trans-Carbonyl­chlorido­bis(ferrocenyl­diphenyl­phosphane-κP)rhodium(I) dichloro­methane mono­solvate and trans-carbonyl­chlorido­bis(ferrocenyl­diphenyl­phosphane-κP)iridium(I) dichloro­methane mono­solvate

The isomorphous crystal structures of the title compounds, [Fe₂M(C₅H₅)₂(C₁₇H₁₄P)Cl(CO)]·CH₂Cl₂ or trans-[MCl(CO)(PPh₂Fc)₂]·CH₂Cl₂ (M = Rh or Ir, and Fc is ferrocenyl), are reported. The data collection for M = Rh was performed at 293 (2) K, while the M = Ir data were collected at 160 (2) K. The compounds crystallize with two independent half-mol­ecules in the asymmetric unit, both occupying inversion centres, and are accompanied by a single dichloro­methane mol­ecule on a general position. Due to the symmetry, there is 0.50/0.50 disorder present in the chloride and carbonyl positions. One mol­ecule in each structure also has a second type of disorder in the chloride and carbonyl positions, which was refined over another two positions of equal distribution. The steric impact of the bulky PPh₂Fc ligands was evaluated using the Tolman cone-angle model, resulting in an average value of 172° for the four mol­ecules in both structures.

S1. Comment

As part of our general interest in phosphane ligands containing ferrocene, a systematic study has been conducted on the PPh₂Fc ligand (Otto & Roodt, 1997; Otto et al., 1998, 2000; Otto, 2001a; Steyl et al., 2001). In addition, the rhodium Vaska systems are often used for ligand-evaluation purposes, as stable crystalline complexes are obtained containing both the CO group and the P atom as suitable handles for spectroscopic studies (Roodt et al., 2003). Even though the Rh Vaska analogue containing the PPh₂Fc ligand was published previously (Otto & Roodt, 2004), we additionally obtained crystals of the isomorphous Rh^I and Ir^I complexes containing a dichloromethane solvent molecule, namely trans-carbonylchloridobis(ferrocenyldiphenylphosphane-κP)rhodium(I) dichloromethane monosolvate, (I), and trans-carbonylchloridobis(ferrocenyldiphenylphosphane-κP)iridium(I) dichloromethane monosolvate, (II), the results of which are reported herein.

The title coordination complexes crystallize with two independent molecules in the asymmetric unit, with each crystallographically independent molecule straddling an inversion centre (at the Rh and Ir metal centre), resulting in a 0.50/0.50 statistical disorder in the Cl^- and CO groups. Each pair of half-molecules is accompanied by a single dichloromethane solvent molecule located on a general position. Molecule 1 of each structure additionally suffers from a second disorder in the Cl^- and CO positions, which has been refined with an equal distribution over two sites (see Fig. 1 and the Refinement section for further details).

Each of these coordination complexes exhibits a distorted square-planar geometry, with the bulky PPh₂Fc ligands in a trans orientation, as expected (Figs. 1 and 2). Due to the disorder in the Cl^- and CO positions, the bond distances associated with these ligands could only be obtained with less than the desirable level of accuracy and additional restraints were required to maintain comparable lengths for identical bonds (Table 1). The bond distances and angles within the PPh₂Fc ligands are within normal ranges, with typically a shorter P—C bond to the ferrocenyl group than those to the Ph groups. The two cyclopentadienyl rings within the ferrocenyl group also display the expected eclipsed conformation typical for mono-substitution. The orientations of the ferrocenyl groups were found to differ by 7.3 (2) and 7.3 (3)° between molecules 1 and 2 for (I) and (II), respectively, as shown by the relevant torsion angles (Table 1).

Isomorphism is not uncommon in molecules containing large ligands that can dominate the packing mode in the crystal structure. Especially in square-planar complexes, large ligands trans to each other can render insignificant any small variations in the linear coordination core of the molecule. In this regard, we have reported the extensive isomorphism observed in a series of complexes, trans-[MRRY(EPh₃)₂], where M = Pt or Pd, R = ?, RY = Cl₂ or MeCl and E = P or As (Otto, 2001b). Discovering that the Rh and Ir Vaska complexes containing the bulky PPh₂Fc ligand are isomorphous should thus not be unexpected at all when they are crystallized from the same solvent. The extent to which the PPh₂Fc ligands dominate the packing results in the two structures being very similar, with major differences limited to slight variations in bond distances and angles of the CO and Cl ligands (Table 1). The major differences in some of the `inner core' geometric parameters include C1A—M1—Cl1A = 165.4 (6)° in (I) and 171.8 (9)° in (II), and O2—C2—M2 = 157.7 (15)° in (I) and 174.8 (17)° in (II).

The average M—P bond distances are within the expected ranges at 2.3352 (13) and 2.3280 (19) Å, as is the case for the average M—Cl bond distances at 2.380 (4) and 2.354 (5) Å for (I) and (II), respectively (see Table 2 for comparative data from the literature). In all complexes listed in Table 2, both the M—P and M—Cl bond distances are slightly longer for Rh than for Ir.

Describing the steric demand of phosphane ligands has been the topic of many studies and a variety of models have been developed (Bunten et al., 2002). In practice, the Tolman cone angle (Tolman, 1977) is still the most commonly used model, due to its simplicity and ease of calculation. Applying this model (using an M—P bond distance of 2.28 Å) to the data here results in values of 171 and 172° for molecules 1 and 2 of (I), respectively, and 172° for both molecules of (II). The Tolman model has been further developed (Otto, 2001c) into the concept of the `effective cone angle', where the crystallographically determined metal—P bond length is used in the calculations. Using this model results in values of 169 and 170° for (I) and 171 and 170° for (II). The steric demand of the PPh₂Fc ligand was previously shown to be very dependent on the orientation of the Fc moiety (Otto et al., 2000). It is, however, clear from the current data that the 7.3 (2) and 7.3 (3)° difference in orientation for the Rh and Ir complexes, respectively, does not result in a significant altering of the steric impact experienced in the two molecules.

Related literature

For related literature, see: Bunten et al. (2002); Otto (2001a, 2001b, 2001c); Otto & Roodt (1997, 2004); Otto et al. (1998, 2000); Roodt et al. (2003); Sollot et al. (1963); Steyl et al. (2001); Tolman (1977).

S2. Experimental

The PPh₂Fc ligand was synthesized according to the literature procedure of Sollot et al. (1963). trans-[RhCl(CO)(PPh₂Fc)₂], (I), was prepared as described previously (Otto & Roodt, 2004). Recrystallization from dichloromethane gave crystals suitable for single-crystal diffraction studies. ³¹P NMR (CDCl₃, δ, p.p.m.): 22.27 (¹J_Rh—P = 127.7 Hz); IR (CH₂Cl₂, ν, cm^-1): 1970. trans-[IrCl(CO)(PPh₂Fc)₂], (II), was prepared under inert conditions by dissolving [Ir(µ-Cl)(COD)]₂ (10 mg, 0.0149 mmol) in a 1:1 mixture of dichloromethane and hexane (10 ml), and PPh₂Fc (23 mg, 0.0606 mmol), dissolved in the same solvent mixture (5 ml), was added dropwise. The reaction mixture was stirred for 5 min, after which CO gas was bubbled through the solution until most of the solvent (90%) had evaporated and complete precipitation occurred. The precipitate was redissolved in dichloromethane and slow evaporation of the solvent yielded crystals of (II) suitable for diffraction studies. ¹H NMR (CDCl₃, δ, p.p.m.): 4.3–4.4 (m, 18H), 7.32–7.50 (m, 20H); IR (KBr, ν, cm^-1): 1958.

S3. Refinement

The Cl^-—M—CO portions of the two structures showed different behaviour for the two independent molecules in the unit cell. In each case, one unit (labelled Rh1 and Ir1) had large thermal vibrations associated with the Cl and CO ligands. These ligands, already disordered in a 50:50 ratio due to the inversion centre, was further split over an additional two positions and refined with independent occupancies summing to 0.50. As the values obtained from the refinment were very similar [for Rh, (I): A = 0.242 (3) and B = 0.258 (3); for Ir, (II): A = 0.235 (4) and B = 0.265 (4)], the values were subsequently fixed at a 0.25 occupancy for each in the final refinement cycles. Several bonding and ellipsoid restraints were applied to ensure that the refinement remained stable.

All H atoms were placed in geometrically idealized positions, with C—H = 0.93 for CH (aryl) and 0.97 Å for CH₂, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) for CH and CH₂. The maximum residual electron density for both structures is located within 0.4 Å of atom Cl4, associated with the dichloromethane solvent molecule, while the minimum residual electron density for both structures is situated within 0.1 Å of atom Cl1B.

Computing details

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The structure of molecule 1 of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms and the statistical disorder in the CO and Cl positions have been omitted for clarity; the random disorder in the CO and Cl positions is indicated. Molecule 2 is numbered accordingly, with the first digit referring to the number of the molecule and the second and third digits to the atom in the molecule. [Symmetry code: (ii) -x, -y + 2, -z + 2.]

Fig. 2. The structure of molecule 2 of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms and the statistical disorder in the CO and Cl positions have been omitted for clarity. Molecule 1 is numbered accordingly, with the first digit referring to the number of the molecule and the second and third digits to the atom in the molecule. [Symmetry code: (ii) -x + 1, -y + 1, -z + 1.]

