research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 712-715
doi:10.1107/S2056989016006058

Crystal structure of bis­­(ethyl­enedi­thio)­tetra­thia­fulvalenium μ2-acetato-bis­­[tri­bromido­rhenate(III)] 1,1,2-tri­chloro­ethane hemisolvate

CROSSMARK_Color_square_no_text.svg
Alexander A. Golichenko,a* Andrey V. Kravchenko,b Irina V. Omelchenko,c Denis M. Chudak,b Vladimir A. Starodub,d Boleslaw Barszcze and Alexander V. Shtemenkoa

aDepartment of Inorganic Chemistry, Ukrainian State University of Chemical Technology, Gagarin Ave. 8, Dnipropetrovsk 49005, Ukraine, bApplied Chemistry Department, V. N. Karazin Kharkiv National University, 4 Svoboda Square, Kharkiv, 61022, Ukraine, cSSI "Institute for Single Crystals" NAS of Ukraine, 60 Nauky Ave., Kharkiv, 61072, Ukraine, dInstitute of Chemistry, Jan Kochanowski University, 25-406 Kielce, Poland, and eInstitute of Molecular Physics, Polish Academy of Sciences, 60-179 Poznan, Poland
*Correspondence e-mail: golichenko_alex@i.ua

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 20 March 2016; accepted 11 April 2016; online 19 April 2016)

The asymmetric unit of the title salt, (C10H8S8)[Re2Br6(CH3COO)]·0.5C2H3Cl3, contains one bis­(ethyl­enedi­thio)­tetra­thia­fulvalene (ET) radical cation, one μ2-acetato-bis­[tri­bromido­rhenate(III)] anion and a 1,1,2-tri­chloro­ethane mol­ecule with half-occupancy disordered about a twofold rotation axis. The tetra­thia­fulvalene fragment adopts an almost planar configuration typical of the ET radical cation. The C atoms of both ethyl­enedi­thio 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 inter­actions [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 inter­ionic electrostatic forces and by C—H⋯Br and C—H⋯S hydrogen bonds. The disordered 1,1,2-tri­chloro­ethane mol­ecules occupy solvent-accessible channels along the b axis.

CCDC reference: 1473493

1. Chemical context

In the past few decades, mol­ecular low-dimensional conducting materials have attracted much inter­est owing to their physical properties, in particular their electrical, magnetic and spectroscopic properties. The packing of radical cations in the crystal and the properties of radical cation salts depend substanti­ally on the type of anions involved (Mori et al., 1999[Mori, T., Mori, H. & Tanaka, Sh. (1999). Bull. Chem. Soc. Jpn, 72, 179-197.]; Mori, 1999[Mori, T. (1999). Bull. Chem. Soc. Jpn, 72, 2011-2027.]). Labile equatorial chloride or bromide groups around the Re26+ cluster unit are the reactive centres in inter­actions with other chemical compounds and biological macromolecules (Shtemenko et al., 2013[Shtemenko, N. I., Chifotides, H. T., Domasevitch, K. V., Golichenko, A. A., Babiy, S. A., Li, Z., Paramonova, K. V., Shtemenko, A. V. & Dunbar, K. R. (2013). J. Inorg. Biochem. 129, 127-134.], 2015[Shtemenko, A. V., Chifotides, H. T., Yegorova, D. E., Shtemenko, N. I. & Dunbar, K. R. (2015). J. Inorg. Biochem. 153, 114-120.]). Only one radical cation salt containing a rhenium–rhenium quadruple bond has been described so far {(ET)2[Re2Cl8] [ET = bis(ethyl­enedi­thio)­tetra­thia­fulvalene]; Reinheimer et al., 2008[Reinheimer, E. W., Galán-Mascarós, J. R., Gómez-García, C. J., Zhao, H., Fourmigué, M. & Dunbar, K. R. (2008). J. Mol. Struct. 890, 81-89.]}. In this context, we present the synthesis and crystal structure of a new radical cation salt of ET with the dirhenium(III) anion [Re2Br6(CH3COO)]−. Neither acetic acid nor acetate was used in the synthesis of this radical cation salt. Evidently, the acetate ligand arose by hydrolysis of CH3CN (Cotton et al., 1991[Cotton, F. A., DeCanio, E. C., Kibala, P. A. & Vidyasagar, K. (1991). Inorg. Chim. Acta, 184, 221-228.]). Complex compounds of dirhenium(III) with one equatorial carboxyl­ato ligand are not well studied, the structure of only three such rhenium compounds having been reported to date (Lau et al., 2000[Lau, S. S., Fanwick, P. E. & Walton, R. A. (2000). Inorg. Chim. Acta, 308, 8-16.]; Vega et al., 2002[Vega, A., Calvo, V., Manzur, J., Spodine, E. & Saillard, J.-Y. (2002). Inorg. Chem. 41, 5382-5387.]; Beck & Zink, 2011[Beck, J. & Zink, G. (2011). J. Chem. Crystallogr. 41, 1185-1189.]).

[Scheme 1]

2. Structural commentary

The title compound (Fig. 1[link]) consists of bis­(ethyl­enedi­thio)­tetra­thia­fulvalene (ET) radical cations, μ2-acetato-bis­[tri­bromido­rhenate(III)] anions and 1,1,2-tri­chloro­ethane mol­ecules in the stoichiometric molar ratio of 1:1:0.5. The solvent mol­ecule is disordered over two orientations of equal occupancy about a twofold rotation axis inter­secting the mid-point of the C—C ethane bond. The tetra­thia­fulvalene fragment adopts an almost planar configuration (r.m.s. deviation = 0.033 Å) that is typical for ET radical cations. The dihedral angle between the five-membered rings is 0.3 (6)°. The carbon atoms of both ethyl­enedi­thio fragments (C4/C5 and C9/C10) are disordered over two sets of sites with occupancy ratios of 0.65:0.35 and 0.77:0.23, respectively.

[Figure 1]
Figure 1
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −[{1\over 2}] − x, y, −z.] Only one component of the disordered 1,1,2-tri­chloro­ethane mol­ecule and the major component of the ET cation are shown. Colour codes: C, grey; H, white; O, red; S, yellow; Cl, green; Br, brown, Re, violet.

