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

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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.009 Å
• Disorder in main residue
• R factor = 0.035
• wR factor = 0.076
• Data-to-parameter ratio = 8.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT213_ALERT_2_A Atom C10     has ADP max/min Ratio .............      10.90 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_A Atom C10B    has ADP max/min Ratio .............      10.90 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT410_ALERT_2_A Short Intra H...H Contact  H30    ..  H24B    ..       1.49 Ang.

Author Response: ...C24B is one fragment of a disordered phenyl ring. It sweeps out an area close to the phenyl ring containing C30. The phenyl ring containing C30 also has moderately large displacement parameters and likely occupies a different orientation when H24B approaches H30.

Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.544     0.983
            Tmin(prime) and Tmax expected:      0.836     0.983
            RR(prime) =      0.650
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.65
PLAT213_ALERT_2_B Atom C7      has ADP max/min Ratio .............       4.40 oblat

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_B Atom C7B     has ADP max/min Ratio .............       4.40 oblat

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.11 Ratio
PLAT301_ALERT_3_B Main Residue  Disorder .........................      31.00 Perc.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT213_ALERT_2_C Atom C11     has ADP max/min Ratio .............       3.40 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_C Atom C17     has ADP max/min Ratio .............       3.20 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_C Atom C21     has ADP max/min Ratio .............       3.10 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_C Atom C11B    has ADP max/min Ratio .............       3.40 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_C Atom C21B    has ADP max/min Ratio .............       3.10 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT213_ALERT_2_C Atom C24B    has ADP max/min Ratio .............       3.60 prola

Author Response: ...These two atoms are disordered fragments of the same atom. Restraints were used to maintain 'phenyl' geometry for both halves of the disordered fragment, and the EADP instruction was used to keep the anisotropic displacement parameters equivalent. The low resolution data is likely responsible for the prolate ellipsoid.

PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.28 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C24    -   C24B    ..       5.82 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         F4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C17
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for       C24B
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C28
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C19B
PLAT245_ALERT_2_C U(iso) H1O     Smaller than U(eq) O1      by ...       0.01 AngSq
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O1     -   H1O    ...       1.04 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C1     -   C2     ...       1.39 Ang.
PLAT410_ALERT_2_C Short Intra H...H Contact  H18    ..  H20     ..       1.90 Ang.

Author Response: ...C24B is one fragment of a disordered phenyl ring. It sweeps out an area close to the phenyl ring containing C30. The phenyl ring containing C30 also has moderately large displacement parameters and likely occupies a different orientation when H24B approaches H30.

PLAT432_ALERT_2_C Short Inter X...Y Contact  C9     ..  C20B    ..       3.16 Ang.
PLAT741_ALERT_1_C Bond    Calc    1.389(6), Rep     1.38970 ......    Missing su
              C1   -C2      1.555   1.555

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           26.29
           From the CIF: _reflns_number_total               3312
           Count of symmetry unique reflns         2500
           Completeness (_total/calc)            132.48%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       812
           Fraction of Friedel pairs measured     0.325
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         15

   3 ALERT level A = In general: serious problem
   6 ALERT level B = Potentially serious problem
  22 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  23 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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

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

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

Crystal data

[RhCl(C18H12F3P)3]·CH4O	F(000) = 1132
Mr = 1119.14	Dx = 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) Å^3	Plate, yellow
Z = 2	0.30 × 0.15 × 0.03 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0308P)^2 + 3.2966P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.016
3312 reflections	Δρmax = 0.67 e Å^−3
372 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—F1^i	0.833 (15)
C8—C9	1.3900	F1—C4^i	1.521 (8)
C8—H8	0.9500	P1—C1^i	1.836 (4)
C9—C10	1.3900	P1—C7^i	1.838 (10)
C9—H9	0.9500	P1—C7B	1.862 (13)
C10—F2	1.350 (13)	P1—C7B^i	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—P2^i	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	C1^i—P1—C7	101.8 (5)
C5—C6—H6	120.0	C1—P1—C7	101.8 (5)
C1—C6—H6	120.0	C1^i—P1—C7^i	101.8 (5)
C8—C7—C12	120.0	C1—P1—C7^i	101.8 (5)
C8—C7—P1	128.1 (9)	C7—P1—C7^i	95.9 (17)
C12—C7—P1	111.9 (9)	C1^i—P1—C7B	111.7 (6)
C7—C8—C9	120.0	C1—P1—C7B	111.7 (6)
C7—C8—H8	120.0	C7^i—P1—C7B	96.7 (3)
C9—C8—H8	120.0	C1^i—P1—C7B^i	111.7 (6)
C10—C9—C8	120.0	C1—P1—C7B^i	111.7 (6)
C10—C9—H9	120.0	C7—P1—C7B^i	96.7 (3)
C8—C9—H9	120.0	C7B—P1—C7B^i	95.6 (19)
F2—C10—C9	117.2 (9)	C1^i—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	C7^i—P1—Rh1	119.4 (7)
C12—C11—H11	120.0	C7B—P1—Rh1	110.6 (8)
C10—C11—H11	120.0	C7B^i—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—P2^i	96.05 (3)
C15—C14—H14	119.5	P2—Rh1—P2^i	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	P2^i—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—C7^i	93.6 (12)
P1—C1—C2—C3	−170.91 (16)	C12—C7—P1—C7^i	−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—C7B^i	104.1 (13)
C2—C3—C4—C5	0.8	C12—C7—P1—C7B^i	−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)	C1^i—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)	C7^i—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	C7B^i—P1—Rh1—P2	−41.3 (9)
P2—C19—C20—C21	−177.8 (3)	C1^i—P1—Rh1—P2^i	−86.36 (4)
C19—C20—C21—C22	0.0	C1—P1—Rh1—P2^i	−86.36 (4)
C20—C21—C22—F4	−178.6 (5)	C7—P1—Rh1—P2^i	35.2 (8)
C20—C21—C22—C23	0.0	C7^i—P1—Rh1—P2^i	152.1 (8)
F4—C22—C23—C24	178.6 (5)	C7B—P1—Rh1—P2^i	41.3 (9)
C21—C22—C23—C24	0.0	C7B^i—P1—Rh1—P2^i	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—P2^i	14.6 (4)
P2—C25—C26—C27	177.5 (5)	C13—P2—Rh1—P2^i	−101.8 (3)
C25—C26—C27—C28	0.4 (10)	C25—P2—Rh1—P2^i	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)	C1^i—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)	C7^i—P1—C7B—C8B	83.8 (14)
C5—C4—F1—F1^i	−90.3 (7)	C7B^i—P1—C7B—C8B	94.3 (12)
C3—C4—F1—F1^i	85.4 (5)	Rh1—P1—C7B—C8B	−151.2 (10)
C5—C4—F1—C4^i	−90.3 (3)	C1^i—P1—C7B—C12B	169.5 (8)
C3—C4—F1—C4^i	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)	C7^i—P1—C7B—C12B	−84.9 (10)
C2—C1—P1—C7^i	130.4 (10)	C7B^i—P1—C7B—C12B	−74.4 (14)
C6—C1—P1—C7^i	−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—C7B^i	126.9 (11)	C7B—C8B—C9B—C10B	0.0
C6—C1—P1—C7B^i	−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—C1^i	−9.8 (14)	C9B—C10B—C11B—C12B	0.0
C12—C7—P1—C1^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^ii	0.95	2.51	3.458 (9)	172
O1—H1O···Cl1^iii	1.03 (5)	2.34 (5)	3.369 (9)	174 (11)

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