(I) trans-Carbonylchloridobis(ferrocenyldiphenylphosphane- κP)rhodium(I) dichloromethane monosolvate

Crystal data

[Fe2Rh(C5H5)2(C17H14P)Cl(CO)]·CH2Cl2	Z = 2
Mr = 991.68	F(000) = 1004
Triclinic, P1	Dx = 1.585 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4520 (19) Å	Cell parameters from 4557 reflections
b = 12.989 (3) Å	θ = 2.3–25.3°
c = 18.067 (4) Å	µ = 1.39 mm^−1
α = 108.05 (3)°	T = 293 K
β = 96.38 (3)°	Rectangle, yellow
γ = 95.21 (3)°	0.30 × 0.15 × 0.05 mm
V = 2077.4 (9) Å^3

Data collection

Siemens SMART CCD diffractometer	10001 independent reflections
Radiation source: rotating anode	5920 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 28.0°, θmin = 1.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1998)	h = −12→12
Tmin = 0.700, Tmax = 0.894	k = −16→17
18195 measured reflections	l = −23→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0666P)^2] where P = (Fo^2 + 2Fc^2)/3
10001 reflections	(Δ/σ)max = 0.001
518 parameters	Δρmax = 1.27 e Å^−3
58 restraints	Δρmin = −1.42 e Å^−3

