Crystal structure of di-μ-isobutyrato-κ4O:O′-bis­[cis-di­chlorido­(dimethyl sulfoxide-κS)rhenium(III)]

Golichenko, A.A.; Shtemenko, A.V.

doi:10.1107/S2056989015017429

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1219-1221

doi:10.1107/S2056989015017429

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Crystal structure of di-μ-isobutyrato-κ⁴O:O′-bis[cis-dichlorido(dimethyl sulfoxide-κS)rhenium(III)]

Alexander A. Golichenko ^a ^* and Alexander V. Shtemenko ^a

^aDepartment of Inorganic Chemistry, Ukrainian State University of Chemical Technology, Gagarin Ave. 8, Dnipropetrovsk 49005, Ukraine
^*Correspondence e-mail: golichenko_alex@i.ua

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 8 September 2015; accepted 17 September 2015; online 26 September 2015)

The title compound, [Re₂(C₃H₇COO)₂Cl₄{(CH₃)₂SO}₂], comprises binuclear complex molecules [Re—Re = 2.24502 (13) Å] involving cis-oriented double carboxylate bridges, four equatorial chloride ions and two weakly bonded O atoms from dimethyl sulfoxide ligands in the axial positions at the Re^III atoms. In the crystal, molecules are linked into corrugated layers parallel to (101) by very weak C—H⋯Cl and C—H⋯O hydrogen-bonding interactions. C—H⋯Cl hydrogen bonding provides the links between layers to consolidate a three-dimensional framework.

Keywords: crystal structure; rhenium(III); cluster; alkylcarboxylate complex; quadruple metal–metal bond; hydrogen bonding.

CCDC reference: 1425634

1. Chemical context

Binuclear rhenium(III) clusters are classical complexes with a unique quadruple metal–metal bond (Cotton et al., 2005 , Golichenko & Shtemenko, 2006 ). In our previous work we have shown that such compounds with chloride and alkylcarboxylate equatorial ligands exhibit antitumor, antiradical and hepato- and nephroprotective biological activity with low toxicity (Dimitrov et al., 1978 , Shtemenko et al., 2007 , 2008 , 2009 , 2013 ).

Labile axial ligands and equatorial chloride groups are the reactive centers in interactions with other chemical compounds and biological macromolecules in vitro and in vivo (Shtemenko et al., 2013). In this context, we present the synthesis and the structure of the title dirhenium(III) complex with isobutyrate equatorial ligands as biologically active groups, which can exhibit antitumor activity in the tetracarboxylate compound Re₂(i-C₃H₇COO)₄Cl₂ (Shtemenko et al., 2007).

2. Structural commentary

The quadruple Re—Re bond [2.24502 (13) Å] is typical for related dicarboxylato clusters (Cotton et al., 2005, Shtemenko et al., 2009) and the coordination of each of the rhenium ions also comprises two chlorides and two oxygen atoms of carboxylate ligands (Fig. 1). The distorted octahedral coordination geometry of Re1 and Re2 is completed by weakly bonded oxygen atoms from dimethyl sulfoxide ligands [Re1—O6 = 2.3282 (15) and Re2—O5 = 2.3938 (15) Å], in trans-positions to the Re—Re bond. This may be compared with a similar weak binding of N- or O-donors, which is characteristic of dicarboxylatodirhenium compounds (Bera et al., 2003 , Shtemenko et al., 2009, Golichenko et al., 2015 ).

Figure 1
The structure of cis-Re₂Cl₄{i-C₃H₇COO}₂·2(CH₃)₂SO, showing displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii.

