Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016798/cv6068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016798/cv6068Isup2.hkl |
CCDC reference: 175975
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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
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.
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.
Fig. 1. Numbering scheme with displacement ellipsoids (30% probability) for the title compound. |
[RhCl(CH3)(C10H15)(C3H9P)] | Dx = 1.421 Mg m−3 |
Mr = 364.69 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 6294 reflections |
a = 8.9295 (18) Å | θ = 2.8–25.4° |
b = 14.792 (3) Å | µ = 1.23 mm−1 |
c = 25.812 (5) Å | T = 293 K |
V = 3409.2 (12) Å3 | Prism, red |
Z = 8 | 0.15 × 0.03 × 0.03 mm |
F(000) = 1504 |
Bruker SMART CCD diffractometer | 5506 independent reflections |
Radiation source: rotating anode | 2862 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
Detector resolution: 512 pixels mm-1 | θmax = 31.9°, θmin = 1.6° |
ω scans | h = −12→13 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −20→21 |
Tmin = 0.789, Tmax = 0.943 | l = −36→37 |
33212 measured reflections |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-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 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −1.36 e Å−3 |
[RhCl(CH3)(C10H15)(C3H9P)] | V = 3409.2 (12) Å3 |
Mr = 364.69 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.9295 (18) Å | µ = 1.23 mm−1 |
b = 14.792 (3) Å | T = 293 K |
c = 25.812 (5) Å | 0.15 × 0.03 × 0.03 mm |
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 = 0.943 | Rint = 0.069 |
33212 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.94 e Å−3 |
5506 reflections | Δρmin = −1.36 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Rh1 | 0.12832 (4) | 0.03649 (2) | 0.375688 (13) | 0.04062 (13) | |
P1 | 0.25862 (15) | 0.13623 (8) | 0.42319 (5) | 0.0573 (3) | |
Cl1 | 0.3596 (2) | −0.03410 (13) | 0.35468 (10) | 0.1085 (7) | |
C1 | 0.0574 (6) | 0.0724 (4) | 0.29544 (17) | 0.0625 (13) | |
C2 | 0.0000 (7) | −0.0168 (4) | 0.3082 (2) | 0.0765 (18) | |
C3 | −0.0952 (6) | −0.0099 (4) | 0.3484 (3) | 0.0711 (16) | |
C4 | −0.1018 (5) | 0.0816 (4) | 0.36464 (19) | 0.0608 (14) | |
C5 | −0.0137 (5) | 0.1319 (3) | 0.33066 (19) | 0.0578 (12) | |
C6 | 0.1513 (6) | 0.2128 (4) | 0.4643 (2) | 0.0861 (19) | |
H6A | 0.0750 | 0.2418 | 0.4440 | 0.129* | |
H6B | 0.2169 | 0.2577 | 0.4786 | 0.129* | |
H6C | 0.1054 | 0.1792 | 0.4918 | 0.129* | |
C7 | 0.3952 (7) | 0.0891 (5) | 0.4681 (2) | 0.098 (2) | |
H7A | 0.3462 | 0.0475 | 0.4911 | 0.147* | |
H7B | 0.4398 | 0.1370 | 0.4879 | 0.147* | |
H7C | 0.4716 | 0.0578 | 0.4490 | 0.147* | |
C8 | 0.3693 (6) | 0.2120 (5) | 0.3838 (2) | 0.092 (2) | |
H8A | 0.3061 | 0.2407 | 0.3586 | 0.138* | |
H8B | 0.4464 | 0.1784 | 0.3665 | 0.138* | |
H8C | 0.4142 | 0.2573 | 0.4055 | 0.138* | |
C9 | 0.1169 (5) | −0.0552 (3) | 0.44538 (15) | 0.0425 (10) | |
H9A | 0.2149 | −0.0784 | 0.4528 | 0.064* | |
