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The title compound, RhCp*Me(Cl)(PMe3) or [RhCl(CH3)(C10H15)(C3H9P)], where Cp* is penta­methyl­cyclo­penta­dienyl, has a pseudo-tetrahedral coordination geometry. The Cp* ligand is planar and η5-coordinated. The molecular structure can be described as a so-called three-legged piano-stool. The rhodium–methyl, rhodium–chlorine and rhodium–phospho­rus distances are 2.255 (4), 2.3764 (18) and 2.2436 (13) Å, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016798/cv6068sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016798/cv6068Isup2.hkl
Contains datablock I

CCDC reference: 175975

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.054
  • wR factor = 0.165
  • Data-to-parameter ratio = 35.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.92 From the CIF: _reflns_number_total 5506 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 5879 Completeness (_total/calc) 93.66% Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The title compound, (I), was first prepared by Jones et al. (1984) and belongs to a group of complexes that have been used extensively in the activation of small molecules (Lefort et al., 1998; Arndtsen et al., 1995). However, there are no reported crystal structures of chloro–methyl complexes of this type.

The coordination geometry around rhodium is pseudo-tetrahedral and the Cp* ligand is planar and η5-coordinated. This gives rise to a three-legged piano-stool where the angles around rhodium involving the monodentate ligands are around 88°. The deviation from idealized tetrahedral angles is probably dictated by the bulky Cp* ligand. Selected bond lengths and angles are given in Table 1. The closest contact between complexes is 2.04 (1) Å and is found between H9A and H9A(-x, -y, 1 - z). This short distance is probably an artefact that arises from the fact that H atoms are placed only to minimize intramolecular interactions. The C9···C9(-x, -y, 1 - z) distance is 3.870 (6) Å and rotation around the Rh—C9 bond makes the C—H distances much longer.

Experimental top

RhCp*Me2(PMe3) was synthesized according to Jones et al. (1984) and recrystallization from petroleum ether afforded red crystals of the title compound as a by-product.

Refinement top

The highest residual electron density is located within 0.5 Å from C9 and Cl1.

Computing details top

Data collection: SMART (Bruker, 1995); cell refinement: SAINT (Bruker, 1995); data reduction: SAINT; 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 top
[Figure 1] Fig. 1. Numbering scheme with displacement ellipsoids (30% probability) for the title compound.
(I) top
Crystal data top
[RhCl(CH3)(C10H15)(C3H9P)]Dx = 1.421 Mg m3
Mr = 364.69Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 6294 reflections
a = 8.9295 (18) Åθ = 2.8–25.4°
b = 14.792 (3) ŵ = 1.23 mm1
c = 25.812 (5) ÅT = 293 K
V = 3409.2 (12) Å3Prism, red
Z = 80.15 × 0.03 × 0.03 mm
F(000) = 1504
Data collection top
Bruker SMART CCD
diffractometer
5506 independent reflections
Radiation source: rotating anode2862 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.069
Detector resolution: 512 pixels mm-1θmax = 31.9°, θmin = 1.6°
ω scansh = 1213
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 2021
Tmin = 0.789, Tmax = 0.943l = 3637
33212 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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0873P)2]
where P = (Fo2 + 2Fc2)/3
5506 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 0.94 e Å3
0 restraintsΔρmin = 1.36 e Å3
Crystal data top
[RhCl(CH3)(C10H15)(C3H9P)]V = 3409.2 (12) Å3
Mr = 364.69Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.9295 (18) ŵ = 1.23 mm1
b = 14.792 (3) ÅT = 293 K
c = 25.812 (5) Å0.15 × 0.03 × 0.03 mm
Data collection top
Bruker SMART CCD
diffractometer
5506 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2862 reflections with I > 2σ(I)
Tmin = 0.789, Tmax = 0.943Rint = 0.069
33212 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.165H-atom parameters constrained
S = 1.00Δρmax = 0.94 e Å3
5506 reflectionsΔρmin = 1.36 e Å3
154 parameters
Special details top

Experimental. Data was collected with a SMART CCD system using ω-scan, -0.2° and 60 s per frame. The detector distance was set to 4.0 cm. The data have 100% completeness out to θ=30.50°. The structure was solved by direct methods and refined by full matrix least squares methods.

Scattering factors, dispersion corrections and absorption coefficients were taken from International Tables for Crystallography, Vol. C. (1992), tables 6.1.1.4, 4.2.6.8 and 4.2.4.2 respectively. The crystallographic raw data frames were integrated, the reflections reduced and corrections were applied for Lorentz and polarization effects.