3. Supramolecular features

Intermolecular bonding is only very weak: it comprises distal, though relatively directional, C—H⋯O and C—H⋯Cl hydrogen-bond interactions between the methine- and methyl-H of the carboxylate and DMSO ligands (Table 1). The shortest bonds found for the chloride acceptors are C6—H6⋯Cl3ⁱⁱ [C6⋯Cl3ⁱⁱ = 3.519 (2) Å; symmetry code (ii): $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z], which unite the molecules into chains along the b axis (Fig. 2). The hydrogen bonds adopted by two methyl groups of DMSO molecules (referenced by a sulfur atoms S2) assemble these chains into corrugated layers parallel to (101). A very weak bond of this type is found also between adjacent layers: C12⋯Cl2ⁱⁱⁱ = 3.751 (3) Å; symmetry code (iii): − $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z] (Table 1). The latter extends the structure into a third direction and provides the formation of a hydrogen-bonded framework.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯O2ⁱ	0.98	2.40	3.324 (3)	156
C6—H6⋯Cl3ⁱⁱ	1.00	2.73	3.519 (2)	136
C12—H12A⋯Cl2ⁱⁱⁱ	0.98	2.82	3.751 (3)	159
C12—H12B⋯Cl3ⁱ	0.98	2.82	3.760 (3)	161
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A fragment of the structure, showing weak C—H⋯O and C—H⋯Cl hydrogen-bond interactions (dashed lines), which assemble the molecules into corrugated layers parallel to (101). [Symmetry codes: (i) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (ii) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.]

4. Synthesis and crystallization

[NBu₄]₂[Re₂Cl₈] (0.2 g, 0.175 mmol) was added to isobutyric acid (10 ml). The mixture was heated for 3 h in a water bath under an inert atmosphere. DMSO (0.5 ml) was then added to the resulting blue solution at room temperature. A dark-blue crystalline product (0.12 g, yield 81%) was obtained after 12 h, was collected by filtration and dried in air.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H were refined using a riding-model approximation, with C—H = 0.98–1.00 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. A rotating model was used for the methyl groups. Six outliers (2 6 1, 3 3 3, $[\overline{2}]$ 4 3, 0 1 1, $[\overline{4}]$ 3 4, 3 3 7) were omitted in the last cycles of refinement.

Table 2
Experimental details

Crystal data
Chemical formula	[Re₂(C₄H₇O₂)₂Cl₄(C₂H₆OS)₂]
M_r	844.65
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	110
a, b, c (Å)	10.5581 (4), 14.7406 (5), 15.6088 (6)
β (°)	100.794 (2)
V (Å³)	2386.26 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	10.78
Crystal size (mm)	0.22 × 0.18 × 0.09

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.133, 0.478
No. of measured, independent and observed [I > 2σ(I)] reflections	93039, 14497, 11921
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.909

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.049, 1.00
No. of reflections	14497
No. of parameters	243
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.71, −1.14
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 (Sheldrick 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1425634

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015017429/rz5165sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017429/rz5165Isup2.hkl

checkCIF report

Chemical context top

Binuclear rhenium(III) clusters are classical complexes with a unique quadruple metal–metal bond (Cotton et al., 2005, Golichenko & Shtemenko, 2006). In our previous works we have shown that such compounds with chloride and alkylcarboxylate equatorial ligands exhibit antitumor, antiradical and hepato- and nephroprotective biological activity with low toxicity (Dimitrov et al., 1978, Shtemenko et al., 2007, 2008, 2009, 2013).

Structural commentary top

The quadruple Re—Re bond [2.24502 (13) Å] is typical for related dicarboxylato clusters (Cotton et al., 2005, Shtemenko et al., 2009) and the coordination of each of the rhenium ions also comprises two chlorides and two oxygen atoms of carboxylate ligands (Fig. 1). The distorted octahedral coordination geometry of Re1 and Re2 is completed by weakly bonded oxygen atoms from dimethyl sulfoxide ligands [Re1—O6 = 2.3282 (15) and Re2—O5 = 2.3938 (15) Å], in a trans-position to the Re—Re bond. This may be compared with a similar weak binding of N- or O-donors, which is characteristic of dicarboxylatodirhenium compounds (Bera et al., 2003, Shtemenko et al., 2009, Golichenko et al., 2015).

