Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034204/is2194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034204/is2194Isup2.hkl |
CCDC reference: 660041
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.005 Å
- R factor = 0.039
- wR factor = 0.099
- Data-to-parameter ratio = 19.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.69 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A solution of trimethylaluminium (295 mg, 4.04 mmol) in 5 ml pentane was added to a red suspension of [Cp*RhCl2]2 (250 mg, 0.405 mmol) in 10 ml pentane at 195 K. After stirring for one minute, diphenylsulfoxide (210 mg, 1.04 mmol) was added to the solution. The temperature was slowly raised to room temperature while stirring for 75 min, giving a yellow solution and a brown oil. At 273 K, water (1 ml) was added dropwise to the solution over the course of 15 min to quench the excess AlMe3 (WARNING: very exothermic reaction). The volatile materials were removed under reduced pressure and the resulting brown oily solid was extracted with methylene chloride (3 × 5 ml) leaving a white residue which was attributed to Al2O3.nH2O. The methylene chloride was removed under reduced pressure and 4 ml of toluene was added to the resulting solid. The addition of 40 ml of pentane to this solution and cooling to 253 K afforded crystals suitable for X-ray crystal structure determination (yield 34%, 130 mg).
H atoms were placed in calculated positions with C–H distances fixed at 0.95 Å (Ar—H) or 0.98 Å (CH3) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Research on pentamethylcyclopentadienyl complexes of rhodium(III) and iridium(III) have lead to the comprehension of the activation of saturated alkanes by transition metals. In the course of our study on the activity of such complexes in alkane functionalization reactions, the synthesis of Cp*RhMe2(DPSO), (I), has been carried out (Cp* = pentamethylcyclopentadienyl, DPSO = diphenylsulfoxide).
The title compound (Fig. 1) is similar to the complex Cp*RhMe2(DMSO), (II), reported by Fooladi et al. (2002) (DMSO = dimethylsulfoxide). While Cp*RhMe2(DPSO) crystallizes in the orthorhombic group Pccn, the DMSO analogue crystallizes in the triclinic space group P1 with two independent molecules per asymmetric unit.
In both complexes, the Rh—S bond lengths [2.2140 (9) Å for (I) and 2.210 (1) and 2.211 (1) Å for (II)] and the angles at the rhodium center are similar (Table 1). However, a major difference is observed in the asymmetry of the coordination of the methyl groups. While all Rh—CH3 bond lengths in (II) are similar [2.090 (5) to 2.103 (5) Å], they differ significantly in (I) [Rh—C1 = 2.196 (3) Å, Rh—C2 = 2.101 (4) Å]. The nature of this difference is unknown and more studies are needed to investigate this discrepancy. While sulfur-coordinated dimethylsulfoxide complexes are common, the number of solid state structures where diphenylsulfoxide is S-bonded are scarce. Indeed, only Pt(II) (Rochon et al., 1997; de Almeida et al., 1992) and Ru(III) (Calligaris et al., 1995) complexes have been reported to have such bonding mode. It is also worth noting that the metric parameters of the DPSO moiety hardly change upon metal coordination. Free DPSO has a S=O bond length of 1.492 (3) Å and S—C bond lengths of 1.793(no e.s.d. available) Å (Yatsenko et al., 1986), while in (I) these distances are 1.489 (2), 1.803 (3) and 1.810 (3) Å, respectively.
For related literature, see: de Almeida et al. (1992); Calligaris et al. (1995); Fooladi et al. (2002); Rochon et al. (1997); Yatsenko et al. (1986).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.
