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Acta Cryst. (2008). E64, m464-m465    [ doi:10.1107/S1600536808003528 ]

trans-Carbonylchloridobis(tri-p-tolylphosphine)rhodium(I) acetone solvate

F. Lorenzini, B. O. Patrick and B. R. James

Abstract top

The title compound, [RhCl(C21H21P)2(CO)]·C3H6O, was precipitated in trace yield from a reaction of RhCl(cod)(THP) with P(p-tol)3 in a 1:1 acetone-d6/CD3OD solution under a hydrogen atmosphere [p-tol = p-tolyl, THP = tris(hydroxymethyl)phosphine, P(CH2OH)3, and cod = 1,5-cyclooctadiene]. The complex displays a square-planar geometry around the RhI atom. The complex molecules and the acetone molecules are linked into a chain along the a axis by intermolecular C-H...Cl and C-H...O hydrogen bonds.

Comment top

We have very recently reported the structure of trans-RhCl(CO)(PEtPh2)2, crystals of which precipitated serendipitously in trace yield from a reaction between PEtPh2 and RhCl(cod)(THP), where cod = 1,5-cyclooctadiene and THP = tris(hydroxymethyl)phosphine, P(CH2OH)3, in an acetone/MeOH solvent mixture under a hydrogen atmosphere (Lorenzini et al., 2008b). Such reaction conditions with a phosphine of general formula PRR'2 (R = or ≠ R') lead to formation of the dihydrido complexes cis,mer-Rh(H)2Cl(PRR'2)3 (when R' = Ph, and R = Me or Cy) (Lorenzini et al., 2008a) or, if the reaction is carried out under Ar, the phosphine–phosphinite derivatives RhCl(PRR'2)[P,P-R'(R)POCH2P(CH2OH)2] and trace amounts of the trans-RhCl(CO)(PRR'2)2 species (Lorenzini et al., 2007b). The THP plays a critical role in formation of the dihydrides and the carbonyl complexes (Lorenzini et al., 2008a); the CO ligand is thought to result from decarbonylation of formaldehyde (Beck et al., 1999), which can be readily formed from transition metal–THP species (Higham et al., 2004; Hoye et al., 1993). A corresponding reaction between the p-tolyl phosphine P(p-tol)3 and RhCl(cod)(THP) has now similarly led to formation of trace amounts of trans-RhCl(CO)[P(p-tol)3]2 that was identified by an X-ray structure as an acetone solvated species. The complex has been synthesized previously in high yield from RhCl3.3H2O (Evans et al., 1990), while the method first reported 50 years ago used [RhCl(CO)2]2 as the precursor (Vallarino, 1957). Our structure is a further example of the 125 or so of the type with a trans-RhCl(CO) moiety associated with two trans phosphorus donor atoms (Cambridge Crystallography Data Base).

Related literature top

For related literature, see: Beck et al. (1999, and references therein); Evans et al. (1990); Higham et al. (2004); Hoye et al. (1993); Lorenzini et al. (2007a,b, 2008a,b); Vallarino (1957).

Experimental top

General. The RhCl(cod)(THP) precursor complex was synthesized by our reported method (Lorenzini et al., 2007a); P(p-tol)3 (a Strem Chemicals product), and the deuterated solvents (Cambridge Isotope Laboratory) were used as received. The reaction between these reagents was performed under Ar or H2 using standard Schlenk techniques. 31P{1H}-NMR spectra were measured in acetone-d6/CD3OD at room temperature (~300 K) on a Bruker AV400 spectrometer, relative to external 85% aq H3PO4.

trans-RhCl(CO)[P(p-tol)3]2.(CH3)2CO. P(p-tol)3 (18.3 µl, 0.059 mmol) in acetone-d6 (0.3 ml) was added to a yellow CD3OD solution (0.3 ml) of RhCl(cod)(THP) (10.2 mg, 0.028 mmol) at room temperature under Ar to give rapid formation of a brown solution. Replacement of the Ar by H2 and subsequent shaking of the vessel resulted in a yellow solution. Over 12 h, a minute quantity of X-ray quality, yellow prism crystals of trans-RhCl(CO)[P(p-tol)3]2.(CH3)2CO deposited from the solution; the 31P{1H} spectrum of the solution revealed a complex mixture of species.