In the anion, each ReIII atom is coordinated by three Br atoms forming ReBr3 units which are linked by a Re—Re multiple bond [2.2174 (10) Å] and a bridging μ2-acetate ligand, forming a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 core. The length of the Re—Re bond is very close to the mean value of 2.222 Å for quadruple bonds (Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]), and the six bromine ligands are arranged into an eclipsed conformation. It is also known that the presence of O,O-bridging ligands in such structures has a negligible effect on the Re—Re bond length [it varies in the range 2.2067 (7)–2.2731 (9) Å for compounds with no bridging ligands and in the range 2.2168 (8)–2.2532 (2) Å for compounds with O,O-bridging ligands (Poineau et al., 2015[Poineau, F., Sattelberger, A. P., Lu, E. & Liddle, S. T. (2015). Molecular Metal-Metal Bonds: Compounds, Synthesis, Properties, edited by S. T. Liddle, pp. 205-216. Weinheim: Wiley-VCH.])]. Thus, the structure of the Re2Br6CH3COO− anion corres­ponds to the typical structure of compounds with quadruple Re—Re bonds in an Re26+ core (Cotton et al., 2005[Cotton, F. A., Murillo, C. A. & Walton, R. A. (2005). Multiple Bonds between Metal Atoms, 3rd ed., pp. 271-376. New York: Springer Science and Business Media Inc.]). The Re—Br and Re—O bonds vary in the ranges 2.435 (3)–2.451 (3) Å and 2.009 (15)–2.040 (16) Å, respectively. The distortion from an ideal cubic geometry is mainly due to the short distance between the O atoms of the acetate group [2.24 (2) Å], while the Br⋯Br separations between adjacent Br atoms vary in the range 3.411 (3)–3.553 (4) Å.

3. Supra­molecular features

In the crystal (Fig. 2[link]), pairs of centrosymmetrically related ET cations are linked in a `head-to-tail' manner into dimers by π–π stacking inter­actions, with centroid-to-centroid separations of 3.836 (8) Å, perpendicular inter­planar distances of 3.518 (6) Å and offsets of 1.52 (2) Å. Pairs of Re2O2Br6 anions are also linked into dimers by additional pairwise Re⋯Br contacts [Br6⋯Re2 = 3.131 (3) Å]. Cationic and anionic dimers are packed into a three-dimensional network by non-directional inter­molecular electrostatic forces and by C—H⋯Br and C—H⋯S hydrogen bonds (Table 1[link]). Solvent-accessible channels along the b axis are occupied by the disordered 1,1,2-tri­chloro­ethane mol­ecules.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C5B—H5BA⋯Br1 0.98 2.77 3.63 (8) 147
C9A—H9AA⋯Br6i 0.97 2.80 3.60 (3) 140
C9B—H9BA⋯S4ii 0.97 2.75 3.46 (10) 130
C9B—H9BB⋯Br6i 0.96 2.61 3.40 (11) 140
C10A—H10A⋯Br4iii 0.97 2.92 3.83 (4) 156
C10A—H10B⋯S3ii 0.97 2.81 3.57 (3) 136
C10B—H10D⋯Br4iii 0.98 2.67 3.61 (11) 161
Symmetry codes: (i) [x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) -x, -y-1, -z; (iii) [-x+{\script{1\over 2}}, y-1, -z].
[Figure 2]
Figure 2
Partial crystal packing of the title compound, with displacement ellipsoids shown at the 50% probability level. Only one component of the disordered 1,1,2-tri­chloro­ethane mol­ecule and the major component of the ET mol­ecule are shown. Colour codes: C, grey, H, white, O, red, S, yellow, Cl, green, Br, brown, Re, violet.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; last update February 2015; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) for related compounds of bis­(ethyl­enedi­thio)­tetra­thia­fulvalene with simple Re-containing anions resulted in eight hits, amongst which one closely related structure containing the ET cation and Re2Cl8 anion (Reinheimer et al., 2008[Reinheimer, E. W., Galán-Mascarós, J. R., Gómez-García, C. J., Zhao, H., Fourmigué, M. & Dunbar, K. R. (2008). J. Mol. Struct. 890, 81-89.]). A search for Re2HalxLy anionic moieties, where Hal is a halogen atom and L is the μ2-carb­oxy­lic group, resulted in nine hits. Some closely related patterns were found, e.g. one containing the (μ2-acetato)-hexa­chlorido­dirhenate anion exhibiting the same structure of the title compound (Vega et al., 2002[Vega, A., Calvo, V., Manzur, J., Spodine, E. & Saillard, J.-Y. (2002). Inorg. Chem. 41, 5382-5387.]), and one containing the di-μ2-acetato-bis­(di­bromido­rhenate) anion (Koz'min et al., 1981[Koz'min, P. A., Surazhskaya, M. D. & Larina, T. B. (1981). Russ. J. Inorg. Chem. 26, 57-60.]).

5. Synthesis and crystallization

The synthesis of the radical cation title salt was performed by galvanostatic anodic oxidation of ET (0.002 mol l−1) in a two-electrode U-shaped glass cell with platinum electrodes. The initial current intensity of 0.1 µA was increased by 0.05 µA per day to a final value of 0.45 µA. A mixture of 1,1,2-tri­chloro­ethane/aceto­nitrile (12:1 v/v) was used as solvent. [(C4H9)4N]2[Re2Br8] (0.008 mol l−1) was used as electrolyte. After a period of 6–7 weeks, black shiny plate-shaped crystals of the title salt suitable for X-ray analysis were formed.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All hydrogen atoms were placed in idealized positions and refined using a riding-model approximation, with C—H = 0.96–0.97 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The 1,1,2-tri­chloro­ethane mol­ecule is disordered over two sets of sites about a twofold rotation axis with equal occupancy. The C4–C5 and C9–C10 groups of the ET cations are disordered over two orientations with occupancy factors of 0.65/0.35 and 0.77/0.23, respectively. These occupancies were initially obtained as free variables by the full-matrix refinement, and were then fixed in the final refinement cycles. The C—C and C—Cl bond lengths in the solvent mol­ecule were constrained to be 1.52 (1) and 1.80 (1) Å, respectively, and the C—Cl bonds of the solvent mol­ecule were restrained to have the same lengths to within 0.01 Å. The C—S and C—C bonds of the disordered fragments of the ET cation were also restrained to have the same lengths to within 0.005 Å. The atoms of each disordered fragment, including the solvent mol­ecule, were restrained to have approximately the same displacement parameters to within 0.02–0.04 Å2. DELU restraints to within 0.01 Å2 were applied to atoms C4B, C5B, C9B, C10B, C1S and Cl2S. In addition, all non-hydrogen atoms of the solvent mol­ecule were restrained to be approximately isotropic to within 0.03–0.06 Å2. Several outlier reflections (67) that were believed to be affected by the contribution of several unresolved minor twin domains were omitted from the final cycles of refinement, reducing the R factor from 0.061 to 0.052. Attempts to refine the structure using a two-component twin model were unsuccessful. Moreover, the crystals of the title compound are stable but show a strong tendency to splicing. The poor quality of the available crystal may account for the rather low bond precision of the C—C bonds and the presence of several large residual density peaks.