Fig. 1. View of the title compound with displacement ellipsoids at the 50% probability level. |
[Rh(CH3)2(C10H15)(C12H10OS)] | F(000) = 1952 |
Mr = 470.46 | Dx = 1.427 Mg m−3 |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 6117 reflections |
a = 14.4164 (15) Å | θ = 2.8–28.4° |
b = 35.646 (4) Å | µ = 0.89 mm−1 |
c = 8.5214 (8) Å | T = 183 K |
V = 4379.1 (8) Å3 | Plate, yellow |
Z = 8 | 0.43 × 0.33 × 0.05 mm |
Bruker P4/SMART 1000 CCD area-detector diffractometer | 4963 independent reflections |
Radiation source: fine-focus sealed tube, K760 | 3473 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
φ and ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | h = −18→18 |
Tmin = 0.769, Tmax = 0.957 | k = −46→44 |
28282 measured reflections | l = −10→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.039P)2 + 7.0043P] where P = (Fo2 + 2Fc2)/3 |
4963 reflections | (Δ/σ)max = 0.001 |
251 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −0.94 e Å−3 |
[Rh(CH3)2(C10H15)(C12H10OS)] | V = 4379.1 (8) Å3 |
Mr = 470.46 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 14.4164 (15) Å | µ = 0.89 mm−1 |
b = 35.646 (4) Å | T = 183 K |
c = 8.5214 (8) Å | 0.43 × 0.33 × 0.05 mm |
Bruker P4/SMART 1000 CCD area-detector diffractometer | 4963 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | 3473 reflections with I > 2σ(I) |
Tmin = 0.769, Tmax = 0.957 | Rint = 0.053 |
28282 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.83 e Å−3 |
4963 reflections | Δρmin = −0.94 e Å−3 |
251 parameters |
Experimental. Crystal decay was monitored by repeating the initial 50 frames at the end of the data collection and analyzing duplicate reflections. |
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 | ||
Rh | 0.494908 (16) | 0.157754 (7) | 0.17044 (3) | 0.02332 (9) | |
S | 0.47396 (5) | 0.09623 (2) | 0.17229 (10) | 0.02366 (17) | |
O | 0.40279 (16) | 0.08105 (7) | 0.0627 (3) | 0.0324 (6) | |
C1 | 0.5718 (2) | 0.15940 (9) | 0.3928 (4) | 0.0244 (7) | |
H1A | 0.5590 | 0.1831 | 0.4469 | 0.037* | |
H1B | 0.6384 | 0.1574 | 0.3716 | 0.037* | |
H1C | 0.5523 | 0.1384 | 0.4593 | 0.037* | |
C2 | 0.3791 (3) | 0.16516 (11) | 0.3167 (5) | 0.0457 (10) | |
H2A | 0.3767 | 0.1912 | 0.3529 | 0.069* | |
H2B | 0.3840 | 0.1484 | 0.4074 | 0.069* | |
H2C | 0.3224 | 0.1593 | 0.2581 | 0.069* | |
C3 | 0.4456 (2) | 0.07566 (9) | 0.3604 (4) | 0.0255 (7) | |
C4 | 0.3525 (2) | 0.07536 (10) | 0.3990 (4) | 0.0323 (8) | |