Refinement top

H atoms were placed in calculated positions [C—H = 0.95 Å (aromatic) and 0.98 Å (methyl)] and refined using a riding-model approximation, with Uiso(H) = 1.2eq(C) and 1.5eq(Cmethyl).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1.  
trans-Carbonylchloridobis(tri-p-tolylphosphine)rhodium(I) acetone solvate top
Crystal data top
[RhCl(C21H21P)2(CO)]·C3H6OZ = 2
Mr = 833.14F000 = 864
Triclinic, P1Dx = 1.308 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 10.784 (2) ÅCell parameters from 5165 reflections
b = 12.859 (3) Åθ = 2.5–25.0º
c = 17.086 (3) ŵ = 0.58 mm−1
α = 70.852 (7)ºT = 173 (2) K
β = 84.790 (7)ºPrism, yellow
γ = 71.012 (6)º0.25 × 0.10 × 0.07 mm
V = 2116.2 (7) Å3
Data collection top
Bruker X8 APEXII
diffractometer		9909 independent reflections
Radiation source: fine-focus sealed tube6378 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.063
T = 173(2) Kθmax = 27.8º
area detector scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −14→14
Tmin = 0.683, Tmax = 0.960k = −16→16
31662 measured reflectionsl = −17→22
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)] = 0.047H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.045P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.008
9909 reflectionsΔρmax = 0.48 e Å−3
477 parametersΔρmin = −0.44 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[RhCl(C21H21P)2(CO)]·C3H6Oγ = 71.012 (6)º
Mr = 833.14V = 2116.2 (7) Å3
Triclinic, P1Z = 2
a = 10.784 (2) ÅMo Kα
b = 12.859 (3) ŵ = 0.58 mm−1
c = 17.086 (3) ÅT = 173 (2) K
α = 70.852 (7)º0.25 × 0.10 × 0.07 mm
β = 84.790 (7)º
Data collection top
Bruker X8 APEXII
diffractometer		9909 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		6378 reflections with I > 2σ(I)
Tmin = 0.683, Tmax = 0.960Rint = 0.063
31662 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047477 parameters
wR(F2) = 0.115H-atom parameters constrained
S = 1.00Δρmax = 0.48 e Å−3
9909 reflectionsΔρmin = −0.44 e Å−3
Special details top

Experimental. The molecule crystallizes with one molecule of acetone in the asymmetric unit.

