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The title compound, methylene bis[bis(N,N-diethyl­amino)­carbeniumdi­thio­carboxyl­ate] penta­chloro­oxo­rhenium, (C21H42N4S4)[ReCl5O], is the result of an unusual dimerization of the ligand bis(N,N-diethyl­amino)­carbeniumdi­thio­carboxyl­ate [(Et2N)2C2S2] upon reaction with [ReOCl3(PPh3)2] in chloro­form under reflux conditions. The compound was obtained as a dicationic moiety, with the molecular [ReOCl5]2- anion providing the charge compensation. The planes of the carbenium and thio­carboxyl­ate moieties are nearly perpendicular to one another and the backbone C-C bond length in the N2CCS2 group is the same as a normal C-C single-bond length.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104006869/fg1741sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104006869/fg1741IIsup2.hkl
Contains datablock II

CCDC reference: 241212

Comment top

The ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate, [(Et2N)2C2S2], (I), was first synthesized by Nakayama et al. (1992, 1995, 2000) and was proposed to possess an interesting inner-salt structure, in which the positive and negative charges are delocalized on the NCN and SCS moieties, although the structure can be drawn as canonical contributions between an inner-salt form and a neutral form.

In previous X-ray structural studies of the rheniumtricarbonyl complexes with ligand (I) (Banerjee et al., 2002), we have observed that the ligand can act as a neutral bridging ligand, as well as a bidentate chelating ligand, maintaining its characteristic inner-salt structural features. As part of our ongoing interest in exploring the versatility of the ligand's binding mode, we have studied the reactions of the ligand with different oxorhenium(V) starting materials. We report here the structural characterization of a new compound, (II), obtained upon refluxing a chloroform solution the common oxorhenium(V) starting material [ReOCl3(PPh3)2] with ligand (I).

A perspective view of (II) is shown in Fig. 1, and selected bond lengths and angles for (II) are given in Table 1. The structure of (II) can be described as a dimer of the [(Et2N)2C2S2] unit connected via a methylene group at the C21 position, maintaining essentially the same structural features of the [(Et2N)2C2S2] ligand. The S1—C21—S3 bridging angle is 113.64 (12) °, a significant deviation from the idealized tetrahedral angle, while the two C=S terminal bonds are oriented trans to one another, thus minimizing the steric interaction between the ligand halves. The Re—O bond length is 1.6796 (17) Å and lies within the range of normal values of Reτb O triple-bond values, [1.68 (3) Å; Banerjee et al., 2000, and references therein). The Re—Cl bond lengths lie in the range 2.3896 (6)–2.4550 (5) Å and are within the range of normal values (Gilli et al., 1982; Sivakumar et al., 1998; Banerjee et al., 2000) The Re–Cl3 bond is the longest bond, as it lies trans to the Reτb O triple bond. The metric parameters for the organic cation are significant, as they define the electronic structure of the ligand. The backbone C9—C10 and C11—12 bonds are longer (ca 0.02 Å) than that of the free ligand, (I) [1.47 (2) Å; Nakayama, 1995]. The C—N bond lengths are shorter and are close to the normal Cδb N double-bond length [1.316 (9) Å; Allen et al., 1987]. The N—C—N bond angles [125.4 (2) and 126.5 (2)°] are close to the value for the free ligand [122 (1)°]. The most significant features of (II) are the dihedral angles between the S/C/S and N/C/N planes, viz. 104.5 (2)° (S4/C11/S3 and N2/C12/N4) and 104.7 (2)° (S1/C10/S2 and N1/C9/N2), respectively, for the two halves of the ligand. These dihedral angles are significantly larger than that observed in the free ligand [98.0 (1)°; Nakayama, 1995]. There are different kinds of C—S bond lengths in the compound. The S2—C10 and S4—C11 bonds [1.615 (2) and 1.635 (2) Å, respectively] are close to the Cδb S double-bond value (Allen et al., 1987) and much shorter than that of the free ligand [1.67 (2)–1.68 (2) Å]. The S1—C10 [1.740 (2) Å] and S3—C11 [1.708 (2) Å] bonds display multiple-bond character. The S1—C21 and S3—C21 bond lengths are 1.800 (2) and 1.801 (2) Å, respectively, and are comparable to the normal C—S single-bond laength [1.79–1.82 (1) Å; Miller et al., 2000].