Supramolecular features top

The title compound adopts a typical molecular structure. Intermolecular bonding is only very weak: it comprises distal, though relatively directional, C—H···O and C—H···Cl hydrogen-bond interactions with the methyl and methine groups of the carboxylate and DMSO ligands (Table 1). The shortest bonds found for the chloride acceptors are C6—H6···Cl3ⁱⁱ [C6···Cl3ⁱⁱ = 3.519 (2) Å; symmetry code (ii): 1/2 - x, 1/2 + y, 1/2 - z], which unite the molecules into chains along the b axis (Fig. 2). The hydrogen bonds adopted by two methyl groups of DMSO molecules (referenced by a sulfur atoms S2) assemble these chains into corrugated layers parallel to the (101) plane. A very weak bond of this type is found also between adjacent layers: C12···Cl2ⁱⁱⁱ = 3.751 (3) Å; symmetry code (iii): -1/2 - x, 1/2 + y, 1/2 - z] (Table 1). The latter extends the structure into a third direction and provides the formation of a hydrogen-bonded framework.

Synthesis and crystallization top

0.2 g (0.175 mmol) of [NBu₄]₂[Re₂Cl₈] was added to 10 ml of isobutyric acid. The mixture was heated for 3 h in a water bath under an inert atmosphere. 0.5 ml of dimethyl sulfoxide was then added to the resulting blue solution at room temperature. A dark-blue crystalline product (0.12 g, yield 81%) was obtained after 12 h, was collected by filtration and dried in air.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All H were refined using a riding-model approximation, with C—H = 0.98–1.00 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. A rotating model was used for the methyl groups. Six outliers (2 6 1, 3 3 3, 2 4 3, 0 1 1, 4 3 4, 3 3 7) were omitted in the last cycles of refinement.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The structure of cis-Re₂Cl₄{i-C₃H₇COO}₂·2(CH₃)₂SO, showing displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A fragment of the structure, showing weak C—H···O and C—H···Cl hydrogen-bond interactions (dashed lines), which assemble the molecules into corrugated layers parallel to the (101) plane. [Symmetry codes: (i) -1/2 + x, 1/2 - y, 1/2 + z; (ii) 1/2 - x, 1/2 + y, 1/2 - z.]

Di-µ-isobutyrato-κ⁴O:O'-bis[cis-dichlorido(dimethyl sulfoxide-κS)rhenium(III)] top

Crystal data top

[Re₂(C₄H₇O₂)₂Cl₄(C₂H₆OS)₂]	F(000) = 1584
M_r = 844.65	D_x = 2.351 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.5581 (4) Å	Cell parameters from 9919 reflections
b = 14.7406 (5) Å	θ = 2.4–39.0°
c = 15.6088 (6) Å	µ = 10.78 mm⁻¹
β = 100.794 (2)°	T = 110 K
V = 2386.26 (15) Å³	Plate, blue
Z = 4	0.22 × 0.18 × 0.09 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	11921 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
phi and ω scans	θ_max = 40.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→18
T_min = 0.133, T_max = 0.478	k = −25→26
93039 measured reflections	l = −28→27
14497 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.049	w = 1/[σ²(F_o²) + (0.0183P)² + 1.7981P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.002
14497 reflections	Δρ_max = 1.71 e Å⁻³
243 parameters	Δρ_min = −1.14 e Å⁻³

Crystal data top

[Re₂(C₄H₇O₂)₂Cl₄(C₂H₆OS)₂]	V = 2386.26 (15) Å³
M_r = 844.65	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.5581 (4) Å	µ = 10.78 mm⁻¹
b = 14.7406 (5) Å	T = 110 K
c = 15.6088 (6) Å	0.22 × 0.18 × 0.09 mm
β = 100.794 (2)°

