Acta Cryst. (2007). E63, m1904 [ doi:10.1107/S1600536807027912 ]
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S)rhodium(III)The title compound, [RhCl3(C2H6S)3], exists as discrete molecules in which the RhIII atom is coordinated by three S atoms from the dimethyl sulfide molecules and three Cl atoms in a mer-octahedral configuration.
The compound was synthesized by dissolving rhodium(III) chloride (Aldrich, 98%) in excess of dimethyl sulfide (Merck, 99%) at 343 K followed by a 12 h reflux. The mixture was then cooled to room temperature. Crystals were obtained after the evaporation of the solvent.
The Flack parameter was refined from 1283 Friedel pairs.
The H atoms are in calculated positions and constrained to ride on the parent C atoms with the C—H distance 0.96 Å and Uiso(H) = 1.5 Ueq(C).
Data collection: IPDS Software (Stoe & Cie, 1997); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
![[Figure 1]](./ng2277fig1thm.gif)
| Fig. 1. Molecular structure of (I), shown with 50% probability displacement ellipsoids. H atoms are shown with arbitrary radii. |
| [RhCl3(C2H6S)3] | F000 = 792 |
| Mr = 395.64 | Dx = 1.812 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 7089 reflections |
| a = 7.9835 (10) Å | θ = 2.1–26.7º |
| b = 13.312 (2) Å | µ = 2.12 mm−1 |
| c = 13.6450 (18) Å | T = 290 (2) K |
| V = 1450.1 (3) Å3 | Needle, brown |
| Z = 4 | 0.2 × 0.1 × 0.1 mm |
| Stoe IPDS II diffractometer | 3037 independent reflections |
| Radiation source: fine-focus sealed tube | 2965 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.016 |
| T = 290(2) K | θmax = 26.7º |
| Area detector, φ oscillation scans | θmin = 2.1º |
| Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | h = −8→10 |
| Tmin = 0.693, Tmax = 0.793 | k = −16→14 |
| 7089 measured reflections | l = −17→17 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.017 | w = 1/[σ2(Fo2) + (0.0163P)2 + 0.5475P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.039 | (Δ/σ)max = 0.001 |
| S = 1.08 | Δρmax = 0.28 e Å−3 |
| 3037 reflections | Δρmin = −0.24 e Å−3 |
| 118 parameters | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 1283 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: −0.02 (3) |
| [RhCl3(C2H6S)3] | V = 1450.1 (3) Å3 |
| Mr = 395.64 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα |
| a = 7.9835 (10) Å | µ = 2.12 mm−1 |
| b = 13.312 (2) Å | T = 290 (2) K |
| c = 13.6450 (18) Å | 0.2 × 0.1 × 0.1 mm |
| Stoe IPDS II diffractometer | 3037 independent reflections |
| Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | 2965 reflections with I > 2σ(I) |
| Tmin = 0.693, Tmax = 0.793 | Rint = 0.016 |
| 7089 measured reflections |
| R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
| wR(F2) = 0.039 | Δρmax = 0.28 e Å−3 |
| S = 1.08 | Δρmin = −0.24 e Å−3 |
| 3037 reflections | Absolute structure: Flack (1983), with 1283 Friedel pairs |
| 118 parameters | Flack parameter: −0.02 (3) |
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. |
| x | y | z | Uiso*/Ueq | ||
| Rh1 | 0.27392 (2) | 0.830500 (13) | 0.232940 (12) | 0.03469 (5) | |
| S1 | 0.15639 (11) | 0.67291 (6) | 0.20553 (5) | 0.05978 (18) | |
| S2 | 0.15091 (10) | 0.88897 (5) | 0.08792 (5) | 0.05395 (17) | |
| S3 | 0.40313 (9) | 0.78043 (5) | 0.38115 (4) | 0.04733 (15) | |