Experimental top

To solution of [ReOCl3PPh3)2] (0.1 g, 0.12 mmol) in chloroform (15 ml) was added the ligand [(Et2N)2C2S2] (0.083 mg, 0. 36 mmol) (Nakayama et al., 1992) and the solution was refluxed for 5 h. The resulting dark-brown reaction mixture was subjected to chromatographic separation (MeOH/CH2Cl2 2:98) using a silica-gel column. The light-pink–orange fraction was collected and evaporated under vacuum to give an orange solid. Yield: 32 mg, 30%. Analysis found: C 29.95, H 5.24, N 6.58%; C21H42Cl5N4OReS4 requires: C 29.35, H 5.04, N 6.52%. Crystals of (II) suitable for single-crystal X-ray diffraction were grown by slow diffusion of a solution of (II) in CH2Cl2 into hexane solution at room temperature.

Refinement top

All H atoms were located in difference Fourier maps and then allowed for as riding atoms, with Uiso(H) values of 1.2Ueq(parent atom). A residual peak of electron density was located in the vicinity of the Re atom. However, the absorption correction could not be adjusted to further minimize this residual. Such residuals are not uncommon in structures containing atoms with large absorption coefficients.

Structure description top

The ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate, [(Et2N)2C2S2], (I), was first synthesized by Nakayama et al. (1992, 1995, 2000) and was proposed to possess an interesting inner-salt structure, in which the positive and negative charges are delocalized on the NCN and SCS moieties, although the structure can be drawn as canonical contributions between an inner-salt form and a neutral form.

In previous X-ray structural studies of the rheniumtricarbonyl complexes with ligand (I) (Banerjee et al., 2002), we have observed that the ligand can act as a neutral bridging ligand, as well as a bidentate chelating ligand, maintaining its characteristic inner-salt structural features. As part of our ongoing interest in exploring the versatility of the ligand's binding mode, we have studied the reactions of the ligand with different oxorhenium(V) starting materials. We report here the structural characterization of a new compound, (II), obtained upon refluxing a chloroform solution the common oxorhenium(V) starting material [ReOCl3(PPh3)2] with ligand (I).

A perspective view of (II) is shown in Fig. 1, and selected bond lengths and angles for (II) are given in Table 1. The structure of (II) can be described as a dimer of the [(Et2N)2C2S2] unit connected via a methylene group at the C21 position, maintaining essentially the same structural features of the [(Et2N)2C2S2] ligand. The S1—C21—S3 bridging angle is 113.64 (12) °, a significant deviation from the idealized tetrahedral angle, while the two C=S terminal bonds are oriented trans to one another, thus minimizing the steric interaction between the ligand halves. The Re—O bond length is 1.6796 (17) Å and lies within the range of normal values of Reτb O triple-bond values, [1.68 (3) Å; Banerjee et al., 2000, and references therein). The Re—Cl bond lengths lie in the range 2.3896 (6)–2.4550 (5) Å and are within the range of normal values (Gilli et al., 1982; Sivakumar et al., 1998; Banerjee et al., 2000) The Re–Cl3 bond is the longest bond, as it lies trans to the Reτb O triple bond. The metric parameters for the organic cation are significant, as they define the electronic structure of the ligand. The backbone C9—C10 and C11—12 bonds are longer (ca 0.02 Å) than that of the free ligand, (I) [1.47 (2) Å; Nakayama, 1995]. The C—N bond lengths are shorter and are close to the normal Cδb N double-bond length [1.316 (9) Å; Allen et al., 1987]. The N—C—N bond angles [125.4 (2) and 126.5 (2)°] are close to the value for the free ligand [122 (1)°]. The most significant features of (II) are the dihedral angles between the S/C/S and N/C/N planes, viz. 104.5 (2)° (S4/C11/S3 and N2/C12/N4) and 104.7 (2)° (S1/C10/S2 and N1/C9/N2), respectively, for the two halves of the ligand. These dihedral angles are significantly larger than that observed in the free ligand [98.0 (1)°; Nakayama, 1995]. There are different kinds of C—S bond lengths in the compound. The S2—C10 and S4—C11 bonds [1.615 (2) and 1.635 (2) Å, respectively] are close to the Cδb S double-bond value (Allen et al., 1987) and much shorter than that of the free ligand [1.67 (2)–1.68 (2) Å]. The S1—C10 [1.740 (2) Å] and S3—C11 [1.708 (2) Å] bonds display multiple-bond character. The S1—C21 and S3—C21 bond lengths are 1.800 (2) and 1.801 (2) Å, respectively, and are comparable to the normal C—S single-bond laength [1.79–1.82 (1) Å; Miller et al., 2000].

