metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 4| April 2008| Pages m512-m513

Chloridotris[tris­­(4-fluoro­phen­yl)phosphine]rhodium(I) methanol solvate

aDepartment of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, Canada BC V6T 1Z1
*Correspondence e-mail: brj@chem.ubc.ca

(Received 15 January 2008; accepted 26 February 2008; online 5 March 2008)

In the title compound, [RhCl{P(p-FC6H4)3}3]·CH3OH, the Rh atom adopts a distorted square-planar geometry. Rh, Cl and one P atom lie on a mirror plane, as does the solvent molecule. There are two inter­molecular hydrogen bonds, one between the methanol O atom and an aryl H atom (2.51 Å), and one between the Cl atom and the hydr­oxy H atom of methanol [2.34 (3) Å]. The complex precipitates in trace amounts from a reaction between RhCl(cod)(thp) [cod is 1,5-cyclo­octa­diene and thp is tris­(hydroxy­meth­yl)phos­phine] and P(p-FC6H4)3 under argon in CD3OD. Two C6H4-F units are disordered over two positions; for one the site occupancy factors are ca. 0.53 and 0.47, for the other the values are ca. 0.64 and 0.36. The methyl H atoms of the solvent molecule are disordered across the mirror plane.

Related literature

For related literature, see: Beck et al. (1999[Beck, C. M., Rathmill, S. E., Park, Y. J., Chen, J., Crabtree, R. H., Liable-Sands, L. M. & Rheingold, A. L. (1999). Organometallics, 18, 5311-5317.]) and references therein; Bennett & Donaldson (1977[Bennett, M. J. & Donaldson, P. B. (1977). Inorg. Chem. 16, 655-660.]); Bennett et al. (1971[Bennett, M. A., Robertson, G. B., Turney, T. W. & Whimp, P. O. (1971). J. Chem. Soc. D, pp. 762-764.]); Evans et al. (1999[Evans, P. A., Incarvito, C. D. & Rheingold, A. L. (1999). Private communication (deposition number: 115178). CCDC, Cambridge, England.]); Higham et al. (2004[Higham, L. J., Whittlesey, M. K. & Wood, P. T. (2004). J. Chem. Soc. Dalton Trans. pp. 4202-4208.]); Hoye et al. (1993[Hoye, P. A. T., Pringle, P. G., Smith, M. B. & Worboys, K. (1993). J. Chem. Soc. Dalton Trans. pp. 269-274.]); Jones et al. (1980[Jones, R. A., Real, F. M., Wilkinson, G., Galas, A. M. R., Hursthouse, M. B. & Malik, K. M. A. (1980). J. Chem. Soc. Dalton Trans. pp. 511-518.]); Lorenzini et al. (2007a[Lorenzini, F., Patrick, B. O. & James, B. R. (2007a). J. Chem. Soc. Dalton Trans. pp. 3224-3226.],b[Lorenzini, F., Patrick, B. O. & James, B. R. (2007b). Inorg. Chem. 46, 8998-9002.],c[Lorenzini, F., Patrick, B. O. & James, B. R. (2007c). Inorg. Chim. Acta, doi:10.1016/j.ica.2007.10.044.], 2008a[Lorenzini, F., Patrick, B. O. & James, B. R. (2008a). Acta Cryst. E64, m179-m180.],b[Lorenzini, F., Patrick, B. O. & James, B. R. (2008b). Acta Cryst. E64, m464-m465.]); Montelatici et al. (1968[Montelatici, S., van der Ent, A., Osborn, J. A. & Wilkinson, G. (1968). J. Chem. Soc. A, pp. 1054-1058.]); Young et al. (1965[Young, J. F., Osborn, J. A., Jardine, F. H. & Wilkinson, G. (1965). Chem. Commun. pp. 131-132.]).

[Scheme 1]

Experimental

Crystal data
  • [RhCl(C18H12F3P)3]·CH4O

  • Mr = 1119.14

  • Monoclinic, C m

  • a = 10.831 (3) Å

  • b = 23.724 (7) Å

  • c = 9.845 (3) Å

  • β = 108.213 (8)°

  • V = 2403.0 (12) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.59 mm−1

  • T = 173.0 (1) K

  • 0.30 × 0.15 × 0.03 mm

Data collection
  • Bruker X8 APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2003[Bruker (2003). SADABS. and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.544, Tmax = 0.983

  • 10921 measured reflections

  • 3312 independent reflections

  • 3094 reflections with I > 2σ(I)

  • Rint = 0.048

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.075

  • S = 1.03

  • 3312 reflections

  • 372 parameters

  • 15 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.67 e Å−3

  • Δρmin = −0.47 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 812 Friedel pairs

  • Flack parameter: −0.03 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3⋯O1i 0.95 2.51 3.458 (9) 172
O1—H1O⋯Cl1ii 1.03 (5) 2.34 (5) 3.369 (9) 174 (11)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z-1.