H4 | 0.3077 | 0.0844 | 0.3265 | 0.039* | |
C5 | 0.3249 (3) | 0.06179 (11) | 0.5439 (5) | 0.0400 (9) | |
H5 | 0.2610 | 0.0616 | 0.5714 | 0.048* | |
C6 | 0.3905 (3) | 0.04847 (12) | 0.6486 (5) | 0.0441 (10) | |
H6 | 0.3718 | 0.0396 | 0.7487 | 0.053* | |
C7 | 0.4830 (3) | 0.04816 (13) | 0.6074 (5) | 0.0452 (10) | |
H7 | 0.5277 | 0.0382 | 0.6781 | 0.054* | |
C8 | 0.5112 (3) | 0.06226 (11) | 0.4634 (4) | 0.0374 (9) | |
H8 | 0.5751 | 0.0627 | 0.4362 | 0.045* | |
C9 | 0.5793 (2) | 0.07126 (9) | 0.1267 (4) | 0.0259 (7) | |
C10 | 0.5722 (3) | 0.03924 (10) | 0.0361 (4) | 0.0347 (8) | |
H10 | 0.5133 | 0.0308 | 0.0009 | 0.042* | |
C11 | 0.6517 (3) | 0.01946 (11) | −0.0030 (5) | 0.0418 (9) | |
H11 | 0.6473 | −0.0027 | −0.0646 | 0.050* | |
C12 | 0.7375 (3) | 0.03196 (10) | 0.0478 (5) | 0.0385 (9) | |
H12 | 0.7918 | 0.0181 | 0.0226 | 0.046* | |
C13 | 0.7445 (3) | 0.06440 (11) | 0.1346 (5) | 0.0395 (9) | |
H13 | 0.8037 | 0.0731 | 0.1675 | 0.047* | |
C14 | 0.6649 (2) | 0.08441 (11) | 0.1743 (4) | 0.0344 (8) | |
H14 | 0.6695 | 0.1069 | 0.2336 | 0.041* | |
C15 | 0.4633 (3) | 0.17269 (11) | −0.0814 (4) | 0.0353 (9) | |
C16 | 0.5617 (2) | 0.16543 (10) | −0.0710 (4) | 0.0282 (8) | |
C17 | 0.6007 (2) | 0.19137 (10) | 0.0347 (4) | 0.0293 (8) | |
C18 | 0.5266 (3) | 0.21465 (10) | 0.0935 (4) | 0.0346 (9) | |
C19 | 0.4430 (3) | 0.20382 (11) | 0.0149 (5) | 0.0387 (9) | |
C20 | 0.3977 (3) | 0.15331 (14) | −0.1917 (5) | 0.0570 (13) | |
H20A | 0.3339 | 0.1566 | −0.1544 | 0.086* | |
H20B | 0.4126 | 0.1265 | −0.1959 | 0.086* | |
H20C | 0.4038 | 0.1642 | −0.2968 | 0.086* | |
C21 | 0.6125 (3) | 0.13685 (11) | −0.1673 (4) | 0.0424 (9) | |
H21A | 0.6235 | 0.1469 | −0.2727 | 0.064* | |
H21B | 0.5752 | 0.1139 | −0.1747 | 0.064* | |
H21C | 0.6721 | 0.1311 | −0.1173 | 0.064* | |
C22 | 0.7017 (3) | 0.19547 (12) | 0.0745 (5) | 0.0467 (10) | |
H22A | 0.7326 | 0.1711 | 0.0632 | 0.070* | |
H22B | 0.7079 | 0.2042 | 0.1830 | 0.070* | |
H22C | 0.7303 | 0.2137 | 0.0033 | 0.070* | |
C23 | 0.5388 (4) | 0.24817 (12) | 0.1981 (5) | 0.0602 (13) | |
H23A | 0.5848 | 0.2425 | 0.2793 | 0.090* | |
H23B | 0.4794 | 0.2544 | 0.2477 | 0.090* | |
H23C | 0.5601 | 0.2696 | 0.1355 | 0.090* | |
C24 | 0.3503 (3) | 0.22286 (14) | 0.0269 (6) | 0.0654 (15) | |
H24A | 0.3436 | 0.2409 | −0.0589 | 0.098* | |
H24B | 0.3459 | 0.2360 | 0.1277 | 0.098* | |
H24C | 0.3009 | 0.2041 | 0.0199 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.02300 (14) | 0.02176 (14) | 0.02520 (14) | 0.00259 (10) | 0.00236 (11) | −0.00017 (10) |
