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Acta Cryst. (2007). E63, m2253    [ doi:10.1107/S1600536807034204 ]

(Diphenyl sulfoxide)dimethyl([eta]5-pentamethylcyclopentadienyl)rhodium(III)

A. Decken, A. Michaud, S. Mathiotte and F.-G. Fontaine

Abstract top

In the title complex, [Rh(CH3)2(C10H15)(C12H10OS)], the RhIII atom is in a distorted tetrahedral coordination environment, coordinated by an [eta]5-pentamethylcyclopentadienyl ring, two methyl groups and the S atom of the diphenyl sulfoxide ligand. The title compound is representative of a very small group of complexes in which the diphenyl sulfoxide ligand is coordinated via the S atom.

Comment top

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.

Related literature top

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).

Experimental top

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).

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. View of the title compound with displacement ellipsoids at the 50% probability level.
(Diphenyl sulfoxide)dimethyl(η5-pentamethylcyclopentadienyl)rhodium(III) top
Crystal data top
[Rh(CH3)2(C10H15)(C12H10OS)]F000 = 1952
Mr = 470.46Dx = 1.427 Mg m−3
Orthorhombic, PccnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 6117 reflections
a = 14.4164 (15) Åθ = 2.8–28.4º
b = 35.646 (4) ŵ = 0.89 mm−1
c = 8.5214 (8) ÅT = 183 (1) K
V = 4379.1 (8) Å3Plate, yellow
Z = 80.43 × 0.33 × 0.05 mm
Data collection top
Bruker P4/SMART 1000 CCD area-detector
diffractometer		3473 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
T = 183(1) Kθmax = 27.5º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997a)		h = −18→18
Tmin = 0.769, Tmax = 0.957k = −46→44
28282 measured reflectionsl = −10→11
4963 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.039P)2 + 7.0043P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
4963 reflectionsΔρmax = 0.83 e Å−3
251 parametersΔρmin = −0.94 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Rh(CH3)2(C10H15)(C12H10OS)]V = 4379.1 (8) Å3
Mr = 470.46Z = 8
Orthorhombic, PccnMo Kα
a = 14.4164 (15) ŵ = 0.89 mm−1
b = 35.646 (4) ÅT = 183 (1) K
c = 8.5214 (8) Å0.43 × 0.33 × 0.05 mm
Data collection top
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 = 0.957Rint = 0.053
28282 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039251 parameters
wR(F2) = 0.099H-atom parameters constrained
S = 1.05Δρmax = 0.83 e Å−3
4963 reflectionsΔρmin = −0.94 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Rh0.494908 (16)0.157754 (7)0.17044 (3)0.02332 (9)
S0.47396 (5)0.09623 (2)0.17229 (10)0.02366 (17)
O0.40279 (16)0.08105 (7)0.0627 (3)0.0324 (6)