Data collection: SAINT (Bruker, 2003[Bruker (2003). SADABS. and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

We have reported recently on the syntheses of water-soluble RhI–thp complexes such as RhCl(cod)(thp), where thp = tris(hydroxymethyl)phosphine, P(CH2OH)3, and cod = 1,5-cyclooctadiene (Lorenzini et al., 2007a). This complex reacts with PRR'2 phosphines (R = or ≠ R') in solution under Ar to generate, concomitantly with R'H, the phosphine-phosphinite derivatives RhCl(PRR'2)[P,P-R'(R)POCH2P(CH2OH)2] in two isomeric cis- and trans-forms, where cis and trans refer to the disposition of the P atoms with the R and R' substituents. In some of these systems, trace amounts of the trans-RhCl(CO)(PRR'2)2 complexes are formed (Lorenzini et al., 2007b), and these have been characterized by X-ray crystallography, for example, for the PEtPh2 and P(p-tolyl)3 systems (Lorenzini et al., 2008b; Lorenzini et al., submitted). The CO ligand almost certainly derives from the formaldehyde (Beck et al., 1999), which can be readily formed from transition metal–thp species (Higham et al., 2004; Hoye et al., 1993). The RhCl(cod)(thp)/phosphine reactions, when carried out under H2, give high yield formation of the dihydrido complexes cis,mer-Rh(H)2Cl(PRR'2)3 (where R' = Ph, and R = Me or Cy), although in some systems (e.g. with PMePh2) partial loss of H2 occurs and the RhCl(PRR'2)3 species has been detected in solution (Lorenzini et al., 2007c). Now, during a reaction of the Rh precursor with P(p-FC6H4)3 in MeOH under Ar, we have found that a few crystals of RhCl[P(p-FC6H4)3]3.CH3OH in low overall yield are precipitated.

The so-called "Wilkinson" hydrogenation catalyst, RhCl(PPh3)3, was first reported in 1965 (Young et al., 1965), and since then 22 Rh(I) complexes of general formula RhCl(PRR'2)3 have been structurally characterized; the first such complex was RhCl(PF2NEt2)2(PPh3) (Bennett et al., 1971), while there are just 3 of the type RhCl(PR3)3 where R = Ph (Bennett & Donaldson, 1977), Me (Jones et al., 1980) and OPh (Evans et al., 1999). The title P(p-FC6H4)3 complex was first isolated in 1968 (Montelatici et al., 1968), but an X-ray structure has not been reported.

Related literature top

For related literature, see: Beck et al. (1999) and references therein; Bennett & Donaldson (1977); Bennett et al. (1971); Evans et al. (1999); Higham et al. (2004); Hoye et al. (1993); Jones et al. (1980); Lorenzini et al. (2007a,b,c, 2008a,b); Montelatici et al. (1968); Young et al. (1965).

Experimental top

General. The RhCl(1,5-cod)(thp) complex was synthesized by our recently reported method (Lorenzini et al., 2007a); P(p-FC6H4)3 was used as received from Strem Chemicals, CD3OD (Cambridge Isotope Laboratory) was used as received. The Rh-phosphine reaction was carried out under Ar using standard Schlenk techniques.

RhCl[P(p-FC6H4)3]3.CH3OH. Addition of P(p-FC6H4)3 (10 mg, 0.031 mmol) in CD3OD (0.5 ml) to a yellow CD3OD solution (0.5 ml) of RhCl(1,5-cod)(thp) (5.6 mg, 0.015 mmol) at room temperature under Ar results in the immediate formation of a brown solution. Over 12 h, a few X-ray quality, yellow plate crystals of the solvated complex deposit from the solution.

Refinement top

The material crystallizes with one molecule of solvent MeOH in the asymmetric unit. Two of the C6H4F substituents are disordered in two orientations and these were refined with constraints to maintain reasonable geometry and thermal parameters. All non-hydrogen atoms were refined anisotropically, while all hydrogen atoms were placed in calculated positions and not refined, except for H10 which was located in a difference map and refined isotropically.

Computing details top

Data collection: SAINT (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound, with atom labeling scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Only major part of disordered molecular moieties are presented.
Chloridotris[tris(4-fluorophenyl)phosphine]rhodium(I) methanol solvate top
Crystal data top
[RhCl(C18H12F3P)3]·CH4OF(000) = 1132
Mr = 1119.14Dx = 1.547 Mg m3
Monoclinic, CmMo Kα radiation, λ = 0.71073 Å
a = 10.831 (3) ÅCell parameters from 3285 reflections
b = 23.724 (7) Åθ = 3.3–23.2°
c = 9.845 (3) ŵ = 0.59 mm1
β = 108.213 (8)°T = 173 K
V = 2403.0 (12) Å3Plate, yellow
Z = 20.30 × 0.15 × 0.03 mm
Data collection top
Bruker X8 APEXII
diffractometer
3312 independent reflections
Radiation source: Fine-focus sealed tube3094 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
Area detector scansθmax = 26.3°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 1312
Tmin = 0.544, Tmax = 0.983k = 2929
10921 measured reflectionsl = 412
Refinement top
Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075 w = 1/[σ2(Fo2) + (0.0308P)2 + 3.2966P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.016
3312 reflectionsΔρmax = 0.67 e Å3
372 parametersΔρmin = 0.47 e Å3
15 restraintsAbsolute structure: Flack (1983), 812 Friedel pairs
Primary atom site location: DirectAbsolute structure parameter: 0.03 (3)
Crystal data top
[RhCl(C18H12F3P)3]·CH4OV = 2403.0 (12) Å3
Mr = 1119.14Z = 2
Monoclinic, CmMo Kα radiation
a = 10.831 (3) ŵ = 0.59 mm1
b = 23.724 (7) ÅT = 173 K
c = 9.845 (3) Å0.30 × 0.15 × 0.03 mm
β = 108.213 (8)°
Data collection top
Bruker X8 APEXII
diffractometer
3312 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
3094 reflections with I > 2σ(I)
Tmin = 0.544, Tmax = 0.983Rint = 0.048
10921 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.67 e Å3
S = 1.03Δρmin = 0.47 e Å3
3312 reflectionsAbsolute structure: Flack (1983), 812 Friedel pairs
372 parametersAbsolute structure parameter: 0.03 (3)
15 restraints
Special details top