Table 2
Experimental details

Crystal data
Chemical formula (C10H8S8)[Re2Br6(C2H3O2)]·0.5C2H3Cl3
Mr 1362.24
Crystal system, space group Monoclinic, I2/a
Temperature (K) 298
a, b, c (Å) 27.1825 (5), 8.53737 (13), 26.0667 (5)
β (°) 100.8440 (17)
V (Å3) 5941.21 (18)
Z 8
Radiation type Mo Kα
μ (mm−1) 16.93
Crystal size (mm) 0.4 × 0.4 × 0.1
 
Data collection
Diffractometer Agilent Xcalibur Sapphire3
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.067, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 36051, 6755, 6304
Rint 0.039
(sin θ/λ)max (Å−1) 0.650
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.137, 1.14
No. of reflections 6755
No. of parameters 334
No. of restraints 99
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 1.77, −1.90
Computer programs: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Supporting information

CCDC reference: 1473493

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016006058/rz5188sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016006058/rz5188Isup2.hkl

checkCIF report


Chemical context top

In the past few decades, molecular low-dimensional conducting materials have attracted much inter­est owing to their physical properties, in particular their electrical, magnetic and spectroscopic properties. The packing of radical cations in the crystal and the properties of radical cation salts depend substanti­ally on the type of anions involved (Mori et al., 1999; Mori, 1999). Labile equatorial chloride or bromide groups around the Re26+ cluster unit are the reactive centres in inter­actions with other chemical compounds and biological macromolecules (Shtemenko et al., 2013, 2015). Only one radical cation salt containing a rhenium–rhenium quadruple bond has been described so far {(ET)2[Re2Cl8] [ET = bis­(ethyl­enedi­thio)­tetra­thia­fulvalene]; Reinheimer et al., 2008}. In this context, we present the synthesis and crystal structure of a new radical cation salt of ET with the dirhenium(III) anion [Re2Br6(CH3COO)]–. Neither acetic acid nor acetate was used in the synthesis of this radical cation salt. Evidently, the acetate ligand arose by hydrolysis of CH3CN (Cotton et al., 1991). Complex compounds of dirhenium(III) with one equatorial carboxyl­ato ligand are not well studied, the structure of only three such rhenium compounds having been reported to date (Lau et al., 2000; Vega et al., 2002; Beck et al., 2011).

Structural commentary top

The title compound (Fig. 1) consists of bis­(ethyl­enedi­thio)­tetra­thia­fulvalene (ET) radical cations, µ2-acetato-bis­[tribromidorhenate(III)] anions and 1,1,2-tri­chloro­ethane molecules in the stoichiometric molar ratio of 1:1:0.5. The solvent molecule is disordered over two orientations of equal occupancy about a twofold rotation axis inter­secting the mid-point of the C—C ethane bond. The tetra­thia­fulvalene fragment of the ET cation adopts an almost planar configuration (r.m.s. deviation = 0.033 Å) that is typical for ET radical cations. The dihedral angle formed by the five-membered rings is 0.3 (6)°. The carbon atoms of both ethyl­enedi­thio fragments (C4/C5 and C9/C10) are disordered over two sets of sites with occupancy ratios of 0.65:0.35 and 0.77:0.23, respectively.

In the anion, each Re atom is coordinated by three Br atoms forming ReBr3 units which are linked by a Re—Re multiple bond [2.2174 (10) Å] and a µ2-acetate ligand, forming a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 core. The length of the Re—-Re bond is very close to the mean value of 2.222 Å for quadruple bonds (Groom et al., 2016), and the six bromine ligands are arranged into an eclipsed conformation. It is also known that the presence of O,O-bridging ligands in such structures has a negligible effect on the Re—-Re bond length [it varies in the range 2.2067 (7)–2.2731 (9) Å for compounds with no bridging ligands and in the range 2.2168 (8)–2.2532 (2) Å for compounds with O,O-bridging ligands (Poineau et al. , 2015)]. Thus, the structure of the Re2Br6CH3COO– anion corresponds to the typical structure of compounds with quadruple Re—Re bonds in an Re26+ core (Cotton et al., 2005). The Re—Br and Re—O bonds vary in the ranges 2.435 (3)–2.451 (3) Å and 2.009 (15)–2.040 (16) Å, respectively. The distortion from an ideal cubic geometry is mainly due to the short distance between the O atoms of the acetate group [2.24 (2) Å], while the Br···Br separations between adjacent Br atoms vary in the range 3.411 (3)–3.553 (4) Å.

Supra­molecular features top

In the crystal (Fig. 2), pairs of centrosymmetrically related ET cations are linked in a `head-to-tail' manner into dimers by π–π stacking inter­actions, with centroid-to-centroid separations of 3.836 (8) Å, perpendicular inter­planar distances of 3.518 (6) Å and offsets of 1.52 (2) Å. Pairs of Re2O2Br6 anions are also linked into dimers by additional pairwise Re···Br contacts [Br6···Re2 = 3.131 (3) Å]. Cationic and anionic dimers are packed into a three-dimensional network by non-directional inter­molecular electrostatic forces and by C—H···Br and C—H···S hydrogen bonds (Table 1). Solvent-accessible channels along the b axis are occupied by the disordered 1,1,2-tri­chloro­ethane molecules.

Database survey top

A search of the Cambridge Structural Database (Version 5.36; last update February 2015; Groom et al., 2016) for related compounds of bis­(ethyl­enedi­thio)­tetra­thia­fulvalene with simple Re-containing anions resulted in eight hits, amongst which one closely related structure containing the ET cation and Re2Cl8 anion (Reinheimer et al., 2008). A search for Re2HalxLy anionic moieties, where Hal is a halogen atom and L is the µ2-carb­oxy­lic group, resulted in nine hits. Some closely related patterns were found, e.g. one containing the (µ2-acetato)-hexa­chloro­dirhenate anion exhibiting the same structure of the title compound (Vega et al., 2002), and one containing the di-µ2-acetato-bis­(dibromidorhenate) anion (Koz'min et al., 1981).

