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

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

doi:10.1107/S1600536808005485

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Pages m512-m513

doi:10.1107/S1600536808005485

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

Fabio Lorenzini,^a Brian O. Patrick ^a and Brian R. James ^a ^*

^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 ) 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

Crystal data

[RhCl(C₁₈H₁₂F₃P)₃]·CH₄O
M_r = 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 ) T_min = 0.544, T_max = 0.983
10921 measured reflections
3312 independent reflections
3094 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Absolute structure: Flack (1983 ), 812 Friedel pairs
Flack parameter: −0.03 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT; data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005485/rk2075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005485/rk2075Isup2.hkl

checkCIF report

Comment top

We have reported recently on the syntheses of water-soluble Rh^I–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.

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

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]·CH₄O	F(000) = 1132
M_r = 1119.14	D_x = 1.547 Mg m⁻³
Monoclinic, Cm	Mo Kα radiation, λ = 0.71073 Å
a = 10.831 (3) Å	Cell parameters from 3285 reflections
b = 23.724 (7) Å	θ = 3.3–23.2°
c = 9.845 (3) Å	µ = 0.59 mm⁻¹
β = 108.213 (8)°	T = 173 K
V = 2403.0 (12) Å³	Plate, yellow
Z = 2	0.30 × 0.15 × 0.03 mm

Data collection top

Bruker X8 APEXII diffractometer	3312 independent reflections
Radiation source: Fine-focus sealed tube	3094 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Area detector scans	θ_max = 26.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −13→12
T_min = 0.544, T_max = 0.983	k = −29→29
10921 measured reflections	l = −4→12

Refinement top

Refinement on F²	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0308P)² + 3.2966P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.016
3312 reflections	Δρ_max = 0.67 e Å⁻³
372 parameters	Δρ_min = −0.47 e Å⁻³
15 restraints	Absolute structure: Flack (1983), 812 Friedel pairs
Primary atom site location: Direct	Absolute structure parameter: −0.03 (3)