H9B | 0.0500 | −0.1045 | 0.4383 | 0.064* | |
H9C | 0.0809 | −0.0217 | 0.4747 | 0.064* | |
C11 | 0.1576 (9) | 0.0954 (7) | 0.2524 (2) | 0.135 (3) | |
H11A | 0.1887 | 0.0410 | 0.2352 | 0.203* | |
H11B | 0.2439 | 0.1266 | 0.2656 | 0.203* | |
H11C | 0.1057 | 0.1337 | 0.2283 | 0.203* | |
C21 | 0.0412 (11) | −0.1013 (5) | 0.2778 (3) | 0.155 (4) | |
H21A | 0.1107 | −0.0858 | 0.2508 | 0.233* | |
H21B | −0.0475 | −0.1268 | 0.2627 | 0.233* | |
H21C | 0.0864 | −0.1447 | 0.3006 | 0.233* | |
C31 | −0.1902 (10) | −0.0857 (6) | 0.3732 (3) | 0.153 (4) | |
H31A | −0.2471 | −0.0613 | 0.4015 | 0.229* | |
H31B | −0.1254 | −0.1326 | 0.3858 | 0.229* | |
H31C | −0.2573 | −0.1102 | 0.3478 | 0.229* | |
C41 | −0.2081 (8) | 0.1181 (6) | 0.4017 (3) | 0.132 (3) | |
H41A | −0.2540 | 0.0695 | 0.4205 | 0.197* | |
H41B | −0.2838 | 0.1518 | 0.3837 | 0.197* | |
H41C | −0.1567 | 0.1573 | 0.4255 | 0.197* | |
C51 | −0.0053 (8) | 0.2339 (3) | 0.3270 (3) | 0.108 (2) | |
H51A | 0.0631 | 0.2506 | 0.3000 | 0.162* | |
H51B | 0.0291 | 0.2581 | 0.3594 | 0.162* | |
H51C | −0.1029 | 0.2576 | 0.3193 | 0.162* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.0427 (2) | 0.03817 (19) | 0.0410 (2) | 0.00554 (13) | 0.00158 (15) | −0.00069 (13) |
P1 | 0.0553 (7) | 0.0559 (7) | 0.0609 (7) | −0.0074 (6) | 0.0000 (6) | −0.0080 (6) |
Cl1 | 0.0939 (14) | 0.1314 (17) | 0.1002 (14) | 0.0398 (11) | 0.0052 (11) | −0.0156 (11) |
C1 | 0.053 (3) | 0.093 (4) | 0.042 (3) | 0.016 (3) | 0.003 (2) | 0.015 (3) |
C2 | 0.091 (4) | 0.058 (3) | 0.081 (4) | 0.025 (3) | −0.051 (4) | −0.020 (3) |
C3 | 0.055 (3) | 0.071 (3) | 0.086 (4) | −0.015 (3) | −0.024 (3) | 0.019 (3) |
C4 | 0.044 (3) | 0.085 (4) | 0.054 (3) | 0.015 (2) | 0.001 (2) | 0.009 (3) |
C5 | 0.061 (3) | 0.045 (2) | 0.067 (3) | 0.009 (2) | −0.014 (3) | 0.004 (2) |
C6 | 0.102 (5) | 0.074 (4) | 0.083 (4) | −0.010 (3) | 0.009 (3) | −0.038 (3) |
C7 | 0.077 (4) | 0.132 (6) | 0.084 (4) | −0.017 (4) | −0.030 (3) | −0.001 (4) |
C8 | 0.082 (5) | 0.080 (4) | 0.115 (6) | −0.023 (3) | 0.007 (3) | 0.014 (3) |
C9 | 0.051 (3) | 0.038 (2) | 0.039 (2) | −0.0003 (18) | −0.0064 (19) | 0.0061 (16) |
C11 | 0.124 (6) | 0.220 (8) | 0.060 (4) | 0.046 (6) | 0.023 (4) | 0.047 (5) |
C21 | 0.239 (10) | 0.099 (5) | 0.127 (6) | 0.064 (6) | −0.111 (7) | −0.061 (5) |
C31 | 0.107 (6) | 0.123 (7) | 0.228 (12) | −0.050 (6) | −0.052 (6) | 0.080 (7) |
C41 | 0.074 (5) | 0.204 (10) | 0.117 (6) | 0.052 (5) | 0.024 (4) | 0.028 (6) |
C51 | 0.133 (6) | 0.054 (3) | 0.136 (6) | 0.014 (4) | −0.039 (5) | 0.016 (4) |
Rh1—C4 | 2.179 (4) | C1—C5 | 1.415 (6) |
Rh1—C5 | 2.225 (4) | C1—C2 | 1.453 (8) |
Rh1—C3 | 2.225 (5) | C1—C11 | 1.466 (8) |
Rh1—C2 | 2.228 (5) | C2—C3 | 1.344 (8) |
Rh1—C1 | 2.230 (4) | C2—C21 | 1.522 (8) |
Rh1—P1 | 2.2436 (13) | C3—C4 | 1.419 (9) |
Rh1—C9 | 2.255 (4) | C3—C31 | 1.545 (10) |
Rh1—Cl1 | 2.3764 (18) | C4—C5 | 1.393 (7) |
P1—C8 | 1.807 (6) | C4—C41 | 1.452 (8) |
P1—C7 | 1.822 (6) | C5—C51 | 1.513 (6) |
P1—C6 | 1.823 (5) | ||
C4—Rh1—C5 | 36.86 (18) | C7—P1—Rh1 | 116.3 (2) |