Synthesis and crystallization top

The synthesis of that radical cation title salt was performed by galvanostatic anodic oxidation of ET (0.002 mol l-1) in a two-electrode U-shaped glass cell with platinum electrodes. The initial current intensity of 0.1 µA was increased by 0.05 µA per day to a final value of 0.45 µA. A mixture of 1,1,2-tri­chloro­ethane/aceto­nitrile (12:1 v/v) was used as solvent. [(C4H9)4N]2[Re2Br8] (0.008 mol l-1) was used as electrolyte. After a period of 6–7 weeks, black shiny plate-shaped crystals of the title salt suitable for X-ray analysis were formed.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were placed in idealized positions and refined using a riding-model approximation, with C—H = 0.96–0.97 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The 1,1,2-tri­chloro­ethane molecule is disordered on two sets of sites about a twofold axis with equal occupancy. The C4–C5 and C9–C10 groups of the ET cations are disordered over two orientations with occupancy factors of 0.65/0.35 and 0.77/0.23, respectively. These occupancies were initially obtained as a free variables by the full-matrix refinement, and were then fixed in the final refinement cycles. The C—C and C—Cl bond lengths in the solvent molecule were constrained to be 1.52 (1) and 1.80 (1) Å, respectively, and the C—Cl bonds of the solvent molecule were restrained to have the same lengths to within 0.01 Å. The C—S and C—C bonds of the disordered fragments of the ET cation were also restrained to have the same lengths to within 0.005 Å. The atoms of each disordered fragment, including the solvent molecule, were restrained to have approximately the same displacement parameters to within 0.02–0.04 Å2. DELU restraints to within 0.01 Å2 were applied to atoms C4B, C5B, C9B, C10B, C1S and Cl2S. In addition, all non-hydrogen atoms of the solvent molecule were restrained to be approximately isotropic to within 0.03–0.06 Å2. Several outlier reflections (67) that were believed to be affected by the contribution of several unresolved minor twin domains were omitted from the final cycles of refinement, reducing the R factor from 0.061 to 0.052. Attempts to refine the structure using a two-component twin model were unsuccessful. Moreover, the crystals of title compound are stable but show a strong tendency to splicing. The poor quality of the available crystal may account for the rather low bond precision of the C—C bonds and the presence of several large residual peaks/holes.

Structure description top

In the past few decades, molecular low-dimensional conducting materials have attracted much inter­est owing to their physical properties, in particular their electrical, magnetic and spectroscopic properties. The packing of radical cations in the crystal and the properties of radical cation salts depend substanti­ally on the type of anions involved (Mori et al., 1999; Mori, 1999). Labile equatorial chloride or bromide groups around the Re26+ cluster unit are the reactive centres in inter­actions with other chemical compounds and biological macromolecules (Shtemenko et al., 2013, 2015). Only one radical cation salt containing a rhenium–rhenium quadruple bond has been described so far {(ET)2[Re2Cl8] [ET = bis­(ethyl­enedi­thio)­tetra­thia­fulvalene]; Reinheimer et al., 2008}. In this context, we present the synthesis and crystal structure of a new radical cation salt of ET with the dirhenium(III) anion [Re2Br6(CH3COO)]–. Neither acetic acid nor acetate was used in the synthesis of this radical cation salt. Evidently, the acetate ligand arose by hydrolysis of CH3CN (Cotton et al., 1991). Complex compounds of dirhenium(III) with one equatorial carboxyl­ato ligand are not well studied, the structure of only three such rhenium compounds having been reported to date (Lau et al., 2000; Vega et al., 2002; Beck et al., 2011).

The title compound (Fig. 1) consists of bis­(ethyl­enedi­thio)­tetra­thia­fulvalene (ET) radical cations, µ2-acetato-bis­[tribromidorhenate(III)] anions and 1,1,2-tri­chloro­ethane molecules in the stoichiometric molar ratio of 1:1:0.5. The solvent molecule is disordered over two orientations of equal occupancy about a twofold rotation axis inter­secting the mid-point of the C—C ethane bond. The tetra­thia­fulvalene fragment of the ET cation adopts an almost planar configuration (r.m.s. deviation = 0.033 Å) that is typical for ET radical cations. The dihedral angle formed by the five-membered rings is 0.3 (6)°. The carbon atoms of both ethyl­enedi­thio fragments (C4/C5 and C9/C10) are disordered over two sets of sites with occupancy ratios of 0.65:0.35 and 0.77:0.23, respectively.

In the anion, each Re atom is coordinated by three Br atoms forming ReBr3 units which are linked by a Re—Re multiple bond [2.2174 (10) Å] and a µ2-acetate ligand, forming a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 core. The length of the Re—-Re bond is very close to the mean value of 2.222 Å for quadruple bonds (Groom et al., 2016), and the six bromine ligands are arranged into an eclipsed conformation. It is also known that the presence of O,O-bridging ligands in such structures has a negligible effect on the Re—-Re bond length [it varies in the range 2.2067 (7)–2.2731 (9) Å for compounds with no bridging ligands and in the range 2.2168 (8)–2.2532 (2) Å for compounds with O,O-bridging ligands (Poineau et al. , 2015)]. Thus, the structure of the Re2Br6CH3COO– anion corresponds to the typical structure of compounds with quadruple Re—Re bonds in an Re26+ core (Cotton et al., 2005). The Re—Br and Re—O bonds vary in the ranges 2.435 (3)–2.451 (3) Å and 2.009 (15)–2.040 (16) Å, respectively. The distortion from an ideal cubic geometry is mainly due to the short distance between the O atoms of the acetate group [2.24 (2) Å], while the Br···Br separations between adjacent Br atoms vary in the range 3.411 (3)–3.553 (4) Å.

In the crystal (Fig. 2), pairs of centrosymmetrically related ET cations are linked in a `head-to-tail' manner into dimers by π–π stacking inter­actions, with centroid-to-centroid separations of 3.836 (8) Å, perpendicular inter­planar distances of 3.518 (6) Å and offsets of 1.52 (2) Å. Pairs of Re2O2Br6 anions are also linked into dimers by additional pairwise Re···Br contacts [Br6···Re2 = 3.131 (3) Å]. Cationic and anionic dimers are packed into a three-dimensional network by non-directional inter­molecular electrostatic forces and by C—H···Br and C—H···S hydrogen bonds (Table 1). Solvent-accessible channels along the b axis are occupied by the disordered 1,1,2-tri­chloro­ethane molecules.

A search of the Cambridge Structural Database (Version 5.36; last update February 2015; Groom et al., 2016) for related compounds of bis­(ethyl­enedi­thio)­tetra­thia­fulvalene with simple Re-containing anions resulted in eight hits, amongst which one closely related structure containing the ET cation and Re2Cl8 anion (Reinheimer et al., 2008). A search for Re2HalxLy anionic moieties, where Hal is a halogen atom and L is the µ2-carb­oxy­lic group, resulted in nine hits. Some closely related patterns were found, e.g. one containing the (µ2-acetato)-hexa­chloro­dirhenate anion exhibiting the same structure of the title compound (Vega et al., 2002), and one containing the di-µ2-acetato-bis­(dibromidorhenate) anion (Koz'min et al., 1981).