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 > 2σ(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
C10.5990 (3)0.2216 (3)0.5635 (2)0.0401 (8)
C20.5919 (4)0.2248 (4)0.4811 (2)0.0593 (11)
H20.65410.24820.44220.071*
C30.4926 (4)0.1932 (4)0.4566 (3)0.0626 (12)
H30.48850.19610.40060.075*
C40.4011 (4)0.1583 (3)0.5109 (3)0.0500 (10)
C50.4086 (4)0.1555 (3)0.5919 (2)0.0497 (9)
H50.34620.13160.63050.060*
C60.5058 (4)0.1871 (3)0.6184 (2)0.0444 (9)
H60.50820.18500.67430.053*
C70.2945 (4)0.1269 (4)0.4820 (3)0.0721 (13)
H7A0.23630.19590.44240.108*
H7B0.24390.09690.52970.108*
H7C0.33390.06730.45520.108*
C80.8679 (3)0.1195 (3)0.6269 (2)0.0376 (8)
C90.9652 (4)0.1031 (3)0.6818 (2)0.0524 (10)
H90.95930.16240.70480.063*
C101.0716 (4)0.0011 (4)0.7039 (2)0.0647 (12)
H101.1376−0.00740.74080.078*
C111.0815 (4)−0.0885 (3)0.6721 (2)0.0580 (11)
C120.9877 (4)−0.0710 (3)0.6161 (2)0.0568 (11)
H120.9946−0.12970.59230.068*
C130.8816 (4)0.0319 (3)0.5932 (2)0.0482 (9)
H130.81820.04170.55400.058*
C141.1942 (5)−0.2021 (4)0.6995 (3)0.0964 (19)
H14A1.1901−0.23890.75930.145*
H14B1.2779−0.18620.68630.145*
H14C1.1870−0.25410.67030.145*
C150.7857 (3)0.3500 (3)0.5080 (2)0.0384 (8)
C160.6944 (4)0.4489 (3)0.4564 (2)0.0509 (9)
H160.60320.45850.46240.061*
C170.7368 (4)0.5328 (3)0.3964 (2)0.0555 (11)
H170.67340.59880.36190.067*
C180.8699 (4)0.5233 (3)0.3852 (2)0.0502 (10)
C190.9593 (4)0.4223 (3)0.4345 (2)0.0537 (10)
H191.05050.41120.42700.064*
C200.9183 (4)0.3373 (3)0.4947 (2)0.0453 (9)
H200.98200.26940.52710.054*
C210.9137 (5)0.6199 (3)0.3232 (3)0.0717 (13)
H21A1.00190.61360.33850.107*
H21B0.85250.69520.32340.107*
H21C0.91510.61300.26760.107*
C220.4778 (3)0.4089 (2)0.8594 (2)0.0339 (7)
C230.3779 (4)0.4611 (3)0.7984 (2)0.0450 (9)
H230.39920.49060.74190.054*
C240.2485 (4)0.4700 (3)0.8197 (2)0.0499 (9)
H240.18250.50660.77740.060*
C250.2130 (4)0.4271 (3)0.9009 (3)0.0510 (10)
C260.3112 (4)0.3759 (3)0.9616 (2)0.0513 (10)
H260.28880.34661.01780.062*
C270.4431 (4)0.3664 (3)0.9419 (2)0.0434 (9)
H270.50850.33110.98450.052*
C280.0725 (4)0.4330 (4)0.9218 (3)0.0729 (13)
H28A0.01580.51360.90090.109*
H28B0.06430.40360.98210.109*
H28C0.04590.38550.89610.109*
C290.6443 (3)0.5526 (2)0.80580 (19)0.0338 (7)
C300.5354 (4)0.6404 (3)0.8164 (2)0.0430 (9)
H300.45550.62450.83420.052*
C310.5418 (4)0.7522 (3)0.8012 (2)0.0520 (10)
H310.46550.81170.80750.062*
C320.6576 (4)0.7778 (3)0.7771 (2)0.0489 (10)
C330.7671 (4)0.6893 (3)0.7667 (2)0.0543 (10)
H330.84740.70500.74980.065*
C340.7607 (4)0.5780 (3)0.7807 (2)0.0462 (9)