Crystal data top

[RhCl(C₁₈H₁₂F₃P)₃]·CH₄O	V = 2403.0 (12) Å³
M_r = 1119.14	Z = 2
Monoclinic, Cm	Mo Kα radiation
a = 10.831 (3) Å	µ = 0.59 mm⁻¹
b = 23.724 (7) Å	T = 173 K
c = 9.845 (3) Å	0.30 × 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)
T_min = 0.544, T_max = 0.983	R_int = 0.048
10921 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	Δρ_max = 0.67 e Å⁻³
S = 1.03	Δρ_min = −0.47 e Å⁻³
3312 reflections	Absolute structure: Flack (1983), 812 Friedel pairs
372 parameters	Absolute 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2479 (3)	0.0000	0.8201 (5)	0.0317 (16)
C2	0.3484 (5)	0.0002 (5)	0.9489 (4)	0.0402 (19)
H2	0.3302	−0.0051	1.0364	0.048*	0.50
C3	0.4758 (4)	0.0083 (6)	0.9494 (6)	0.049 (4)	0.50
H3	0.5444	0.0098	1.0375	0.059*	0.50
C4	0.5028 (4)	0.0142 (4)	0.8210 (8)	0.044 (4)	0.50
C5	0.4023 (6)	0.0127 (4)	0.6922 (6)	0.038 (4)	0.50
H5	0.4207	0.0167	0.6045	0.046*	0.50
C6	0.2748 (5)	0.0053 (4)	0.6917 (4)	0.042 (2)	0.50
H6	0.2062	0.0040	0.6037	0.051*	0.50
C7	0.0049 (17)	−0.0575 (8)	0.721 (2)	0.018 (3)	0.533 (12)
C8	0.0491 (13)	−0.0863 (8)	0.6226 (19)	0.039 (3)	0.533 (12)
H8	0.1295	−0.0761	0.6098	0.047*	0.533 (12)
C9	−0.0245 (12)	−0.1298 (7)	0.5426 (13)	0.048 (4)	0.533 (12)
H9	0.0057	−0.1495	0.4750	0.058*	0.533 (12)
C10	−0.1423 (11)	−0.1447 (5)	0.5614 (13)	0.041 (3)	0.533 (12)
C11	−0.1864 (11)	−0.1159 (6)	0.6603 (16)	0.042 (3)	0.533 (12)
H11	−0.2669	−0.1260	0.6731	0.050*	0.533 (12)
C12	−0.1129 (16)	−0.0723 (8)	0.7403 (19)	0.024 (2)	0.533 (12)
H12	−0.1430	−0.0527	0.8078	0.029*	0.533 (12)
F2	−0.2133 (11)	−0.1847 (4)	0.4740 (9)	0.060 (3)	0.533 (12)
C13	−0.0508 (5)	0.1306 (2)	1.1071 (5)	0.0280 (11)
C14	−0.1577 (5)	0.0973 (2)	1.0925 (7)	0.0429 (14)
H14	−0.1535	0.0581	1.0741	0.051*
C15	−0.2723 (6)	0.1201 (3)	1.1043 (7)	0.0586 (19)
H15	−0.3464	0.0969	1.0928	0.070*
C16	−0.2767 (6)	0.1756 (3)	1.1322 (7)	0.0537 (17)
C17	−0.1751 (8)	0.2093 (3)	1.1419 (10)	0.076 (3)
H17	−0.1804	0.2486	1.1584	0.091*
C18	−0.0642 (7)	0.1867 (2)	1.1280 (8)	0.061 (2)
H18	0.0067	0.2111	1.1330	0.073*
C19	0.2189 (3)	0.11444 (16)	1.2662 (4)	0.0291 (11)	0.637 (11)
C20	0.2075 (5)	0.1632 (2)	1.3398 (6)	0.037 (2)	0.637 (11)
H20	0.1344	0.1872	1.3032	0.044*	0.637 (11)
C21	0.3031 (5)	0.1768 (2)	1.4668 (6)	0.049 (3)	0.637 (11)
H21	0.2954	0.2101	1.5171	0.058*	0.637 (11)
C22	0.4101 (4)	0.1417 (2)	1.5203 (4)	0.0458 (15)	0.637 (11)
C23	0.4214 (5)	0.0929 (2)	1.4468 (6)	0.054 (3)	0.637 (11)
H23	0.4945	0.0689	1.4833	0.064*	0.637 (11)
C24	0.3258 (5)	0.0793 (2)	1.3197 (6)	0.050 (3)	0.637 (11)
H24	0.3336	0.0460	1.2694	0.060*	0.637 (11)
C25	0.1512 (5)	0.14409 (19)	0.9781 (5)	0.0245 (10)
C26	0.0727 (5)	0.1841 (2)	0.8909 (6)	0.0413 (13)
H26	−0.0157	0.1870	0.8876	0.050*
C27	0.1193 (5)	0.2199 (2)	0.8088 (6)	0.0450 (14)
H27	0.0638	0.2473	0.7500	0.054*