C10.5718 (2)0.15940 (9)0.3928 (4)0.0244 (7)
H1A0.55900.18310.44690.037*
H1B0.63840.15740.37160.037*
H1C0.55230.13840.45930.037*
C20.3791 (3)0.16516 (11)0.3167 (5)0.0457 (10)
H2A0.37670.19120.35290.069*
H2B0.38400.14840.40740.069*
H2C0.32240.15930.25810.069*
C30.4456 (2)0.07566 (9)0.3604 (4)0.0255 (7)
C40.3525 (2)0.07536 (10)0.3990 (4)0.0323 (8)
H40.30770.08440.32650.039*
C50.3249 (3)0.06179 (11)0.5439 (5)0.0400 (9)
H50.26100.06160.57140.048*
C60.3905 (3)0.04847 (12)0.6486 (5)0.0441 (10)
H60.37180.03960.74870.053*
C70.4830 (3)0.04816 (13)0.6074 (5)0.0452 (10)
H70.52770.03820.67810.054*
C80.5112 (3)0.06226 (11)0.4634 (4)0.0374 (9)
H80.57510.06270.43620.045*
C90.5793 (2)0.07126 (9)0.1267 (4)0.0259 (7)
C100.5722 (3)0.03924 (10)0.0361 (4)0.0347 (8)
H100.51330.03080.00090.042*
C110.6517 (3)0.01946 (11)−0.0030 (5)0.0418 (9)
H110.6473−0.0027−0.06460.050*
C120.7375 (3)0.03196 (10)0.0478 (5)0.0385 (9)
H120.79180.01810.02260.046*
C130.7445 (3)0.06440 (11)0.1346 (5)0.0395 (9)
H130.80370.07310.16750.047*
C140.6649 (2)0.08441 (11)0.1743 (4)0.0344 (8)
H140.66950.10690.23360.041*
C150.4633 (3)0.17269 (11)−0.0814 (4)0.0353 (9)
C160.5617 (2)0.16543 (10)−0.0710 (4)0.0282 (8)
C170.6007 (2)0.19137 (10)0.0347 (4)0.0293 (8)
C180.5266 (3)0.21465 (10)0.0935 (4)0.0346 (9)
C190.4430 (3)0.20382 (11)0.0149 (5)0.0387 (9)
C200.3977 (3)0.15331 (14)−0.1917 (5)0.0570 (13)
H20A0.33390.1566−0.15440.086*
H20B0.41260.1265−0.19590.086*
H20C0.40380.1642−0.29680.086*
C210.6125 (3)0.13685 (11)−0.1673 (4)0.0424 (9)
H21A0.62350.1469−0.27270.064*
H21B0.57520.1139−0.17470.064*
H21C0.67210.1311−0.11730.064*
C220.7017 (3)0.19547 (12)0.0745 (5)0.0467 (10)
H22A0.73260.17110.06320.070*
H22B0.70790.20420.18300.070*
H22C0.73030.21370.00330.070*
C230.5388 (4)0.24817 (12)0.1981 (5)0.0602 (13)
H23A0.58480.24250.27930.090*
H23B0.47940.25440.24770.090*
H23C0.56010.26960.13550.090*
C240.3503 (3)0.22286 (14)0.0269 (6)0.0654 (15)
H24A0.34360.2409−0.05890.098*
H24B0.34590.23600.12770.098*
H24C0.30090.20410.01990.098*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh0.02300 (14)0.02176 (14)0.02520 (14)0.00259 (10)0.00236 (11)−0.00017 (10)
S0.0210 (4)0.0238 (4)0.0261 (4)0.0002 (3)0.0001 (3)−0.0004 (3)
O0.0261 (12)0.0347 (14)0.0365 (13)−0.0026 (11)−0.0048 (10)−0.0037 (11)
C10.0375 (19)0.0146 (15)0.0211 (15)−0.0030 (14)0.0045 (14)−0.0020 (13)
C20.048 (2)0.037 (2)0.052 (2)0.0100 (18)0.022 (2)0.0004 (19)
C30.0271 (17)0.0192 (16)0.0302 (18)−0.0038 (13)0.0046 (14)0.0011 (13)
C40.0265 (18)0.031 (2)0.039 (2)−0.0032 (15)−0.0001 (15)0.0012 (16)
C50.033 (2)0.042 (2)0.045 (2)−0.0079 (17)0.0102 (18)−0.0047 (19)