Special details

Experimental. The intensity data was collected on a Siemens SMART CCD diffractometer using an exposure time of 25 s/frame. A total of 1250 frames were collected with a frame width of 0.2° covering up to θ = 56.0°; a 99.2% completeness was accomplished at 28.00°. The first 50 frames were recollected at the end of each data collection to check for decay; none was found.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rh1	0.0000	1.0000	1.0000	0.03252 (14)
Cl1A	−0.1146 (5)	0.9353 (4)	0.8680 (3)	0.03252 (14)	0.25
C1A	−0.1261 (18)	0.9433 (14)	0.9109 (9)	0.03252 (14)	0.25
O1A	−0.1856 (13)	0.9204 (9)	0.8503 (7)	0.03252 (14)	0.25
Cl1B	−0.0442 (5)	0.9514 (4)	0.8598 (2)	0.03252 (14)	0.25
C1B	−0.060 (2)	0.9635 (15)	0.8986 (8)	0.03252 (14)	0.25
O1B	−0.1068 (14)	0.9302 (9)	0.8271 (7)	0.03252 (14)	0.25
P1	0.10423 (11)	0.83877 (9)	0.97563 (7)	0.0303 (3)
Fe1	−0.19038 (7)	0.64444 (5)	0.94785 (4)	0.03981 (18)
C111	0.1945 (5)	0.8087 (3)	1.0598 (3)	0.0345 (10)
C112	0.1263 (5)	0.8182 (4)	1.1249 (3)	0.0464 (12)
H112	0.0380	0.8445	1.1269	0.056*
C113	0.1884 (7)	0.7891 (5)	1.1873 (3)	0.0617 (15)
H113	0.1404	0.7934	1.2301	0.074*
C114	0.3202 (7)	0.7542 (5)	1.1858 (4)	0.0687 (17)
H114	0.3628	0.7363	1.2283	0.082*
C115	0.3892 (6)	0.7456 (5)	1.1228 (4)	0.0681 (17)
H115	0.4792	0.7221	1.1224	0.082*
C116	0.3269 (5)	0.7714 (4)	1.0592 (3)	0.0506 (13)
H116	0.3743	0.7636	1.0157	0.061*
C121	0.2443 (4)	0.8420 (3)	0.9143 (3)	0.0345 (10)
C122	0.3342 (6)	0.9388 (4)	0.9284 (3)	0.0578 (15)
H122	0.3218	1.0011	0.9684	0.069*
C123	0.4413 (6)	0.9429 (5)	0.8835 (4)	0.0735 (19)
H123	0.5017	1.0079	0.8937	0.088*
C124	0.4599 (6)	0.8530 (5)	0.8243 (4)	0.0663 (17)
H124	0.5320	0.8572	0.7939	0.080*
C125	0.3741 (6)	0.7571 (5)	0.8093 (3)	0.0611 (16)
H125	0.3876	0.6955	0.7690	0.073*
C126	0.2663 (5)	0.7519 (4)	0.8546 (3)	0.0509 (13)
H126	0.2076	0.6861	0.8443	0.061*
C131	−0.0042 (4)	0.7090 (3)	0.9244 (3)	0.0352 (10)
C132	−0.1149 (5)	0.6844 (4)	0.8588 (3)	0.0480 (13)
H132	−0.1494	0.7341	0.8360	0.058*
C133	−0.1631 (6)	0.5705 (5)	0.8343 (3)	0.0640 (17)
H133	−0.2339	0.5328	0.7921	0.077*
C134	−0.0865 (6)	0.5242 (4)	0.8841 (4)	0.0610 (16)
H134	−0.0990	0.4512	0.8813	0.073*
C135	0.0126 (5)	0.6075 (4)	0.9391 (3)	0.0457 (12)
H135	0.0780	0.5986	0.9783	0.055*
C141	−0.2558 (6)	0.7578 (5)	1.0385 (3)	0.0550 (14)
H141	−0.2094	0.8282	1.0647	0.066*
C142	−0.3605 (5)	0.7274 (5)	0.9721 (4)	0.0622 (16)
H142	−0.3959	0.7733	0.9461	0.075*
C143	−0.4026 (6)	0.6145 (6)	0.9518 (4)	0.077 (2)
H143	−0.4717	0.5726	0.9100	0.092*
C144	−0.3225 (7)	0.5752 (5)	1.0055 (4)	0.0717 (19)
H144	−0.3287	0.5032	1.0052	0.086*
C145	−0.2323 (6)	0.6643 (5)	1.0592 (4)	0.0626 (16)
H145	−0.1678	0.6622	1.1013	0.075*
Rh2	0.5000	0.5000	0.5000	0.03466 (14)
Cl2	0.5256 (5)	0.6146 (3)	0.63371 (19)	0.0789 (9)	0.50
C2	0.5070 (16)	0.5829 (10)	0.5930 (7)	0.0687 (10)	0.50
O2	0.5568 (14)	0.6296 (10)	0.6634 (5)	0.0762 (12)	0.50
P2	0.42352 (12)	0.35186 (9)	0.53968 (7)	0.0339 (3)
Fe2	0.10676 (7)	0.23933 (5)	0.41303 (4)	0.04052 (18)
C211	0.5783 (5)	0.2868 (4)	0.5636 (3)	0.0371 (11)
C212	0.7000 (6)	0.3500 (5)	0.6075 (3)	0.0578 (15)
H212	0.7033	0.4256	0.6255	0.069*
C213	0.8199 (6)	0.3025 (6)	0.6257 (4)	0.0696 (18)
H213	0.9025	0.3464	0.6560	0.084*
C214	0.8163 (6)	0.1930 (6)	0.5997 (4)	0.0661 (17)
H214	0.8959	0.1610	0.6120	0.079*
C215	0.6978 (7)	0.1312 (5)	0.5562 (4)	0.085 (2)
H215	0.6960	0.0558	0.5376	0.102*
C216	0.5784 (6)	0.1760 (4)	0.5382 (4)	0.0736 (19)
H216	0.4964	0.1306	0.5083	0.088*
C221	0.3447 (5)	0.3903 (3)	0.6302 (3)	0.0337 (10)
C222	0.3826 (6)	0.3519 (4)	0.6916 (3)	0.0556 (14)
H222	0.4527	0.3055	0.6879	0.067*
C223	0.3181 (7)	0.3814 (5)	0.7581 (4)	0.0727 (18)
H223	0.3461	0.3553	0.7992	0.087*
C224	0.2136 (6)	0.4485 (4)	0.7652 (3)	0.0555 (14)
H224	0.1704	0.4679	0.8105	0.067*
C225	0.1735 (5)	0.4868 (4)	0.7045 (3)	0.0472 (12)
H225	0.1018	0.5319	0.7081	0.057*
C226	0.2388 (5)	0.4588 (4)	0.6382 (3)	0.0413 (11)
H226	0.2116	0.4863	0.5977	0.050*
C231	0.2951 (5)	0.2374 (4)	0.4786 (3)	0.0371 (11)
C232	0.1780 (5)	0.1867 (4)	0.5042 (3)	0.0446 (12)
H232	0.1535	0.2081	0.5547	0.054*
C233	0.1059 (6)	0.0986 (4)	0.4398 (3)	0.0523 (14)
H233	0.0243	0.0530	0.4401	0.063*
C234	0.1785 (6)	0.0912 (4)	0.3748 (3)	0.0534 (14)
H234	0.1543	0.0388	0.3253	0.064*
C235	0.2941 (5)	0.1767 (4)	0.3974 (3)	0.0453 (12)
H235	0.3582	0.1910	0.3652	0.054*
C241	0.0893 (6)	0.3962 (4)	0.4219 (3)	0.0557 (14)
H241	0.1569	0.4562	0.4499	0.067*
C242	−0.0232 (6)	0.3551 (5)	0.4504 (4)	0.0599 (15)
H242	−0.0444	0.3818	0.5014	0.072*
C243	−0.1015 (7)	0.2652 (5)	0.3895 (5)	0.077 (2)
H243	−0.1837	0.2229	0.3929	0.093*
C244	−0.0330 (8)	0.2511 (6)	0.3227 (4)	0.082 (2)
H244	−0.0611	0.1976	0.2739	0.098*
C245	0.0854 (7)	0.3325 (5)	0.3430 (3)	0.0663 (17)
H245	0.1503	0.3426	0.3099	0.080*
C3	0.2715 (14)	0.0346 (12)	0.7278 (9)	0.2379 (17)
H3A	0.2222	−0.0376	0.7202	0.285*
H3B	0.3256	0.0589	0.7804	0.285*
Cl3	0.3897 (5)	0.0164 (4)	0.6683 (3)	0.2417 (16)
Cl4	0.1550 (5)	0.1079 (4)	0.7305 (2)	0.2333 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
Cl1A	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
C1A	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
O1A	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
Cl1B	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
C1B	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
O1B	0.0383 (3)	0.0309 (3)	0.0287 (3)	0.0117 (2)	0.0063 (2)	0.0077 (2)
P1	0.0315 (6)	0.0296 (6)	0.0315 (6)	0.0081 (5)	0.0092 (5)	0.0098 (5)
Fe1	0.0349 (4)	0.0404 (4)	0.0454 (4)	0.0022 (3)	0.0128 (3)	0.0141 (3)
C111	0.034 (2)	0.034 (2)	0.038 (3)	0.0088 (19)	0.0041 (19)	0.014 (2)
C112	0.049 (3)	0.051 (3)	0.042 (3)	0.014 (2)	0.008 (2)	0.016 (2)
C113	0.079 (4)	0.069 (4)	0.043 (3)	0.009 (3)	0.009 (3)	0.026 (3)
C114	0.067 (4)	0.086 (5)	0.064 (4)	0.009 (3)	−0.015 (3)	0.048 (4)
C115	0.051 (3)	0.087 (5)	0.082 (5)	0.028 (3)	0.003 (3)	0.046 (4)
C116	0.040 (3)	0.056 (3)	0.063 (4)	0.013 (2)	0.011 (2)	0.028 (3)
C121	0.034 (2)	0.036 (2)	0.037 (3)	0.0058 (19)	0.0093 (19)	0.016 (2)
C122	0.066 (4)	0.038 (3)	0.071 (4)	0.003 (3)	0.024 (3)	0.017 (3)
C123	0.060 (4)	0.067 (4)	0.101 (5)	−0.011 (3)	0.030 (4)	0.038 (4)
C124	0.052 (3)	0.094 (5)	0.060 (4)	0.006 (3)	0.028 (3)	0.030 (4)
C125	0.055 (3)	0.074 (4)	0.047 (3)	0.007 (3)	0.025 (3)	0.003 (3)
C126	0.048 (3)	0.048 (3)	0.051 (3)	0.002 (2)	0.022 (2)	0.005 (2)
C131	0.033 (2)	0.036 (2)	0.037 (3)	0.0047 (19)	0.013 (2)	0.010 (2)
C132	0.056 (3)	0.052 (3)	0.033 (3)	−0.004 (2)	0.005 (2)	0.013 (2)
C133	0.072 (4)	0.058 (4)	0.041 (3)	−0.023 (3)	0.016 (3)	−0.008 (3)
C134	0.070 (4)	0.040 (3)	0.073 (4)	0.004 (3)	0.035 (3)	0.010 (3)
C135	0.041 (3)	0.035 (3)	0.065 (4)	0.010 (2)	0.025 (2)	0.015 (2)
C141	0.049 (3)	0.058 (3)	0.062 (4)	0.013 (3)	0.027 (3)	0.016 (3)
C142	0.038 (3)	0.076 (4)	0.085 (5)	0.020 (3)	0.018 (3)	0.035 (4)
C143	0.035 (3)	0.096 (5)	0.089 (5)	−0.009 (3)	0.020 (3)	0.016 (4)
C144	0.063 (4)	0.066 (4)	0.104 (6)	0.007 (3)	0.051 (4)	0.040 (4)
C145	0.055 (3)	0.084 (4)	0.063 (4)	0.015 (3)	0.030 (3)	0.036 (3)
Rh2	0.0473 (3)	0.0296 (3)	0.0325 (3)	0.0106 (2)	0.0134 (2)	0.0136 (2)
Cl2	0.112 (2)	0.0621 (17)	0.0422 (18)	−0.0347 (16)	0.0178 (18)	−0.0008 (16)
C2	0.1020 (18)	0.0519 (17)	0.0387 (17)	−0.0247 (16)	0.0152 (18)	0.0036 (16)
O2	0.109 (2)	0.060 (2)	0.041 (2)	−0.030 (2)	0.014 (2)	0.000 (2)
P2	0.0402 (6)	0.0319 (6)	0.0351 (7)	0.0111 (5)	0.0089 (5)	0.0158 (5)
Fe2	0.0502 (4)	0.0348 (4)	0.0360 (4)	0.0149 (3)	0.0016 (3)	0.0096 (3)
C211	0.040 (3)	0.039 (3)	0.039 (3)	0.011 (2)	0.011 (2)	0.019 (2)
C212	0.053 (3)	0.052 (3)	0.074 (4)	0.001 (3)	−0.002 (3)	0.034 (3)
C213	0.043 (3)	0.089 (5)	0.084 (5)	−0.001 (3)	−0.007 (3)	0.047 (4)
C214	0.055 (4)	0.087 (5)	0.071 (4)	0.036 (3)	0.014 (3)	0.039 (4)
C215	0.077 (5)	0.061 (4)	0.105 (6)	0.035 (4)	−0.016 (4)	0.011 (4)
C216	0.064 (4)	0.046 (3)	0.100 (5)	0.017 (3)	−0.014 (3)	0.015 (3)
C221	0.039 (2)	0.031 (2)	0.035 (3)	0.0089 (19)	0.0066 (19)	0.0138 (19)
C222	0.065 (3)	0.069 (4)	0.059 (4)	0.040 (3)	0.029 (3)	0.041 (3)
C223	0.093 (5)	0.104 (5)	0.055 (4)	0.050 (4)	0.035 (3)	0.056 (4)
C224	0.062 (3)	0.061 (4)	0.048 (3)	0.017 (3)	0.024 (3)	0.018 (3)
C225	0.052 (3)	0.042 (3)	0.046 (3)	0.017 (2)	0.012 (2)	0.007 (2)
C226	0.045 (3)	0.041 (3)	0.037 (3)	0.011 (2)	−0.002 (2)	0.012 (2)
C231	0.044 (3)	0.034 (2)	0.037 (3)	0.014 (2)	0.004 (2)	0.016 (2)
C232	0.049 (3)	0.041 (3)	0.048 (3)	0.006 (2)	0.003 (2)	0.022 (2)
C233	0.051 (3)	0.039 (3)	0.069 (4)	0.002 (2)	0.000 (3)	0.024 (3)
C234	0.068 (4)	0.031 (3)	0.053 (3)	0.015 (2)	−0.002 (3)	0.003 (2)
C235	0.055 (3)	0.039 (3)	0.045 (3)	0.021 (2)	0.014 (2)	0.010 (2)
C241	0.070 (4)	0.045 (3)	0.056 (4)	0.025 (3)	0.002 (3)	0.019 (3)
C242	0.065 (4)	0.060 (4)	0.058 (4)	0.031 (3)	0.010 (3)	0.016 (3)
C243	0.055 (4)	0.075 (5)	0.096 (6)	0.011 (3)	−0.011 (4)	0.026 (4)
C244	0.100 (5)	0.073 (5)	0.058 (4)	0.031 (4)	−0.035 (4)	0.012 (4)
C245	0.094 (5)	0.072 (4)	0.049 (4)	0.037 (4)	0.010 (3)	0.035 (3)
C3	0.225 (3)	0.231 (3)	0.214 (3)	0.017 (3)	0.073 (3)	0.000 (3)
Cl3	0.235 (3)	0.232 (3)	0.218 (3)	0.023 (3)	0.081 (3)	0.002 (3)
Cl4	0.214 (3)	0.231 (3)	0.208 (3)	0.008 (3)	0.065 (3)	−0.002 (3)

Geometric parameters (Å, º)