C28	0.2439 (5)	0.2159 (2)	0.8121 (6)	0.0354 (12)
C29	0.3242 (6)	0.1770 (3)	0.8920 (8)	0.0560 (18)
H29	0.4116	0.1740	0.8918	0.067*
C30	0.2765 (5)	0.1413 (2)	0.9747 (8)	0.0524 (18)
H30	0.3330	0.1137	1.0315	0.063*
F1	0.6241 (6)	0.0176 (3)	0.8185 (10)	0.078 (3)	0.50
F3	−0.3864 (4)	0.19782 (18)	1.1463 (5)	0.0806 (13)
F4	0.5006 (3)	0.1544 (2)	1.6443 (4)	0.0669 (13)
F5	0.2899 (3)	0.25244 (13)	0.7328 (4)	0.0531 (9)
P1	0.08546 (18)	0.0000	0.84167 (19)	0.0197 (4)
P2	0.09765 (13)	0.09686 (4)	1.09570 (12)	0.0229 (3)
Cl1	0.05281 (19)	0.0000	1.2983 (2)	0.0321 (5)
Rh1	0.08365 (4)	0.0000	1.06599 (4)	0.01826 (13)
O1	0.7332 (8)	0.0000	0.2629 (9)	0.120 (4)
C31	0.7118 (13)	0.0000	0.3817 (15)	0.104 (5)
H31A	0.7165	−0.0387	0.4179	0.156*	0.50
H31B	0.6250	0.0154	0.3695	0.156*	0.50
H31C	0.7772	0.0233	0.4500	0.156*	0.50
C7B	−0.0176 (19)	−0.0581 (10)	0.739 (2)	0.018 (3)	0.467 (12)
C8B	0.0088 (14)	−0.0833 (10)	0.623 (2)	0.039 (3)	0.467 (12)
H8B	0.0889	−0.0759	0.6062	0.047*	0.467 (12)
C9B	−0.0818 (13)	−0.1192 (8)	0.5333 (15)	0.048 (4)	0.467 (12)
H9B	−0.0637	−0.1364	0.4545	0.058*	0.467 (12)
C10B	−0.1989 (12)	−0.1299 (6)	0.5585 (15)	0.041 (3)	0.467 (12)
C11B	−0.2254 (14)	−0.1048 (8)	0.6739 (19)	0.042 (3)	0.467 (12)
H11B	−0.3054	−0.1121	0.6912	0.050*	0.467 (12)
C12B	−0.135 (2)	−0.0689 (10)	0.764 (2)	0.024 (2)	0.467 (12)
H12B	−0.1528	−0.0517	0.8430	0.029*	0.467 (12)
F2B	−0.2822 (12)	−0.1659 (5)	0.4806 (11)	0.061 (3)	0.467 (12)
C19B	0.2189 (3)	0.11444 (16)	1.2662 (4)	0.0291 (11)	0.363 (11)
C20B	0.1878 (8)	0.1313 (8)	1.3842 (10)	0.038 (4)	0.363 (11)
H20B	0.0990	0.1368	1.3766	0.046*	0.363 (11)
C21B	0.2825 (8)	0.1408 (8)	1.5153 (10)	0.047 (5)	0.363 (11)
H21B	0.2589	0.1464	1.5995	0.056*	0.363 (11)
C22B	0.4101 (4)	0.1417 (2)	1.5203 (4)	0.0458 (15)	0.363 (11)
C23B	0.4461 (8)	0.1307 (11)	1.4004 (11)	0.067 (7)	0.363 (11)
H23B	0.5349	0.1330	1.4049	0.080*	0.363 (11)
C24B	0.3518 (8)	0.1163 (11)	1.2728 (11)	0.079 (9)	0.363 (11)
H24B	0.3761	0.1077	1.1905	0.095*	0.363 (11)
H1O	0.833 (5)	0.0000	0.282 (14)	0.11 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.029 (4)	0.038 (4)	0.026 (4)	0.000	0.006 (3)	0.000
C2	0.028 (4)	0.060 (5)	0.028 (4)	0.000	0.001 (3)	0.000
C3	0.020 (4)	0.074 (12)	0.048 (6)	−0.007 (7)	0.002 (4)	0.004 (8)
C4	0.032 (5)	0.023 (9)	0.083 (9)	0.005 (4)	0.028 (6)	−0.001 (5)
C5	0.043 (6)	0.022 (11)	0.060 (7)	−0.002 (4)	0.033 (6)	0.002 (4)
C6	0.028 (4)	0.068 (7)	0.029 (4)	−0.002 (10)	0.008 (3)	−0.003 (10)
C7	0.024 (6)	0.028 (3)	0.008 (5)	−0.006 (4)	0.011 (4)	0.003 (3)
C8	0.051 (8)	0.047 (4)	0.031 (3)	−0.025 (7)	0.031 (6)	−0.012 (3)
C9	0.065 (11)	0.048 (7)	0.033 (4)	−0.021 (8)	0.016 (7)	−0.021 (4)
C10	0.026 (7)	0.037 (7)	0.034 (4)	−0.011 (5)	−0.028 (6)	0.005 (5)
C11	0.011 (8)	0.059 (7)	0.044 (5)	−0.008 (6)	−0.009 (5)	0.023 (5)
C12	0.017 (6)	0.039 (4)	0.020 (6)	−0.007 (4)	0.009 (4)	0.006 (3)