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
(II) top
Crystal data top
(C21H42N4S4)[ReCl5O]F(000) = 1712
Mr = 858.28Dx = 1.694 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 11209 reflections
a = 13.1381 (5) Åθ = 1.8–31.5°
b = 16.3486 (7) ŵ = 4.28 mm1
c = 15.7094 (6) ÅT = 90 K
β = 94.003 (1)°Block, orange
V = 3366.0 (2) Å30.23 × 0.16 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-dectector
diffractometer
11209 independent reflections
Radiation source: fine-focus sealed tube10065 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 512 pixels mm-1θmax = 31.5°, θmin = 1.8°
φ and ω scansh = 1919
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
k = 2423
Tmin = 0.440, Tmax = 0.674l = 2323
43155 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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.031P)2 + 2.8947P]
where P = (Fo2 + 2Fc2)/3
11209 reflections(Δ/σ)max = 0.003
333 parametersΔρmax = 1.83 e Å3
0 restraintsΔρmin = 0.47 e Å3
Crystal data top
(C21H42N4S4)[ReCl5O]V = 3366.0 (2) Å3
Mr = 858.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.1381 (5) ŵ = 4.28 mm1
b = 16.3486 (7) ÅT = 90 K
c = 15.7094 (6) Å0.23 × 0.16 × 0.10 mm
β = 94.003 (1)°
Data collection top
Bruker SMART APEX CCD area-dectector
diffractometer
11209 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
10065 reflections with I > 2σ(I)
Tmin = 0.440, Tmax = 0.674Rint = 0.028
43155 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.064H-atom parameters constrained
S = 1.07Δρmax = 1.83 e Å3
11209 reflectionsΔρmin = 0.47 e Å3
333 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.

