆] · ½(18-Crown-6 · CH₃CN)

Abstract

Abstract The title compounds were prepared by the reaction of titanium tetrachloride with 15-crown-5 and antimony pentachloride, and by the reaction of vanadium trichloride with 18-crown-6 and antimony pentachloride in the presence of traces of water in acetonitrile solution, respectively. The complexes were characterized by IR spectroscopy and by X-ray structure determinations. [TiCl 3 (15-crown-5)(CH 3 CN)][SbCl 6 ]: Space group Pnma, Z = 4, 1355 observed unique reflections, R = 0.035. Lattice dimensions at -80 °C: a = 1987(1), b = 1742.2(6), c = 111.0(2) pm. The compound consists of SbCl 6 - anions and cations [TiCl 3 (15-crown-5)(CH 3 CN)] + , in which the titanium atom is coordinated octahedrally by three chlorine atoms in facial arrangement, by the nitrogen atom of the acetonitrile molecule, and by two oxygen atoms of the crown ether molecule. [VCl(OH)(18-crown-6 )(CH 3 CN) 2 ][SbCl 6 ] · ½(18-crown-6 · CH 3 CN); Space group P 1̄, 3936 observed unique reflections, R = 0.714. Lattice dimensions at -80 °C: a = 1194.2(6), b = 1349.8(6), c = 1365.5(6) pm, α = 93.55(4)°, β = 111.23(4)°, γ = 93.15(4)°. The compound consists of SbCl 6 - anions, included 18-crown-6 and acetonitrile molecules, and cations [VCl(OH)(18-crown-6)(CH 3 CN) 2 ] + , in which the vanadium atom is octahedrally coordinated by two nitrogen atoms of the acetonitrile molecules in trans positions, by a chlorine atom and a hydroxyl group in cis position, and by two oxygen atoms of the crown ether molecule. One of the acetonitrile molecules forms weak hydrogen bridges with two oxygen atoms of the included crown ether molecule as well as with one chlorine atom of the SbCl 6 - ion.