Geometry. All s.u.s' (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.s' are taken into account individually in the estimation of s.u.s' in distances, angles and torsion angles; correlations between s.u.s' in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.s' is used for estimating s.u.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*/UeqOcc. (<1)
C10.2479 (3)0.00000.8201 (5)0.0317 (16)
C20.3484 (5)0.0002 (5)0.9489 (4)0.0402 (19)
H20.33020.00511.03640.048*0.50
C30.4758 (4)0.0083 (6)0.9494 (6)0.049 (4)0.50
H30.54440.00981.03750.059*0.50
C40.5028 (4)0.0142 (4)0.8210 (8)0.044 (4)0.50
C50.4023 (6)0.0127 (4)0.6922 (6)0.038 (4)0.50
H50.42070.01670.60450.046*0.50
C60.2748 (5)0.0053 (4)0.6917 (4)0.042 (2)0.50
H60.20620.00400.60370.051*0.50
C70.0049 (17)0.0575 (8)0.721 (2)0.018 (3)0.533 (12)
C80.0491 (13)0.0863 (8)0.6226 (19)0.039 (3)0.533 (12)
H80.12950.07610.60980.047*0.533 (12)
C90.0245 (12)0.1298 (7)0.5426 (13)0.048 (4)0.533 (12)
H90.00570.14950.47500.058*0.533 (12)
C100.1423 (11)0.1447 (5)0.5614 (13)0.041 (3)0.533 (12)
C110.1864 (11)0.1159 (6)0.6603 (16)0.042 (3)0.533 (12)
H110.26690.12600.67310.050*0.533 (12)
C120.1129 (16)0.0723 (8)0.7403 (19)0.024 (2)0.533 (12)
H120.14300.05270.80780.029*0.533 (12)
F20.2133 (11)0.1847 (4)0.4740 (9)0.060 (3)0.533 (12)
C130.0508 (5)0.1306 (2)1.1071 (5)0.0280 (11)
C140.1577 (5)0.0973 (2)1.0925 (7)0.0429 (14)
H140.15350.05811.07410.051*
C150.2723 (6)0.1201 (3)1.1043 (7)0.0586 (19)
H150.34640.09691.09280.070*
C160.2767 (6)0.1756 (3)1.1322 (7)0.0537 (17)
C170.1751 (8)0.2093 (3)1.1419 (10)0.076 (3)
H170.18040.24861.15840.091*
C180.0642 (7)0.1867 (2)1.1280 (8)0.061 (2)
H180.00670.21111.13300.073*
C190.2189 (3)0.11444 (16)1.2662 (4)0.0291 (11)0.637 (11)
C200.2075 (5)0.1632 (2)1.3398 (6)0.037 (2)0.637 (11)
H200.13440.18721.30320.044*0.637 (11)
C210.3031 (5)0.1768 (2)1.4668 (6)0.049 (3)0.637 (11)
H210.29540.21011.51710.058*0.637 (11)
C220.4101 (4)0.1417 (2)1.5203 (4)0.0458 (15)0.637 (11)
C230.4214 (5)0.0929 (2)1.4468 (6)0.054 (3)0.637 (11)
H230.49450.06891.48330.064*0.637 (11)
C240.3258 (5)0.0793 (2)1.3197 (6)0.050 (3)0.637 (11)
H240.33360.04601.26940.060*0.637 (11)
C250.1512 (5)0.14409 (19)0.9781 (5)0.0245 (10)
C260.0727 (5)0.1841 (2)0.8909 (6)0.0413 (13)
H260.01570.18700.88760.050*
C270.1193 (5)0.2199 (2)0.8088 (6)0.0450 (14)
H270.06380.24730.75000.054*
C280.2439 (5)0.2159 (2)0.8121 (6)0.0354 (12)
C290.3242 (6)0.1770 (3)0.8920 (8)0.0560 (18)
H290.41160.17400.89180.067*
C300.2765 (5)0.1413 (2)0.9747 (8)0.0524 (18)
H300.33300.11371.03150.063*
F10.6241 (6)0.0176 (3)0.8185 (10)0.078 (3)0.50
F30.3864 (4)0.19782 (18)1.1463 (5)0.0806 (13)
F40.5006 (3)0.1544 (2)1.6443 (4)0.0669 (13)
F50.2899 (3)0.25244 (13)0.7328 (4)0.0531 (9)
P10.08546 (18)0.00000.84167 (19)0.0197 (4)
P20.09765 (13)0.09686 (4)1.09570 (12)0.0229 (3)
Cl10.05281 (19)0.00001.2983 (2)0.0321 (5)
Rh10.08365 (4)0.00001.06599 (4)0.01826 (13)