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 > σ(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. Highest peak 1.82 at 0.9835 0.2405 0.0204 [0.74 A from Re1] Deepest hole -0.47 at 0.0643 0.1918 0.0451 [1.20 A from Cl2]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Re10.527008 (6)0.696602 (5)0.487325 (5)0.01556 (3)
Cl10.56523 (5)0.68897 (3)0.34104 (3)0.02233 (11)
Cl20.35210 (4)0.72002 (3)0.43906 (4)0.02062 (10)
Cl30.55376 (4)0.84493 (3)0.47914 (3)0.01948 (10)
Cl40.49064 (4)0.72411 (3)0.63348 (3)0.01993 (10)
Cl50.70669 (4)0.69182 (3)0.53003 (4)0.02193 (10)
S10.23796 (4)0.07465 (4)0.64456 (3)0.01979 (10)
S20.44490 (4)0.00497 (4)0.67031 (4)0.02377 (11)
S30.33135 (4)0.05591 (3)0.47577 (3)0.01641 (9)
S40.10904 (5)0.10405 (5)0.45207 (4)0.03147 (14)
O10.51257 (14)0.59535 (10)0.49998 (11)0.0234 (3)
N10.26601 (15)0.11146 (12)0.76211 (12)0.0179 (3)
N20.28109 (15)0.01116 (12)0.84195 (12)0.0193 (4)
N30.20680 (16)0.05274 (12)0.27073 (12)0.0209 (4)
N40.20663 (14)0.07070 (12)0.34890 (12)0.0182 (3)
C10.3892 (2)0.18456 (18)0.85998 (18)0.0308 (6)
H1A0.41920.13260.88030.046*
H1B0.39590.22510.90590.046*
H1C0.42490.20410.81120.046*
C20.27751 (18)0.17193 (14)0.83301 (15)0.0209 (4)
H2A0.24130.15200.88220.025*
H2B0.24650.22470.81410.025*
C30.24901 (18)0.14949 (14)0.67623 (14)0.0208 (4)
H3A0.26680.10970.63210.025*
H3B0.29410.19770.67250.025*
C40.1394 (2)0.1756 (2)0.65947 (18)0.0333 (6)
H4A0.09530.12720.65670.050*
H4B0.13150.20520.60510.050*
H4C0.12010.21150.70570.050*
C50.2601 (3)0.03196 (18)0.99382 (16)0.0342 (6)
H5A0.29430.01631.01940.051*
H5B0.20860.05151.03120.051*
H5C0.31050.07520.98660.051*
C60.2091 (2)0.00954 (16)0.90794 (16)0.0257 (5)
H6A0.16370.03790.91530.031*
H6B0.16590.05590.88700.031*
C70.4436 (2)0.07757 (19)0.89654 (18)0.0333 (6)
H7A0.48250.04250.85990.050*
H7B0.47760.13080.90350.050*
H7C0.44010.05170.95250.050*
C80.33634 (19)0.08960 (15)0.85568 (15)0.0230 (4)
H8A0.34030.11770.80020.028*
H8B0.29760.12520.89280.028*
C90.28891 (17)0.03281 (14)0.77096 (13)0.0180 (4)
C100.32944 (17)0.01113 (13)0.69539 (13)0.0177 (4)
C110.21236 (17)0.05829 (14)0.42455 (13)0.0185 (4)
C120.20880 (16)0.01000 (14)0.34226 (13)0.0174 (4)
C130.17542 (18)0.11199 (15)0.42693 (15)0.0219 (4)
H13A0.22860.15170.44720.026*
H13B0.16840.07100.47250.026*
C140.0748 (2)0.1563 (2)0.40878 (17)0.0326 (6)
H14A0.08100.19510.36190.049*
H14B0.05720.18590.46000.049*
H14C0.02110.11640.39270.049*
C150.23491 (19)0.12923 (15)0.28213 (16)0.0248 (5)
H15A0.23310.18550.30520.030*
H15B0.18380.12590.23280.030*
C160.3402 (2)0.11255 (17)0.2518 (2)0.0328 (6)
H16A0.39150.11830.29980.049*