C60.051 (2)0.045 (2)0.036 (2)−0.010 (2)0.0111 (19)0.0015 (18)
C70.042 (2)0.052 (3)0.041 (2)0.000 (2)0.0000 (18)0.017 (2)
C80.0275 (19)0.050 (2)0.0353 (19)−0.0002 (17)0.0027 (16)0.0117 (17)
C90.0243 (16)0.0219 (17)0.0315 (17)0.0013 (13)0.0014 (14)−0.0014 (14)
C100.0310 (19)0.0267 (19)0.046 (2)−0.0088 (15)0.0036 (17)−0.0037 (17)
C110.040 (2)0.027 (2)0.059 (3)−0.0026 (16)0.013 (2)−0.0113 (18)
C120.031 (2)0.030 (2)0.055 (2)0.0067 (16)0.0111 (18)−0.0013 (18)
C130.0238 (17)0.037 (2)0.058 (2)0.0000 (16)0.0022 (17)−0.0061 (18)
C140.0256 (17)0.037 (2)0.041 (2)0.0011 (15)0.0008 (17)−0.0105 (18)
C150.0308 (19)0.040 (2)0.035 (2)−0.0006 (17)−0.0004 (16)0.0124 (17)
C160.0337 (19)0.0260 (18)0.0250 (16)0.0008 (14)0.0004 (14)0.0040 (14)
C170.0303 (18)0.0273 (18)0.0303 (18)−0.0025 (15)0.0051 (15)0.0042 (15)
C180.047 (2)0.0193 (17)0.037 (2)0.0023 (16)0.0128 (17)0.0060 (15)
C190.0326 (19)0.036 (2)0.047 (2)0.0112 (16)0.0079 (18)0.0183 (19)
C200.050 (3)0.076 (3)0.045 (3)−0.013 (2)−0.017 (2)0.011 (2)
C210.052 (2)0.044 (2)0.032 (2)0.0043 (19)0.0101 (19)−0.0053 (18)
C220.034 (2)0.052 (3)0.054 (3)−0.0127 (19)0.0044 (19)0.002 (2)
C230.098 (4)0.027 (2)0.056 (3)−0.003 (2)0.024 (3)−0.005 (2)
C240.049 (3)0.070 (3)0.078 (3)0.036 (2)0.015 (2)0.032 (3)
Geometric parameters (Å, °) top
Rh—C22.101 (4)C11—C121.384 (5)
Rh—C182.180 (3)C11—H110.9500
Rh—C12.196 (3)C12—C131.377 (5)
Rh—S2.2140 (9)C12—H120.9500
Rh—C192.239 (4)C13—C141.392 (5)
Rh—C152.258 (4)C13—H130.9500
Rh—C172.258 (3)C14—H140.9500
Rh—C162.288 (3)C15—C191.411 (6)
S—O1.489 (2)C15—C161.445 (5)
S—C91.803 (3)C15—C201.502 (6)
S—C31.810 (3)C16—C171.408 (5)
C1—H1A0.9800C16—C211.499 (5)
C1—H1B0.9800C17—C181.442 (5)
C1—H1C0.9800C17—C221.502 (5)
C2—H2A0.9800C18—C191.432 (6)
C2—H2B0.9800C18—C231.501 (6)
C2—H2C0.9800C19—C241.502 (5)
C3—C81.376 (5)C20—H20A0.9800
C3—C41.381 (5)C20—H20B0.9800
C4—C51.385 (5)C20—H20C0.9800
C4—H40.9500C21—H21A0.9800
C5—C61.384 (6)C21—H21B0.9800
C5—H50.9500C21—H21C0.9800
C6—C71.380 (6)C22—H22A0.9800
C6—H60.9500C22—H22B0.9800
C7—C81.387 (5)C22—H22C0.9800
C7—H70.9500C23—H23A0.9800
C8—H80.9500C23—H23B0.9800
C9—C141.381 (5)C23—H23C0.9800
C9—C101.382 (5)C24—H24A0.9800
C10—C111.386 (5)C24—H24B0.9800
C10—H100.9500C24—H24C0.9800
C2—Rh—C18103.19 (15)C12—C11—H11120.0
C2—Rh—C183.44 (15)C10—C11—H11120.0
C18—Rh—C197.40 (13)C13—C12—C11120.3 (3)
C2—Rh—S90.68 (11)C13—C12—H12119.9
C18—Rh—S162.25 (10)C11—C12—H12119.9
C1—Rh—S95.11 (8)C12—C13—C14120.0 (4)
C2—Rh—C1989.62 (15)C12—C13—H13120.0
C18—Rh—C1937.79 (15)C14—C13—H13120.0
C1—Rh—C19131.29 (14)C9—C14—C13119.4 (3)
S—Rh—C19133.25 (11)C9—C14—H14120.3
C2—Rh—C15111.98 (16)C13—C14—H14120.3
C18—Rh—C1562.42 (14)C19—C15—C16108.0 (3)