O10.7332 (8)0.00000.2629 (9)0.120 (4)
C310.7118 (13)0.00000.3817 (15)0.104 (5)
H31A0.71650.03870.41790.156*0.50
H31B0.62500.01540.36950.156*0.50
H31C0.77720.02330.45000.156*0.50
C7B0.0176 (19)0.0581 (10)0.739 (2)0.018 (3)0.467 (12)
C8B0.0088 (14)0.0833 (10)0.623 (2)0.039 (3)0.467 (12)
H8B0.08890.07590.60620.047*0.467 (12)
C9B0.0818 (13)0.1192 (8)0.5333 (15)0.048 (4)0.467 (12)
H9B0.06370.13640.45450.058*0.467 (12)
C10B0.1989 (12)0.1299 (6)0.5585 (15)0.041 (3)0.467 (12)
C11B0.2254 (14)0.1048 (8)0.6739 (19)0.042 (3)0.467 (12)
H11B0.30540.11210.69120.050*0.467 (12)
C12B0.135 (2)0.0689 (10)0.764 (2)0.024 (2)0.467 (12)
H12B0.15280.05170.84300.029*0.467 (12)
F2B0.2822 (12)0.1659 (5)0.4806 (11)0.061 (3)0.467 (12)
C19B0.2189 (3)0.11444 (16)1.2662 (4)0.0291 (11)0.363 (11)
C20B0.1878 (8)0.1313 (8)1.3842 (10)0.038 (4)0.363 (11)
H20B0.09900.13681.37660.046*0.363 (11)
C21B0.2825 (8)0.1408 (8)1.5153 (10)0.047 (5)0.363 (11)
H21B0.25890.14641.59950.056*0.363 (11)
C22B0.4101 (4)0.1417 (2)1.5203 (4)0.0458 (15)0.363 (11)
C23B0.4461 (8)0.1307 (11)1.4004 (11)0.067 (7)0.363 (11)
H23B0.53490.13301.40490.080*0.363 (11)
C24B0.3518 (8)0.1163 (11)1.2728 (11)0.079 (9)0.363 (11)
H24B0.37610.10771.19050.095*0.363 (11)
H1O0.833 (5)0.00000.282 (14)0.11 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.029 (4)0.038 (4)0.026 (4)0.0000.006 (3)0.000
C20.028 (4)0.060 (5)0.028 (4)0.0000.001 (3)0.000
C30.020 (4)0.074 (12)0.048 (6)0.007 (7)0.002 (4)0.004 (8)
C40.032 (5)0.023 (9)0.083 (9)0.005 (4)0.028 (6)0.001 (5)
C50.043 (6)0.022 (11)0.060 (7)0.002 (4)0.033 (6)0.002 (4)
C60.028 (4)0.068 (7)0.029 (4)0.002 (10)0.008 (3)0.003 (10)
C70.024 (6)0.028 (3)0.008 (5)0.006 (4)0.011 (4)0.003 (3)
C80.051 (8)0.047 (4)0.031 (3)0.025 (7)0.031 (6)0.012 (3)
C90.065 (11)0.048 (7)0.033 (4)0.021 (8)0.016 (7)0.021 (4)
C100.026 (7)0.037 (7)0.034 (4)0.011 (5)0.028 (6)0.005 (5)
C110.011 (8)0.059 (7)0.044 (5)0.008 (6)0.009 (5)0.023 (5)
C120.017 (6)0.039 (4)0.020 (6)0.007 (4)0.009 (4)0.006 (3)
F20.072 (7)0.051 (5)0.044 (5)0.021 (5)0.001 (5)0.021 (4)
C130.037 (3)0.026 (3)0.023 (3)0.010 (2)0.013 (2)0.008 (2)
C140.033 (3)0.042 (3)0.047 (4)0.011 (2)0.002 (3)0.015 (3)
C150.031 (3)0.073 (5)0.065 (5)0.014 (3)0.004 (3)0.021 (4)
C160.059 (4)0.063 (4)0.049 (4)0.040 (3)0.030 (3)0.023 (3)
C170.116 (6)0.033 (4)0.116 (7)0.039 (4)0.089 (6)0.027 (4)
C180.084 (5)0.028 (3)0.098 (6)0.011 (3)0.069 (4)0.010 (3)
C190.037 (3)0.023 (2)0.028 (3)0.002 (2)0.010 (2)0.001 (2)
C200.027 (4)0.040 (5)0.040 (5)0.004 (4)0.006 (4)0.016 (4)
C210.045 (5)0.046 (6)0.055 (7)0.005 (5)0.015 (5)0.040 (5)
C220.043 (3)0.062 (4)0.029 (3)0.005 (3)0.005 (3)0.007 (3)
C230.062 (7)0.046 (6)0.038 (6)0.014 (5)0.006 (5)0.004 (5)
C240.057 (6)0.037 (6)0.036 (6)0.010 (5)0.012 (5)0.010 (5)
C250.029 (3)0.022 (2)0.021 (2)0.002 (2)0.005 (2)0.0011 (19)
C260.034 (3)0.049 (3)0.043 (3)0.008 (3)0.016 (3)0.019 (3)
C270.047 (3)0.047 (3)0.038 (3)0.009 (3)0.010 (3)0.020 (3)