Rh1—C1B^i	1.756 (14)	Rh2—C2^ii	1.682 (12)
Rh1—C1B	1.756 (14)	Rh2—P2	2.3358 (13)
Rh1—C1A^i	1.798 (14)	Rh2—P2^ii	2.3358 (13)
Rh1—C1A	1.798 (14)	Rh2—Cl2^ii	2.385 (3)
Rh1—P1	2.3345 (12)	Rh2—Cl2	2.385 (3)
Rh1—P1^i	2.3345 (12)	Cl2—O2	0.550 (10)
Rh1—Cl1A^i	2.364 (4)	Cl2—C2	0.715 (11)
Rh1—Cl1A	2.364 (4)	C2—O2	1.242 (14)
Rh1—Cl1B^i	2.390 (4)	P2—C231	1.806 (5)
Rh1—Cl1B	2.390 (4)	P2—C221	1.819 (5)
C1A—O1A	1.112 (16)	P2—C211	1.831 (5)
C1B—O1B	1.243 (16)	C211—C212	1.359 (7)
P1—C131	1.805 (5)	C211—C216	1.369 (7)
P1—C121	1.824 (4)	C212—C213	1.395 (7)
P1—C111	1.826 (5)	C212—H212	0.9300
C111—C112	1.381 (6)	C213—C214	1.349 (8)
C111—C116	1.383 (6)	C213—H213	0.9300
C112—C113	1.383 (7)	C214—C215	1.328 (8)
C112—H112	0.9300	C214—H214	0.9300
C113—C114	1.364 (8)	C215—C216	1.369 (7)
C113—H113	0.9300	C215—H215	0.9300
C114—C115	1.354 (8)	C216—H216	0.9300
C114—H114	0.9300	C221—C222	1.376 (6)
C115—C116	1.379 (7)	C221—C226	1.389 (6)
C115—H115	0.9300	C222—C223	1.372 (7)
C116—H116	0.9300	C222—H222	0.9300
C121—C126	1.374 (6)	C223—C224	1.367 (7)
C121—C122	1.389 (6)	C223—H223	0.9300
C122—C123	1.374 (8)	C224—C225	1.369 (7)
C122—H122	0.9300	C224—H224	0.9300
C123—C124	1.358 (8)	C225—C226	1.372 (7)
C123—H123	0.9300	C225—H225	0.9300
C124—C125	1.357 (8)	C226—H226	0.9300
C124—H124	0.9300	C231—C232	1.430 (6)
C125—C126	1.385 (7)	C231—C235	1.433 (6)
C125—H125	0.9300	C232—C233	1.409 (7)
C126—H126	0.9300	C232—H232	0.9300
C131—C132	1.425 (6)	C233—C234	1.406 (8)
C131—C135	1.441 (6)	C233—H233	0.9300
C132—C133	1.421 (7)	C234—C235	1.412 (7)
C132—H132	0.9300	C234—H234	0.9300
C133—C134	1.402 (8)	C235—H235	0.9300
C133—H133	0.9300	C241—C242	1.369 (8)
C134—C135	1.406 (7)	C241—C245	1.403 (8)
C134—H134	0.9300	C241—H241	0.9300
C135—H135	0.9300	C242—C243	1.410 (8)
C141—C142	1.395 (8)	C242—H242	0.9300
C141—C145	1.406 (8)	C243—C244	1.403 (10)
C141—H141	0.9300	C243—H243	0.9300
C142—C143	1.404 (8)	C244—C245	1.399 (9)
C142—H142	0.9300	C244—H244	0.9300
C143—C144	1.410 (9)	C245—H245	0.9300
C143—H143	0.9300	C3—Cl4	1.515 (11)
C144—C145	1.396 (9)	C3—Cl3	1.618 (11)
C144—H144	0.9300	C3—H3A	0.9700
C145—H145	0.9300	C3—H3B	0.9700
Rh2—C2	1.682 (12)
C1A^i—Rh1—C1A	180.000 (6)	C144—C145—H145	125.9
P1—Rh1—P1^i	180.000 (1)	C141—C145—H145	125.9
C1B—Rh1—Cl1A^i	170.4 (7)	C2—Rh2—C2^ii	180.000 (3)
C1A^i—Rh1—Cl1A^i	14.6 (6)	C2—Rh2—P2	89.1 (4)
C1A—Rh1—Cl1A^i	165.4 (6)	C2^ii—Rh2—P2	90.9 (4)
P1—Rh1—Cl1A^i	91.64 (12)	C2—Rh2—P2^ii	90.9 (4)
P1^i—Rh1—Cl1A^i	88.36 (12)	C2^ii—Rh2—P2^ii	89.1 (4)
C1A^i—Rh1—Cl1A	165.4 (6)	P2—Rh2—P2^ii	180.0
P1—Rh1—Cl1A	88.36 (12)	C2—Rh2—Cl2^ii	176.2 (6)
P1^i—Rh1—Cl1A	91.64 (12)	P2—Rh2—Cl2^ii	91.20 (11)
C1B^i—Rh1—Cl1B^i	8.5 (7)	P2^ii—Rh2—Cl2^ii	88.80 (11)
C1B—Rh1—Cl1B^i	171.5 (7)	C2^ii—Rh2—Cl2	176.2 (6)
P1—Rh1—Cl1B^i	95.46 (11)	P2—Rh2—Cl2	88.80 (11)
P1^i—Rh1—Cl1B^i	84.54 (11)	P2^ii—Rh2—Cl2	91.20 (11)
C1B^i—Rh1—Cl1B	171.5 (7)	O2—Cl2—C2	158 (2)
C1A^i—Rh1—Cl1B	147.9 (6)	O2—Cl2—Rh2	149.1 (19)
P1—Rh1—Cl1B	84.54 (11)	Cl2—C2—Rh2	167.2 (19)
P1^i—Rh1—Cl1B	95.46 (11)	O2—C2—Rh2	157.7 (15)
O1A—Cl1A—C1A	98.5 (17)	C231—P2—C221	101.1 (2)
O1A—Cl1A—Rh1	134.0 (12)	C231—P2—C211	103.0 (2)
Cl1A—C1A—Rh1	129.3 (18)	C221—P2—C211	103.9 (2)
O1A—C1A—Rh1	165.9 (18)	C231—P2—Rh2	123.34 (15)
C1B—Cl1B—O1B	117 (2)	C221—P2—Rh2	113.70 (14)
O1B—Cl1B—Rh1	138.5 (12)	C211—P2—Rh2	109.69 (15)
Cl1B—C1B—Rh1	150 (2)	C212—C211—C216	117.7 (5)
O1B—C1B—Rh1	175.1 (17)	C212—C211—P2	119.5 (4)
C131—P1—C121	103.2 (2)	C216—C211—P2	122.8 (4)
C131—P1—C111	100.2 (2)	C211—C212—C213	120.6 (5)
C121—P1—C111	103.9 (2)	C211—C212—H212	119.7
C131—P1—Rh1	119.96 (15)	C213—C212—H212	119.7
C121—P1—Rh1	109.57 (15)	C214—C213—C212	120.2 (5)
C111—P1—Rh1	117.90 (15)	C214—C213—H213	119.9
C112—C111—C116	118.4 (4)	C212—C213—H213	119.9
C112—C111—P1	119.5 (3)	C215—C214—C213	119.3 (5)
C116—C111—P1	122.0 (4)	C215—C214—H214	120.4
C111—C112—C113	120.5 (5)	C213—C214—H214	120.4
C111—C112—H112	119.7	C214—C215—C216	121.6 (6)
C113—C112—H112	119.7	C214—C215—H215	119.2
C114—C113—C112	119.9 (5)	C216—C215—H215	119.2
C114—C113—H113	120.1	C211—C216—C215	120.7 (6)
C112—C113—H113	120.1	C211—C216—H216	119.7
C115—C114—C113	120.3 (5)	C215—C216—H216	119.7
C115—C114—H114	119.8	C222—C221—C226	117.5 (4)
C113—C114—H114	119.8	C222—C221—P2	122.8 (3)
C114—C115—C116	120.5 (5)	C226—C221—P2	119.7 (3)
C114—C115—H115	119.7	C223—C222—C221	120.8 (5)
C116—C115—H115	119.7	C223—C222—H222	119.6
C115—C116—C111	120.3 (5)	C221—C222—H222	119.6
C115—C116—H116	119.8	C224—C223—C222	121.2 (5)
C111—C116—H116	119.8	C224—C223—H223	119.4
C126—C121—C122	117.9 (4)	C222—C223—H223	119.4
C126—C121—P1	122.8 (3)	C223—C224—C225	118.9 (5)
C122—C121—P1	119.2 (4)	C223—C224—H224	120.5
C123—C122—C121	120.3 (5)	C225—C224—H224	120.5
C123—C122—H122	119.9	C224—C225—C226	120.1 (5)
C121—C122—H122	119.9	C224—C225—H225	119.9
C124—C123—C122	120.6 (5)	C226—C225—H225	119.9
C124—C123—H123	119.7	C225—C226—C221	121.4 (5)
C122—C123—H123	119.7	C225—C226—H226	119.3
C125—C124—C123	120.5 (5)	C221—C226—H226	119.3
C125—C124—H124	119.8	C232—C231—C235	106.9 (4)
C123—C124—H124	119.8	C232—C231—P2	125.7 (4)
C124—C125—C126	119.3 (5)	C235—C231—P2	127.4 (4)
C124—C125—H125	120.3	C233—C232—C231	108.3 (5)
C126—C125—H125	120.3	C233—C232—H232	125.9
C121—C126—C125	121.3 (5)	C231—C232—H232	125.9
C121—C126—H126	119.3	C234—C233—C232	108.3 (5)
C125—C126—H126	119.3	C234—C233—H233	125.8
C132—C131—C135	106.6 (4)	C232—C233—H233	125.8
C132—C131—P1	127.5 (4)	C233—C234—C235	108.6 (5)
C135—C131—P1	125.8 (4)	C233—C234—H234	125.7
