Synthesis and structure of (4-fluorobenzyl)triphenylphosphonium hexachlorozirconate [Ph3PCH2C6H4F-4][ZrCl6]

(4-Fluorobenzyl)triphenylphosphonium hexachlorozirconate [Ph3PCH2C6H4F-4]2[ZrCl6]2- (1) have been synthesized via the reaction of (4-fluorobenzyl)triphenylphosphoniun chloride with zirconium tetrachloride in acetonitrile solution. The structure of the compound was characterized by IR, 1Н, 13С{1Н} and 19F{1Н} NMR-spectroscopy, elemental analysis, and single-crystal X-ray diffraction. According to the X-ray data the crystals of complex 1 consist of two types of tetrahedral (4-fluorobenzyl)triphenylphosphoniun cations (the СРС angles are 99.44(13)°-114.94(12)°, the P-C distances are 1.706(2)-1.935(3) Å) and octahedral anions [ZrCl6]2- (the СlZrCl trans-angles are 177.35(3)°-178.62(3)°, the Zr-Cl distances are 2.4308(9)-2.5350(11) Å). The structure of complex 1 is formed due to weak hydrogen bonds between cations and anions. The IR spectrum of complex 1 contains an intense band of stretching vibrations of the F-CAr bond at 997 cm-1, a band of vibrations of the P-СAr bonds at 1439 cm-1, and bands of bending and stretching vibrations of C-H at 743 and 3059, 2912 cm-1. In the 31Р NMR spectrum of complex 1 the characteristic signal is a doublet due to long-range interaction at the fluorine atom (J = 8.8 Hz). All signals of carbon atoms in the 13C NMR spectrum, due to direct and long-range interactions with fluorine and phosphorus atoms, are observed in the form of doublets and doublet-doublets.