| Cl1 | 0.04246 (9) | 0.86245 (7) | 0.33444 (5) | 0.0681 (2) | |
| Cl2 | 0.38670 (10) | 0.98917 (5) | 0.27322 (5) | 0.06140 (18) | |
| Cl3 | 0.50634 (10) | 0.79376 (7) | 0.13543 (5) | 0.0654 (2) | |
| C11 | 0.2440 (5) | 0.6116 (2) | 0.1013 (3) | 0.0790 (10) | |
| H11A | 0.3600 | 0.5972 | 0.1134 | 0.095* | |
| H11B | 0.2343 | 0.6545 | 0.0451 | 0.095* | |
| H11C | 0.1848 | 0.5500 | 0.0894 | 0.095* | |
| C12 | −0.0530 (4) | 0.6866 (3) | 0.1598 (3) | 0.0839 (12) | |
| H12A | −0.1209 | 0.7194 | 0.2082 | 0.101* | |
| H12B | −0.0988 | 0.6215 | 0.1456 | 0.101* | |
| H12C | −0.0512 | 0.7263 | 0.1010 | 0.101* | |
| C21 | 0.2849 (7) | 0.9835 (2) | 0.0363 (2) | 0.0870 (13) | |
| H21A | 0.3885 | 0.9533 | 0.0161 | 0.104* | |
| H21B | 0.3070 | 1.0342 | 0.0846 | 0.104* | |
| H21C | 0.2308 | 1.0135 | −0.0193 | 0.104* | |
| C22 | −0.0265 (6) | 0.9645 (4) | 0.1181 (3) | 0.1057 (16) | |
| H22A | −0.1115 | 0.9232 | 0.1472 | 0.127* | |
| H22B | −0.0697 | 0.9952 | 0.0596 | 0.127* | |
| H22C | 0.0064 | 1.0159 | 0.1636 | 0.127* | |
| C31 | 0.3508 (5) | 0.6535 (3) | 0.4118 (2) | 0.0690 (9) | |
| H31A | 0.2335 | 0.6492 | 0.4268 | 0.083* | |
| H31B | 0.4149 | 0.6327 | 0.4678 | 0.083* | |
| H31C | 0.3760 | 0.6105 | 0.3573 | 0.083* | |
| C32 | 0.6223 (4) | 0.7626 (3) | 0.3596 (3) | 0.0796 (11) | |
| H32A | 0.6722 | 0.8255 | 0.3413 | 0.096* | |
| H32B | 0.6377 | 0.7148 | 0.3078 | 0.096* | |
| H32C | 0.6746 | 0.7381 | 0.4183 | 0.096* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Rh1 | 0.03557 (8) | 0.04055 (8) | 0.02795 (7) | −0.00209 (7) | 0.00126 (6) | −0.00432 (6) |
| S1 | 0.0891 (5) | 0.0511 (3) | 0.0391 (3) | −0.0230 (4) | −0.0130 (3) | 0.0006 (3) |
| S2 | 0.0735 (5) | 0.0478 (3) | 0.0406 (3) | 0.0079 (3) | −0.0169 (3) | −0.0056 (3) |
| S3 | 0.0523 (4) | 0.0567 (4) | 0.0330 (3) | −0.0014 (3) | −0.0059 (3) | −0.0039 (3) |
| Cl1 | 0.0431 (4) | 0.1089 (7) | 0.0523 (4) | −0.0039 (4) | 0.0116 (3) | −0.0301 (4) |
| Cl2 | 0.0819 (5) | 0.0494 (3) | 0.0530 (3) | −0.0191 (3) | −0.0068 (4) | −0.0064 (3) |
| Cl3 | 0.0523 (4) | 0.0961 (6) | 0.0478 (3) | 0.0098 (4) | 0.0156 (3) | −0.0042 (4) |
| C11 | 0.089 (3) | 0.0612 (17) | 0.087 (2) | 0.0176 (19) | −0.029 (2) | −0.0321 (16) |
| C12 | 0.064 (2) | 0.105 (3) | 0.083 (2) | −0.036 (2) | 0.0082 (17) | −0.033 (2) |
| C21 | 0.143 (4) | 0.066 (2) | 0.0520 (17) | −0.012 (2) | −0.005 (2) | 0.0160 (14) |
| C22 | 0.101 (3) | 0.123 (4) | 0.094 (3) | 0.060 (3) | −0.034 (3) | −0.019 (3) |
| C31 | 0.084 (2) | 0.072 (2) | 0.0515 (16) | −0.0090 (17) | −0.0111 (15) | 0.0156 (15) |
| C32 | 0.0433 (16) | 0.121 (3) | 0.075 (2) | −0.0062 (18) | −0.0167 (16) | 0.011 (2) |
| Rh1—S1 | 2.3283 (8) | C12—H12A | 0.9600 |
| Rh1—Cl3 | 2.3350 (7) | C12—H12B | 0.9600 |
| Rh1—S2 | 2.3422 (7) | C12—H12C | 0.9600 |
| Rh1—Cl1 | 2.3481 (7) | C21—H21A | 0.9600 |
| Rh1—Cl2 | 2.3609 (7) | C21—H21B | 0.9600 |
| Rh1—S3 | 2.3660 (7) | C21—H21C | 0.9600 |
| S1—C11 | 1.782 (3) | C22—H22A | 0.9600 |
| S1—C12 | 1.793 (4) | C22—H22B | 0.9600 |
| S2—C22 | 1.785 (4) | C22—H22C | 0.9600 |
| S2—C21 | 1.795 (4) | C31—H31A | 0.9600 |
| S3—C32 | 1.790 (3) | C31—H31B | 0.9600 |
| S3—C31 | 1.790 (3) | C31—H31C | 0.9600 |
| C11—H11A | 0.9600 | C32—H32A | 0.9600 |
| C11—H11B | 0.9600 | C32—H32B | 0.9600 |
| C11—H11C | 0.9600 | C32—H32C | 0.9600 |
| S1—Rh1—Cl3 | 92.29 (3) | S1—C12—H12A | 109.5 |