C133—C132—C131	107.9 (5)	C235—C234—H234	125.7
C133—C132—H132	126.1	C234—C235—C231	107.9 (5)
C131—C132—H132	126.1	C234—C235—H235	126.1
C134—C133—C132	108.9 (5)	C231—C235—H235	126.1
C134—C133—H133	125.6	C242—C241—C245	108.4 (6)
C132—C133—H133	125.6	C242—C241—H241	125.8
C133—C134—C135	108.1 (5)	C245—C241—H241	125.8
C133—C134—H134	126.0	C241—C242—C243	108.4 (6)
C135—C134—H134	126.0	C241—C242—H242	125.8
C134—C135—C131	108.6 (5)	C243—C242—H242	125.8
C134—C135—H135	125.7	C244—C243—C242	107.7 (6)
C131—C135—H135	125.7	C244—C243—H243	126.1
C142—C141—C145	108.5 (5)	C242—C243—H243	126.1
C142—C141—H141	125.7	C245—C244—C243	107.3 (6)
C145—C141—H141	125.7	C245—C244—H244	126.4
C141—C142—C143	107.3 (6)	C243—C244—H244	126.4
C141—C142—H142	126.3	C244—C245—C241	108.2 (6)
C143—C142—H142	126.3	C244—C245—H245	125.9
C142—C143—C144	108.6 (6)	C241—C245—H245	125.9
C142—C143—H143	125.7	Cl4—C3—Cl3	126.1 (12)
C144—C143—H143	125.7	Cl4—C3—H3A	105.8
C145—C144—C143	107.4 (6)	Cl3—C3—H3A	105.8
C145—C144—H144	126.3	Cl4—C3—H3B	105.8
C143—C144—H144	126.3	Cl3—C3—H3B	105.8
C144—C145—C141	108.2 (6)	H3A—C3—H3B	106.2
Rh1—P1—C131—C141	−50.1 (2)	C124—C125—C126—C121	0.1 (9)
Rh2—P2—C231—C241	−42.8 (2)	C121—P1—C131—C132	−82.3 (4)
C1B—Rh1—Cl1A—O1A	−154 (4)	C111—P1—C131—C132	170.7 (4)
C1A^i—Rh1—Cl1A—O1A	−167 (3)	Rh1—P1—C131—C132	39.9 (5)
P1—Rh1—Cl1A—O1A	114.9 (16)	C121—P1—C131—C135	92.9 (4)
P1^i—Rh1—Cl1A—O1A	−65.1 (16)	C111—P1—C131—C135	−14.2 (4)
P1—Rh1—Cl1A—C1A	102 (2)	Rh1—P1—C131—C135	−145.0 (3)
P1^i—Rh1—Cl1A—C1A	−78 (2)	C135—C131—C132—C133	−0.3 (5)
Cl1B^i—Rh1—Cl1A—C1A	−1 (2)	P1—C131—C132—C133	175.6 (4)
Cl1B—Rh1—Cl1A—C1A	179 (2)	C131—C132—C133—C134	1.0 (6)
Rh1—Cl1A—C1A—O1A	170.9 (18)	C132—C133—C134—C135	−1.4 (6)
O1A—Cl1A—C1A—Rh1	−170.9 (18)	C133—C134—C135—C131	1.2 (6)
C1B^i—Rh1—C1A—Cl1A	−174.4 (17)	C132—C131—C135—C134	−0.6 (5)
C1B—Rh1—C1A—Cl1A	5.6 (17)	P1—C131—C135—C134	−176.5 (3)
P1—Rh1—C1A—Cl1A	−78 (2)	C145—C141—C142—C143	0.3 (6)
P1^i—Rh1—C1A—Cl1A	102 (2)	C141—C142—C143—C144	−0.6 (6)
Cl1B^i—Rh1—C1A—Cl1A	179.6 (14)	C142—C143—C144—C145	0.6 (6)
Cl1B—Rh1—C1A—Cl1A	−0.4 (14)	C143—C144—C145—C141	−0.4 (6)
Rh1—Cl1A—O1A—C1A	−7.4 (15)	C142—C141—C145—C144	0.0 (6)
C1B—Rh1—Cl1B—O1B	−11 (4)	P2—Rh2—Cl2—O2	78 (3)
C1A^i—Rh1—Cl1B—O1B	−174.4 (18)	P2^ii—Rh2—Cl2—O2	−102 (3)
C1A—Rh1—Cl1B—O1B	5.6 (18)	Cl2^ii—Rh2—P2—C231	−32.0 (2)
P1—Rh1—Cl1B—O1B	107.3 (16)	Cl2—Rh2—P2—C231	148.0 (2)
P1^i—Rh1—Cl1B—O1B	−72.7 (16)	C2—Rh2—P2—C221	21.4 (5)
Cl1A—Rh1—Cl1B—O1B	5.3 (15)	C2^ii—Rh2—P2—C221	−158.6 (5)
Rh1—Cl1B—C1B—O1B	−172 (3)	Cl2^ii—Rh2—P2—C221	−154.8 (2)
O1B—Cl1B—C1B—Rh1	172 (3)	Cl2—Rh2—P2—C221	25.2 (2)
P1^i—Rh1—C1B—Cl1B	119 (4)	C2—Rh2—P2—C211	−94.4 (5)
C1B^i—Rh1—P1—C131	124.2 (7)	C2^ii—Rh2—P2—C211	85.6 (5)
C1B—Rh1—P1—C131	−55.8 (7)	Cl2^ii—Rh2—P2—C211	89.4 (2)
C1A^i—Rh1—P1—C131	148.2 (6)	Cl2—Rh2—P2—C211	−90.6 (2)
C1A—Rh1—P1—C131	−31.8 (6)	C231—P2—C211—C212	177.7 (4)
Cl1A^i—Rh1—P1—C131	133.9 (2)	C221—P2—C211—C212	−77.2 (5)
Cl1A—Rh1—P1—C131	−46.1 (2)	Rh2—P2—C211—C212	44.7 (5)
Cl1B^i—Rh1—P1—C131	116.8 (2)	C231—P2—C211—C216	−1.5 (5)
Cl1B—Rh1—P1—C131	−63.2 (2)	C221—P2—C211—C216	103.7 (5)
C1B^i—Rh1—P1—C121	−116.8 (7)	Rh2—P2—C211—C216	−134.4 (5)
C1B—Rh1—P1—C121	63.2 (7)	C216—C211—C212—C213	−0.1 (9)
C1A^i—Rh1—P1—C121	−92.9 (6)	P2—C211—C212—C213	−179.3 (4)
Cl1A^i—Rh1—P1—C121	−107.2 (2)	C211—C212—C213—C214	0.2 (10)
Cl1A—Rh1—P1—C121	72.8 (2)	C212—C213—C214—C215	0.3 (10)
Cl1B^i—Rh1—P1—C121	−124.3 (2)	C213—C214—C215—C216	−1.0 (12)
Cl1B—Rh1—P1—C121	55.7 (2)	C212—C211—C216—C215	−0.5 (10)
C1B^i—Rh1—P1—C111	1.7 (7)	P2—C211—C216—C215	178.7 (5)
C1B—Rh1—P1—C111	−178.3 (7)	C214—C215—C216—C211	1.1 (12)
C1A^i—Rh1—P1—C111	25.6 (6)	C231—P2—C221—C222	93.7 (4)
C1A—Rh1—P1—C111	−154.4 (6)	C211—P2—C221—C222	−12.9 (5)
Cl1A^i—Rh1—P1—C111	11.3 (2)	Rh2—P2—C221—C222	−132.1 (4)
Cl1A—Rh1—P1—C111	−168.7 (2)	C231—P2—C221—C226	−84.6 (4)
Cl1B^i—Rh1—P1—C111	−5.8 (2)	C211—P2—C221—C226	168.9 (4)
Cl1B—Rh1—P1—C111	174.2 (2)	Rh2—P2—C221—C226	49.7 (4)
C131—P1—C111—C112	−84.3 (4)	C226—C221—C222—C223	−0.4 (8)
C121—P1—C111—C112	169.2 (4)	P2—C221—C222—C223	−178.7 (5)
Rh1—P1—C111—C112	47.7 (4)	C221—C222—C223—C224	0.7 (10)
C131—P1—C111—C116	92.5 (4)	C222—C223—C224—C225	−0.2 (10)
C121—P1—C111—C116	−14.0 (4)	C223—C224—C225—C226	−0.7 (8)
Rh1—P1—C111—C116	−135.4 (3)	C224—C225—C226—C221	1.0 (8)
C116—C111—C112—C113	−1.2 (7)	C222—C221—C226—C225	−0.4 (7)
P1—C111—C112—C113	175.8 (4)	P2—C221—C226—C225	177.9 (4)
C111—C112—C113—C114	2.2 (8)	C221—P2—C231—C232	−8.0 (4)
C112—C113—C114—C115	−1.5 (9)	C211—P2—C231—C232	99.2 (4)
C113—C114—C115—C116	−0.4 (10)	Rh2—P2—C231—C232	−136.4 (3)
C114—C115—C116—C111	1.4 (9)	C221—P2—C231—C235	175.3 (4)
C112—C111—C116—C115	−0.6 (7)	C211—P2—C231—C235	−77.5 (4)
P1—C111—C116—C115	−177.5 (4)	Rh2—P2—C231—C235	47.0 (4)
C131—P1—C121—C126	−11.6 (5)	C235—C231—C232—C233	−1.0 (5)
C111—P1—C121—C126	92.6 (5)	P2—C231—C232—C233	−178.3 (3)
Rh1—P1—C121—C126	−140.5 (4)	C231—C232—C233—C234	1.7 (6)
C131—P1—C121—C122	169.0 (4)	C232—C233—C234—C235	−1.8 (6)
C111—P1—C121—C122	−86.7 (4)	C233—C234—C235—C231	1.1 (5)
Rh1—P1—C121—C122	40.1 (4)	C232—C231—C235—C234	0.0 (5)
C126—C121—C122—C123	0.0 (8)	P2—C231—C235—C234	177.1 (3)
P1—C121—C122—C123	179.4 (5)	C245—C241—C242—C243	−0.8 (6)
C121—C122—C123—C124	0.7 (10)	C241—C242—C243—C244	0.8 (7)
C122—C123—C124—C125	−0.9 (11)	C242—C243—C244—C245	−0.4 (7)
C123—C124—C125—C126	0.5 (10)	C243—C244—C245—C241	−0.1 (7)
C122—C121—C126—C125	−0.4 (8)	C242—C241—C245—C244	0.5 (6)
P1—C121—C126—C125	−179.7 (4)

Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C235—H235···Cl2^ii	0.93	2.65	3.300 (7)	127

Symmetry code: (ii) −x+1, −y+1, −z+1.

(II) trans-carbonylchloridobis(ferrocenyldiphenylphosphane- κP)iridium(I) dichloromethane monosolvate

Crystal data

[Fe2Ir(C5H5)2(C17H14P)Cl(CO)]·CH2Cl2	Z = 2
Mr = 1080.97	F(000) = 1068
Triclinic, P1	Dx = 1.728 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.436 (5) Å	Cell parameters from 4091 reflections
b = 12.978 (5) Å	θ = 2.4–24.6°
c = 18.091 (5) Å	µ = 4.19 mm^−1
α = 107.903 (5)°	T = 160 K
β = 96.269 (5)°	Needle, orange
γ = 95.225 (5)°	0.24 × 0.05 × 0.04 mm
V = 2077.3 (15) Å^3

Data collection

Siemens SMART CCD diffractometer	9994 independent reflections
Radiation source: rotating anode	5972 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ω scans	θmax = 28.0°, θmin = 1.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1998)	h = −12→12
Tmin = 0.433, Tmax = 0.850	k = −15→17
18144 measured reflections	l = −23→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0386P)^2] where P = (Fo^2 + 2Fc^2)/3
9994 reflections	(Δ/σ)max = 0.001
518 parameters	Δρmax = 1.44 e Å^−3
58 restraints	Δρmin = −1.32 e Å^−3