H340.83640.51890.77300.055*
C350.6639 (5)0.8986 (3)0.7602 (3)0.0728 (14)
H35A0.60540.95210.71330.109*
H35B0.75400.89920.74690.109*
H35C0.63630.92300.80940.109*
C360.7593 (3)0.3203 (3)0.91027 (19)0.0358 (8)
C370.7520 (3)0.3574 (3)0.9795 (2)0.0404 (8)
H370.68270.42370.98330.048*
C380.8462 (4)0.2972 (3)1.0428 (2)0.0495 (9)
H380.83900.32241.08990.059*
C390.9505 (4)0.2012 (3)1.0386 (2)0.0546 (10)
C400.9580 (4)0.1654 (3)0.9697 (2)0.0545 (10)
H401.02870.10010.96580.065*
C410.8637 (3)0.2234 (3)0.9056 (2)0.0445 (9)
H410.87060.19710.85900.053*
C421.0588 (5)0.1410 (4)1.1040 (3)0.0855 (16)
H42A1.08310.05691.11590.128*
H42B1.02810.16051.15470.128*
H42C1.13540.16651.08370.128*
C430.7044 (4)0.4689 (3)0.6425 (2)0.0429 (8)
C440.3191 (5)0.0384 (4)0.8769 (3)0.0736 (13)
C450.3625 (8)−0.0618 (5)0.9469 (4)0.163 (3)
H45A0.3399−0.12560.93910.245*
H45B0.3198−0.04530.99660.245*
H45C0.4578−0.08360.95350.245*
C460.3191 (6)0.1494 (4)0.8789 (4)0.122 (2)
H46A0.39960.16440.85400.183*
H46B0.31480.14930.93650.183*
H46C0.24280.21010.84760.183*
O10.7199 (3)0.5543 (2)0.60038 (16)0.0644 (8)
O20.2868 (6)0.0305 (5)0.8141 (3)0.174 (2)
P10.73025 (9)0.25561 (7)0.60066 (5)0.0366 (2)
P20.64329 (8)0.40376 (6)0.82266 (5)0.0322 (2)
Cl10.65594 (10)0.15903 (7)0.80268 (5)0.0504 (2)
Rh10.68398 (3)0.33396 (2)0.710084 (16)0.03563 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.042 (2)0.0352 (18)0.042 (2)−0.0043 (16)−0.0072 (17)−0.0173 (16)
C20.058 (3)0.082 (3)0.049 (2)−0.023 (2)0.005 (2)−0.036 (2)
C30.062 (3)0.083 (3)0.056 (3)−0.021 (2)−0.010 (2)−0.039 (2)
C40.045 (2)0.042 (2)0.064 (3)−0.0063 (18)−0.015 (2)−0.0221 (19)
C50.048 (2)0.0373 (19)0.060 (3)−0.0108 (17)−0.0059 (19)−0.0121 (18)
C60.052 (2)0.0347 (18)0.045 (2)−0.0094 (17)−0.0073 (18)−0.0127 (16)
C70.061 (3)0.071 (3)0.093 (3)−0.018 (2)−0.026 (3)−0.032 (3)
C80.041 (2)0.0357 (18)0.0349 (19)−0.0133 (15)0.0020 (16)−0.0092 (15)
C90.059 (3)0.050 (2)0.050 (2)−0.014 (2)−0.009 (2)−0.0178 (19)
C100.052 (3)0.074 (3)0.050 (3)−0.004 (2)−0.014 (2)−0.008 (2)
C110.058 (3)0.051 (2)0.042 (2)0.002 (2)0.007 (2)−0.0048 (19)
C120.073 (3)0.037 (2)0.051 (2)−0.004 (2)0.009 (2)−0.0171 (18)
C130.057 (2)0.044 (2)0.044 (2)−0.0122 (19)−0.0021 (18)−0.0185 (17)
C140.092 (4)0.081 (3)0.060 (3)0.030 (3)0.008 (3)−0.008 (3)
C150.045 (2)0.0369 (18)0.0330 (19)−0.0080 (16)−0.0008 (16)−0.0153 (15)
C160.047 (2)0.056 (2)0.039 (2)−0.0055 (19)0.0022 (18)−0.0115 (18)
C170.072 (3)0.042 (2)0.035 (2)−0.001 (2)−0.004 (2)−0.0052 (17)
C180.069 (3)0.039 (2)0.042 (2)−0.018 (2)0.002 (2)−0.0110 (17)