C280.047 (3)0.032 (3)0.030 (3)0.014 (2)0.015 (2)0.005 (2)
C290.038 (3)0.045 (4)0.093 (6)0.004 (3)0.032 (4)0.014 (4)
C300.033 (3)0.037 (3)0.090 (6)0.004 (3)0.023 (3)0.020 (3)
F10.032 (3)0.097 (10)0.119 (7)0.008 (3)0.041 (4)0.013 (5)
F30.075 (3)0.090 (3)0.090 (3)0.056 (2)0.043 (2)0.019 (2)
F40.047 (2)0.094 (3)0.046 (2)0.003 (2)0.0053 (18)0.032 (2)
F50.074 (2)0.0430 (19)0.050 (2)0.0210 (16)0.0305 (17)0.0044 (16)
P10.0215 (9)0.0229 (10)0.0141 (9)0.0000.0044 (7)0.000
P20.0313 (7)0.0197 (5)0.0174 (8)0.0021 (6)0.0073 (6)0.0005 (4)
Cl10.0425 (12)0.0369 (11)0.0193 (9)0.0000.0133 (8)0.000
Rh10.0222 (3)0.0185 (2)0.0137 (2)0.0000.00499 (19)0.000
O10.072 (6)0.245 (13)0.037 (5)0.0000.006 (4)0.000
C310.086 (10)0.177 (16)0.060 (9)0.0000.038 (8)0.000
C7B0.024 (6)0.028 (3)0.008 (5)0.006 (4)0.011 (4)0.003 (3)
C8B0.051 (8)0.047 (4)0.031 (3)0.025 (7)0.031 (6)0.012 (3)
C9B0.065 (11)0.048 (7)0.033 (4)0.021 (8)0.016 (7)0.021 (4)
C10B0.026 (7)0.037 (7)0.034 (4)0.011 (5)0.028 (6)0.005 (5)
C11B0.011 (8)0.059 (7)0.044 (5)0.008 (6)0.009 (5)0.023 (5)
C12B0.017 (6)0.039 (4)0.020 (6)0.007 (4)0.009 (4)0.006 (3)
F2B0.059 (7)0.054 (7)0.046 (6)0.026 (5)0.017 (5)0.012 (5)
C19B0.037 (3)0.023 (2)0.028 (3)0.002 (2)0.010 (2)0.001 (2)
C20B0.032 (8)0.055 (12)0.031 (9)0.011 (8)0.012 (7)0.018 (8)
C21B0.044 (10)0.057 (13)0.037 (10)0.028 (9)0.009 (8)0.031 (9)
C22B0.043 (3)0.062 (4)0.029 (3)0.005 (3)0.005 (3)0.007 (3)
C23B0.026 (9)0.13 (2)0.049 (12)0.016 (11)0.014 (8)0.003 (12)
C24B0.080 (15)0.13 (2)0.015 (8)0.065 (15)0.002 (9)0.008 (11)
Geometric parameters (Å, º) top
C1—C21.3897C23—H230.9500
C1—C61.3888C24—H240.9500
C1—P11.836 (4)C25—C301.370 (7)
C2—C31.3922C25—C261.381 (7)
C2—H20.9500C25—P21.831 (5)
C3—C41.3900C26—C271.372 (7)
C3—H30.9500C26—H260.9500
C4—F11.324 (7)C27—C281.343 (7)
C4—C51.3900C27—H270.9500
C5—C61.3900C28—C291.343 (8)
C5—H50.9500C28—F51.360 (6)
C6—H60.9500C29—C301.381 (8)
C7—C81.3900C29—H290.9500
C7—C121.3900C30—H300.9500
C7—P11.838 (10)F1—F1i0.833 (15)
C8—C91.3900F1—C4i1.521 (8)
C8—H80.9500P1—C1i1.836 (4)
C9—C101.3900P1—C7i1.838 (10)
C9—H90.9500P1—C7B1.862 (13)
C10—F21.350 (13)P1—C7Bi1.862 (13)
C10—C111.3900P1—Rh12.215 (2)
C11—C121.3900P2—Rh12.3153 (12)
C11—H110.9500Cl1—Rh12.412 (2)
C12—H120.9500Rh1—P2i2.3153 (12)
C13—C181.362 (7)O1—C311.262 (15)
C13—C141.372 (7)O1—H1O1.07 (4)
C13—P21.830 (5)C31—H31A0.9800
C14—C151.391 (8)C31—H31B0.9800
C14—H140.9500C31—H31C0.9800
C15—C161.351 (9)C7B—C8B1.3900
C15—H150.9500C7B—C12B1.3900
C16—C171.339 (10)C8B—C9B1.3900
C16—F31.346 (6)C8B—H8B0.9500
C17—C181.361 (8)C9B—C10B1.3900
C17—H170.9500C9B—H9B0.9500
C18—H180.9500C10B—F2B1.303 (15)
C19—C201.3900C10B—C11B1.3900
C19—C241.3900C11B—C12B1.3900
C19—P21.827 (3)C11B—H11B0.9500
C20—C211.3900C12B—H12B0.9500
C20—H200.9500C20B—C21B1.393 (8)
C21—C221.3900C20B—H20B0.9500
C21—H210.9500C21B—H21B0.9500
C22—F41.340 (4)C23B—C24B1.392 (8)
C22—C231.3900C23B—H23B0.9500
C23—C241.3900C24B—H24B0.9500