C1—Rh—C15156.32 (13)C19—C15—C20126.5 (4)
S—Rh—C15102.30 (11)C16—C15—C20125.1 (4)
C19—Rh—C1536.57 (14)C19—C15—Rh71.0 (2)
C2—Rh—C17140.72 (14)C16—C15—Rh72.62 (19)
C18—Rh—C1737.87 (13)C20—C15—Rh127.8 (3)
C1—Rh—C1795.00 (12)C17—C16—C15108.2 (3)
S—Rh—C17128.43 (9)C17—C16—C21127.0 (3)
C19—Rh—C1762.17 (13)C15—C16—C21124.6 (3)
C15—Rh—C1761.57 (13)C17—C16—Rh70.81 (19)
C2—Rh—C16148.57 (15)C15—C16—Rh70.32 (19)
C18—Rh—C1661.97 (13)C21—C16—Rh128.1 (2)
C1—Rh—C16124.07 (12)C16—C17—C18107.8 (3)
S—Rh—C16100.50 (9)C16—C17—C22126.5 (3)
C19—Rh—C1661.37 (13)C18—C17—C22125.7 (3)
C15—Rh—C1637.06 (13)C16—C17—Rh73.1 (2)
C17—Rh—C1636.07 (12)C18—C17—Rh68.12 (19)
O—S—C9105.44 (15)C22—C17—Rh126.2 (3)
O—S—C3104.63 (15)C19—C18—C17107.8 (3)
C9—S—C3100.44 (16)C19—C18—C23126.2 (4)
O—S—Rh116.70 (11)C17—C18—C23125.3 (4)
C9—S—Rh111.88 (11)C19—C18—Rh73.3 (2)
C3—S—Rh116.00 (11)C17—C18—Rh74.01 (19)
Rh—C1—H1A109.5C23—C18—Rh125.9 (3)
Rh—C1—H1B109.5C15—C19—C18108.0 (3)
H1A—C1—H1B109.5C15—C19—C24125.4 (4)
Rh—C1—H1C109.5C18—C19—C24126.5 (4)
H1A—C1—H1C109.5C15—C19—Rh72.4 (2)
H1B—C1—H1C109.5C18—C19—Rh68.86 (19)
Rh—C2—H2A109.5C24—C19—Rh126.0 (3)
Rh—C2—H2B109.5C15—C20—H20A109.5
H2A—C2—H2B109.5C15—C20—H20B109.5
Rh—C2—H2C109.5H20A—C20—H20B109.5
H2A—C2—H2C109.5C15—C20—H20C109.5
H2B—C2—H2C109.5H20A—C20—H20C109.5
C8—C3—C4120.9 (3)H20B—C20—H20C109.5
C8—C3—S123.4 (3)C16—C21—H21A109.5
C4—C3—S115.7 (3)C16—C21—H21B109.5
C3—C4—C5119.6 (4)H21A—C21—H21B109.5
C3—C4—H4120.2C16—C21—H21C109.5
C5—C4—H4120.2H21A—C21—H21C109.5
C6—C5—C4119.9 (4)H21B—C21—H21C109.5
C6—C5—H5120.1C17—C22—H22A109.5
C4—C5—H5120.1C17—C22—H22B109.5
C7—C6—C5120.0 (4)H22A—C22—H22B109.5
C7—C6—H6120.0C17—C22—H22C109.5
C5—C6—H6120.0H22A—C22—H22C109.5
C6—C7—C8120.3 (4)H22B—C22—H22C109.5
C6—C7—H7119.8C18—C23—H23A109.5
C8—C7—H7119.8C18—C23—H23B109.5
C3—C8—C7119.3 (3)H23A—C23—H23B109.5
C3—C8—H8120.4C18—C23—H23C109.5
C7—C8—H8120.4H23A—C23—H23C109.5
C14—C9—C10120.7 (3)H23B—C23—H23C109.5
C14—C9—S121.5 (3)C19—C24—H24A109.5
C10—C9—S117.8 (3)C19—C24—H24B109.5
C9—C10—C11119.6 (3)H24A—C24—H24B109.5
C9—C10—H10120.2C19—C24—H24C109.5
C11—C10—H10120.2H24A—C24—H24C109.5
C12—C11—C10120.0 (4)H24B—C24—H24C109.5
Table 1
Selected geometric parameters (Å, °) top
Rh—C22.101 (4)S—O1.489 (2)
Rh—C12.196 (3)S—C91.803 (3)
Rh—S2.2140 (9)S—C31.810 (3)
C2—Rh—C183.44 (15)C1—Rh—S95.11 (8)
C2—Rh—S90.68 (11)
Acknowledgements top

The authors acknowledge the financial support of the National Sciences and Engineering Research Council of Canada and the Fonds Québecois de la Recherche sur la Nature et les Technologies.

references
References top

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