C190.052 (2)0.047 (2)0.058 (3)−0.0141 (19)0.003 (2)−0.014 (2)
C200.051 (2)0.0350 (18)0.044 (2)−0.0099 (17)−0.0031 (18)−0.0073 (16)
C210.096 (4)0.054 (3)0.061 (3)−0.028 (3)0.004 (3)−0.008 (2)
C220.044 (2)0.0234 (15)0.0396 (19)−0.0116 (14)−0.0024 (16)−0.0148 (14)
C230.053 (2)0.046 (2)0.042 (2)−0.0219 (18)−0.0039 (18)−0.0140 (17)
C240.046 (2)0.048 (2)0.059 (3)−0.0163 (18)−0.0058 (19)−0.0172 (19)
C250.051 (2)0.048 (2)0.067 (3)−0.0218 (19)0.011 (2)−0.032 (2)
C260.061 (3)0.048 (2)0.050 (2)−0.024 (2)0.009 (2)−0.0179 (19)
C270.058 (2)0.0387 (19)0.039 (2)−0.0208 (18)−0.0018 (18)−0.0134 (16)
C280.061 (3)0.086 (3)0.090 (3)−0.037 (3)0.020 (3)−0.042 (3)
C290.046 (2)0.0251 (15)0.0323 (18)−0.0110 (15)−0.0060 (15)−0.0097 (13)
C300.049 (2)0.0307 (17)0.052 (2)−0.0097 (16)−0.0042 (18)−0.0186 (16)
C310.063 (3)0.0278 (17)0.064 (3)−0.0041 (18)−0.014 (2)−0.0193 (17)
C320.073 (3)0.0269 (17)0.048 (2)−0.0181 (19)−0.022 (2)−0.0059 (16)
C330.064 (3)0.041 (2)0.064 (3)−0.029 (2)−0.009 (2)−0.0082 (19)
C340.046 (2)0.0339 (18)0.061 (2)−0.0130 (17)−0.0028 (18)−0.0166 (17)
C350.103 (4)0.0286 (19)0.087 (3)−0.024 (2)−0.035 (3)−0.006 (2)
C360.044 (2)0.0261 (16)0.0368 (19)−0.0108 (15)−0.0026 (15)−0.0084 (14)
C370.047 (2)0.0356 (18)0.038 (2)−0.0117 (16)−0.0026 (17)−0.0117 (15)
C380.059 (3)0.054 (2)0.037 (2)−0.021 (2)−0.0058 (18)−0.0114 (18)
C390.054 (3)0.050 (2)0.053 (2)−0.017 (2)−0.011 (2)−0.0023 (19)
C400.052 (2)0.0330 (19)0.069 (3)−0.0040 (18)−0.006 (2)−0.0101 (19)
C410.047 (2)0.0332 (18)0.054 (2)−0.0105 (17)−0.0046 (18)−0.0162 (17)
C420.077 (3)0.093 (4)0.064 (3)−0.014 (3)−0.030 (3)0.001 (3)
C430.053 (2)0.0378 (19)0.040 (2)−0.0105 (17)0.0023 (17)−0.0192 (17)
C440.086 (4)0.065 (3)0.079 (3)−0.020 (3)−0.011 (3)−0.035 (3)
C450.255 (10)0.069 (4)0.099 (5)−0.003 (5)0.012 (5)0.008 (4)
C460.131 (5)0.068 (4)0.176 (6)−0.039 (4)0.006 (5)−0.044 (4)
O10.098 (2)0.0425 (15)0.0528 (17)−0.0303 (16)0.0102 (16)−0.0095 (13)
O20.221 (6)0.186 (5)0.152 (5)−0.071 (4)−0.059 (4)−0.078 (4)
P10.0443 (5)0.0336 (5)0.0346 (5)−0.0106 (4)−0.0017 (4)−0.0153 (4)
P20.0424 (5)0.0236 (4)0.0335 (5)−0.0105 (4)−0.0028 (4)−0.0116 (3)
Cl10.0841 (7)0.0353 (4)0.0416 (5)−0.0291 (5)0.0002 (5)−0.0145 (4)
Rh10.04978 (18)0.02744 (14)0.03398 (16)−0.01380 (12)0.00046 (12)−0.01354 (11)
Geometric parameters (Å, °) top
C1—C61.390 (5)C25—C261.389 (5)
C1—C21.403 (5)C25—C281.508 (5)
C1—P11.830 (3)C26—C271.407 (5)
C2—C31.401 (5)C26—H260.95
C2—H20.95C27—H270.95
C3—C41.373 (5)C28—H28A0.98
C3—H30.95C28—H28B0.98
C4—C51.382 (5)C28—H28C0.98
C4—C71.505 (5)C29—C301.386 (4)