Data collection top

Siemens SMART CCD area-detector diffractometer	14497 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	11921 reflections with I > 2σ(I)
T_min = 0.133, T_max = 0.478	R_int = 0.040
93039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.049	H-atom parameters constrained
S = 1.00	Δρ_max = 1.71 e Å⁻³
14497 reflections	Δρ_min = −1.14 e Å⁻³
243 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Re1	−0.06723 (2)	0.17363 (2)	0.27880 (2)	0.01130 (2)
Re2	0.10986 (2)	0.16371 (2)	0.21905 (2)	0.01147 (2)
Cl1	−0.01954 (5)	0.08982 (4)	0.40554 (3)	0.02107 (9)
Cl2	−0.19965 (5)	0.05974 (3)	0.21084 (3)	0.01810 (8)
Cl3	0.06421 (5)	0.04494 (3)	0.12210 (3)	0.01726 (8)
Cl4	0.25202 (5)	0.07759 (3)	0.31739 (3)	0.02151 (9)
S1	0.41251 (5)	0.24240 (4)	0.20176 (3)	0.01935 (9)
S2	−0.23871 (5)	0.25929 (3)	0.42297 (3)	0.01756 (9)
O1	−0.14493 (13)	0.26371 (9)	0.18365 (9)	0.0142 (2)
O2	0.02927 (14)	0.25241 (9)	0.12399 (9)	0.0145 (2)
O3	0.18421 (14)	0.27603 (9)	0.28722 (9)	0.0159 (3)
O4	0.01121 (14)	0.28533 (9)	0.34802 (9)	0.0158 (3)
O5	0.28531 (14)	0.20575 (10)	0.14988 (10)	0.0189 (3)
O6	−0.24413 (14)	0.23612 (10)	0.32675 (9)	0.0189 (3)
C1	−0.07803 (18)	0.29012 (12)	0.12848 (12)	0.0133 (3)
C2	−0.1181 (2)	0.37225 (13)	0.07331 (14)	0.0181 (4)
H2	−0.1090	0.3585	0.0120	0.022*
C3	−0.2560 (2)	0.40050 (17)	0.07314 (17)	0.0274 (5)
H3A	−0.2788	0.4516	0.0330	0.041*
H3B	−0.2647	0.4188	0.1321	0.041*
H3C	−0.3138	0.3494	0.0542	0.041*
C4	−0.0227 (3)	0.44808 (16)	0.1087 (2)	0.0354 (6)
H4A	0.0658	0.4260	0.1125	0.053*
H4B	−0.0358	0.4662	0.1668	0.053*
H4C	−0.0371	0.5004	0.0694	0.053*
C5	0.1204 (2)	0.31512 (13)	0.33854 (12)	0.0152 (3)
C6	0.1796 (2)	0.39547 (14)	0.38935 (14)	0.0197 (4)
H6	0.2283	0.4313	0.3518	0.024*
C7	0.0785 (3)	0.4565 (2)	0.4167 (2)	0.0469 (8)
H7A	0.0176	0.4764	0.3649	0.070*
H7B	0.1206	0.5095	0.4476	0.070*
H7C	0.0321	0.4229	0.4554	0.070*
C8	0.2750 (3)	0.36103 (19)	0.46883 (17)	0.0337 (6)
H8A	0.3380	0.3207	0.4495	0.051*
H8B	0.2282	0.3276	0.5074	0.051*
H8C	0.3200	0.4127	0.5004	0.051*
C9	0.4146 (3)	0.36054 (17)	0.1775 (2)	0.0360 (6)
H9A	0.4047	0.3689	0.1143	0.054*
H9B	0.4968	0.3868	0.2065	0.054*
H9C	0.3435	0.3908	0.1984	0.054*
C10	0.5306 (2)	0.20667 (18)	0.14113 (18)	0.0291 (5)
H10A	0.5367	0.1403	0.1425	0.044*
H10B	0.6144	0.2329	0.1669	0.044*
H10C	0.5057	0.2272	0.0806	0.044*