Synthesis and crystallization top

The synthesis of that radical cation title salt was performed by galvanostatic anodic oxidation of ET (0.002 mol l-1) in a two-electrode U-shaped glass cell with platinum electrodes. The initial current intensity of 0.1 µA was increased by 0.05 µA per day to a final value of 0.45 µA. A mixture of 1,1,2-tri­chloro­ethane/aceto­nitrile (12:1 v/v) was used as solvent. [(C4H9)4N]2[Re2Br8] (0.008 mol l-1) was used as electrolyte. After a period of 6–7 weeks, black shiny plate-shaped crystals of the title salt suitable for X-ray analysis were formed.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were placed in idealized positions and refined using a riding-model approximation, with C—H = 0.96–0.97 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The 1,1,2-tri­chloro­ethane molecule is disordered on two sets of sites about a twofold axis with equal occupancy. The C4–C5 and C9–C10 groups of the ET cations are disordered over two orientations with occupancy factors of 0.65/0.35 and 0.77/0.23, respectively. These occupancies were initially obtained as a free variables by the full-matrix refinement, and were then fixed in the final refinement cycles. The C—C and C—Cl bond lengths in the solvent molecule were constrained to be 1.52 (1) and 1.80 (1) Å, respectively, and the C—Cl bonds of the solvent molecule were restrained to have the same lengths to within 0.01 Å. The C—S and C—C bonds of the disordered fragments of the ET cation were also restrained to have the same lengths to within 0.005 Å. The atoms of each disordered fragment, including the solvent molecule, were restrained to have approximately the same displacement parameters to within 0.02–0.04 Å2. DELU restraints to within 0.01 Å2 were applied to atoms C4B, C5B, C9B, C10B, C1S and Cl2S. In addition, all non-hydrogen atoms of the solvent molecule were restrained to be approximately isotropic to within 0.03–0.06 Å2. Several outlier reflections (67) that were believed to be affected by the contribution of several unresolved minor twin domains were omitted from the final cycles of refinement, reducing the R factor from 0.061 to 0.052. Attempts to refine the structure using a two-component twin model were unsuccessful. Moreover, the crystals of title compound are stable but show a strong tendency to splicing. The poor quality of the available crystal may account for the rather low bond precision of the C—C bonds and the presence of several large residual peaks/holes.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) -1/2 - x, y, -z.] Only one component of the disordered 1,1,2-trichloroethane molecule and the major component of the ET cation are shown. Colour codes: C, grey; H, white; O, red; S, yellow; Cl, green; Br, brown, Re, violet.
[Figure 2] Fig. 2. Partial crystal packing of the title compound, with displacement ellipsoids shown at the 50% probability level. Only one component of the disordered 1,1,2-trichloroethane molecules and the major component of the ET molecule are shown. Colour codes: C, grey, H, white, O, red, S, yellow, Cl, green, Br, brown, Re, violet.
Bis(ethylenedithio)tetrathiafulvalenium µ2-acetato-bis[tribromidorhenate(III)] 1,1,2-trichloroethane hemisolvate top
Crystal data top
(C10H8S8)[Re2Br6(C2H3O2)]·0.5C2H3Cl3F(000) = 4960
Mr = 1362.24Dx = 3.046 Mg m−3
Monoclinic, I2/aMo Kα radiation, λ = 0.71073 Å
a = 27.1825 (5) ÅCell parameters from 18811 reflections
b = 8.53737 (13) Åθ = 2.9–30.7°
c = 26.0667 (5) ŵ = 16.93 mm−1
β = 100.8440 (17)°T = 298 K
V = 5941.21 (18) Å3Block, metallic dark violet
Z = 80.4 × 0.4 × 0.1 mm
Data collection top
Agilent Xcalibur Sapphire3
diffractometer		6755 independent reflections
Radiation source: Enhance (Mo) X-ray Source6304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 16.1827 pixels mm-1θmax = 27.5°, θmin = 2.9°
ω scansh = −35→35
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		k = −11→9
Tmin = 0.067, Tmax = 1.000l = −33→33
36051 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0534P)2 + 229.8497P]
where P = (Fo2 + 2Fc2)/3
6755 reflections(Δ/σ)max = 0.001
334 parametersΔρmax = 1.77 e Å−3
99 restraintsΔρmin = −1.90 e Å−3
Crystal data top
(C10H8S8)[Re2Br6(C2H3O2)]·0.5C2H3Cl3V = 5941.21 (18) Å3
Mr = 1362.24Z = 8
Monoclinic, I2/aMo Kα radiation
a = 27.1825 (5) ŵ = 16.93 mm−1
b = 8.53737 (13) ÅT = 298 K
c = 26.0667 (5) Å0.4 × 0.4 × 0.1 mm
β = 100.8440 (17)°
Data collection top
Agilent Xcalibur Sapphire3
diffractometer		6755 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		6304 reflections with I > 2σ(I)
Tmin = 0.067, Tmax = 1.000Rint = 0.039
36051 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05299 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0534P)2 + 229.8497P]
where P = (Fo2 + 2Fc2)/3
6755 reflectionsΔρmax = 1.77 e Å−3
334 parametersΔρmin = −1.90 e Å−3
Special details top

