Rerefinement of the crystal structure of trichloridosulfonium(IV) hexachloridouranate(V), (SCl3)[UCl6

Holger Lars Deubner,Florian Kraus,Sergei I Ivlev

doi:10.1107/s2414314620009608

Abstract

Single crystals of tri-chlorido-sulfonium-(IV) hexa-chlorido-uranate(V) were obtained from the reaction of uranium(IV) chloride with an excess of disulfur dichloride and studied by single-crystal X-ray diffraction. In comparison with the structure model reported previously [Sawodny et al. (1983 ▸). Z. Anorg. Allg. Chem. 499, 81-88.], the lattice parameters and fractional atomic coordinates were determined to a much higher precision, leading overall to an improved structure model. The ionic compound contains trigonal-pyramidal (SCl3)+ cations and slightly distorted octa-hedral [UCl6]- anions. The structure was refined as an inversion twin with a twin ratio of 4.4:1.

Highlights

Single crystals of trichloridosulfonium(IV) hexachloridouranate(V) were obtained from the reaction of uranium(IV) chloride with an excess of disulfur dichloride and studied by single-crystal X-ray diffraction
The structure was refined as an inversion twin with a twin ratio of 4.4:1
We explored the reaction of uranium tetrachloride with disulfur dichloride out of curiosity

Summary

Structure description

We explored the reaction of uranium tetrachloride with disulfur dichloride out of curiosity. We investigated whether the latter compound could be a potential solvent for uranium halides During these studies, high-quality single crystals of (SCl3)[UCl6] were obtained. In comparison, Sawodny et al (1983) reported slightly shorter S—Cl bond lengths for (SCl3)[UCl6] at 293 K (Table 1). These atomic distances are in good agreement with those reported for the ionic compound -[SCl3][SbCl6] [1.979 (5) to 1.992 (7) Aat 169 K; Minkwitz et al, 1992]. Atomic coordinates of the previously reported (SCl3)[UCl6] structure (Sawodny et al, 1983) were used for refinement. Computer programs: X-AREA (Stoe, 2016), SHELXL (Sheldrick, 2015), DIAMOND (Brandenburg, 2019) and publCIF (Westrip, 2010)

Data collection

Special details