S | 0.0210 (4) | 0.0238 (4) | 0.0261 (4) | 0.0002 (3) | 0.0001 (3) | −0.0004 (3) |
O | 0.0261 (12) | 0.0347 (14) | 0.0365 (13) | −0.0026 (11) | −0.0048 (10) | −0.0037 (11) |
C1 | 0.0375 (19) | 0.0146 (15) | 0.0211 (15) | −0.0030 (14) | 0.0045 (14) | −0.0020 (13) |
C2 | 0.048 (2) | 0.037 (2) | 0.052 (2) | 0.0100 (18) | 0.022 (2) | 0.0004 (19) |
C3 | 0.0271 (17) | 0.0192 (16) | 0.0302 (18) | −0.0038 (13) | 0.0046 (14) | 0.0011 (13) |
C4 | 0.0265 (18) | 0.031 (2) | 0.039 (2) | −0.0032 (15) | −0.0001 (15) | 0.0012 (16) |
C5 | 0.033 (2) | 0.042 (2) | 0.045 (2) | −0.0079 (17) | 0.0102 (18) | −0.0047 (19) |
C6 | 0.051 (2) | 0.045 (2) | 0.036 (2) | −0.010 (2) | 0.0111 (19) | 0.0015 (18) |
C7 | 0.042 (2) | 0.052 (3) | 0.041 (2) | 0.000 (2) | 0.0000 (18) | 0.017 (2) |
C8 | 0.0275 (19) | 0.050 (2) | 0.0353 (19) | −0.0002 (17) | 0.0027 (16) | 0.0117 (17) |
C9 | 0.0243 (16) | 0.0219 (17) | 0.0315 (17) | 0.0013 (13) | 0.0014 (14) | −0.0014 (14) |
C10 | 0.0310 (19) | 0.0267 (19) | 0.046 (2) | −0.0088 (15) | 0.0036 (17) | −0.0037 (17) |
C11 | 0.040 (2) | 0.027 (2) | 0.059 (3) | −0.0026 (16) | 0.013 (2) | −0.0113 (18) |
C12 | 0.031 (2) | 0.030 (2) | 0.055 (2) | 0.0067 (16) | 0.0111 (18) | −0.0013 (18) |
C13 | 0.0238 (17) | 0.037 (2) | 0.058 (2) | 0.0000 (16) | 0.0022 (17) | −0.0061 (18) |
C14 | 0.0256 (17) | 0.037 (2) | 0.041 (2) | 0.0011 (15) | 0.0008 (17) | −0.0105 (18) |
C15 | 0.0308 (19) | 0.040 (2) | 0.035 (2) | −0.0006 (17) | −0.0004 (16) | 0.0124 (17) |
C16 | 0.0337 (19) | 0.0260 (18) | 0.0250 (16) | 0.0008 (14) | 0.0004 (14) | 0.0040 (14) |
C17 | 0.0303 (18) | 0.0273 (18) | 0.0303 (18) | −0.0025 (15) | 0.0051 (15) | 0.0042 (15) |
C18 | 0.047 (2) | 0.0193 (17) | 0.037 (2) | 0.0023 (16) | 0.0128 (17) | 0.0060 (15) |
C19 | 0.0326 (19) | 0.036 (2) | 0.047 (2) | 0.0112 (16) | 0.0079 (18) | 0.0183 (19) |
C20 | 0.050 (3) | 0.076 (3) | 0.045 (3) | −0.013 (2) | −0.017 (2) | 0.011 (2) |
C21 | 0.052 (2) | 0.044 (2) | 0.032 (2) | 0.0043 (19) | 0.0101 (19) | −0.0053 (18) |
C22 | 0.034 (2) | 0.052 (3) | 0.054 (3) | −0.0127 (19) | 0.0044 (19) | 0.002 (2) |
C23 | 0.098 (4) | 0.027 (2) | 0.056 (3) | −0.003 (2) | 0.024 (3) | −0.005 (2) |
C24 | 0.049 (3) | 0.070 (3) | 0.078 (3) | 0.036 (2) | 0.015 (2) | 0.032 (3) |
Rh—C2 | 2.101 (4) | C11—C12 | 1.384 (5) |
Rh—C18 | 2.180 (3) | C11—H11 | 0.9500 |
Rh—C1 | 2.196 (3) | C12—C13 | 1.377 (5) |
Rh—S | 2.2140 (9) | C12—H12 | 0.9500 |