Experimental. Absorption correction: CrysAlisPro (Agilent, 2014) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.0279 (2)−0.3844 (7)0.1248 (2)0.0486 (13)
S2−0.0188 (2)−0.1562 (6)0.0484 (2)0.0411 (11)
S3−0.0801 (3)−0.0100 (7)0.1157 (3)0.0532 (14)
S4−0.0284 (3)−0.2886 (8)0.2057 (2)0.0602 (17)
S50.0889 (2)−0.5248 (8)0.0393 (2)0.0484 (13)
S60.0408 (2)−0.2918 (6)−0.0354 (2)0.0436 (12)
S70.0915 (3)−0.3875 (7)−0.1204 (2)0.0586 (17)
S80.1502 (3)−0.6653 (9)−0.0297 (2)0.0590 (16)
C10.0209 (7)−0.313 (2)0.0627 (7)0.034 (4)
C2−0.0374 (7)−0.152 (2)0.1079 (8)0.037 (4)
C3−0.0160 (8)−0.262 (3)0.1431 (8)0.043 (5)
C4−0.065 (3)−0.122 (6)0.220 (3)0.064 (11)0.35
H4A−0.1001−0.15370.21650.077*0.35
H4B−0.0538−0.09090.25630.077*0.35
C4A−0.0391 (15)−0.084 (3)0.2196 (15)0.056 (8)0.65
H4AA−0.0440−0.07500.25540.067*0.65
H4AB−0.0094−0.02420.21660.067*0.65
C5A−0.0822 (16)−0.015 (5)0.1850 (9)0.060 (9)0.65
H5AA−0.08640.09090.19650.072*0.65
H5AB−0.1118−0.07370.18930.072*0.65
C5B−0.062 (3)0.011 (9)0.1862 (9)0.061 (12)0.35
H5BA−0.02720.04630.19330.073*0.35
H5BB−0.08170.09500.19670.073*0.35
C60.0472 (7)−0.372 (2)0.0258 (7)0.035 (4)
C70.1061 (8)−0.523 (2)−0.0214 (8)0.039 (4)
C80.0834 (9)−0.415 (2)−0.0558 (8)0.044 (5)
C9A0.1534 (9)−0.479 (4)−0.1154 (13)0.057 (8)0.77
H9AA0.1634−0.4736−0.14920.068*0.77
H9AB0.1777−0.4205−0.09080.068*0.77
C9B0.134 (4)−0.548 (10)−0.130 (4)0.05 (2)0.23
H9BA0.1153−0.6449−0.13620.060*0.23
H9BB0.1493−0.5262−0.15960.060*0.23
C10A0.1547 (13)−0.643 (4)−0.0988 (9)0.051 (7)0.77
H10A0.1857−0.6902−0.10450.061*0.77
H10B0.1272−0.6987−0.12020.061*0.77
C10B0.173 (4)−0.566 (13)−0.083 (3)0.05 (2)0.23
H10C0.1860−0.4639−0.07150.059*0.23
H10D0.2006−0.6266−0.09230.059*0.23
Re10.12639 (3)0.02771 (9)0.15999 (3)0.0325 (2)
Re20.18894 (3)0.19389 (8)0.18533 (3)0.0285 (2)
Br10.05027 (9)0.1855 (3)0.15459 (12)0.0621 (7)
Br20.10600 (9)−0.1027 (3)0.23712 (10)0.0541 (6)
Br30.11180 (11)0.0172 (4)0.06499 (10)0.0623 (7)
Br40.20677 (9)0.2898 (3)0.10198 (9)0.0529 (6)
Br50.15056 (10)0.4496 (3)0.19753 (11)0.0560 (6)
Br60.20369 (9)0.1635 (3)0.28134 (8)0.0476 (5)
O10.2381 (6)0.0139 (18)0.1841 (6)0.047 (3)
O20.1742 (6)−0.1510 (17)0.1587 (6)0.046 (3)
C110.2221 (8)−0.129 (2)0.1733 (7)0.039 (4)
C120.2582 (11)−0.260 (3)0.1768 (12)0.066 (7)
H12A0.2756−0.25510.14800.100*
H12B0.2404−0.35780.17560.100*
H12C0.2819−0.25330.20900.100*
Cl1S−0.1993 (6)0.0569 (19)0.0673 (6)0.150 (6)
Cl2S−0.2811 (11)0.288 (3)0.0317 (11)0.140 (10)0.50
C1S−0.2592 (9)0.090 (4)0.0257 (5)0.15 (2)
H1S−0.28480.00990.02390.180*
H1SA−0.27180.19180.03360.180*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.052 (3)0.062 (3)0.035 (2)0.022 (3)0.013 (2)0.012 (2)
S20.053 (3)0.036 (2)0.037 (2)0.010 (2)0.016 (2)0.008 (2)
S30.064 (4)0.044 (3)0.055 (3)0.018 (3)0.022 (3)0.001 (2)
S40.080 (4)0.065 (4)0.043 (3)0.015 (3)0.032 (3)0.013 (3)
S50.049 (3)0.065 (4)0.034 (2)0.018 (3)0.014 (2)0.010 (2)
S60.062 (3)0.036 (2)0.036 (2)0.009 (2)0.017 (2)0.0036 (19)
S70.102 (5)0.041 (3)0.040 (3)0.018 (3)0.032 (3)0.006 (2)
S80.064 (4)0.075 (4)0.042 (3)0.028 (3)0.020 (3)0.008 (3)
C10.033 (9)0.043 (10)0.028 (8)0.000 (8)0.008 (7)0.002 (7)
C20.040 (10)0.038 (10)0.036 (9)−0.002 (8)0.015 (8)0.000 (8)
C30.049 (11)0.050 (12)0.033 (9)0.010 (9)0.015 (8)0.007 (9)
C40.071 (17)0.065 (16)0.061 (15)0.002 (14)0.025 (14)−0.003 (12)
C4A0.070 (18)0.053 (15)0.057 (15)0.000 (14)0.040 (14)−0.015 (13)
C5A0.074 (19)0.059 (17)0.058 (15)0.008 (16)0.043 (14)−0.007 (14)
C5B0.066 (18)0.061 (16)0.060 (16)0.000 (14)0.023 (13)−0.004 (12)
C60.039 (10)0.039 (10)0.030 (8)−0.002 (8)0.011 (7)0.002 (7)
C70.042 (10)0.045 (11)0.031 (9)0.004 (8)0.012 (8)−0.004 (8)
C80.067 (14)0.036 (10)0.030 (9)−0.010 (10)0.014 (9)−0.007 (8)
C9A0.07 (2)0.061 (19)0.050 (17)−0.023 (17)0.030 (16)−0.004 (15)
C9B0.05 (2)0.05 (3)0.05 (2)0.000 (17)0.013 (15)0.001 (17)
C10A0.058 (18)0.050 (17)0.050 (16)0.014 (15)0.025 (14)0.003 (14)
C10B0.05 (2)0.05 (3)0.05 (2)0.000 (17)0.013 (15)−0.001 (17)
Re10.0300 (4)0.0326 (4)0.0333 (4)−0.0033 (3)0.0025 (3)0.0011 (3)
Re20.0294 (4)0.0276 (3)0.0275 (3)−0.0007 (2)0.0027 (3)0.0040 (2)
Br10.0443 (12)0.0641 (15)0.0752 (17)0.0068 (11)0.0042 (11)0.0085 (13)