C11	−0.3361 (3)	0.17496 (16)	0.46035 (17)	0.0286 (5)
H11A	−0.4191	0.1709	0.4200	0.043*
H11B	−0.3508	0.1913	0.5186	0.043*
H11C	−0.2922	0.1162	0.4631	0.043*
C12	−0.3441 (3)	0.35344 (17)	0.42132 (18)	0.0338 (6)
H12A	−0.3087	0.4057	0.3950	0.051*
H12B	−0.3529	0.3685	0.4811	0.051*
H12C	−0.4289	0.3381	0.3870	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.01040 (3)	0.01222 (3)	0.01171 (3)	−0.00114 (2)	0.00320 (2)	0.00002 (2)
Re2	0.00953 (3)	0.01154 (3)	0.01360 (3)	0.00081 (2)	0.00288 (2)	0.00041 (2)
Cl1	0.0222 (2)	0.0241 (2)	0.0166 (2)	−0.00111 (18)	0.00305 (17)	0.00674 (16)
Cl2	0.0161 (2)	0.01640 (19)	0.0219 (2)	−0.00426 (15)	0.00380 (17)	−0.00305 (15)
Cl3	0.0169 (2)	0.01521 (19)	0.0201 (2)	0.00138 (15)	0.00460 (16)	−0.00402 (14)
Cl4	0.0167 (2)	0.0215 (2)	0.0244 (2)	0.00463 (17)	−0.00088 (18)	0.00541 (17)
S1	0.0130 (2)	0.0223 (2)	0.0230 (2)	−0.00283 (17)	0.00407 (18)	−0.00136 (17)
S2	0.0194 (2)	0.0189 (2)	0.0162 (2)	−0.00284 (17)	0.00824 (17)	−0.00281 (15)
O1	0.0120 (6)	0.0153 (6)	0.0159 (6)	0.0000 (5)	0.0041 (5)	0.0022 (4)
O2	0.0133 (6)	0.0153 (6)	0.0157 (6)	0.0025 (5)	0.0048 (5)	0.0026 (4)
O3	0.0136 (6)	0.0161 (6)	0.0186 (6)	−0.0023 (5)	0.0044 (5)	−0.0023 (5)
O4	0.0156 (7)	0.0163 (6)	0.0162 (6)	−0.0038 (5)	0.0050 (5)	−0.0034 (5)
O5	0.0108 (6)	0.0225 (7)	0.0238 (7)	−0.0020 (5)	0.0040 (5)	−0.0011 (5)
O6	0.0164 (7)	0.0255 (7)	0.0167 (7)	−0.0009 (5)	0.0076 (5)	−0.0038 (5)
C1	0.0134 (8)	0.0128 (7)	0.0135 (8)	0.0015 (6)	0.0022 (6)	−0.0002 (5)
C2	0.0175 (9)	0.0170 (8)	0.0199 (9)	0.0037 (7)	0.0034 (7)	0.0046 (6)
C3	0.0184 (10)	0.0275 (11)	0.0353 (13)	0.0065 (8)	0.0025 (9)	0.0084 (9)
C4	0.0254 (12)	0.0162 (10)	0.0617 (18)	−0.0007 (8)	0.0004 (12)	0.0048 (10)
C5	0.0161 (9)	0.0132 (8)	0.0155 (8)	−0.0013 (6)	0.0015 (7)	−0.0012 (6)
C6	0.0206 (10)	0.0179 (9)	0.0204 (9)	−0.0062 (7)	0.0028 (7)	−0.0044 (7)
C7	0.0375 (16)	0.0298 (14)	0.072 (2)	−0.0008 (11)	0.0079 (15)	−0.0319 (14)
C8	0.0341 (14)	0.0370 (14)	0.0254 (12)	−0.0122 (11)	−0.0065 (10)	−0.0026 (9)
C9	0.0340 (14)	0.0203 (11)	0.0549 (17)	−0.0051 (10)	0.0113 (13)	−0.0022 (10)
C10	0.0134 (9)	0.0340 (13)	0.0412 (14)	0.0010 (8)	0.0083 (9)	−0.0067 (10)
C11	0.0379 (14)	0.0239 (11)	0.0294 (12)	−0.0072 (9)	0.0206 (11)	−0.0015 (8)
C12	0.0494 (17)	0.0237 (11)	0.0322 (13)	0.0104 (11)	0.0172 (12)	−0.0002 (9)