H16B0.35460.15170.20700.049*
H16C0.34250.05680.22900.049*
C170.2428 (2)0.13907 (15)0.26885 (15)0.0239 (5)
H17A0.19400.17190.23200.029*
H17B0.24480.16220.32720.029*
C180.3472 (2)0.14469 (18)0.2355 (2)0.0357 (6)
H18A0.34550.12080.17820.054*
H18B0.36780.20220.23300.054*
H18C0.39620.11470.27360.054*
C190.1568 (2)0.02289 (17)0.18869 (15)0.0289 (5)
H19A0.16590.06380.14340.035*
H19B0.18970.02870.17210.035*
C200.0441 (2)0.00819 (17)0.19656 (18)0.0338 (6)
H20A0.01130.05950.21160.051*
H20B0.01300.01190.14200.051*
H20C0.03520.03260.24120.051*
C210.31190 (19)0.12135 (14)0.56544 (13)0.0198 (4)
H21A0.27690.17180.54450.024*
H21B0.37920.13730.59260.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re10.02031 (4)0.01289 (4)0.01363 (4)0.00065 (3)0.00217 (3)0.00047 (3)
Cl10.0321 (3)0.0199 (2)0.0157 (2)0.0035 (2)0.0062 (2)0.00073 (18)
Cl20.0214 (2)0.0188 (2)0.0212 (2)0.00087 (19)0.00135 (19)0.00199 (19)
Cl30.0221 (2)0.0140 (2)0.0225 (2)0.00073 (18)0.00293 (19)0.00165 (17)
Cl40.0257 (2)0.0204 (2)0.0140 (2)0.00225 (19)0.00389 (18)0.00136 (18)
Cl50.0212 (2)0.0203 (2)0.0242 (3)0.00323 (19)0.0004 (2)0.00134 (19)
S10.0233 (3)0.0202 (2)0.0158 (2)0.0043 (2)0.00117 (19)0.00278 (19)
S20.0196 (2)0.0292 (3)0.0227 (3)0.0026 (2)0.0028 (2)0.0029 (2)
S30.0181 (2)0.0166 (2)0.0141 (2)0.00019 (18)0.00176 (17)0.00108 (18)
S40.0257 (3)0.0434 (4)0.0248 (3)0.0162 (3)0.0022 (2)0.0066 (3)
O10.0343 (9)0.0156 (7)0.0206 (8)0.0016 (7)0.0033 (7)0.0011 (6)
N10.0230 (9)0.0154 (8)0.0153 (8)0.0033 (7)0.0013 (7)0.0014 (6)
N20.0235 (9)0.0184 (8)0.0164 (8)0.0018 (7)0.0040 (7)0.0010 (7)
N30.0283 (10)0.0195 (9)0.0143 (8)0.0004 (8)0.0024 (7)0.0006 (7)
N40.0199 (8)0.0181 (8)0.0163 (8)0.0001 (7)0.0005 (7)0.0015 (7)
C10.0289 (13)0.0355 (14)0.0275 (12)0.0117 (11)0.0007 (10)0.0043 (10)
C20.0256 (11)0.0173 (10)0.0200 (10)0.0025 (8)0.0024 (8)0.0039 (8)
C30.0258 (11)0.0186 (10)0.0184 (9)0.0006 (8)0.0041 (8)0.0022 (8)
C40.0291 (13)0.0455 (16)0.0249 (12)0.0037 (12)0.0013 (10)0.0062 (11)
C50.0552 (18)0.0287 (13)0.0203 (11)0.0052 (12)0.0136 (11)0.0019 (10)
C60.0295 (12)0.0234 (11)0.0259 (11)0.0019 (9)0.0133 (10)0.0020 (9)
C70.0298 (13)0.0405 (15)0.0295 (13)0.0070 (12)0.0011 (10)0.0002 (11)
C80.0300 (12)0.0219 (11)0.0169 (10)0.0021 (9)0.0012 (8)0.0010 (8)
C90.0197 (9)0.0192 (10)0.0150 (9)0.0032 (8)0.0008 (7)0.0019 (7)
C100.0225 (10)0.0176 (9)0.0127 (8)0.0001 (8)0.0001 (7)0.0003 (7)
C110.0211 (10)0.0194 (10)0.0146 (9)0.0030 (8)0.0022 (7)0.0002 (7)
C120.0182 (9)0.0189 (10)0.0148 (9)0.0007 (8)0.0019 (7)0.0023 (7)
C130.0243 (11)0.0205 (10)0.0208 (10)0.0037 (9)0.0003 (8)0.0019 (8)
C140.0266 (12)0.0476 (17)0.0244 (12)0.0140 (12)0.0070 (10)0.0082 (11)