C2—C1—C6120.2C27—C26—C25121.6 (5)
C2—C1—P1113.6 (3)C27—C26—H26119.2
C6—C1—P1125.9 (3)C25—C26—H26119.2
C1—C2—C3119.8C28—C27—C26119.6 (5)
C1—C2—H2120.1C28—C27—H27120.2
C3—C2—H2120.1C26—C27—H27120.2
C4—C3—C2120.0C29—C28—C27121.6 (5)
C4—C3—H3120.0C29—C28—F5119.2 (5)
C2—C3—H3120.0C27—C28—F5119.1 (5)
F1—C4—C5118.9 (6)C28—C29—C30118.3 (5)
F1—C4—C3120.9 (6)C28—C29—H29120.8
C5—C4—C3120.0C30—C29—H29120.8
C6—C5—C4120.0C25—C30—C29122.7 (5)
C6—C5—H5120.0C25—C30—H30118.7
C4—C5—H5120.0C29—C30—H30118.7
C5—C6—C1120.0C1i—P1—C7101.8 (5)
C5—C6—H6120.0C1—P1—C7101.8 (5)
C1—C6—H6120.0C1i—P1—C7i101.8 (5)
C8—C7—C12120.0C1—P1—C7i101.8 (5)
C8—C7—P1128.1 (9)C7—P1—C7i95.9 (17)
C12—C7—P1111.9 (9)C1i—P1—C7B111.7 (6)
C7—C8—C9120.0C1—P1—C7B111.7 (6)
C7—C8—H8120.0C7i—P1—C7B96.7 (3)
C9—C8—H8120.0C1i—P1—C7Bi111.7 (6)
C10—C9—C8120.0C1—P1—C7Bi111.7 (6)
C10—C9—H9120.0C7—P1—C7Bi96.7 (3)
C8—C9—H9120.0C7B—P1—C7Bi95.6 (19)
F2—C10—C9117.2 (9)C1i—P1—Rh1115.00 (17)
F2—C10—C11122.7 (9)C1—P1—Rh1115.00 (17)
C9—C10—C11120.0C7—P1—Rh1119.4 (7)
C12—C11—C10120.0C7i—P1—Rh1119.4 (7)
C12—C11—H11120.0C7B—P1—Rh1110.6 (8)
C10—C11—H11120.0C7Bi—P1—Rh1110.6 (8)
C11—C12—C7120.0C19—P2—C13103.7 (2)
C11—C12—H12120.0C19—P2—C2599.3 (2)
C7—C12—H12120.0C13—P2—C25103.3 (2)
C18—C13—C14116.9 (5)C19—P2—Rh1110.04 (13)
C18—C13—P2125.0 (4)C13—P2—Rh1114.65 (18)
C14—C13—P2118.1 (4)C25—P2—Rh1123.28 (16)
C13—C14—C15120.9 (6)P1—Rh1—P296.05 (3)
C13—C14—H14119.5P1—Rh1—P2i96.05 (3)
C15—C14—H14119.5P2—Rh1—P2i165.90 (5)
C16—C15—C14119.0 (6)P1—Rh1—Cl1172.92 (8)
C16—C15—H15120.5P2—Rh1—Cl184.45 (3)
C14—C15—H15120.5P2i—Rh1—Cl184.45 (3)
C17—C16—F3119.4 (6)C31—O1—H1O103 (5)
C17—C16—C15121.1 (5)O1—C31—H31A109.5
F3—C16—C15119.4 (6)O1—C31—H31B109.5
C16—C17—C18119.2 (6)H31A—C31—H31B109.5
C16—C17—H17120.4O1—C31—H31C109.5
C18—C17—H17120.4H31A—C31—H31C109.5
C17—C18—C13122.7 (6)H31B—C31—H31C109.5
C17—C18—H18118.7C8B—C7B—C12B120.0
C13—C18—H18118.7C8B—C7B—P1121.4 (11)
C20—C19—C24120.0C12B—C7B—P1117.7 (10)
C20—C19—P2120.9 (2)C7B—C8B—C9B120.0
C24—C19—P2119.0 (2)C7B—C8B—H8B120.0
C19—C20—C21120.0C9B—C8B—H8B120.0
C19—C20—H20120.0C10B—C9B—C8B120.0
C21—C20—H20120.0C10B—C9B—H9B120.0
C20—C21—C22120.0C8B—C9B—H9B120.0
C20—C21—H21120.0F2B—C10B—C11B118.7 (11)
C22—C21—H21120.0F2B—C10B—C9B121.2 (11)
F4—C22—C23120.2 (4)C11B—C10B—C9B120.0
F4—C22—C21119.8 (4)C10B—C11B—C12B120.0
C23—C22—C21120.0C10B—C11B—H11B120.0
C24—C23—C22120.0C12B—C11B—H11B120.0
C24—C23—H23120.0C11B—C12B—C7B120.0
C22—C23—H23120.0C11B—C12B—H12B120.0
C23—C24—C19120.0C7B—C12B—H12B120.0
C23—C24—H24120.0C21B—C20B—H20B119.0
C19—C24—H24120.0C20B—C21B—H21B120.7
C30—C25—C26116.1 (5)C24B—C23B—H23B120.2
C30—C25—P2119.9 (4)C23B—C24B—H24B120.1
C26—C25—P2124.0 (4)
C6—C1—C2—C32.8C8—C7—P1—C7i93.6 (12)
P1—C1—C2—C3170.91 (16)C12—C7—P1—C7i87.8 (10)
C1—C2—C3—C42.2C12—C7—P1—C7B7 (9)
C2—C3—C4—F1174.8 (7)C8—C7—P1—C7Bi104.1 (13)
C2—C3—C4—C50.8C12—C7—P1—C7Bi77.3 (10)
F1—C4—C5—C6175.7 (7)C8—C7—P1—Rh1137.7 (10)
C3—C4—C5—C60.0C12—C7—P1—Rh140.9 (11)
