Crystal structure of bis-(ethyl-enedi-thio)-tetra-thia-fulvalenium μ2-acetato-bis-[tri-bromido-rhenate(III)] 1,1,2-tri-chloro-ethane hemisolvate

Alexander A Golichenko; Andrey V Kravchenko; Irina V Omelchenko; Denis M Chudak; Vladimir A Starodub; Boleslaw Barszcz; Alexander V Shtemenko

doi:10.1107/S2056989016006058

Crystal structure of bis-(ethyl-enedi-thio)-tetra-thia-fulvalenium μ2-acetato-bis-[tri-bromido-rhenate(III)] 1,1,2-tri-chloro-ethane hemisolvate

Acta Crystallogr E Crystallogr Commun. 2016 Apr 19;72(Pt 5):712-5. doi: 10.1107/S2056989016006058. eCollection 2016 May 1.

Authors

Alexander A Golichenko¹, Andrey V Kravchenko², Irina V Omelchenko³, Denis M Chudak², Vladimir A Starodub⁴, Boleslaw Barszcz⁵, Alexander V Shtemenko¹

Affiliations

¹ Department of Inorganic Chemistry, Ukrainian State University of Chemical Technology, Gagarin Ave. 8, Dnipropetrovsk 49005, Ukraine.
² Applied Chemistry Department, V. N. Karazin Kharkiv National University, 4 Svoboda Square, Kharkiv, 61022, Ukraine.
³ SSI "Institute for Single Crystals" NAS of Ukraine, 60 Nauky Ave., Kharkiv, 61072, Ukraine.
⁴ Institute of Chemistry, Jan Kochanowski University, 25-406 Kielce, Poland.
⁵ Institute of Molecular Physics, Polish Academy of Sciences, 60-179 Poznan, Poland.

Abstract

The asymmetric unit of the title salt, (C10H8S8)[Re2Br6(CH3COO)]·0.5C2H3Cl3, contains one bis-(ethyl-enedi-thio)-tetra-thia-fulvalene (ET) radical cation, one μ2-acetato-bis-[tri-bromido-rhenate(III)] anion and a 1,1,2-tri-chloro-ethane mol-ecule with half-occupancy disordered about a twofold rotation axis. The tetra-thia-fulvalene fragment adopts an almost planar configuration typical of the ET radical cation. The C atoms of both ethyl-enedi-thio fragments in the cation are disordered over two orientations with occupancy factors 0.65:0.35 and 0.77:0.23. In the anion, six Br atoms and a μ2-acetate ligand form a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 dinuclear centre. In the crystal, centrosymmetrically related ET cations and Re2O2Br6 anions are linked into dimers by π-π stacking inter-actions [centroid-to-centroid distance = 3.826 (8) Å] and by pairs of additional Re⋯Br contacts [3.131 (3) Å], respectively. The dimers are further packed into a three-dimensional network by non-directional inter-ionic electrostatic forces and by C-H⋯Br and C-H⋯S hydrogen bonds. The disordered 1,1,2-tri-chloro-ethane mol-ecules occupy solvent-accessible channels along the b axis.

Keywords: bis(ethylenedithio)tetrathiafulvalene; crystal structure; quadruple metal–metal bond; radical cation salt; rhenium.