Geometric parameters (Å, º) top

Re1—O1	2.0459 (13)	C3—H3C	0.9800
Re1—O4	2.0565 (13)	C4—H4A	0.9800
Re1—Re2	2.2450 (1)	C4—H4B	0.9800
Re1—Cl1	2.3065 (5)	C4—H4C	0.9800
Re1—Cl2	2.3115 (5)	C5—C6	1.495 (3)
Re1—O6	2.3282 (15)	C6—C7	1.517 (4)
Re2—O2	2.0401 (13)	C6—C8	1.531 (3)
Re2—O3	2.0437 (14)	C6—H6	1.0000
Re2—Cl3	2.3052 (5)	C7—H7A	0.9800
Re2—Cl4	2.3147 (5)	C7—H7B	0.9800
Re2—O5	2.3938 (15)	C7—H7C	0.9800
S1—O5	1.5310 (15)	C8—H8A	0.9800
S1—C10	1.780 (2)	C8—H8B	0.9800
S1—C9	1.783 (3)	C8—H8C	0.9800
S2—O6	1.5308 (15)	C9—H9A	0.9800
S2—C12	1.776 (3)	C9—H9B	0.9800
S2—C11	1.780 (2)	C9—H9C	0.9800
O1—C1	1.273 (2)	C10—H10A	0.9800
O2—C1	1.276 (2)	C10—H10B	0.9800
O3—C5	1.276 (2)	C10—H10C	0.9800
O4—C5	1.268 (3)	C11—H11A	0.9800
C1—C2	1.500 (3)	C11—H11B	0.9800
C2—C3	1.514 (3)	C11—H11C	0.9800
C2—C4	1.536 (3)	C12—H12A	0.9800
C2—H2	1.0000	C12—H12B	0.9800
C3—H3A	0.9800	C12—H12C	0.9800
C3—H3B	0.9800