Rh—C19 | 2.239 (4) | C13—C14 | 1.392 (5) |
Rh—C15 | 2.258 (4) | C13—H13 | 0.9500 |
Rh—C17 | 2.258 (3) | C14—H14 | 0.9500 |
Rh—C16 | 2.288 (3) | C15—C19 | 1.411 (6) |
S—O | 1.489 (2) | C15—C16 | 1.445 (5) |
S—C9 | 1.803 (3) | C15—C20 | 1.502 (6) |
S—C3 | 1.810 (3) | C16—C17 | 1.408 (5) |
C1—H1A | 0.9800 | C16—C21 | 1.499 (5) |
C1—H1B | 0.9800 | C17—C18 | 1.442 (5) |
C1—H1C | 0.9800 | C17—C22 | 1.502 (5) |
C2—H2A | 0.9800 | C18—C19 | 1.432 (6) |
C2—H2B | 0.9800 | C18—C23 | 1.501 (6) |
C2—H2C | 0.9800 | C19—C24 | 1.502 (5) |
C3—C8 | 1.376 (5) | C20—H20A | 0.9800 |
C3—C4 | 1.381 (5) | C20—H20B | 0.9800 |
C4—C5 | 1.385 (5) | C20—H20C | 0.9800 |
C4—H4 | 0.9500 | C21—H21A | 0.9800 |
C5—C6 | 1.384 (6) | C21—H21B | 0.9800 |
C5—H5 | 0.9500 | C21—H21C | 0.9800 |
C6—C7 | 1.380 (6) | C22—H22A | 0.9800 |
C6—H6 | 0.9500 | C22—H22B | 0.9800 |
C7—C8 | 1.387 (5) | C22—H22C | 0.9800 |
C7—H7 | 0.9500 | C23—H23A | 0.9800 |
C8—H8 | 0.9500 | C23—H23B | 0.9800 |
C9—C14 | 1.381 (5) | C23—H23C | 0.9800 |
C9—C10 | 1.382 (5) | C24—H24A | 0.9800 |
C10—C11 | 1.386 (5) | C24—H24B | 0.9800 |
C10—H10 | 0.9500 | C24—H24C | 0.9800 |
C2—Rh—C18 | 103.19 (15) | C12—C11—H11 | 120.0 |
C2—Rh—C1 | 83.44 (15) | C10—C11—H11 | 120.0 |
C18—Rh—C1 | 97.40 (13) | C13—C12—C11 | 120.3 (3) |
C2—Rh—S | 90.68 (11) | C13—C12—H12 | 119.9 |
C18—Rh—S | 162.25 (10) | C11—C12—H12 | 119.9 |
C1—Rh—S | 95.11 (8) | C12—C13—C14 | 120.0 (4) |
C2—Rh—C19 | 89.62 (15) | C12—C13—H13 | 120.0 |
C18—Rh—C19 | 37.79 (15) | C14—C13—H13 | 120.0 |
C1—Rh—C19 | 131.29 (14) | C9—C14—C13 | 119.4 (3) |
S—Rh—C19 | 133.25 (11) | C9—C14—H14 | 120.3 |
C2—Rh—C15 | 111.98 (16) | C13—C14—H14 | 120.3 |
C18—Rh—C15 | 62.42 (14) | C19—C15—C16 | 108.0 (3) |
C1—Rh—C15 | 156.32 (13) | C19—C15—C20 | 126.5 (4) |
S—Rh—C15 | 102.30 (11) | C16—C15—C20 | 125.1 (4) |
C19—Rh—C15 | 36.57 (14) | C19—C15—Rh | 71.0 (2) |
C2—Rh—C17 | 140.72 (14) | C16—C15—Rh | 72.62 (19) |
C18—Rh—C17 | 37.87 (13) | C20—C15—Rh | 127.8 (3) |
C1—Rh—C17 | 95.00 (12) | C17—C16—C15 | 108.2 (3) |
S—Rh—C17 | 128.43 (9) | C17—C16—C21 | 127.0 (3) |
C19—Rh—C17 | 62.17 (13) | C15—C16—C21 | 124.6 (3) |
C15—Rh—C17 | 61.57 (13) | C17—C16—Rh | 70.81 (19) |
C2—Rh—C16 | 148.57 (15) | C15—C16—Rh | 70.32 (19) |
C18—Rh—C16 | 61.97 (13) | C21—C16—Rh | 128.1 (2) |
C1—Rh—C16 | 124.07 (12) | C16—C17—C18 | 107.8 (3) |
S—Rh—C16 | 100.50 (9) | C16—C17—C22 | 126.5 (3) |
C19—Rh—C16 | 61.37 (13) | C18—C17—C22 | 125.7 (3) |
C15—Rh—C16 | 37.06 (13) | C16—C17—Rh | 73.1 (2) |