F2	0.072 (7)	0.051 (5)	0.044 (5)	−0.021 (5)	−0.001 (5)	−0.021 (4)
C13	0.037 (3)	0.026 (3)	0.023 (3)	0.010 (2)	0.013 (2)	0.008 (2)
C14	0.033 (3)	0.042 (3)	0.047 (4)	0.011 (2)	0.002 (3)	−0.015 (3)
C15	0.031 (3)	0.073 (5)	0.065 (5)	0.014 (3)	0.004 (3)	−0.021 (4)
C16	0.059 (4)	0.063 (4)	0.049 (4)	0.040 (3)	0.030 (3)	0.023 (3)
C17	0.116 (6)	0.033 (4)	0.116 (7)	0.039 (4)	0.089 (6)	0.027 (4)
C18	0.084 (5)	0.028 (3)	0.098 (6)	0.011 (3)	0.069 (4)	0.010 (3)
C19	0.037 (3)	0.023 (2)	0.028 (3)	0.002 (2)	0.010 (2)	−0.001 (2)
C20	0.027 (4)	0.040 (5)	0.040 (5)	−0.004 (4)	0.006 (4)	−0.016 (4)
C21	0.045 (5)	0.046 (6)	0.055 (7)	−0.005 (5)	0.015 (5)	−0.040 (5)
C22	0.043 (3)	0.062 (4)	0.029 (3)	−0.005 (3)	0.005 (3)	−0.007 (3)
C23	0.062 (7)	0.046 (6)	0.038 (6)	0.014 (5)	−0.006 (5)	−0.004 (5)
C24	0.057 (6)	0.037 (6)	0.036 (6)	0.010 (5)	−0.012 (5)	−0.010 (5)
C25	0.029 (3)	0.022 (2)	0.021 (2)	−0.002 (2)	0.005 (2)	−0.0011 (19)
C26	0.034 (3)	0.049 (3)	0.043 (3)	0.008 (3)	0.016 (3)	0.019 (3)
C27	0.047 (3)	0.047 (3)	0.038 (3)	0.009 (3)	0.010 (3)	0.020 (3)
C28	0.047 (3)	0.032 (3)	0.030 (3)	−0.014 (2)	0.015 (2)	−0.005 (2)
C29	0.038 (3)	0.045 (4)	0.093 (6)	−0.004 (3)	0.032 (4)	0.014 (4)
C30	0.033 (3)	0.037 (3)	0.090 (6)	0.004 (3)	0.023 (3)	0.020 (3)
F1	0.032 (3)	0.097 (10)	0.119 (7)	−0.008 (3)	0.041 (4)	−0.013 (5)
F3	0.075 (3)	0.090 (3)	0.090 (3)	0.056 (2)	0.043 (2)	0.019 (2)
F4	0.047 (2)	0.094 (3)	0.046 (2)	−0.003 (2)	−0.0053 (18)	−0.032 (2)
F5	0.074 (2)	0.0430 (19)	0.050 (2)	−0.0210 (16)	0.0305 (17)	0.0044 (16)
P1	0.0215 (9)	0.0229 (10)	0.0141 (9)	0.000	0.0044 (7)	0.000
P2	0.0313 (7)	0.0197 (5)	0.0174 (8)	0.0021 (6)	0.0073 (6)	−0.0005 (4)
Cl1	0.0425 (12)	0.0369 (11)	0.0193 (9)	0.000	0.0133 (8)	0.000
Rh1	0.0222 (3)	0.0185 (2)	0.0137 (2)	0.000	0.00499 (19)	0.000
O1	0.072 (6)	0.245 (13)	0.037 (5)	0.000	0.006 (4)	0.000
C31	0.086 (10)	0.177 (16)	0.060 (9)	0.000	0.038 (8)	0.000
C7B	0.024 (6)	0.028 (3)	0.008 (5)	−0.006 (4)	0.011 (4)	0.003 (3)
C8B	0.051 (8)	0.047 (4)	0.031 (3)	−0.025 (7)	0.031 (6)	−0.012 (3)
C9B	0.065 (11)	0.048 (7)	0.033 (4)	−0.021 (8)	0.016 (7)	−0.021 (4)
C10B	0.026 (7)	0.037 (7)	0.034 (4)	−0.011 (5)	−0.028 (6)	0.005 (5)
C11B	0.011 (8)	0.059 (7)	0.044 (5)	−0.008 (6)	−0.009 (5)	0.023 (5)
C12B	0.017 (6)	0.039 (4)	0.020 (6)	−0.007 (4)	0.009 (4)	0.006 (3)
F2B	0.059 (7)	0.054 (7)	0.046 (6)	−0.026 (5)	−0.017 (5)	−0.012 (5)
C19B	0.037 (3)	0.023 (2)	0.028 (3)	0.002 (2)	0.010 (2)	−0.001 (2)
C20B	0.032 (8)	0.055 (12)	0.031 (9)	−0.011 (8)	0.012 (7)	−0.018 (8)
C21B	0.044 (10)	0.057 (13)	0.037 (10)	−0.028 (9)	0.009 (8)	−0.031 (9)
C22B	0.043 (3)	0.062 (4)	0.029 (3)	−0.005 (3)	0.005 (3)	−0.007 (3)
C23B	0.026 (9)	0.13 (2)	0.049 (12)	0.016 (11)	0.014 (8)	0.003 (12)
C24B	0.080 (15)	0.13 (2)	0.015 (8)	0.065 (15)	0.002 (9)	−0.008 (11)