Special details

Experimental. The intensity data was collected on a Siemens SMART CCD 1 K diffractometer using an exposure time of 10 s/frame. A total of 1350 frames were collected with a frame width of 0.3° covering up to θ = 28.0° with 99.3% completeness accomplished. The first 50 frames were recollected at the end of each data collection to check for decay; none was found.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ir1	0.0000	1.0000	1.0000	0.02625 (11)
Cl1A	−0.1245 (8)	0.9324 (6)	0.8718 (3)	0.02625 (11)	0.25
C1A	−0.116 (3)	0.947 (2)	0.9097 (11)	0.02625 (11)	0.25
O1A	−0.1689 (19)	0.9243 (14)	0.8396 (9)	0.02625 (11)	0.25
Cl1B	−0.0552 (8)	0.9494 (6)	0.8625 (3)	0.02625 (11)	0.25
C1B	−0.060 (3)	0.968 (2)	0.9005 (10)	0.02625 (11)	0.25
O1B	−0.095 (2)	0.9352 (15)	0.8285 (9)	0.02625 (11)	0.25
P1	0.10449 (18)	0.83919 (14)	0.97508 (9)	0.0256 (4)
Fe1	−0.19047 (10)	0.64416 (8)	0.94740 (6)	0.0337 (2)
C111	0.1946 (7)	0.8094 (5)	1.0592 (4)	0.0304 (15)
C112	0.1253 (8)	0.8179 (6)	1.1251 (4)	0.0387 (18)
H112	0.0342	0.8436	1.1266	0.046*
C113	0.1856 (9)	0.7901 (7)	1.1870 (4)	0.053 (2)
H113	0.1364	0.7968	1.2310	0.064*
C114	0.3142 (10)	0.7534 (8)	1.1863 (5)	0.062 (3)
H114	0.3547	0.7326	1.2292	0.075*
C115	0.3869 (9)	0.7460 (7)	1.1233 (5)	0.061 (2)
H115	0.4793	0.7225	1.1237	0.073*
C116	0.3271 (8)	0.7721 (6)	1.0606 (5)	0.0456 (19)
H116	0.3775	0.7645	1.0169	0.055*
C121	0.2476 (7)	0.8419 (5)	0.9136 (4)	0.0298 (15)
C122	0.3363 (8)	0.9383 (6)	0.9279 (4)	0.0451 (19)
H122	0.3224	1.0023	0.9679	0.054*
C123	0.4468 (10)	0.9410 (7)	0.8829 (5)	0.062 (2)
H123	0.5111	1.0062	0.8935	0.074*
C124	0.4621 (9)	0.8496 (8)	0.8237 (5)	0.054 (2)
H124	0.5362	0.8526	0.7925	0.065*
C125	0.3741 (9)	0.7546 (7)	0.8083 (4)	0.056 (2)
H125	0.3869	0.6918	0.7668	0.067*
C126	0.2647 (7)	0.7493 (6)	0.8536 (4)	0.0415 (19)
H126	0.2028	0.6831	0.8435	0.050*
C131	−0.0034 (7)	0.7093 (5)	0.9236 (4)	0.0290 (15)
C132	−0.1118 (8)	0.6830 (6)	0.8579 (4)	0.0435 (19)
H132	−0.1449	0.7332	0.8334	0.052*
C133	−0.1635 (9)	0.5704 (7)	0.8343 (4)	0.054 (2)
H133	−0.2378	0.5321	0.7923	0.065*
C134	−0.0839 (9)	0.5253 (6)	0.8849 (5)	0.052 (2)
H134	−0.0955	0.4507	0.8822	0.062*
C135	0.0154 (8)	0.6088 (6)	0.9398 (4)	0.0397 (18)
H135	0.0823	0.6005	0.9801	0.048*
C141	−0.2590 (8)	0.7577 (7)	1.0370 (5)	0.049 (2)
H141	−0.2134	0.8300	1.0638	0.059*
C142	−0.3611 (9)	0.7267 (8)	0.9708 (5)	0.059 (2)
H142	−0.3965	0.7731	0.9433	0.071*
C143	−0.4034 (9)	0.6127 (8)	0.9514 (6)	0.062 (3)
H143	−0.4742	0.5691	0.9092	0.074*
C144	−0.3229 (10)	0.5758 (8)	1.0050 (6)	0.068 (3)
H144	−0.3279	0.5025	1.0052	0.081*
C145	−0.2335 (9)	0.6652 (7)	1.0584 (5)	0.054 (2)
H145	−0.1673	0.6638	1.1015	0.065*
Ir2	0.5000	0.5000	0.5000	0.02909 (11)
Cl2	0.5257 (6)	0.6130 (4)	0.6322 (2)	0.0595 (10)	0.50
C2	0.526 (2)	0.5731 (14)	0.5923 (9)	0.0509 (10)	0.50
O2	0.5565 (16)	0.6268 (11)	0.6658 (6)	0.0568 (12)	0.50
P2	0.42512 (19)	0.35151 (14)	0.53915 (10)	0.0294 (4)
Fe2	0.10788 (11)	0.23977 (8)	0.41240 (6)	0.0356 (2)
C211	0.5796 (7)	0.2861 (6)	0.5632 (4)	0.0318 (16)
C212	0.7015 (8)	0.3478 (7)	0.6075 (5)	0.049 (2)
H212	0.7048	0.4249	0.6261	0.058*
C213	0.8210 (9)	0.3015 (8)	0.6262 (5)	0.063 (3)
H213	0.9046	0.3466	0.6578	0.076*
C214	0.8184 (9)	0.1908 (7)	0.5992 (5)	0.053 (2)
H214	0.9006	0.1586	0.6113	0.063*
C215	0.6998 (10)	0.1280 (8)	0.5557 (6)	0.078 (3)
H215	0.6977	0.0509	0.5375	0.094*
C216	0.5787 (9)	0.1743 (7)	0.5367 (5)	0.061 (3)
H216	0.4954	0.1286	0.5054	0.073*
C221	0.3455 (7)	0.3882 (5)	0.6299 (4)	0.0285 (15)
C222	0.3815 (9)	0.3492 (7)	0.6909 (4)	0.052 (2)
H222	0.4502	0.2992	0.6858	0.063*
C223	0.3222 (10)	0.3795 (8)	0.7588 (5)	0.064 (3)
H223	0.3540	0.3553	0.8015	0.077*
C224	0.2127 (8)	0.4475 (6)	0.7639 (4)	0.046 (2)
H224	0.1669	0.4668	0.8095	0.055*
C225	0.1725 (8)	0.4858 (6)	0.7034 (4)	0.0403 (18)
H225	0.0989	0.5317	0.7069	0.048*
C226	0.2392 (8)	0.4576 (6)	0.6372 (4)	0.0395 (18)
H226	0.2124	0.4858	0.5958	0.047*
C231	0.2961 (7)	0.2378 (5)	0.4777 (4)	0.0313 (16)
C232	0.1779 (8)	0.1858 (6)	0.5031 (4)	0.0376 (17)
H232	0.1519	0.2071	0.5544	0.045*
C233	0.1072 (8)	0.0973 (6)	0.4381 (5)	0.050 (2)
H233	0.0243	0.0498	0.4381	0.060*
C234	0.1799 (9)	0.0915 (6)	0.3737 (5)	0.047 (2)
H234	0.1555	0.0389	0.3229	0.057*
C235	0.2955 (8)	0.1770 (6)	0.3971 (4)	0.0396 (18)
H235	0.3620	0.1917	0.3646	0.047*
C241	0.0911 (9)	0.3982 (6)	0.4218 (4)	0.047 (2)
H241	0.1590	0.4600	0.4508	0.056*
C242	−0.0225 (9)	0.3552 (7)	0.4514 (5)	0.056 (2)
H242	−0.0444	0.3807	0.5035	0.067*
C243	−0.1000 (10)	0.2647 (7)	0.3878 (6)	0.071 (3)
H243	−0.1845	0.2202	0.3895	0.085*
C244	−0.0273 (11)	0.2541 (9)	0.3223 (5)	0.072 (3)
H244	−0.0535	0.1998	0.2723	0.087*
C245	0.0899 (10)	0.3367 (7)	0.3430 (5)	0.054 (2)
H245	0.1564	0.3489	0.3097	0.065*
C3	0.2694 (17)	0.0340 (17)	0.7159 (12)	0.245 (2)
H3A	0.2128	−0.0396	0.6966	0.294*
H3B	0.3169	0.0409	0.7691	0.294*
Cl3	0.3924 (7)	0.0191 (5)	0.6685 (4)	0.244 (2)
Cl4	0.1573 (7)	0.1062 (5)	0.7328 (4)	0.245 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
Cl1A	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
C1A	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
O1A	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
Cl1B	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
C1B	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
O1B	0.0283 (2)	0.0269 (2)	0.0243 (2)	0.00819 (18)	0.00529 (17)	0.00756 (17)
P1	0.0232 (9)	0.0262 (9)	0.0287 (9)	0.0056 (7)	0.0081 (7)	0.0086 (7)
Fe1	0.0270 (5)	0.0359 (6)	0.0399 (6)	0.0006 (4)	0.0115 (4)	0.0134 (5)
C111	0.026 (4)	0.027 (4)	0.034 (4)	−0.002 (3)	0.002 (3)	0.005 (3)
C112	0.037 (4)	0.044 (5)	0.035 (4)	0.008 (4)	0.003 (3)	0.013 (3)
C113	0.065 (6)	0.062 (6)	0.044 (5)	0.019 (5)	0.015 (4)	0.027 (4)
C114	0.061 (6)	0.088 (7)	0.043 (5)	0.013 (5)	−0.013 (4)	0.034 (5)
C115	0.035 (5)	0.071 (6)	0.087 (7)	0.013 (5)	−0.006 (5)	0.045 (6)
C116	0.038 (5)	0.052 (5)	0.054 (5)	0.009 (4)	0.013 (4)	0.025 (4)
C121	0.026 (4)	0.034 (4)	0.034 (4)	0.005 (3)	0.011 (3)	0.014 (3)
C122	0.045 (5)	0.033 (4)	0.057 (5)	0.002 (4)	0.013 (4)	0.013 (4)
C123	0.064 (6)	0.053 (6)	0.078 (6)	−0.006 (5)	0.029 (5)	0.034 (5)
C124	0.040 (5)	0.078 (7)	0.058 (5)	0.016 (5)	0.028 (4)	0.032 (5)
C125	0.056 (6)	0.067 (6)	0.041 (4)	0.004 (5)	0.029 (4)	0.006 (4)
C126	0.033 (4)	0.042 (4)	0.046 (4)	−0.003 (3)	0.022 (4)	0.006 (4)
C131	0.027 (4)	0.029 (4)	0.033 (4)	0.002 (3)	0.018 (3)	0.010 (3)
C132	0.047 (5)	0.049 (5)	0.034 (4)	−0.008 (4)	0.007 (4)	0.016 (4)
C133	0.049 (5)	0.057 (6)	0.041 (4)	−0.021 (4)	0.019 (4)	−0.003 (4)
C134	0.054 (5)	0.031 (4)	0.064 (5)	−0.003 (4)	0.024 (5)	0.003 (4)
C135	0.036 (4)	0.034 (4)	0.051 (4)	0.006 (3)	0.020 (4)	0.012 (4)
C141	0.038 (5)	0.053 (5)	0.057 (5)	0.010 (4)	0.022 (4)	0.010 (4)
C142	0.041 (5)	0.073 (7)	0.077 (6)	0.023 (5)	0.022 (5)	0.034 (5)
C143	0.028 (5)	0.074 (7)	0.081 (7)	−0.006 (5)	0.022 (5)	0.022 (6)
C144	0.061 (6)	0.066 (7)	0.091 (7)	0.003 (5)	0.038 (6)	0.040 (6)
C145	0.051 (5)	0.073 (6)	0.049 (5)	0.011 (5)	0.031 (4)	0.027 (5)
Ir2	0.0375 (3)	0.0269 (2)	0.0275 (2)	0.00832 (19)	0.01182 (18)	0.01179 (18)
Cl2	0.083 (2)	0.0490 (18)	0.0347 (17)	−0.0200 (17)	0.0143 (19)	0.0027 (17)
C2	0.0719 (18)	0.0415 (17)	0.0328 (16)	−0.0097 (16)	0.0125 (18)	0.0057 (16)
O2	0.079 (2)	0.047 (2)	0.034 (2)	−0.016 (2)	0.012 (2)	0.004 (2)
P2	0.0320 (10)	0.0295 (10)	0.0321 (9)	0.0082 (8)	0.0081 (8)	0.0153 (8)
Fe2	0.0410 (6)	0.0326 (6)	0.0330 (5)	0.0119 (5)	0.0011 (5)	0.0099 (4)
C211	0.033 (4)	0.035 (4)	0.038 (4)	0.013 (3)	0.013 (3)	0.021 (3)
C212	0.044 (5)	0.045 (5)	0.058 (5)	0.002 (4)	−0.002 (4)	0.022 (4)
C213	0.033 (5)	0.096 (8)	0.070 (6)	−0.003 (5)	−0.008 (4)	0.047 (6)
C214	0.040 (5)	0.062 (6)	0.068 (6)	0.024 (5)	0.002 (4)	0.035 (5)
C215	0.065 (7)	0.054 (6)	0.103 (8)	0.034 (5)	−0.009 (6)	0.008 (6)
C216	0.048 (5)	0.044 (5)	0.080 (6)	0.016 (4)	−0.014 (5)	0.009 (5)
C221	0.026 (4)	0.032 (4)	0.031 (3)	0.004 (3)	0.005 (3)	0.014 (3)
C222	0.058 (5)	0.072 (6)	0.047 (5)	0.027 (5)	0.017 (4)	0.040 (4)
C223	0.081 (7)	0.090 (7)	0.051 (5)	0.037 (6)	0.039 (5)	0.050 (5)
C224	0.051 (5)	0.052 (5)	0.039 (4)	0.010 (4)	0.023 (4)	0.016 (4)
C225	0.035 (4)	0.036 (4)	0.047 (4)	0.011 (3)	0.012 (4)	0.004 (4)
C226	0.043 (4)	0.044 (5)	0.029 (4)	0.012 (4)	0.003 (3)	0.008 (3)
C231	0.032 (4)	0.028 (4)	0.036 (4)	0.011 (3)	0.002 (3)	0.013 (3)
C232	0.044 (5)	0.036 (4)	0.035 (4)	0.004 (4)	0.004 (3)	0.015 (3)
C233	0.039 (5)	0.040 (5)	0.071 (6)	−0.004 (4)	−0.006 (4)	0.024 (4)
C234	0.066 (6)	0.022 (4)	0.053 (5)	0.019 (4)	0.011 (4)	0.007 (4)
C235	0.044 (5)	0.037 (4)	0.041 (4)	0.018 (4)	0.010 (4)	0.014 (4)
C241	0.056 (5)	0.035 (4)	0.052 (5)	0.018 (4)	0.007 (4)	0.015 (4)
C242	0.064 (6)	0.049 (5)	0.058 (5)	0.031 (5)	0.016 (5)	0.011 (4)
C243	0.053 (6)	0.055 (6)	0.104 (8)	0.016 (5)	−0.013 (6)	0.031 (6)
C244	0.075 (7)	0.091 (8)	0.052 (6)	0.026 (6)	−0.017 (5)	0.028 (6)
C245	0.068 (6)	0.058 (6)	0.048 (5)	0.023 (5)	0.007 (4)	0.030 (4)
C3	0.214 (5)	0.234 (5)	0.237 (5)	−0.002 (4)	0.093 (4)	−0.011 (4)
Cl3	0.218 (5)	0.233 (5)	0.234 (4)	0.001 (4)	0.097 (4)	−0.007 (4)
Cl4	0.209 (5)	0.235 (5)	0.237 (5)	−0.005 (4)	0.090 (4)	−0.013 (4)

Geometric parameters (Å, º)