C150.0270 (11)0.0196 (11)0.0289 (12)0.0030 (9)0.0093 (9)0.0067 (9)
C160.0305 (13)0.0245 (12)0.0454 (16)0.0017 (10)0.0176 (12)0.0027 (11)
C170.0327 (12)0.0181 (10)0.0203 (10)0.0024 (9)0.0034 (9)0.0049 (8)
C180.0271 (13)0.0271 (13)0.0520 (18)0.0026 (10)0.0031 (12)0.0123 (12)
C190.0442 (15)0.0287 (12)0.0128 (9)0.0016 (11)0.0048 (9)0.0030 (9)
C200.0428 (15)0.0283 (13)0.0276 (12)0.0067 (12)0.0162 (11)0.0020 (10)
C210.0308 (11)0.0157 (9)0.0127 (9)0.0024 (8)0.0004 (8)0.0009 (7)
Geometric parameters (Å, º) top
Re1—O11.6796 (17)C5—H5B0.9800
Re1—Cl12.3896 (6)C5—H5C0.9800
Re1—Cl22.3998 (6)C6—H6A0.9900
Re1—Cl52.4099 (6)C6—H6B0.9900
Re1—Cl42.4199 (5)C7—C81.521 (4)
Re1—Cl32.4550 (5)C7—H7A0.9800
S1—C101.740 (2)C7—H7B0.9800
S1—C211.800 (2)C7—H7C0.9800
S2—C101.615 (2)C8—H8A0.9900
S3—C111.708 (2)C8—H8B0.9900
S3—C211.801 (2)C9—C101.516 (3)
S4—C111.634 (2)C11—C121.513 (3)
N1—C91.326 (3)C13—C141.517 (3)
N1—C31.488 (3)C13—H13A0.9900
N1—C21.489 (3)C13—H13B0.9900
N2—C91.337 (3)C14—H14A0.9800
N2—C81.482 (3)C14—H14B0.9800
N2—C61.490 (3)C14—H14C0.9800
N3—C121.322 (3)C15—C161.519 (3)
N3—C191.487 (3)C15—H15A0.9900
N3—C171.489 (3)C15—H15B0.9900
N4—C121.324 (3)C16—H16A0.9800
N4—C131.482 (3)C16—H16B0.9800
N4—C151.486 (3)C16—H16C0.9800
C1—C21.513 (4)C17—C181.505 (4)
C1—H1A0.9800C17—H17A0.9900
C1—H1B0.9800C17—H17B0.9900
C1—H1C0.9800C18—H18A0.9800
C2—H2A0.9900C18—H18B0.9800
C2—H2B0.9900C18—H18C0.9800
C3—C41.508 (4)C19—C201.513 (4)
C3—H3A0.9900C19—H19A0.9900
C3—H3B0.9900C19—H19B0.9900
C4—H4A0.9800C20—H20A0.9800
C4—H4B0.9800C20—H20B0.9800
C4—H4C0.9800C20—H20C0.9800
C5—C61.509 (4)C21—H21A0.9900
C5—H5A0.9800C21—H21B0.9900
O1—Re1—Cl195.48 (6)N2—C8—H8A109.1
O1—Re1—Cl294.65 (6)C7—C8—H8A109.1
Cl1—Re1—Cl288.01 (2)N2—C8—H8B109.1
O1—Re1—Cl592.96 (6)C7—C8—H8B109.1
Cl1—Re1—Cl589.91 (2)H8A—C8—H8B107.9
Cl2—Re1—Cl5172.271 (19)N1—C9—N2125.4 (2)
O1—Re1—Cl492.26 (6)N1—C9—C10117.84 (19)
Cl1—Re1—Cl4172.263 (19)N2—C9—C10116.77 (19)
Cl2—Re1—Cl491.260 (19)C9—C10—S2120.08 (16)
Cl5—Re1—Cl489.79 (2)C9—C10—S1111.91 (15)
O1—Re1—Cl3175.95 (6)S2—C10—S1128.00 (13)
Cl1—Re1—Cl387.753 (18)C12—C11—S4119.22 (16)
Cl2—Re1—Cl387.898 (19)C12—C11—S3111.31 (16)
Cl5—Re1—Cl384.581 (18)S4—C11—S3129.47 (14)
Cl4—Re1—Cl384.523 (18)N3—C12—N4126.5 (2)
C10—S1—C21100.44 (11)N3—C12—C11116.6 (2)
C11—S3—C21100.36 (11)N4—C12—C11116.90 (19)
C9—N1—C3121.26 (18)N4—C13—C14110.47 (19)
C9—N1—C2123.72 (19)N4—C13—H13A109.6
C3—N1—C2113.69 (18)C14—C13—H13A109.6
C9—N2—C8121.42 (19)N4—C13—H13B109.6
C9—N2—C6123.2 (2)C14—C13—H13B109.6
C8—N2—C6115.06 (19)H13A—C13—H13B108.1
C12—N3—C19123.0 (2)C13—C14—H14A109.5