Geometric parameters (Å, º) top

C1—C2	1.3897	C23—H23	0.9500
C1—C6	1.3888	C24—H24	0.9500
C1—P1	1.836 (4)	C25—C30	1.370 (7)
C2—C3	1.3922	C25—C26	1.381 (7)
C2—H2	0.9500	C25—P2	1.831 (5)
C3—C4	1.3900	C26—C27	1.372 (7)
C3—H3	0.9500	C26—H26	0.9500
C4—F1	1.324 (7)	C27—C28	1.343 (7)
C4—C5	1.3900	C27—H27	0.9500
C5—C6	1.3900	C28—C29	1.343 (8)
C5—H5	0.9500	C28—F5	1.360 (6)
C6—H6	0.9500	C29—C30	1.381 (8)
C7—C8	1.3900	C29—H29	0.9500
C7—C12	1.3900	C30—H30	0.9500
C7—P1	1.838 (10)	F1—F1ⁱ	0.833 (15)
C8—C9	1.3900	F1—C4ⁱ	1.521 (8)
C8—H8	0.9500	P1—C1ⁱ	1.836 (4)
C9—C10	1.3900	P1—C7ⁱ	1.838 (10)
C9—H9	0.9500	P1—C7B	1.862 (13)
C10—F2	1.350 (13)	P1—C7Bⁱ	1.862 (13)
C10—C11	1.3900	P1—Rh1	2.215 (2)
C11—C12	1.3900	P2—Rh1	2.3153 (12)
C11—H11	0.9500	Cl1—Rh1	2.412 (2)
C12—H12	0.9500	Rh1—P2ⁱ	2.3153 (12)
C13—C18	1.362 (7)	O1—C31	1.262 (15)
C13—C14	1.372 (7)	O1—H1O	1.07 (4)
C13—P2	1.830 (5)	C31—H31A	0.9800
C14—C15	1.391 (8)	C31—H31B	0.9800
C14—H14	0.9500	C31—H31C	0.9800
C15—C16	1.351 (9)	C7B—C8B	1.3900
C15—H15	0.9500	C7B—C12B	1.3900
C16—C17	1.339 (10)	C8B—C9B	1.3900
C16—F3	1.346 (6)	C8B—H8B	0.9500
C17—C18	1.361 (8)	C9B—C10B	1.3900
C17—H17	0.9500	C9B—H9B	0.9500
C18—H18	0.9500	C10B—F2B	1.303 (15)
C19—C20	1.3900	C10B—C11B	1.3900
C19—C24	1.3900	C11B—C12B	1.3900
C19—P2	1.827 (3)	C11B—H11B	0.9500
C20—C21	1.3900	C12B—H12B	0.9500
C20—H20	0.9500	C20B—C21B	1.393 (8)
C21—C22	1.3900	C20B—H20B	0.9500
C21—H21	0.9500	C21B—H21B	0.9500
C22—F4	1.340 (4)	C23B—C24B	1.392 (8)
C22—C23	1.3900	C23B—H23B	0.9500
C23—C24	1.3900	C24B—H24B	0.9500