C5—C61.397 (5)C29—C341.395 (5)
C5—H50.95C29—P21.843 (3)
C6—H60.95C30—C311.399 (4)
C7—H7A0.98C30—H300.95
C7—H7B0.98C31—C321.387 (5)
C7—H7C0.98C31—H310.95
C8—C131.387 (4)C32—C331.394 (5)
C8—C91.389 (5)C32—C351.506 (4)
C8—P11.840 (3)C33—C341.396 (4)
C9—C101.397 (5)C33—H330.95
C9—H90.95C34—H340.95
C10—C111.399 (6)C35—H35A0.98
C10—H100.95C35—H35B0.98
C11—C121.368 (5)C35—H35C0.98
C11—C141.526 (5)C36—C371.400 (4)
C12—C131.404 (5)C36—C411.401 (4)
C12—H120.95C36—P21.836 (3)
C13—H130.95C37—C381.392 (5)
C14—H14A0.98C37—H370.95
C14—H14B0.98C38—C391.391 (5)
C14—H14C0.98C38—H380.95
C15—C201.391 (5)C39—C401.385 (5)
C15—C161.405 (5)C39—C421.515 (5)
C15—P11.837 (3)C40—C411.401 (5)
C16—C171.391 (5)C40—H400.95
C16—H160.95C41—H410.95
C17—C181.400 (5)C42—H42A0.98
C17—H170.95C42—H42B0.98
C18—C191.393 (5)C42—H42C0.98
C18—C211.523 (5)C43—O11.154 (4)
C19—C201.394 (5)C43—Rh11.812 (4)
C19—H190.95C44—O21.203 (6)
C20—H200.95C44—C451.417 (6)
C21—H21A0.98C44—C461.438 (6)
C21—H21B0.98C45—H45A0.98
C21—H21C0.98C45—H45B0.98
C22—C271.398 (4)C45—H45C0.98
C22—C231.405 (5)C46—H46A0.98
C22—P21.825 (3)C46—H46B0.98
C23—C241.387 (5)C46—H46C0.98
C23—H230.95P1—Rh12.3449 (9)
C24—C251.385 (5)P2—Rh12.3283 (9)
C24—H240.95Cl1—Rh12.3822 (9)
C6—C1—C2118.3 (3)C26—C27—H27120.0
C6—C1—P1119.8 (3)C25—C28—H28A109.5
C2—C1—P1121.9 (3)C25—C28—H28B109.5
C3—C2—C1119.7 (4)H28A—C28—H28B109.5
C3—C2—H2120.2C25—C28—H28C109.5
C1—C2—H2120.2H28A—C28—H28C109.5
C4—C3—C2122.1 (4)H28B—C28—H28C109.5
C4—C3—H3119.0C30—C29—C34118.4 (3)
C2—C3—H3119.0C30—C29—P2123.4 (3)
C3—C4—C5117.9 (3)C34—C29—P2118.1 (2)
C3—C4—C7120.6 (4)C29—C30—C31120.7 (3)
C5—C4—C7121.5 (4)C29—C30—H30119.7
C4—C5—C6121.5 (4)C31—C30—H30119.7
C4—C5—H5119.2C32—C31—C30121.2 (3)
C6—C5—H5119.2C32—C31—H31119.4
C1—C6—C5120.5 (3)C30—C31—H31119.4
C1—C6—H6119.7C31—C32—C33118.0 (3)
C5—C6—H6119.7C31—C32—C35121.1 (4)
C4—C7—H7A109.5C33—C32—C35120.9 (4)
C4—C7—H7B109.5C32—C33—C34121.0 (4)
H7A—C7—H7B109.5C32—C33—H33119.5
C4—C7—H7C109.5C34—C33—H33119.5
H7A—C7—H7C109.5C29—C34—C33120.6 (3)
H7B—C7—H7C109.5C29—C34—H34119.7
C13—C8—C9117.6 (3)C33—C34—H34119.7
C13—C8—P1123.2 (3)C32—C35—H35A109.5
C9—C8—P1119.2 (3)C32—C35—H35B109.5
C8—C9—C10121.4 (4)H35A—C35—H35B109.5
C8—C9—H9119.3C32—C35—H35C109.5
C10—C9—H9119.3H35A—C35—H35C109.5
C9—C10—C11120.4 (4)H35B—C35—H35C109.5
C9—C10—H10119.8C37—C36—C41118.8 (3)
C11—C10—H10119.8C37—C36—P2121.0 (2)
C12—C11—C10118.1 (4)C41—C36—P2120.0 (3)
C12—C11—C14121.6 (4)C38—C37—C36120.1 (3)
C10—C11—C14120.4 (4)C38—C37—H37119.9
C11—C12—C13121.5 (4)C36—C37—H37119.9