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
Rh10.12832 (4)0.03649 (2)0.375688 (13)0.04062 (13)
P10.25862 (15)0.13623 (8)0.42319 (5)0.0573 (3)
Cl10.3596 (2)0.03410 (13)0.35468 (10)0.1085 (7)
C10.0574 (6)0.0724 (4)0.29544 (17)0.0625 (13)
C20.0000 (7)0.0168 (4)0.3082 (2)0.0765 (18)
C30.0952 (6)0.0099 (4)0.3484 (3)0.0711 (16)
C40.1018 (5)0.0816 (4)0.36464 (19)0.0608 (14)
C50.0137 (5)0.1319 (3)0.33066 (19)0.0578 (12)
C60.1513 (6)0.2128 (4)0.4643 (2)0.0861 (19)
H6A0.07500.24180.44400.129*
H6B0.21690.25770.47860.129*
H6C0.10540.17920.49180.129*
C70.3952 (7)0.0891 (5)0.4681 (2)0.098 (2)
H7A0.34620.04750.49110.147*
H7B0.43980.13700.48790.147*
H7C0.47160.05780.44900.147*
C80.3693 (6)0.2120 (5)0.3838 (2)0.092 (2)
H8A0.30610.24070.35860.138*
H8B0.44640.17840.36650.138*
H8C0.41420.25730.40550.138*
C90.1169 (5)0.0552 (3)0.44538 (15)0.0425 (10)
H9A0.21490.07840.45280.064*
H9B0.05000.10450.43830.064*
H9C0.08090.02170.47470.064*
C110.1576 (9)0.0954 (7)0.2524 (2)0.135 (3)
H11A0.18870.04100.23520.203*
H11B0.24390.12660.26560.203*
H11C0.10570.13370.22830.203*
C210.0412 (11)0.1013 (5)0.2778 (3)0.155 (4)
H21A0.11070.08580.25080.233*
H21B0.04750.12680.26270.233*
H21C0.08640.14470.30060.233*
C310.1902 (10)0.0857 (6)0.3732 (3)0.153 (4)
H31A0.24710.06130.40150.229*
H31B0.12540.13260.38580.229*
H31C0.25730.11020.34780.229*
C410.2081 (8)0.1181 (6)0.4017 (3)0.132 (3)
H41A0.25400.06950.42050.197*
H41B0.28380.15180.38370.197*
H41C0.15670.15730.42550.197*
C510.0053 (8)0.2339 (3)0.3270 (3)0.108 (2)
H51A0.06310.25060.30000.162*
H51B0.02910.25810.35940.162*
H51C0.10290.25760.31930.162*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh10.0427 (2)0.03817 (19)0.0410 (2)0.00554 (13)0.00158 (15)0.00069 (13)
P10.0553 (7)0.0559 (7)0.0609 (7)0.0074 (6)0.0000 (6)0.0080 (6)
Cl10.0939 (14)0.1314 (17)0.1002 (14)0.0398 (11)0.0052 (11)0.0156 (11)
C10.053 (3)0.093 (4)0.042 (3)0.016 (3)0.003 (2)0.015 (3)
C20.091 (4)0.058 (3)0.081 (4)0.025 (3)0.051 (4)0.020 (3)
C30.055 (3)0.071 (3)0.086 (4)0.015 (3)0.024 (3)0.019 (3)
C40.044 (3)0.085 (4)0.054 (3)0.015 (2)0.001 (2)0.009 (3)
C50.061 (3)0.045 (2)0.067 (3)0.009 (2)0.014 (3)0.004 (2)
C60.102 (5)0.074 (4)0.083 (4)0.010 (3)0.009 (3)0.038 (3)
C70.077 (4)0.132 (6)0.084 (4)0.017 (4)0.030 (3)0.001 (4)
C80.082 (5)0.080 (4)0.115 (6)0.023 (3)0.007 (3)0.014 (3)
C90.051 (3)0.038 (2)0.039 (2)0.0003 (18)0.0064 (19)0.0061 (16)
C110.124 (6)0.220 (8)0.060 (4)0.046 (6)0.023 (4)0.047 (5)
C210.239 (10)0.099 (5)0.127 (6)0.064 (6)0.111 (7)0.061 (5)
C310.107 (6)0.123 (7)0.228 (12)0.050 (6)0.052 (6)0.080 (7)
C410.074 (5)0.204 (10)0.117 (6)0.052 (5)0.024 (4)0.028 (6)
C510.133 (6)0.054 (3)0.136 (6)0.014 (4)0.039 (5)0.016 (4)
Geometric parameters (Å, º) top
Rh1—C42.179 (4)C1—C51.415 (6)
Rh1—C52.225 (4)C1—C21.453 (8)
Rh1—C32.225 (5)C1—C111.466 (8)
Rh1—C22.228 (5)C2—C31.344 (8)
Rh1—C12.230 (4)C2—C211.522 (8)
Rh1—P12.2436 (13)C3—C41.419 (9)
Rh1—C92.255 (4)C3—C311.545 (10)
Rh1—Cl12.3764 (18)C4—C51.393 (7)
P1—C81.807 (6)C4—C411.452 (8)
P1—C71.822 (6)C5—C511.513 (6)
P1—C61.823 (5)
C4—Rh1—C536.86 (18)C7—P1—Rh1116.3 (2)
C4—Rh1—C337.6 (2)C6—P1—Rh1116.97 (19)
C5—Rh1—C361.24 (18)C5—C1—C2105.1 (4)
C4—Rh1—C261.4 (2)C5—C1—C11128.0 (6)
C5—Rh1—C261.50 (17)C2—C1—C11126.7 (6)
C3—Rh1—C235.1 (2)C5—C1—Rh171.3 (3)
C4—Rh1—C162.45 (18)C2—C1—Rh170.9 (3)
C5—Rh1—C137.04 (17)C11—C1—Rh1125.8 (4)
C3—Rh1—C161.6 (2)C3—C2—C1109.3 (5)
C2—Rh1—C138.0 (2)C3—C2—C21127.8 (7)
C4—Rh1—P1111.05 (16)C1—C2—C21122.9 (7)
C5—Rh1—P199.44 (12)C3—C2—Rh172.3 (3)
C3—Rh1—P1147.3 (2)C1—C2—Rh171.1 (3)
C2—Rh1—P1157.84 (17)C21—C2—Rh1124.7 (4)
C1—Rh1—P1119.88 (15)C2—C3—C4109.0 (5)
C4—Rh1—C9104.23 (18)C2—C3—C31127.8 (7)
C5—Rh1—C9140.56 (17)C4—C3—C31123.1 (7)
C3—Rh1—C991.53 (19)C2—C3—Rh172.5 (3)
C2—Rh1—C9112.8 (2)C4—C3—Rh169.5 (3)
C1—Rh1—C9150.61 (18)C31—C3—Rh1125.8 (4)
P1—Rh1—C989.02 (11)C5—C4—C3107.4 (5)
C4—Rh1—Cl1157.51 (15)C5—C4—C41125.8 (6)
C5—Rh1—Cl1130.90 (15)C3—C4—C41125.3 (6)
C3—Rh1—Cl1124.8 (2)C5—C4—Rh173.3 (3)
C2—Rh1—Cl196.50 (17)C3—C4—Rh173.0 (3)
C1—Rh1—Cl198.03 (14)C41—C4—Rh1130.1 (4)
P1—Rh1—Cl187.88 (6)C4—C5—C1109.0 (4)
C9—Rh1—Cl187.55 (12)C4—C5—C51126.8 (5)
C8—P1—C7103.3 (3)C1—C5—C51123.9 (5)
C8—P1—C6103.2 (3)C4—C5—Rh169.8 (3)
C7—P1—C6102.7 (3)C1—C5—Rh171.7 (2)
C8—P1—Rh1112.6 (2)C51—C5—Rh1129.5 (4)