| S1—Rh1—S2 | 89.70 (3) | S1—C12—H12B | 109.5 |
| Cl3—Rh1—S2 | 85.49 (3) | H12A—C12—H12B | 109.5 |
| S1—Rh1—Cl1 | 86.60 (3) | S1—C12—H12C | 109.5 |
| Cl3—Rh1—Cl1 | 177.97 (3) | H12A—C12—H12C | 109.5 |
| S2—Rh1—Cl1 | 96.21 (3) | H12B—C12—H12C | 109.5 |
| S1—Rh1—Cl2 | 175.67 (3) | S2—C21—H21A | 109.5 |
| Cl3—Rh1—Cl2 | 90.97 (3) | S2—C21—H21B | 109.5 |
| S2—Rh1—Cl2 | 93.40 (3) | H21A—C21—H21B | 109.5 |
| Cl1—Rh1—Cl2 | 90.04 (3) | S2—C21—H21C | 109.5 |
| S1—Rh1—S3 | 93.40 (3) | H21A—C21—H21C | 109.5 |
| Cl3—Rh1—S3 | 94.68 (3) | H21B—C21—H21C | 109.5 |
| S2—Rh1—S3 | 176.89 (3) | S2—C22—H22A | 109.5 |
| Cl1—Rh1—S3 | 83.68 (3) | S2—C22—H22B | 109.5 |
| Cl2—Rh1—S3 | 83.50 (3) | H22A—C22—H22B | 109.5 |
| C11—S1—C12 | 97.72 (17) | S2—C22—H22C | 109.5 |
| C11—S1—Rh1 | 112.51 (13) | H22A—C22—H22C | 109.5 |
| C12—S1—Rh1 | 109.86 (14) | H22B—C22—H22C | 109.5 |
| C22—S2—C21 | 99.7 (2) | S3—C31—H31A | 109.5 |
| C22—S2—Rh1 | 108.98 (15) | S3—C31—H31B | 109.5 |
| C21—S2—Rh1 | 108.32 (13) | H31A—C31—H31B | 109.5 |
| C32—S3—C31 | 98.14 (19) | S3—C31—H31C | 109.5 |
| C32—S3—Rh1 | 108.87 (12) | H31A—C31—H31C | 109.5 |
| C31—S3—Rh1 | 111.35 (10) | H31B—C31—H31C | 109.5 |
| S1—C11—H11A | 109.5 | S3—C32—H32A | 109.5 |
| S1—C11—H11B | 109.5 | S3—C32—H32B | 109.5 |
| H11A—C11—H11B | 109.5 | H32A—C32—H32B | 109.5 |
| S1—C11—H11C | 109.5 | S3—C32—H32C | 109.5 |
| H11A—C11—H11C | 109.5 | H32A—C32—H32C | 109.5 |
| H11B—C11—H11C | 109.5 | H32B—C32—H32C | 109.5 |
| Rh1—S1 | 2.3283 (8) | S1—C11 | 1.782 (3) |
| Rh1—Cl3 | 2.3350 (7) | S1—C12 | 1.793 (4) |
| Rh1—S2 | 2.3422 (7) | S2—C22 | 1.785 (4) |
| Rh1—Cl1 | 2.3481 (7) | S2—C21 | 1.795 (4) |
| Rh1—Cl2 | 2.3609 (7) | S3—C32 | 1.790 (3) |
| Rh1—S3 | 2.3660 (7) | S3—C31 | 1.790 (3) |
Abbasi, A., Azizi, F., Eriksson, L. & Sandström, M. (2006). Acta Cryst. E62, m2651–m2652.
Alessio, E. (2004). Chem. Rev. 104, 4203–4242.
Brandenburg, K. (1999). DIAMOND. Version 2.1e. Crystal Impact GbR, Bonn, Germany. [Please check year - Version 2.1e normally in 2001, and 2.1c in 1999]
Calligaris, M. (2004). Coord. Chem. Rev. 248, 351–375.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
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Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Versions 1.171.29.2. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. [Reference not cited - may it be removed?]
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Stoe & Cie (1997). IPDS Software (Version 2.87) and X-RED (Version 1.09). Stoe & Cie GmbH, Darmstadt, Germany.
One aim of the current study is to investigate the nature of Rh—S bonds and to make a comparison with analogous compounds such as the sulfoxide complexes (Abbasi, et al., 2006; Calligaris, 2004; Alessio, 2004). Interest in the use of the dimethyl sulfide ligand arises from its involvement in the homogeneous hydrogenation of olefinic substrates (James et al. 1968).
The rhodium(III) ion is octahedrally coordinated by the sulfur atoms of the three dimethyl sulfide molecules, and three chlorine atoms in a mer octahedral configuration (Fig. 1). The Rh—S bond distance in for the sulfur trans to the chlorine [2.328 (1) Å] is longer than that cis to the chlorine [2.283 (1) Å], which indicates strongr π-back bonding from metal to sulfur (Abbasi et al., 2006).