Darstellung und Schwingungsspektren von Thiotrichlorosilicat und -germanat. Die Kristallstruktur von NEt4[SiSCl3] · 0,5 CCl4/ Preparation and Synthesis of Thiotrichloro Silicate and Germanate. Crystal Structure of NEt4[SiSCl3] · 0.5 CCl4

Abstract

NEt₄[SiSCl₃] · 0.5CCl₄ was obtained from NEt₄SH and SiCl₄ in liquid H₂S and subsequent crystallization from CH₂Cl₂/CCl₄. The analogous reaction with GeCl₄ was performed without solvent at room temperature. Raman and IR spectra are in accord with simple anionic species with C_3v symmetry. The crystal structure of NEt₄[SiSCl₃] · 0.5 CCl₄ was determined from X-ray diffraction data (849 independent observed reflexions, R - 0.030). Crystal data: tetragonal, space group P4̄c2 , Z = 4, a = 1196.0, c = 1200.7 pm. Both, cation and anion occupy positions on twofold rotation axes, with the consequence of positional disorder for the [SiSCl₃]^- ion by statistical superposition of the sulfur and one chlorine position. The general packing of cations and anions resembles the NaCl type, the CCl₄ molecules occupying interstices. NEt₄[GeSCl₃] · 0.5 CCl₄ is isotypic (a = 1204, c = 1201 pm); NEt₄[GeSCl₃] also crystallizes in the tetragonal system (a = 1048.4, c = 1274.4 pm).