C17—Rh—C16 | 36.07 (12) | C18—C17—Rh | 68.12 (19) |
O—S—C9 | 105.44 (15) | C22—C17—Rh | 126.2 (3) |
O—S—C3 | 104.63 (15) | C19—C18—C17 | 107.8 (3) |
C9—S—C3 | 100.44 (16) | C19—C18—C23 | 126.2 (4) |
O—S—Rh | 116.70 (11) | C17—C18—C23 | 125.3 (4) |
C9—S—Rh | 111.88 (11) | C19—C18—Rh | 73.3 (2) |
C3—S—Rh | 116.00 (11) | C17—C18—Rh | 74.01 (19) |
Rh—C1—H1A | 109.5 | C23—C18—Rh | 125.9 (3) |
Rh—C1—H1B | 109.5 | C15—C19—C18 | 108.0 (3) |
H1A—C1—H1B | 109.5 | C15—C19—C24 | 125.4 (4) |
Rh—C1—H1C | 109.5 | C18—C19—C24 | 126.5 (4) |
H1A—C1—H1C | 109.5 | C15—C19—Rh | 72.4 (2) |
H1B—C1—H1C | 109.5 | C18—C19—Rh | 68.86 (19) |
Rh—C2—H2A | 109.5 | C24—C19—Rh | 126.0 (3) |
Rh—C2—H2B | 109.5 | C15—C20—H20A | 109.5 |
H2A—C2—H2B | 109.5 | C15—C20—H20B | 109.5 |
Rh—C2—H2C | 109.5 | H20A—C20—H20B | 109.5 |
H2A—C2—H2C | 109.5 | C15—C20—H20C | 109.5 |
H2B—C2—H2C | 109.5 | H20A—C20—H20C | 109.5 |
C8—C3—C4 | 120.9 (3) | H20B—C20—H20C | 109.5 |
C8—C3—S | 123.4 (3) | C16—C21—H21A | 109.5 |
C4—C3—S | 115.7 (3) | C16—C21—H21B | 109.5 |
C3—C4—C5 | 119.6 (4) | H21A—C21—H21B | 109.5 |
C3—C4—H4 | 120.2 | C16—C21—H21C | 109.5 |
C5—C4—H4 | 120.2 | H21A—C21—H21C | 109.5 |
C6—C5—C4 | 119.9 (4) | H21B—C21—H21C | 109.5 |
C6—C5—H5 | 120.1 | C17—C22—H22A | 109.5 |
C4—C5—H5 | 120.1 | C17—C22—H22B | 109.5 |
C7—C6—C5 | 120.0 (4) | H22A—C22—H22B | 109.5 |
C7—C6—H6 | 120.0 | C17—C22—H22C | 109.5 |
C5—C6—H6 | 120.0 | H22A—C22—H22C | 109.5 |
C6—C7—C8 | 120.3 (4) | H22B—C22—H22C | 109.5 |
C6—C7—H7 | 119.8 | C18—C23—H23A | 109.5 |
C8—C7—H7 | 119.8 | C18—C23—H23B | 109.5 |
C3—C8—C7 | 119.3 (3) | H23A—C23—H23B | 109.5 |
C3—C8—H8 | 120.4 | C18—C23—H23C | 109.5 |
C7—C8—H8 | 120.4 | H23A—C23—H23C | 109.5 |
C14—C9—C10 | 120.7 (3) | H23B—C23—H23C | 109.5 |
C14—C9—S | 121.5 (3) | C19—C24—H24A | 109.5 |
C10—C9—S | 117.8 (3) | C19—C24—H24B | 109.5 |
C9—C10—C11 | 119.6 (3) | H24A—C24—H24B | 109.5 |
C9—C10—H10 | 120.2 | C19—C24—H24C | 109.5 |
C11—C10—H10 | 120.2 | H24A—C24—H24C | 109.5 |
C12—C11—C10 | 120.0 (4) | H24B—C24—H24C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [Rh(CH3)2(C10H15)(C12H10OS)] |
Mr | 470.46 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 183 |
a, b, c (Å) | 14.4164 (15), 35.646 (4), 8.5214 (8) |
V (Å3) | 4379.1 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.43 × 0.33 × 0.05 |
Data collection | |
Diffractometer | Bruker P4/SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997a) |