C12—N3—C17122.03 (19)C13—C14—H14B109.5
C19—N3—C17114.53 (19)H14A—C14—H14B109.5
C12—N4—C13121.85 (19)C13—C14—H14C109.5
C12—N4—C15125.3 (2)H14A—C14—H14C109.5
C13—N4—C15112.81 (19)H14B—C14—H14C109.5
C2—C1—H1A109.5N4—C15—C16112.6 (2)
C2—C1—H1B109.5N4—C15—H15A109.1
H1A—C1—H1B109.5C16—C15—H15A109.1
C2—C1—H1C109.5N4—C15—H15B109.1
H1A—C1—H1C109.5C16—C15—H15B109.1
H1B—C1—H1C109.5H15A—C15—H15B107.8
N1—C2—C1110.2 (2)C15—C16—H16A109.5
N1—C2—H2A109.6C15—C16—H16B109.5
C1—C2—H2A109.6H16A—C16—H16B109.5
N1—C2—H2B109.6C15—C16—H16C109.5
C1—C2—H2B109.6H16A—C16—H16C109.5
H2A—C2—H2B108.1H16B—C16—H16C109.5
N1—C3—C4110.97 (19)N3—C17—C18111.3 (2)
N1—C3—H3A109.4N3—C17—H17A109.4
C4—C3—H3A109.4C18—C17—H17A109.4
N1—C3—H3B109.4N3—C17—H17B109.4
C4—C3—H3B109.4C18—C17—H17B109.4
H3A—C3—H3B108.0H17A—C17—H17B108.0
C3—C4—H4A109.5C17—C18—H18A109.5
C3—C4—H4B109.5C17—C18—H18B109.5
H4A—C4—H4B109.5H18A—C18—H18B109.5
C3—C4—H4C109.5C17—C18—H18C109.5
H4A—C4—H4C109.5H18A—C18—H18C109.5
H4B—C4—H4C109.5H18B—C18—H18C109.5
C6—C5—H5A109.5N3—C19—C20110.9 (2)
C6—C5—H5B109.5N3—C19—H19A109.5
H5A—C5—H5B109.5C20—C19—H19A109.5
C6—C5—H5C109.5N3—C19—H19B109.5
H5A—C5—H5C109.5C20—C19—H19B109.5
H5B—C5—H5C109.5H19A—C19—H19B108.0
N2—C6—C5114.4 (2)C19—C20—H20A109.5
N2—C6—H6A108.7C19—C20—H20B109.5
C5—C6—H6A108.7H20A—C20—H20B109.5
N2—C6—H6B108.7C19—C20—H20C109.5
C5—C6—H6B108.7H20A—C20—H20C109.5
H6A—C6—H6B107.6H20B—C20—H20C109.5
C8—C7—H7A109.5S1—C21—S3113.63 (12)
C8—C7—H7B109.5S1—C21—H21A108.8
H7A—C7—H7B109.5S3—C21—H21A108.8
C8—C7—H7C109.5S1—C21—H21B108.8
H7A—C7—H7C109.5S3—C21—H21B108.8
H7B—C7—H7C109.5H21A—C21—H21B107.7
N2—C8—C7112.3 (2)
C9—N1—C2—C167.6 (3)C21—S3—C11—S42.4 (2)
C3—N1—C2—C199.3 (2)C19—N3—C12—N428.4 (4)
C9—N1—C3—C4113.2 (3)C17—N3—C12—N4159.7 (2)
C2—N1—C3—C479.5 (3)C19—N3—C12—C11150.6 (2)
C9—N2—C6—C5116.0 (3)C17—N3—C12—C1121.3 (3)
C8—N2—C6—C570.3 (3)C13—N4—C12—N3159.5 (2)
C9—N2—C8—C787.2 (3)C15—N4—C12—N321.0 (4)
C6—N2—C8—C799.0 (2)C13—N4—C12—C1119.5 (3)
C3—N1—C9—N2162.6 (2)C15—N4—C12—C11159.9 (2)
C2—N1—C9—N231.4 (3)S4—C11—C12—N374.9 (3)
C3—N1—C9—C1018.7 (3)S3—C11—C12—N3104.8 (2)
C2—N1—C9—C10147.2 (2)S4—C11—C12—N4104.3 (2)
C8—N2—C9—N1161.1 (2)S3—C11—C12—N476.1 (2)
C6—N2—C9—N125.7 (3)C12—N4—C13—C14112.1 (2)
C8—N2—C9—C1017.6 (3)C15—N4—C13—C1468.4 (3)
C6—N2—C9—C10155.7 (2)C12—N4—C15—C1653.2 (3)
N1—C9—C10—S274.3 (2)C13—N4—C15—C16126.2 (2)
N2—C9—C10—S2104.5 (2)C12—N3—C17—C18102.5 (3)
N1—C9—C10—S1105.0 (2)C19—N3—C17—C1885.0 (3)
N2—C9—C10—S176.2 (2)C12—N3—C19—C2060.5 (3)
C21—S1—C10—C9176.11 (16)C17—N3—C19—C20111.9 (2)
C21—S1—C10—S24.71 (19)C10—S1—C21—S377.21 (14)
C21—S3—C11—C12177.25 (16)C11—S3—C21—S173.40 (15)