C4—Rh1—C3 | 37.6 (2) | C6—P1—Rh1 | 116.97 (19) |
C5—Rh1—C3 | 61.24 (18) | C5—C1—C2 | 105.1 (4) |
C4—Rh1—C2 | 61.4 (2) | C5—C1—C11 | 128.0 (6) |
C5—Rh1—C2 | 61.50 (17) | C2—C1—C11 | 126.7 (6) |
C3—Rh1—C2 | 35.1 (2) | C5—C1—Rh1 | 71.3 (3) |
C4—Rh1—C1 | 62.45 (18) | C2—C1—Rh1 | 70.9 (3) |
C5—Rh1—C1 | 37.04 (17) | C11—C1—Rh1 | 125.8 (4) |
C3—Rh1—C1 | 61.6 (2) | C3—C2—C1 | 109.3 (5) |
C2—Rh1—C1 | 38.0 (2) | C3—C2—C21 | 127.8 (7) |
C4—Rh1—P1 | 111.05 (16) | C1—C2—C21 | 122.9 (7) |
C5—Rh1—P1 | 99.44 (12) | C3—C2—Rh1 | 72.3 (3) |
C3—Rh1—P1 | 147.3 (2) | C1—C2—Rh1 | 71.1 (3) |
C2—Rh1—P1 | 157.84 (17) | C21—C2—Rh1 | 124.7 (4) |
C1—Rh1—P1 | 119.88 (15) | C2—C3—C4 | 109.0 (5) |
C4—Rh1—C9 | 104.23 (18) | C2—C3—C31 | 127.8 (7) |
C5—Rh1—C9 | 140.56 (17) | C4—C3—C31 | 123.1 (7) |
C3—Rh1—C9 | 91.53 (19) | C2—C3—Rh1 | 72.5 (3) |
C2—Rh1—C9 | 112.8 (2) | C4—C3—Rh1 | 69.5 (3) |
C1—Rh1—C9 | 150.61 (18) | C31—C3—Rh1 | 125.8 (4) |
P1—Rh1—C9 | 89.02 (11) | C5—C4—C3 | 107.4 (5) |
C4—Rh1—Cl1 | 157.51 (15) | C5—C4—C41 | 125.8 (6) |
C5—Rh1—Cl1 | 130.90 (15) | C3—C4—C41 | 125.3 (6) |
C3—Rh1—Cl1 | 124.8 (2) | C5—C4—Rh1 | 73.3 (3) |
C2—Rh1—Cl1 | 96.50 (17) | C3—C4—Rh1 | 73.0 (3) |
C1—Rh1—Cl1 | 98.03 (14) | C41—C4—Rh1 | 130.1 (4) |
P1—Rh1—Cl1 | 87.88 (6) | C4—C5—C1 | 109.0 (4) |
C9—Rh1—Cl1 | 87.55 (12) | C4—C5—C51 | 126.8 (5) |
C8—P1—C7 | 103.3 (3) | C1—C5—C51 | 123.9 (5) |
C8—P1—C6 | 103.2 (3) | C4—C5—Rh1 | 69.8 (3) |
C7—P1—C6 | 102.7 (3) | C1—C5—Rh1 | 71.7 (2) |
C8—P1—Rh1 | 112.6 (2) | C51—C5—Rh1 | 129.5 (4) |
Experimental details
Crystal data | |
Chemical formula | [RhCl(CH3)(C10H15)(C3H9P)] |
Mr | 364.69 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.9295 (18), 14.792 (3), 25.812 (5) |
V (Å3) | 3409.2 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.23 |
Crystal size (mm) | 0.15 × 0.03 × 0.03 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.789, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33212, 5506, 2862 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.744 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.165, 1.00 |
No. of reflections | 5506 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.94, −1.36 |
Computer programs: SMART (Bruker, 1995), SAINT (Bruker, 1995), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.
Rh1—C4 | 2.179 (4) | P1—C8 | 1.807 (6) |
Rh1—C5 | 2.225 (4) | P1—C7 | 1.822 (6) |
Rh1—C3 | 2.225 (5) | P1—C6 | 1.823 (5) |
Rh1—C2 | 2.228 (5) | C1—C5 | 1.415 (6) |
Rh1—C1 | 2.230 (4) | C1—C2 | 1.453 (8) |
Rh1—P1 | 2.2436 (13) | C2—C3 | 1.344 (8) |
Rh1—C9 | 2.255 (4) | C3—C4 | 1.419 (9) |
Rh1—Cl1 | 2.3764 (18) | C4—C5 | 1.393 (7) |
P1—Rh1—C9 | 89.02 (11) | C7—P1—Rh1 | 116.3 (2) |
P1—Rh1—Cl1 | 87.88 (6) | C6—P1—Rh1 | 116.97 (19) |
C9—Rh1—Cl1 | 87.55 (12) | C5—C1—C2 | 105.1 (4) |
C8—P1—C7 | 103.3 (3) | C3—C2—C1 | 109.3 (5) |
C8—P1—C6 | 103.2 (3) | C2—C3—C4 | 109.0 (5) |
C7—P1—C6 | 102.7 (3) | C5—C4—C3 | 107.4 (5) |
C8—P1—Rh1 | 112.6 (2) | C4—C5—C1 | 109.0 (4) |
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.