C2—C1—C6	120.2	C27—C26—C25	121.6 (5)
C2—C1—P1	113.6 (3)	C27—C26—H26	119.2
C6—C1—P1	125.9 (3)	C25—C26—H26	119.2
C1—C2—C3	119.8	C28—C27—C26	119.6 (5)
C1—C2—H2	120.1	C28—C27—H27	120.2
C3—C2—H2	120.1	C26—C27—H27	120.2
C4—C3—C2	120.0	C29—C28—C27	121.6 (5)
C4—C3—H3	120.0	C29—C28—F5	119.2 (5)
C2—C3—H3	120.0	C27—C28—F5	119.1 (5)
F1—C4—C5	118.9 (6)	C28—C29—C30	118.3 (5)
F1—C4—C3	120.9 (6)	C28—C29—H29	120.8
C5—C4—C3	120.0	C30—C29—H29	120.8
C6—C5—C4	120.0	C25—C30—C29	122.7 (5)
C6—C5—H5	120.0	C25—C30—H30	118.7
C4—C5—H5	120.0	C29—C30—H30	118.7
C5—C6—C1	120.0	C1ⁱ—P1—C7	101.8 (5)
C5—C6—H6	120.0	C1—P1—C7	101.8 (5)
C1—C6—H6	120.0	C1ⁱ—P1—C7ⁱ	101.8 (5)
C8—C7—C12	120.0	C1—P1—C7ⁱ	101.8 (5)
C8—C7—P1	128.1 (9)	C7—P1—C7ⁱ	95.9 (17)
C12—C7—P1	111.9 (9)	C1ⁱ—P1—C7B	111.7 (6)
C7—C8—C9	120.0	C1—P1—C7B	111.7 (6)
C7—C8—H8	120.0	C7ⁱ—P1—C7B	96.7 (3)
C9—C8—H8	120.0	C1ⁱ—P1—C7Bⁱ	111.7 (6)
C10—C9—C8	120.0	C1—P1—C7Bⁱ	111.7 (6)
C10—C9—H9	120.0	C7—P1—C7Bⁱ	96.7 (3)
C8—C9—H9	120.0	C7B—P1—C7Bⁱ	95.6 (19)
F2—C10—C9	117.2 (9)	C1ⁱ—P1—Rh1	115.00 (17)
F2—C10—C11	122.7 (9)	C1—P1—Rh1	115.00 (17)
C9—C10—C11	120.0	C7—P1—Rh1	119.4 (7)
C12—C11—C10	120.0	C7ⁱ—P1—Rh1	119.4 (7)
C12—C11—H11	120.0	C7B—P1—Rh1	110.6 (8)
C10—C11—H11	120.0	C7Bⁱ—P1—Rh1	110.6 (8)
C11—C12—C7	120.0	C19—P2—C13	103.7 (2)
C11—C12—H12	120.0	C19—P2—C25	99.3 (2)
C7—C12—H12	120.0	C13—P2—C25	103.3 (2)
C18—C13—C14	116.9 (5)	C19—P2—Rh1	110.04 (13)
C18—C13—P2	125.0 (4)	C13—P2—Rh1	114.65 (18)
C14—C13—P2	118.1 (4)	C25—P2—Rh1	123.28 (16)
C13—C14—C15	120.9 (6)	P1—Rh1—P2	96.05 (3)
C13—C14—H14	119.5	P1—Rh1—P2ⁱ	96.05 (3)
C15—C14—H14	119.5	P2—Rh1—P2ⁱ	165.90 (5)
C16—C15—C14	119.0 (6)	P1—Rh1—Cl1	172.92 (8)
C16—C15—H15	120.5	P2—Rh1—Cl1	84.45 (3)
C14—C15—H15	120.5	P2ⁱ—Rh1—Cl1	84.45 (3)
C17—C16—F3	119.4 (6)	C31—O1—H1O	103 (5)
C17—C16—C15	121.1 (5)	O1—C31—H31A	109.5
F3—C16—C15	119.4 (6)	O1—C31—H31B	109.5
C16—C17—C18	119.2 (6)	H31A—C31—H31B	109.5
C16—C17—H17	120.4	O1—C31—H31C	109.5
C18—C17—H17	120.4	H31A—C31—H31C	109.5
C17—C18—C13	122.7 (6)	H31B—C31—H31C	109.5
C17—C18—H18	118.7	C8B—C7B—C12B	120.0
C13—C18—H18	118.7	C8B—C7B—P1	121.4 (11)
C20—C19—C24	120.0	C12B—C7B—P1	117.7 (10)
C20—C19—P2	120.9 (2)	C7B—C8B—C9B	120.0
C24—C19—P2	119.0 (2)	C7B—C8B—H8B	120.0
C19—C20—C21	120.0	C9B—C8B—H8B	120.0
C19—C20—H20	120.0	C10B—C9B—C8B	120.0
C21—C20—H20	120.0	C10B—C9B—H9B	120.0
C20—C21—C22	120.0	C8B—C9B—H9B	120.0
C20—C21—H21	120.0	F2B—C10B—C11B	118.7 (11)
C22—C21—H21	120.0	F2B—C10B—C9B	121.2 (11)
F4—C22—C23	120.2 (4)	C11B—C10B—C9B	120.0
F4—C22—C21	119.8 (4)	C10B—C11B—C12B	120.0
C23—C22—C21	120.0	C10B—C11B—H11B	120.0
C24—C23—C22	120.0	C12B—C11B—H11B	120.0
C24—C23—H23	120.0	C11B—C12B—C7B	120.0
C22—C23—H23	120.0	C11B—C12B—H12B	120.0
C23—C24—C19	120.0	C7B—C12B—H12B	120.0
C23—C24—H24	120.0	C21B—C20B—H20B	119.0
C19—C24—H24	120.0	C20B—C21B—H21B	120.7
C30—C25—C26	116.1 (5)	C24B—C23B—H23B	120.2
C30—C25—P2	119.9 (4)	C23B—C24B—H24B	120.1
C26—C25—P2	124.0 (4)