Experimental details

Crystal data
Chemical formula(C21H42N4S4)[ReCl5O]
Mr858.28
Crystal system, space groupMonoclinic, P21/n
Temperature (K)90
a, b, c (Å)13.1381 (5), 16.3486 (7), 15.7094 (6)
β (°) 94.003 (1)
V3)3366.0 (2)
Z4
Radiation typeMo Kα
µ (mm1)4.28
Crystal size (mm)0.23 × 0.16 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD area-dectector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.440, 0.674
No. of measured, independent and
observed [I > 2σ(I)] reflections
43155, 11209, 10065
Rint0.028
(sin θ/λ)max1)0.735
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.064, 1.07
No. of reflections11209
No. of parameters333
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.83, 0.47

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Re1—O11.6796 (17)S3—C111.708 (2)
Re1—Cl12.3896 (6)S3—C211.801 (2)
Re1—Cl22.3998 (6)S4—C111.634 (2)
Re1—Cl52.4099 (6)N1—C91.326 (3)
Re1—Cl42.4199 (5)N1—C31.488 (3)
Re1—Cl32.4550 (5)N1—C21.489 (3)
S1—C101.740 (2)N2—C91.337 (3)
S1—C211.800 (2)C9—C101.516 (3)
S2—C101.615 (2)C11—C121.513 (3)
O1—Re1—Cl195.48 (6)C9—C10—S2120.08 (16)
O1—Re1—Cl294.65 (6)C9—C10—S1111.91 (15)
O1—Re1—Cl592.96 (6)S2—C10—S1128.00 (13)
O1—Re1—Cl492.26 (6)C12—C11—S4119.22 (16)
O1—Re1—Cl3175.95 (6)S4—C11—S3129.47 (14)
N1—C9—N2125.4 (2)N3—C12—N4126.5 (2)
N1—C9—C10117.84 (19)N3—C12—C11116.6 (2)
N2—C9—C10116.77 (19)
 

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