Tmin, Tmax | 0.769, 0.957 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28282, 4963, 3473 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.099, 1.05 |
No. of reflections | 4963 |
No. of parameters | 251 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.94 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 2006), SAINT, SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL (Sheldrick, 2000), SHELXTL.
Rh—C2 | 2.101 (4) | S—O | 1.489 (2) |
Rh—C1 | 2.196 (3) | S—C9 | 1.803 (3) |
Rh—S | 2.2140 (9) | S—C3 | 1.810 (3) |
C2—Rh—C1 | 83.44 (15) | C1—Rh—S | 95.11 (8) |
C2—Rh—S | 90.68 (11) |
Research on pentamethylcyclopentadienyl complexes of rhodium(III) and iridium(III) have lead to the comprehension of the activation of saturated alkanes by transition metals. In the course of our study on the activity of such complexes in alkane functionalization reactions, the synthesis of Cp*RhMe2(DPSO), (I), has been carried out (Cp* = pentamethylcyclopentadienyl, DPSO = diphenylsulfoxide).
The title compound (Fig. 1) is similar to the complex Cp*RhMe2(DMSO), (II), reported by Fooladi et al. (2002) (DMSO = dimethylsulfoxide). While Cp*RhMe2(DPSO) crystallizes in the orthorhombic group Pccn, the DMSO analogue crystallizes in the triclinic space group P1 with two independent molecules per asymmetric unit.
In both complexes, the Rh—S bond lengths [2.2140 (9) Å for (I) and 2.210 (1) and 2.211 (1) Å for (II)] and the angles at the rhodium center are similar (Table 1). However, a major difference is observed in the asymmetry of the coordination of the methyl groups. While all Rh—CH3 bond lengths in (II) are similar [2.090 (5) to 2.103 (5) Å], they differ significantly in (I) [Rh—C1 = 2.196 (3) Å, Rh—C2 = 2.101 (4) Å]. The nature of this difference is unknown and more studies are needed to investigate this discrepancy. While sulfur-coordinated dimethylsulfoxide complexes are common, the number of solid state structures where diphenylsulfoxide is S-bonded are scarce. Indeed, only Pt(II) (Rochon et al., 1997; de Almeida et al., 1992) and Ru(III) (Calligaris et al., 1995) complexes have been reported to have such bonding mode. It is also worth noting that the metric parameters of the DPSO moiety hardly change upon metal coordination. Free DPSO has a S=O bond length of 1.492 (3) Å and S—C bond lengths of 1.793(no e.s.d. available) Å (Yatsenko et al., 1986), while in (I) these distances are 1.489 (2), 1.803 (3) and 1.810 (3) Å, respectively.