Br20.0564 (13)0.0555 (13)0.0517 (12)−0.0093 (10)0.0140 (10)0.0070 (10)
Br30.0602 (15)0.0809 (18)0.0408 (11)−0.0144 (13)−0.0036 (10)−0.0037 (11)
Br40.0481 (12)0.0703 (15)0.0389 (11)−0.0074 (11)0.0047 (9)0.0135 (10)
Br50.0561 (13)0.0389 (11)0.0737 (16)0.0048 (10)0.0142 (12)0.0065 (11)
Br60.0513 (12)0.0517 (12)0.0388 (10)−0.0108 (10)0.0056 (9)0.0051 (9)
O10.050 (9)0.041 (8)0.048 (8)0.002 (7)0.005 (7)0.004 (7)
O20.056 (9)0.034 (7)0.048 (8)−0.001 (6)0.009 (7)−0.004 (6)
C110.056 (12)0.033 (9)0.031 (9)0.005 (9)0.014 (8)−0.001 (8)
C120.074 (18)0.048 (14)0.085 (19)0.023 (13)0.034 (15)0.014 (13)
Cl1S0.133 (11)0.148 (12)0.153 (12)0.021 (9)−0.014 (9)−0.014 (10)
Cl2S0.15 (2)0.115 (17)0.14 (2)0.048 (16)−0.024 (17)0.005 (15)
C1S0.15 (4)0.12 (2)0.19 (4)0.02 (3)0.05 (3)−0.01 (3)
Geometric parameters (Å, º) top
S1—C11.708 (19)C7—C81.35 (3)
S1—C31.72 (2)C9A—H9AA0.9700
S2—C11.71 (2)C9A—H9AB0.9700
S2—C21.72 (2)C9A—C10A1.46 (5)
S3—C21.72 (2)C9B—H9BA0.9700
S3—C5A1.82 (2)C9B—H9BB0.9700
S3—C5B1.82 (2)C9B—C10B1.46 (14)
S4—C31.74 (2)C10A—H10A0.9700
S4—C41.82 (2)C10A—H10B0.9700
S4—C4A1.82 (2)C10B—H10C0.9700
S5—C61.72 (2)C10B—H10D0.9700
S5—C71.73 (2)Re1—Re22.2174 (10)
S6—C61.716 (19)Re1—Br12.451 (3)
S6—C81.72 (2)Re1—Br22.451 (2)
S7—C81.75 (2)Re1—Br32.435 (3)
S7—C9A1.84 (2)Re1—O22.009 (15)
S7—C9B1.84 (2)Re2—Br42.454 (2)
S8—C71.75 (2)Re2—Br52.465 (2)
S8—C10A1.84 (2)Re2—Br62.473 (2)
S8—C10B1.84 (2)Re2—O12.040 (16)
C1—C61.40 (3)O1—C111.30 (3)
C2—C31.36 (3)O2—C111.30 (3)
C4—H4A0.9700C11—C121.48 (3)
C4—H4B0.9700C12—H12A0.9600
C4—C5B1.46 (4)C12—H12B0.9600
C4A—H4AA0.9700C12—H12C0.9600
C4A—H4AB0.9700Cl1S—C1S1.800 (16)
C4A—C5A1.46 (4)Cl2S—C1S1.81 (2)
C5A—H5AA0.9700Cl2S—H1SA0.8557
C5A—H5AB0.9700C1S—C1Si1.515 (18)
C5B—H5BA0.9700C1S—H1S0.9700
C5B—H5BB0.9700C1S—H1SA0.9703
C1—S1—C394.9 (10)C10A—C9A—H9AA108.9
C1—S2—C295.6 (9)C10A—C9A—H9AB108.9
C2—S3—C5A104.3 (14)S7—C9B—H9BA109.6
C2—S3—C5B97 (3)S7—C9B—H9BB109.6
C5A—S3—C5B19 (3)H9BA—C9B—H9BB108.1
C3—S4—C4108 (2)C10B—C9B—S7110 (7)
C3—S4—C4A97.4 (15)C10B—C9B—H9BA109.6
C4A—S4—C425 (3)C10B—C9B—H9BB109.6
C6—S5—C794.9 (9)S8—C10A—H10A109.0
C6—S6—C894.9 (10)S8—C10A—H10B109.0
C8—S7—C9A98.9 (13)C9A—C10A—S8113 (2)
C8—S7—C9B103 (3)C9A—C10A—H10A109.0
C9A—S7—C9B26 (4)C9A—C10A—H10B109.0
C7—S8—C10A102.8 (12)H10A—C10A—H10B107.8
C7—S8—C10B96 (4)S8—C10B—H10C109.1
C10B—S8—C10A28 (4)S8—C10B—H10D109.1
S1—C1—S2116.1 (11)C9B—C10B—S8112 (7)
C6—C1—S1122.7 (15)C9B—C10B—H10C109.1
C6—C1—S2121.1 (15)C9B—C10B—H10D109.1
S3—C2—S2116.0 (12)H10C—C10B—H10D107.9
C3—C2—S2115.7 (15)Re2—Re1—Br1104.91 (8)
C3—C2—S3128.3 (16)Re2—Re1—Br2108.99 (7)
S1—C3—S4116.6 (12)Re2—Re1—Br3107.19 (7)
C2—C3—S1117.5 (15)Br1—Re1—Br288.73 (10)
C2—C3—S4125.9 (17)Br3—Re1—Br189.29 (11)
S4—C4—H4A109.2Br3—Re1—Br2143.01 (9)
S4—C4—H4B109.2O2—Re1—Re291.6 (4)
H4A—C4—H4B107.9O2—Re1—Br1163.4 (4)
C5B—C4—S4112 (5)O2—Re1—Br285.2 (5)
C5B—C4—H4A109.2O2—Re1—Br386.4 (4)
C5B—C4—H4B109.2Re1—Re2—Br4102.59 (6)
S4—C4A—H4AA108.8Re1—Re2—Br5106.59 (7)
S4—C4A—H4AB108.8Re1—Re2—Br6101.74 (6)
H4AA—C4A—H4AB107.7Br4—Re2—Br588.72 (9)
C5A—C4A—S4114 (3)Br4—Re2—Br6155.47 (8)
C5A—C4A—H4AA108.8Br5—Re2—Br687.39 (9)
C5A—C4A—H4AB108.8O1—Re2—Re188.9 (4)
S3—C5A—H5AA108.1O1—Re2—Br489.9 (5)
S3—C5A—H5AB108.1O1—Re2—Br5164.3 (4)
C4A—C5A—S3117 (2)O1—Re2—Br687.4 (5)
C4A—C5A—H5AA108.1C11—O1—Re2120.9 (14)
C4A—C5A—H5AB108.1C11—O2—Re1119.9 (13)
H5AA—C5A—H5AB107.3O1—C11—C12120 (2)
S3—C5B—H5BA107.3O2—C11—O1118.4 (18)
S3—C5B—H5BB107.3O2—C11—C12121 (2)
C4—C5B—S3120 (5)C11—C12—H12A109.5
C4—C5B—H5BA107.3C11—C12—H12B109.5
C4—C5B—H5BB107.3C11—C12—H12C109.5
H5BA—C5B—H5BB106.9H12A—C12—H12B109.5
S6—C6—S5116.3 (11)H12A—C12—H12C109.5
C1—C6—S5122.5 (15)H12B—C12—H12C109.5
C1—C6—S6121.2 (15)C1S—Cl2S—H1SA8.9
S5—C7—S8114.5 (12)Cl1S—C1S—Cl2S112 (2)
C8—C7—S5116.4 (16)Cl1S—C1S—H1S118.6
C8—C7—S8129.0 (16)Cl1S—C1S—H1SA109.2
S6—C8—S7115.3 (13)Cl2S—C1S—H1S114.7
C7—C8—S6117.5 (16)Cl2S—C1S—H1SA7.8
C7—C8—S7127.2 (18)C1Si—C1S—Cl1S97 (2)
S7—C9A—H9AA108.9C1Si—C1S—Cl2S104.2 (12)
S7—C9A—H9AB108.9C1Si—C1S—H1S108.0
H9AA—C9A—H9AB107.7C1Si—C1S—H1SA112.0
C10A—C9A—S7114 (2)H1S—C1S—H1SA111.3