Experimental details

Crystal data
Chemical formula[RhCl(CH3)(C10H15)(C3H9P)]
Mr364.69
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)8.9295 (18), 14.792 (3), 25.812 (5)
V3)3409.2 (12)
Z8
Radiation typeMo Kα
µ (mm1)1.23
Crystal size (mm)0.15 × 0.03 × 0.03
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.789, 0.943
No. of measured, independent and
observed [I > 2σ(I)] reflections
33212, 5506, 2862
Rint0.069
(sin θ/λ)max1)0.744
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.165, 1.00
No. of reflections5506
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.94, 1.36

Computer programs: SMART (Bruker, 1995), SAINT (Bruker, 1995), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.

Selected geometric parameters (Å, º) top
Rh1—C42.179 (4)P1—C81.807 (6)
Rh1—C52.225 (4)P1—C71.822 (6)
Rh1—C32.225 (5)P1—C61.823 (5)
Rh1—C22.228 (5)C1—C51.415 (6)
Rh1—C12.230 (4)C1—C21.453 (8)
Rh1—P12.2436 (13)C2—C31.344 (8)
Rh1—C92.255 (4)C3—C41.419 (9)
Rh1—Cl12.3764 (18)C4—C51.393 (7)
P1—Rh1—C989.02 (11)C7—P1—Rh1116.3 (2)
P1—Rh1—Cl187.88 (6)C6—P1—Rh1116.97 (19)
C9—Rh1—Cl187.55 (12)C5—C1—C2105.1 (4)
C8—P1—C7103.3 (3)C3—C2—C1109.3 (5)
C8—P1—C6103.2 (3)C2—C3—C4109.0 (5)
C7—P1—C6102.7 (3)C5—C4—C3107.4 (5)
C8—P1—Rh1112.6 (2)C4—C5—C1109.0 (4)
 

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