O1—Re1—O4	85.93 (6)	C2—C3—H3C	109.5
O1—Re1—Re2	89.58 (4)	H3A—C3—H3C	109.5
O4—Re1—Re2	89.18 (4)	H3B—C3—H3C	109.5
O1—Re1—Cl1	164.51 (4)	C2—C4—H4A	109.5
O4—Re1—Cl1	88.65 (4)	C2—C4—H4B	109.5
Re2—Re1—Cl1	104.857 (14)	H4A—C4—H4B	109.5
O1—Re1—Cl2	90.71 (4)	C2—C4—H4C	109.5
O4—Re1—Cl2	166.43 (4)	H4A—C4—H4C	109.5
Re2—Re1—Cl2	103.960 (13)	H4B—C4—H4C	109.5
Cl1—Re1—Cl2	91.189 (19)	O4—C5—O3	121.00 (17)
O1—Re1—O6	74.92 (5)	O4—C5—C6	120.74 (18)
O4—Re1—O6	77.45 (6)	O3—C5—C6	118.24 (18)
Re2—Re1—O6	160.04 (4)	C5—C6—C7	111.87 (19)
Cl1—Re1—O6	89.75 (4)	C5—C6—C8	108.26 (18)
Cl2—Re1—O6	88.98 (4)	C7—C6—C8	111.1 (2)
O2—Re2—O3	85.80 (6)	C5—C6—H6	108.5
O2—Re2—Re1	89.66 (4)	C7—C6—H6	108.5
O3—Re2—Re1	89.97 (4)	C8—C6—H6	108.5
O2—Re2—Cl3	90.11 (4)	C6—C7—H7A	109.5
O3—Re2—Cl3	165.87 (4)	C6—C7—H7B	109.5
Re1—Re2—Cl3	103.544 (13)	H7A—C7—H7B	109.5
O2—Re2—Cl4	164.60 (4)	C6—C7—H7C	109.5
O3—Re2—Cl4	87.76 (4)	H7A—C7—H7C	109.5
Re1—Re2—Cl4	104.318 (15)	H7B—C7—H7C	109.5
Cl3—Re2—Cl4	92.789 (18)	C6—C8—H8A	109.5
O2—Re2—O5	76.03 (5)	C6—C8—H8B	109.5
O3—Re2—O5	76.76 (5)	H8A—C8—H8B	109.5
Re1—Re2—O5	161.00 (4)	C6—C8—H8C	109.5
Cl3—Re2—O5	89.13 (4)	H8A—C8—H8C	109.5
Cl4—Re2—O5	88.89 (4)	H8B—C8—H8C	109.5
O5—S1—C10	104.28 (10)	S1—C9—H9A	109.5
O5—S1—C9	106.08 (12)	S1—C9—H9B	109.5
C10—S1—C9	97.94 (14)	H9A—C9—H9B	109.5
O6—S2—C12	104.59 (11)	S1—C9—H9C	109.5
O6—S2—C11	104.36 (10)	H9A—C9—H9C	109.5
C12—S2—C11	98.71 (14)	H9B—C9—H9C	109.5
C1—O1—Re1	119.46 (12)	S1—C10—H10A	109.5
C1—O2—Re2	119.54 (12)	S1—C10—H10B	109.5
C5—O3—Re2	119.74 (13)	H10A—C10—H10B	109.5
C5—O4—Re1	120.10 (13)	S1—C10—H10C	109.5
S1—O5—Re2	121.94 (8)	H10A—C10—H10C	109.5
S2—O6—Re1	121.25 (8)	H10B—C10—H10C	109.5
O1—C1—O2	121.00 (17)	S2—C11—H11A	109.5
O1—C1—C2	120.20 (17)	S2—C11—H11B	109.5
O2—C1—C2	118.55 (17)	H11A—C11—H11B	109.5
C1—C2—C3	112.98 (18)	S2—C11—H11C	109.5
C1—C2—C4	106.60 (17)	H11A—C11—H11C	109.5
C3—C2—C4	111.48 (19)	H11B—C11—H11C	109.5
C1—C2—H2	108.6	S2—C12—H12A	109.5
C3—C2—H2	108.6	S2—C12—H12B	109.5
C4—C2—H2	108.6	H12A—C12—H12B	109.5
C2—C3—H3A	109.5	S2—C12—H12C	109.5
C2—C3—H3B	109.5	H12A—C12—H12C	109.5
H3A—C3—H3B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O2ⁱ	0.98	2.40	3.324 (3)	156
C6—H6···Cl3ⁱⁱ	1.00	2.73	3.519 (2)	136
C12—H12A···Cl2ⁱⁱⁱ	0.98	2.82	3.751 (3)	159
C12—H12B···Cl3ⁱ	0.98	2.82	3.760 (3)	161

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x−1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O2ⁱ	0.98	2.40	3.324 (3)	156
C6—H6···Cl3ⁱⁱ	1.00	2.73	3.519 (2)	136
C12—H12A···Cl2ⁱⁱⁱ	0.98	2.82	3.751 (3)	159
C12—H12B···Cl3ⁱ	0.98	2.82	3.760 (3)	161

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x−1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Re₂(C₄H₇O₂)₂Cl₄(C₂H₆OS)₂]
M_r	844.65
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	110
a, b, c (Å)	10.5581 (4), 14.7406 (5), 15.6088 (6)
β (°)	100.794 (2)
V (Å³)	2386.26 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.78
Crystal size (mm)	0.22 × 0.18 × 0.09

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.133, 0.478
No. of measured, independent and observed [I > 2σ(I)] reflections	93039, 14497, 11921
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.909

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.049, 1.00
No. of reflections	14497
No. of parameters	243
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.71, −1.14

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).

Acknowledgements

This work was supported by the fund Grant for Science Research (No. 0111U000111) from the Ministry of Education and Science of Ukraine. We also thank COST Action CM 1105 for supporting this study. We thank Joseph H. Reibenspies (Texas A&M University, College Station, USA) and Professor Konstantin V. Domasevitch (National Taras Shevchenko University of Kyiv, Ukraine) for providing facilities for a portion of these studies, and helpful discussions.

References

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Volume 71| Part 10| October 2015| Pages 1219-1221

doi:10.1107/S2056989015017429

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