C6—C1—C2—C3	2.8	C8—C7—P1—C7ⁱ	93.6 (12)
P1—C1—C2—C3	−170.91 (16)	C12—C7—P1—C7ⁱ	−87.8 (10)
C1—C2—C3—C4	−2.2	C12—C7—P1—C7B	7 (9)
C2—C3—C4—F1	−174.8 (7)	C8—C7—P1—C7Bⁱ	104.1 (13)
C2—C3—C4—C5	0.8	C12—C7—P1—C7Bⁱ	−77.3 (10)
F1—C4—C5—C6	175.7 (7)	C8—C7—P1—Rh1	−137.7 (10)
C3—C4—C5—C6	0.0	C12—C7—P1—Rh1	40.9 (11)
C4—C5—C6—C1	0.6	C20—C19—P2—C13	−27.6 (5)
C2—C1—C6—C5	−2.0	C24—C19—P2—C13	154.7 (4)
P1—C1—C6—C5	170.89 (19)	C20—C19—P2—C25	78.7 (5)
C12—C7—C8—C9	0.0	C24—C19—P2—C25	−99.1 (4)
P1—C7—C8—C9	178.5 (18)	C20—C19—P2—Rh1	−150.6 (4)
C7—C8—C9—C10	0.0	C24—C19—P2—Rh1	31.6 (4)
C8—C9—C10—F2	175.7 (11)	C18—C13—P2—C19	58.3 (6)
C8—C9—C10—C11	0.0	C14—C13—P2—C19	−122.2 (4)
F2—C10—C11—C12	−175.5 (11)	C18—C13—P2—C25	−44.9 (6)
C9—C10—C11—C12	0.0	C14—C13—P2—C25	134.5 (4)
C10—C11—C12—C7	0.0	C18—C13—P2—Rh1	178.3 (5)
C8—C7—C12—C11	0.0	C14—C13—P2—Rh1	−2.2 (5)
P1—C7—C12—C11	−178.8 (15)	C30—C25—P2—C19	55.9 (5)
C18—C13—C14—C15	−2.4 (9)	C26—C25—P2—C19	−123.3 (5)
P2—C13—C14—C15	178.1 (5)	C30—C25—P2—C13	162.5 (5)
C13—C14—C15—C16	−0.8 (10)	C26—C25—P2—C13	−16.7 (5)
C14—C15—C16—C17	3.1 (11)	C30—C25—P2—Rh1	−65.7 (5)
C14—C15—C16—F3	−178.8 (6)	C26—C25—P2—Rh1	115.1 (4)
F3—C16—C17—C18	179.8 (7)	C1ⁱ—P1—Rh1—P2	86.36 (4)
C15—C16—C17—C18	−2.1 (12)	C1—P1—Rh1—P2	86.36 (4)
C16—C17—C18—C13	−1.4 (13)	C7—P1—Rh1—P2	−152.1 (8)
C14—C13—C18—C17	3.5 (11)	C7ⁱ—P1—Rh1—P2	−35.2 (8)
P2—C13—C18—C17	−177.0 (6)	C7B—P1—Rh1—P2	−145.9 (9)
C24—C19—C20—C21	0.0	C7Bⁱ—P1—Rh1—P2	−41.3 (9)
P2—C19—C20—C21	−177.8 (3)	C1ⁱ—P1—Rh1—P2ⁱ	−86.36 (4)
C19—C20—C21—C22	0.0	C1—P1—Rh1—P2ⁱ	−86.36 (4)
C20—C21—C22—F4	−178.6 (5)	C7—P1—Rh1—P2ⁱ	35.2 (8)
C20—C21—C22—C23	0.0	C7ⁱ—P1—Rh1—P2ⁱ	152.1 (8)
F4—C22—C23—C24	178.6 (5)	C7B—P1—Rh1—P2ⁱ	41.3 (9)
C21—C22—C23—C24	0.0	C7Bⁱ—P1—Rh1—P2ⁱ	145.9 (9)
C22—C23—C24—C19	0.0	C19—P2—Rh1—P1	−134.29 (16)
C20—C19—C24—C23	0.0	C13—P2—Rh1—P1	109.30 (18)
P2—C19—C24—C23	177.8 (3)	C25—P2—Rh1—P1	−17.8 (2)
C30—C25—C26—C27	−1.7 (9)	C19—P2—Rh1—P2ⁱ	14.6 (4)
P2—C25—C26—C27	177.5 (5)	C13—P2—Rh1—P2ⁱ	−101.8 (3)
C25—C26—C27—C28	0.4 (10)	C25—P2—Rh1—P2ⁱ	131.1 (3)
C26—C27—C28—C29	1.3 (10)	C19—P2—Rh1—Cl1	52.81 (16)
C26—C27—C28—F5	−178.5 (5)	C13—P2—Rh1—Cl1	−63.59 (18)
C27—C28—C29—C30	−1.5 (10)	C25—P2—Rh1—Cl1	169.3 (2)
F5—C28—C29—C30	178.3 (6)	C1ⁱ—P1—C7B—C8B	−21.7 (15)