C11—C12—H12119.2C39—C38—C37121.5 (3)
C13—C12—H12119.2C39—C38—H38119.2
C8—C13—C12120.9 (3)C37—C38—H38119.2
C8—C13—H13119.6C40—C39—C38118.2 (3)
C12—C13—H13119.6C40—C39—C42119.9 (4)
C11—C14—H14A109.5C38—C39—C42121.8 (4)
C11—C14—H14B109.5C39—C40—C41121.5 (3)
H14A—C14—H14B109.5C39—C40—H40119.2
C11—C14—H14C109.5C41—C40—H40119.2
H14A—C14—H14C109.5C36—C41—C40119.8 (3)
H14B—C14—H14C109.5C36—C41—H41120.1
C20—C15—C16117.9 (3)C40—C41—H41120.1
C20—C15—P1121.3 (3)C39—C42—H42A109.5
C16—C15—P1120.0 (3)C39—C42—H42B109.5
C17—C16—C15120.2 (4)H42A—C42—H42B109.5
C17—C16—H16119.9C39—C42—H42C109.5
C15—C16—H16119.9H42A—C42—H42C109.5
C16—C17—C18122.2 (3)H42B—C42—H42C109.5
C16—C17—H17118.9O1—C43—Rh1178.5 (3)
C18—C17—H17118.9O2—C44—C45120.1 (5)
C19—C18—C17116.7 (3)O2—C44—C46119.4 (6)
C19—C18—C21121.9 (4)C45—C44—C46120.5 (5)
C17—C18—C21121.3 (4)C44—C45—H45A109.5
C18—C19—C20121.7 (4)C44—C45—H45B109.5
C18—C19—H19119.2H45A—C45—H45B109.5
C20—C19—H19119.2C44—C45—H45C109.5
C15—C20—C19121.2 (3)H45A—C45—H45C109.5
C15—C20—H20119.4H45B—C45—H45C109.5
C19—C20—H20119.4C44—C46—H46A109.5
C18—C21—H21A109.5C44—C46—H46B109.5
C18—C21—H21B109.5H46A—C46—H46B109.5
H21A—C21—H21B109.5C44—C46—H46C109.5
C18—C21—H21C109.5H46A—C46—H46C109.5
H21A—C21—H21C109.5H46B—C46—H46C109.5
H21B—C21—H21C109.5C1—P1—C15105.08 (16)
C27—C22—C23118.2 (3)C1—P1—C8104.96 (15)
C27—C22—P2125.8 (3)C15—P1—C8103.74 (15)
C23—C22—P2115.9 (3)C1—P1—Rh1117.85 (12)
C24—C23—C22120.6 (3)C15—P1—Rh1112.37 (10)
C24—C23—H23119.7C8—P1—Rh1111.61 (11)
C22—C23—H23119.7C22—P2—C36108.70 (15)
C25—C24—C23121.8 (4)C22—P2—C29102.88 (14)
C25—C24—H24119.1C36—P2—C29101.69 (14)
C23—C24—H24119.1C22—P2—Rh1109.37 (10)
C24—C25—C26117.9 (4)C36—P2—Rh1115.03 (11)
C24—C25—C28120.6 (4)C29—P2—Rh1118.15 (11)
C26—C25—C28121.5 (4)C43—Rh1—P291.43 (10)
C25—C26—C27121.6 (4)C43—Rh1—P190.55 (10)
C25—C26—H26119.2P2—Rh1—P1177.46 (3)
C27—C26—H26119.2C43—Rh1—Cl1178.12 (10)
C22—C27—C26119.9 (3)P2—Rh1—Cl186.69 (3)
C22—C27—H27120.0P1—Rh1—Cl191.33 (3)
C6—C1—C2—C3−0.2 (6)C37—C38—C39—C42175.2 (4)
P1—C1—C2—C3177.3 (3)C38—C39—C40—C41−0.1 (6)
C1—C2—C3—C4−0.3 (6)C42—C39—C40—C41−176.1 (4)
C2—C3—C4—C50.4 (6)C37—C36—C41—C400.2 (5)
C2—C3—C4—C7179.0 (4)P2—C36—C41—C40174.9 (3)
C3—C4—C5—C60.1 (5)C39—C40—C41—C360.4 (6)
C7—C4—C5—C6−178.6 (3)C6—C1—P1—C15−157.5 (3)
C2—C1—C6—C50.6 (5)C2—C1—P1—C1525.0 (3)
P1—C1—C6—C5−176.9 (2)C6—C1—P1—C893.4 (3)
C4—C5—C6—C1−0.5 (5)C2—C1—P1—C8−84.0 (3)
C13—C8—C9—C10−1.4 (6)C6—C1—P1—Rh1−31.5 (3)
P1—C8—C9—C10179.8 (3)C2—C1—P1—Rh1151.1 (3)
C8—C9—C10—C11−1.2 (6)C20—C15—P1—C1−138.6 (3)