C4—C5—C6—C10.6C20—C19—P2—C1327.6 (5)
C2—C1—C6—C52.0C24—C19—P2—C13154.7 (4)
P1—C1—C6—C5170.89 (19)C20—C19—P2—C2578.7 (5)
C12—C7—C8—C90.0C24—C19—P2—C2599.1 (4)
P1—C7—C8—C9178.5 (18)C20—C19—P2—Rh1150.6 (4)
C7—C8—C9—C100.0C24—C19—P2—Rh131.6 (4)
C8—C9—C10—F2175.7 (11)C18—C13—P2—C1958.3 (6)
C8—C9—C10—C110.0C14—C13—P2—C19122.2 (4)
F2—C10—C11—C12175.5 (11)C18—C13—P2—C2544.9 (6)
C9—C10—C11—C120.0C14—C13—P2—C25134.5 (4)
C10—C11—C12—C70.0C18—C13—P2—Rh1178.3 (5)
C8—C7—C12—C110.0C14—C13—P2—Rh12.2 (5)
P1—C7—C12—C11178.8 (15)C30—C25—P2—C1955.9 (5)
C18—C13—C14—C152.4 (9)C26—C25—P2—C19123.3 (5)
P2—C13—C14—C15178.1 (5)C30—C25—P2—C13162.5 (5)
C13—C14—C15—C160.8 (10)C26—C25—P2—C1316.7 (5)
C14—C15—C16—C173.1 (11)C30—C25—P2—Rh165.7 (5)
C14—C15—C16—F3178.8 (6)C26—C25—P2—Rh1115.1 (4)
F3—C16—C17—C18179.8 (7)C1i—P1—Rh1—P286.36 (4)
C15—C16—C17—C182.1 (12)C1—P1—Rh1—P286.36 (4)
C16—C17—C18—C131.4 (13)C7—P1—Rh1—P2152.1 (8)
C14—C13—C18—C173.5 (11)C7i—P1—Rh1—P235.2 (8)
P2—C13—C18—C17177.0 (6)C7B—P1—Rh1—P2145.9 (9)
C24—C19—C20—C210.0C7Bi—P1—Rh1—P241.3 (9)
P2—C19—C20—C21177.8 (3)C1i—P1—Rh1—P2i86.36 (4)
C19—C20—C21—C220.0C1—P1—Rh1—P2i86.36 (4)
C20—C21—C22—F4178.6 (5)C7—P1—Rh1—P2i35.2 (8)
C20—C21—C22—C230.0C7i—P1—Rh1—P2i152.1 (8)
F4—C22—C23—C24178.6 (5)C7B—P1—Rh1—P2i41.3 (9)
C21—C22—C23—C240.0C7Bi—P1—Rh1—P2i145.9 (9)
C22—C23—C24—C190.0C19—P2—Rh1—P1134.29 (16)
C20—C19—C24—C230.0C13—P2—Rh1—P1109.30 (18)
P2—C19—C24—C23177.8 (3)C25—P2—Rh1—P117.8 (2)
C30—C25—C26—C271.7 (9)C19—P2—Rh1—P2i14.6 (4)
P2—C25—C26—C27177.5 (5)C13—P2—Rh1—P2i101.8 (3)
C25—C26—C27—C280.4 (10)C25—P2—Rh1—P2i131.1 (3)
C26—C27—C28—C291.3 (10)C19—P2—Rh1—Cl152.81 (16)
C26—C27—C28—F5178.5 (5)C13—P2—Rh1—Cl163.59 (18)
C27—C28—C29—C301.5 (10)C25—P2—Rh1—Cl1169.3 (2)
F5—C28—C29—C30178.3 (6)C1i—P1—C7B—C8B21.7 (15)
C26—C25—C30—C291.5 (10)C1—P1—C7B—C8B21.7 (15)
P2—C25—C30—C29177.7 (6)C7—P1—C7B—C8B2 (9)
C28—C29—C30—C250.0 (11)C7i—P1—C7B—C8B83.8 (14)
C5—C4—F1—F1i90.3 (7)C7Bi—P1—C7B—C8B94.3 (12)
C3—C4—F1—F1i85.4 (5)Rh1—P1—C7B—C8B151.2 (10)
C5—C4—F1—C4i90.3 (3)C1i—P1—C7B—C12B169.5 (8)
C3—C4—F1—C4i85.4 (4)C1—P1—C7B—C12B169.5 (8)
C2—C1—P1—C7130.9 (10)C7—P1—C7B—C12B171 (10)
C6—C1—P1—C755.8 (10)C7i—P1—C7B—C12B84.9 (10)
C2—C1—P1—C7i130.4 (10)C7Bi—P1—C7B—C12B74.4 (14)
C6—C1—P1—C7i42.9 (10)Rh1—P1—C7B—C12B40.1 (13)
C2—C1—P1—C7B127.4 (11)C12B—C7B—C8B—C9B0.0
C6—C1—P1—C7B59.3 (11)P1—C7B—C8B—C9B168.4 (19)
C2—C1—P1—C7Bi126.9 (11)C7B—C8B—C9B—C10B0.0
C6—C1—P1—C7Bi46.4 (11)C8B—C9B—C10B—F2B176.0 (14)
C2—C1—P1—Rh10.2 (5)C8B—C9B—C10B—C11B0.0
C6—C1—P1—Rh1173.6 (5)F2B—C10B—C11B—C12B176.1 (13)
C8—C7—P1—C1i9.8 (14)C9B—C10B—C11B—C12B0.0
C12—C7—P1—C1i168.8 (7)C10B—C11B—C12B—C7B0.0
C8—C7—P1—C19.8 (14)C8B—C7B—C12B—C11B0.0
C12—C7—P1—C1168.8 (7)P1—C7B—C12B—C11B168.9 (19)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1ii0.952.513.458 (9)172
O1—H1O···Cl1iii1.03 (5)2.34 (5)3.369 (9)174 (11)
Symmetry codes: (ii) x, y, z+1; (iii) x+1, y, z1.