C26—C25—C30—C29	1.5 (10)	C1—P1—C7B—C8B	−21.7 (15)
P2—C25—C30—C29	−177.7 (6)	C7—P1—C7B—C8B	−2 (9)
C28—C29—C30—C25	0.0 (11)	C7ⁱ—P1—C7B—C8B	83.8 (14)
C5—C4—F1—F1ⁱ	−90.3 (7)	C7Bⁱ—P1—C7B—C8B	94.3 (12)
C3—C4—F1—F1ⁱ	85.4 (5)	Rh1—P1—C7B—C8B	−151.2 (10)
C5—C4—F1—C4ⁱ	−90.3 (3)	C1ⁱ—P1—C7B—C12B	169.5 (8)
C3—C4—F1—C4ⁱ	85.4 (4)	C1—P1—C7B—C12B	169.5 (8)
C2—C1—P1—C7	−130.9 (10)	C7—P1—C7B—C12B	−171 (10)
C6—C1—P1—C7	55.8 (10)	C7ⁱ—P1—C7B—C12B	−84.9 (10)
C2—C1—P1—C7ⁱ	130.4 (10)	C7Bⁱ—P1—C7B—C12B	−74.4 (14)
C6—C1—P1—C7ⁱ	−42.9 (10)	Rh1—P1—C7B—C12B	40.1 (13)
C2—C1—P1—C7B	−127.4 (11)	C12B—C7B—C8B—C9B	0.0
C6—C1—P1—C7B	59.3 (11)	P1—C7B—C8B—C9B	−168.4 (19)
C2—C1—P1—C7Bⁱ	126.9 (11)	C7B—C8B—C9B—C10B	0.0
C6—C1—P1—C7Bⁱ	−46.4 (11)	C8B—C9B—C10B—F2B	−176.0 (14)
C2—C1—P1—Rh1	−0.2 (5)	C8B—C9B—C10B—C11B	0.0
C6—C1—P1—Rh1	−173.6 (5)	F2B—C10B—C11B—C12B	176.1 (13)
C8—C7—P1—C1ⁱ	−9.8 (14)	C9B—C10B—C11B—C12B	0.0
C12—C7—P1—C1ⁱ	168.8 (7)	C10B—C11B—C12B—C7B	0.0
C8—C7—P1—C1	−9.8 (14)	C8B—C7B—C12B—C11B	0.0
C12—C7—P1—C1	168.8 (7)	P1—C7B—C12B—C11B	168.9 (19)

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱⁱ	0.95	2.51	3.458 (9)	172
O1—H1O···Cl1ⁱⁱⁱ	1.03 (5)	2.34 (5)	3.369 (9)	174 (11)

Symmetry codes: (ii) x, y, z+1; (iii) x+1, y, z−1.

Experimental details

Crystal data
Chemical formula	[RhCl(C₁₈H₁₂F₃P)₃]·CH₄O
M_r	1119.14
Crystal system, space group	Monoclinic, Cm
Temperature (K)	173
a, b, c (Å)	10.831 (3), 23.724 (7), 9.845 (3)
β (°)	108.213 (8)
V (Å³)	2403.0 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.30 × 0.15 × 0.03

Data collection
Diffractometer	Bruker X8 APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.544, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	10921, 3312, 3094
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.075, 1.03
No. of reflections	3312
No. of parameters	372
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.47
Absolute structure	Flack (1983), 812 Friedel pairs
Absolute structure parameter	−0.03 (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···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.95	2.51	3.458 (9)	172.0
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.

Acknowledgements

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

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