C9—C10—C11—C123.0 (6)C16—C15—P1—C152.1 (3)
C9—C10—C11—C14−177.1 (4)C20—C15—P1—C8−28.7 (3)
C10—C11—C12—C13−2.3 (6)C16—C15—P1—C8162.0 (3)
C14—C11—C12—C13177.7 (4)C20—C15—P1—Rh192.0 (3)
C9—C8—C13—C122.1 (5)C16—C15—P1—Rh1−77.3 (3)
P1—C8—C13—C12−179.2 (3)C13—C8—P1—C123.0 (3)
C11—C12—C13—C8−0.2 (6)C9—C8—P1—C1−158.4 (3)
C20—C15—C16—C17−2.6 (5)C13—C8—P1—C15−87.1 (3)
P1—C15—C16—C17167.0 (3)C9—C8—P1—C1591.6 (3)
C15—C16—C17—C18−0.4 (6)C13—C8—P1—Rh1151.7 (3)
C16—C17—C18—C193.0 (5)C9—C8—P1—Rh1−29.6 (3)
C16—C17—C18—C21−175.8 (3)C27—C22—P2—C365.7 (3)
C17—C18—C19—C20−2.7 (5)C23—C22—P2—C36−174.6 (2)
C21—C18—C19—C20176.1 (3)C27—C22—P2—C29−101.5 (3)
C16—C15—C20—C192.9 (5)C23—C22—P2—C2978.1 (3)
P1—C15—C20—C19−166.6 (3)C27—C22—P2—Rh1132.1 (2)
C18—C19—C20—C15−0.2 (5)C23—C22—P2—Rh1−48.3 (2)
C27—C22—C23—C240.0 (5)C37—C36—P2—C22−61.6 (3)
P2—C22—C23—C24−179.7 (2)C41—C36—P2—C22123.7 (3)
C22—C23—C24—C25−0.8 (5)C37—C36—P2—C2946.4 (3)
C23—C24—C25—C261.1 (5)C41—C36—P2—C29−128.2 (3)
C23—C24—C25—C28−177.2 (3)C37—C36—P2—Rh1175.4 (2)
C24—C25—C26—C27−0.7 (5)C41—C36—P2—Rh10.8 (3)
C28—C25—C26—C27177.6 (3)C30—C29—P2—C22−3.3 (3)
C23—C22—C27—C260.5 (5)C34—C29—P2—C22177.0 (3)
P2—C22—C27—C26−179.9 (2)C30—C29—P2—C36−115.8 (3)
C25—C26—C27—C22−0.1 (5)C34—C29—P2—C3664.5 (3)
C34—C29—C30—C310.8 (5)C30—C29—P2—Rh1117.3 (3)
P2—C29—C30—C31−178.9 (3)C34—C29—P2—Rh1−62.4 (3)
C29—C30—C31—C32−1.6 (6)C22—P2—Rh1—C43117.67 (16)
C30—C31—C32—C331.4 (6)C36—P2—Rh1—C43−119.70 (16)
C30—C31—C32—C35179.5 (3)C29—P2—Rh1—C430.54 (17)
C31—C32—C33—C34−0.5 (6)C22—P2—Rh1—Cl1−62.38 (11)
C35—C32—C33—C34−178.6 (4)C36—P2—Rh1—Cl160.25 (12)
C30—C29—C34—C330.1 (5)C29—P2—Rh1—Cl1−179.51 (12)
P2—C29—C34—C33179.8 (3)C1—P1—Rh1—C43−114.47 (17)
C32—C33—C34—C29−0.2 (6)C15—P1—Rh1—C437.91 (16)
C41—C36—C37—C38−1.0 (5)C8—P1—Rh1—C43123.98 (16)
P2—C36—C37—C38−175.7 (3)C1—P1—Rh1—Cl165.64 (13)
C36—C37—C38—C391.3 (5)C15—P1—Rh1—Cl1−171.98 (12)
C37—C38—C39—C40−0.7 (6)C8—P1—Rh1—Cl1−55.92 (12)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O2i0.952.383.302 (8)163
C46—H46A···Cl10.982.813.773 (7)168
Symmetry codes: (i) x+1, y, z.
Table 1
Selected geometric parameters (Å, °) top
C43—Rh11.812 (4)P2—Rh12.3283 (9)
P1—Rh12.3449 (9)Cl1—Rh12.3822 (9)
C43—Rh1—P291.43 (10)C43—Rh1—Cl1178.12 (10)
C43—Rh1—P190.55 (10)P2—Rh1—Cl186.69 (3)
P2—Rh1—P1177.46 (3)P1—Rh1—Cl191.33 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O2i0.952.383.302 (8)163
C46—H46A···Cl10.982.813.773 (7)168
Symmetry codes: (i) x+1, y, z.
references
References top

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