Experimental details

Crystal data
Chemical formula[RhCl(C18H12F3P)3]·CH4O
Mr1119.14
Crystal system, space groupMonoclinic, Cm
Temperature (K)173
a, b, c (Å)10.831 (3), 23.724 (7), 9.845 (3)
β (°) 108.213 (8)
V3)2403.0 (12)
Z2
Radiation typeMo Kα
µ (mm1)0.59
Crystal size (mm)0.30 × 0.15 × 0.03
Data collection
DiffractometerBruker X8 APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.544, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
10921, 3312, 3094
Rint0.048
(sin θ/λ)max1)0.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.075, 1.03
No. of reflections3312
No. of parameters372
No. of restraints15
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.67, 0.47
Absolute structureFlack (1983), 812 Friedel pairs
Absolute structure parameter0.03 (3)

Computer programs: SAINT (Bruker, 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.952.513.458 (9)172.0
O1—H1O···Cl1ii1.03 (5)2.34 (5)3.369 (9)174 (11)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z1.
 

Acknowledgements

The authors thank the Natural Sciences and Engineering Research Council of Canada for financial support via a Discovery Grant.

References

First citationAltomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBeck, C. M., Rathmill, S. E., Park, Y. J., Chen, J., Crabtree, R. H., Liable-Sands, L. M. & Rheingold, A. L. (1999). Organometallics, 18, 5311–5317.  Web of Science CSD CrossRef CAS Google Scholar
First citationBennett, M. J. & Donaldson, P. B. (1977). Inorg. Chem. 16, 655–660.  CSD CrossRef CAS Web of Science Google Scholar
First citationBennett, M. A., Robertson, G. B., Turney, T. W. & Whimp, P. O. (1971). J. Chem. Soc. D, pp. 762–764.  Google Scholar
First citationBruker (2003). SADABS. and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationEvans, P. A., Incarvito, C. D. & Rheingold, A. L. (1999). Private communication (deposition number: 115178). CCDC, Cambridge, England.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHigham, L. J., Whittlesey, M. K. & Wood, P. T. (2004). J. Chem. Soc. Dalton Trans. pp. 4202–4208.  CSD CrossRef Google Scholar
First citationHoye, P. A. T., Pringle, P. G., Smith, M. B. & Worboys, K. (1993). J. Chem. Soc. Dalton Trans. pp. 269–274.  CrossRef Web of Science Google Scholar
First citationJones, R. A., Real, F. M., Wilkinson, G., Galas, A. M. R., Hursthouse, M. B. & Malik, K. M. A. (1980). J. Chem. Soc. Dalton Trans. pp. 511–518.  CSD CrossRef Web of Science Google Scholar
First citationLorenzini, F., Patrick, B. O. & James, B. R. (2007a). J. Chem. Soc. Dalton Trans. pp. 3224–3226.  CSD CrossRef Google Scholar
First citationLorenzini, F., Patrick, B. O. & James, B. R. (2007b). Inorg. Chem. 46, 8998–9002.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationLorenzini, F., Patrick, B. O. & James, B. R. (2007c). Inorg. Chim. Acta, doi:10.1016/j.ica.2007.10.044.  Google Scholar
First citationLorenzini, F., Patrick, B. O. & James, B. R. (2008a). Acta Cryst. E64, m179–m180.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLorenzini, F., Patrick, B. O. & James, B. R. (2008b). Acta Cryst. E64, m464–m465.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationMontelatici, S., van der Ent, A., Osborn, J. A. & Wilkinson, G. (1968). J. Chem. Soc. A, pp. 1054–1058.  CrossRef Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYoung, J. F., Osborn, J. A., Jardine, F. H. & Wilkinson, G. (1965). Chem. Commun. pp. 131–132.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 4| April 2008| Pages m512-m513
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds