mer-Trichloridotris(dimethyl sulfide-κS)rhodium(III)

The title compound, [RhCl₃(C₂H₆S)₃], exists as discrete mol­ecules in which the Rh^III atom is coordinated by three S atoms from the dimethyl sulfide mol­ecules and three Cl atoms in a mer-octa­hedral configuration.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](S-C) = 0.004 Å
• R factor = 0.016
• wR factor = 0.039
• Data-to-parameter ratio = 25.7

checkCIF/PLATON results

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Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Rh1    -   Cl3     ..       6.33 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Rh1    -   S3      ..       6.11 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Rh1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.72
           From the CIF: _reflns_number_total               3037
           Count of symmetry unique reflns         1773
           Completeness (_total/calc)            171.29%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1264
           Fraction of Friedel pairs measured     0.713
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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).

Related literature

For the related dimethyl sulfoxide compound, see Abbasi et al. (2006).

For related literature, see: Alessio (2004); Calligaris (2004); James et al. (1968).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5 U_eq(C).

Computing details

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.

Figures

Fig. 1. Molecular structure of (I), shown with 50% probability displacement ellipsoids. H atoms are shown with arbitrary radii.

mer-Trichloridotris(dimethyl sulfide-κS)rhodium(III)

Crystal data

[RhCl3(C2H6S)3]	F(000) = 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 = 2.1–26.7°
b = 13.312 (2) Å	µ = 2.12 mm^−1
c = 13.6450 (18) Å	T = 290 K
V = 1450.1 (3) Å^3	Needle, brown
Z = 4	0.2 × 0.1 × 0.1 mm

Data collection

Stoe IPDS II diffractometer	3037 independent reflections
Radiation source: fine-focus sealed tube	2965 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Area detector, φ oscillation scans	θmax = 26.7°, θmin = 2.1°
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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.017	H-atom parameters constrained
wR(F^2) = 0.039	w = 1/[σ^2(Fo^2) + (0.0163P)^2 + 0.5475P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3037 reflections	Δρmax = 0.28 e Å^−3
118 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1283 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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