S1—C1—C6—S50 (3)C7—S8—C10A—C9A40 (3)
S1—C1—C6—S6−177.4 (11)C7—S8—C10B—C9B−63 (7)
S2—C1—C6—S5177.7 (11)C8—S6—C6—S50.2 (14)
S2—C1—C6—S60 (2)C8—S6—C6—C1178.1 (17)
S2—C2—C3—S12 (3)C8—S7—C9A—C10A58 (3)
S2—C2—C3—S4−178.8 (14)C8—S7—C9B—C10B−42 (7)
S3—C2—C3—S1−177.1 (13)C9A—S7—C8—S6158.8 (15)
S3—C2—C3—S42 (3)C9A—S7—C8—C7−22 (2)
S4—C4—C5B—S358 (9)C9A—S7—C9B—C10B42 (6)
S4—C4A—C5A—S3−61 (4)C9B—S7—C8—S6−175 (4)
S5—C7—C8—S61 (2)C9B—S7—C8—C74 (4)
S5—C7—C8—S7−178.2 (13)C9B—S7—C9A—C10A−43 (8)
S7—C9A—C10A—S8−71 (3)C10A—S8—C7—S5174.5 (16)
S7—C9B—C10B—S877 (9)C10A—S8—C7—C8−4 (3)
S8—C7—C8—S6179.3 (13)C10A—S8—C10B—C9B43 (6)
S8—C7—C8—S70 (3)C10B—S8—C7—S5−158 (4)
C1—S1—C3—S4176.8 (14)C10B—S8—C7—C823 (4)
C1—S1—C3—C2−4 (2)C10B—S8—C10A—C9A−40 (8)
C1—S2—C2—S3−179.7 (12)Re1—Re2—O1—C11−3.2 (15)
C1—S2—C2—C30.9 (19)Re1—O2—C11—O1−6 (2)
C2—S2—C1—S1−3.7 (13)Re1—O2—C11—C12175.2 (17)
C2—S2—C1—C6178.7 (17)Re2—Re1—O2—C113.0 (15)
C2—S3—C5A—C4A22 (4)Re2—O1—C11—O26 (3)
C2—S3—C5B—C4−61 (7)Re2—O1—C11—C12−175.0 (17)
C3—S1—C1—S24.6 (14)Br1—Re1—Re2—Br4−90.90 (10)
C3—S1—C1—C6−177.8 (18)Br1—Re1—Re2—Br51.54 (11)
C3—S4—C4—C5B−19 (7)Br1—Re1—Re2—Br692.30 (10)
C3—S4—C4A—C5A63 (3)Br1—Re1—Re2—O1179.4 (5)
C4—S4—C3—S1168 (3)Br1—Re1—O2—C11−174.7 (11)
C4—S4—C3—C2−11 (4)Br2—Re1—Re2—Br4175.23 (10)
C4—S4—C4A—C5A−54 (6)Br2—Re1—Re2—Br5−92.32 (10)
C4A—S4—C3—S1144.9 (18)Br2—Re1—Re2—Br6−1.56 (10)
C4A—S4—C3—C2−34 (3)Br2—Re1—Re2—O185.6 (5)
C4A—S4—C4—C5B50 (4)Br2—Re1—O2—C11−105.9 (15)
C5A—S3—C2—S2−169.7 (19)Br3—Re1—Re2—Br43.05 (11)
C5A—S3—C2—C310 (3)Br3—Re1—Re2—Br595.49 (11)
C5A—S3—C5B—C453 (6)Br3—Re1—Re2—Br6−173.75 (10)
C5B—S3—C2—S2−152 (3)Br3—Re1—Re2—O1−86.6 (5)
C5B—S3—C2—C328 (3)Br3—Re1—O2—C11110.1 (15)
C5B—S3—C5A—C4A−48 (8)Br4—Re2—O1—C11−105.8 (15)
C6—S5—C7—S8−179.3 (12)Br5—Re2—O1—C11169.2 (11)
C6—S5—C7—C8−0.5 (19)Br6—Re2—O1—C1198.6 (15)
C6—S6—C8—S7178.5 (13)O2—Re1—Re2—Br489.8 (5)
C6—S6—C8—C7−0.6 (19)O2—Re1—Re2—Br5−177.8 (5)
C7—S5—C6—S60.1 (14)O2—Re1—Re2—Br6−87.0 (5)
C7—S5—C6—C1−177.7 (18)O2—Re1—Re2—O10.1 (6)
Symmetry code: (i) −x−1/2, y, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5B—H5BA···Br10.982.773.63 (8)147
C9A—H9AA···Br6ii0.972.803.60 (3)140
C9B—H9BA···S4iii0.972.753.46 (10)130
C9B—H9BB···Br6ii0.962.613.40 (11)140
C10A—H10A···Br4iv0.972.923.83 (4)156
C10A—H10B···S3iii0.972.813.57 (3)136
C10B—H10D···Br4iv0.982.673.61 (11)161
Symmetry codes: (ii) x, −y−1/2, z−1/2; (iii) −x, −y−1, −z; (iv) −x+1/2, y−1, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5B—H5BA···Br10.982.773.63 (8)147
C9A—H9AA···Br6i0.972.803.60 (3)140
C9B—H9BA···S4ii0.972.753.46 (10)130
C9B—H9BB···Br6i0.962.613.40 (11)140
C10A—H10A···Br4iii0.972.923.83 (4)156
C10A—H10B···S3ii0.972.813.57 (3)136
C10B—H10D···Br4iii0.982.673.61 (11)161
Symmetry codes: (i) x, −y−1/2, z−1/2; (ii) −x, −y−1, −z; (iii) −x+1/2, y−1, −z.

Experimental details

Crystal data
Chemical formula(C10H8S8)[Re2Br6(C2H3O2)]·0.5C2H3Cl3
Mr1362.24
Crystal system, space groupMonoclinic, I2/a
Temperature (K)298
a, b, c (Å)27.1825 (5), 8.53737 (13), 26.0667 (5)
β (°) 100.8440 (17)
V (Å3)5941.21 (18)
Z8
Radiation typeMo Kα
µ (mm−1)16.93
Crystal size (mm)0.4 × 0.4 × 0.1
Data collection
DiffractometerAgilent Xcalibur Sapphire3
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2014)
Tmin, Tmax0.067, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		36051, 6755, 6304
Rint0.039
(sin θ/λ)max (Å−1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.137, 1.14
No. of reflections6755
No. of parameters334
No. of restraints99
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0534P)2 + 229.8497P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)1.77, −1.90

Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

This work was supported by a grant for Science Research (No. 0111U000111) from the Ministry of Education and Science of Ukraine. We also thank COST Action CM1105 for supporting this study.

References

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ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 712-715
doi:10.1107/S2056989016006058
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