Ir1—C1B	1.736 (17)	Ir2—C2	1.626 (15)
Ir1—C1B^i	1.736 (17)	Ir2—P2^ii	2.3270 (19)
Ir1—C1A	1.767 (18)	Ir2—P2	2.3270 (19)
Ir1—C1A^i	1.767 (18)	Ir2—Cl2^ii	2.362 (3)
Ir1—P1^i	2.3290 (18)	Ir2—Cl2	2.362 (3)
Ir1—P1	2.3290 (18)	Cl2—O2	0.609 (11)
Ir1—Cl1A	2.345 (5)	Cl2—C2	0.747 (15)
Ir1—Cl1A^i	2.345 (5)	C2—O2	1.283 (17)
Ir1—Cl1B	2.354 (4)	P2—C231	1.807 (7)
Ir1—Cl1B^i	2.354 (4)	P2—C221	1.828 (6)
C1A—O1A	1.244 (19)	P2—C211	1.830 (7)
C1B—O1B	1.235 (19)	C211—C212	1.357 (10)
P1—C131	1.806 (7)	C211—C216	1.380 (10)
P1—C111	1.824 (7)	C212—C213	1.383 (10)
P1—C121	1.845 (6)	C212—H212	0.9500
C111—C116	1.382 (9)	C213—C214	1.364 (12)
C111—C112	1.402 (9)	C213—H213	0.9500
C112—C113	1.362 (9)	C214—C215	1.336 (12)
C112—H112	0.9500	C214—H214	0.9500
C113—C114	1.343 (11)	C215—C216	1.397 (10)
C113—H113	0.9500	C215—H215	0.9500
C114—C115	1.376 (11)	C216—H216	0.9500
C114—H114	0.9500	C221—C222	1.372 (9)
C115—C116	1.361 (10)	C221—C226	1.399 (9)
C115—H115	0.9500	C222—C223	1.367 (10)
C116—H116	0.9500	C222—H222	0.9500
C121—C122	1.377 (9)	C223—C224	1.411 (10)
C121—C126	1.385 (9)	C223—H223	0.9500
C122—C123	1.395 (10)	C224—C225	1.366 (10)
C122—H122	0.9500	C224—H224	0.9500
C123—C124	1.363 (11)	C225—C226	1.378 (9)
C123—H123	0.9500	C225—H225	0.9500
C124—C125	1.357 (11)	C226—H226	0.9500
C124—H124	0.9500	C231—C235	1.429 (9)
C125—C126	1.396 (9)	C231—C232	1.441 (9)
C125—H125	0.9500	C232—C233	1.417 (10)
C126—H126	0.9500	C232—H232	0.9500
C131—C132	1.414 (9)	C233—C234	1.401 (10)
C131—C135	1.443 (9)	C233—H233	0.9500
C132—C133	1.413 (10)	C234—C235	1.411 (10)
C132—H132	0.9500	C234—H234	0.9500
C133—C134	1.415 (11)	C235—H235	0.9500
C133—H133	0.9500	C241—C242	1.396 (11)
C134—C135	1.410 (10)	C241—C245	1.403 (10)
C134—H134	0.9500	C241—H241	0.9500
C135—H135	0.9500	C242—C243	1.438 (11)
C141—C142	1.381 (11)	C242—H242	0.9500
C141—C145	1.402 (11)	C243—C244	1.410 (13)
C141—H141	0.9500	C243—H243	0.9500
C142—C143	1.420 (12)	C244—C245	1.399 (12)
C142—H142	0.9500	C244—H244	0.9500
C143—C144	1.391 (12)	C245—H245	0.9500
C143—H143	0.9500	C3—Cl4	1.472 (13)
C144—C145	1.395 (12)	C3—Cl3	1.509 (13)
C144—H144	0.9500	C3—H3A	0.9900
C145—H145	0.9500	C3—H3B	0.9900
Ir2—C2^ii	1.626 (15)
C1B—Ir1—P1^i	89.9 (9)	C145—C144—H144	125.9
C1B^i—Ir1—P1^i	90.1 (9)	C144—C145—C141	107.6 (8)
C1A—Ir1—P1^i	88.9 (9)	C144—C145—H145	126.2
C1A^i—Ir1—P1^i	91.1 (9)	C141—C145—H145	126.2
C1B—Ir1—P1	90.1 (9)	C2^ii—Ir2—P2^ii	87.3 (6)
C1B^i—Ir1—P1	89.9 (9)	C2—Ir2—P2^ii	92.7 (6)
C1A—Ir1—P1	91.1 (9)	C2^ii—Ir2—P2	92.7 (6)
C1A^i—Ir1—P1	88.9 (9)	C2—Ir2—P2	87.3 (6)
C1A^i—Ir1—Cl1A	171.8 (9)	C2—Ir2—Cl2^ii	176.3 (7)
P1^i—Ir1—Cl1A	91.65 (17)	P2^ii—Ir2—Cl2^ii	88.99 (13)
P1—Ir1—Cl1A	88.35 (17)	P2—Ir2—Cl2^ii	91.01 (13)
C1A—Ir1—Cl1A^i	171.8 (9)	C2^ii—Ir2—Cl2	176.3 (7)
P1^i—Ir1—Cl1A^i	88.35 (17)	P2^ii—Ir2—Cl2	91.01 (13)
P1—Ir1—Cl1A^i	91.65 (17)	P2—Ir2—Cl2	88.99 (13)
C1B^i—Ir1—Cl1B	173.1 (10)	O2—Cl2—C2	142 (3)
P1^i—Ir1—Cl1B	95.17 (17)	O2—Cl2—Ir2	150.0 (18)
P1—Ir1—Cl1B	84.83 (17)	Cl2—C2—Ir2	168 (2)
C1B—Ir1—Cl1B^i	173.1 (10)	O2—C2—Ir2	174.8 (17)
P1^i—Ir1—Cl1B^i	84.83 (17)	C231—P2—C221	100.9 (3)
P1—Ir1—Cl1B^i	95.17 (17)	C231—P2—C211	103.3 (3)
C1A—Cl1A—O1A	146 (3)	C221—P2—C211	103.2 (3)
O1A—Cl1A—Ir1	164.7 (19)	C231—P2—Ir2	122.9 (2)
Cl1A—C1A—Ir1	149 (3)	C221—P2—Ir2	114.0 (2)
O1A—C1A—Ir1	163 (2)	C211—P2—Ir2	110.3 (2)
O1B—Cl1B—C1B	140 (3)	C212—C211—C216	117.5 (7)
O1B—Cl1B—Ir1	158 (2)	C212—C211—P2	120.2 (5)
Cl1B—C1B—Ir1	155 (3)	C216—C211—P2	122.3 (6)
O1B—C1B—Ir1	173 (2)	C211—C212—C213	121.9 (8)
C131—P1—C111	100.5 (3)	C211—C212—H212	119.0
C131—P1—C121	102.8 (3)	C213—C212—H212	119.0
C111—P1—C121	103.4 (3)	C214—C213—C212	119.7 (8)
C131—P1—Ir1	120.1 (2)	C214—C213—H213	120.1
C111—P1—Ir1	117.4 (2)	C212—C213—H213	120.1
C121—P1—Ir1	110.3 (2)	C215—C214—C213	119.7 (8)
C116—C111—C112	116.6 (6)	C215—C214—H214	120.1
C116—C111—P1	123.5 (6)	C213—C214—H214	120.1
C112—C111—P1	119.8 (5)	C214—C215—C216	120.7 (8)
C113—C112—C111	121.4 (7)	C214—C215—H215	119.6
C113—C112—H112	119.3	C216—C215—H215	119.6
C111—C112—H112	119.3	C211—C216—C215	120.4 (8)
C114—C113—C112	120.6 (8)	C211—C216—H216	119.8
C114—C113—H113	119.7	C215—C216—H216	119.8
C112—C113—H113	119.7	C222—C221—C226	117.8 (6)
C113—C114—C115	119.7 (7)	C222—C221—P2	123.7 (5)
C113—C114—H114	120.1	C226—C221—P2	118.5 (5)
C115—C114—H114	120.1	C223—C222—C221	122.5 (7)
C116—C115—C114	120.4 (8)	C223—C222—H222	118.8
C116—C115—H115	119.8	C221—C222—H222	118.8
C114—C115—H115	119.8	C222—C223—C224	118.5 (7)
C115—C116—C111	121.3 (7)	C222—C223—H223	120.7
C115—C116—H116	119.3	C224—C223—H223	120.7
C111—C116—H116	119.3	C225—C224—C223	120.2 (7)
C122—C121—C126	120.5 (6)	C225—C224—H224	119.9
C122—C121—P1	118.7 (5)	C223—C224—H224	119.9
C126—C121—P1	120.8 (5)	C224—C225—C226	119.8 (7)
C121—C122—C123	119.3 (7)	C224—C225—H225	120.1
C121—C122—H122	120.3	C226—C225—H225	120.1
C123—C122—H122	120.3	C225—C226—C221	121.2 (7)
C124—C123—C122	119.7 (8)	C225—C226—H226	119.4
C124—C123—H123	120.1	C221—C226—H226	119.4
C122—C123—H123	120.1	C235—C231—C232	106.4 (6)
C125—C124—C123	121.5 (7)	C235—C231—P2	127.7 (6)
C125—C124—H124	119.2	C232—C231—P2	125.8 (5)
C123—C124—H124	119.2	C233—C232—C231	108.0 (6)
C124—C125—C126	119.8 (7)	C233—C232—H232	126.0
C124—C125—H125	120.1	C231—C232—H232	126.0
C126—C125—H125	120.1	C234—C233—C232	108.5 (7)
C121—C126—C125	119.2 (7)	C234—C233—H233	125.7
C121—C126—H126	120.4	C232—C233—H233	125.7
C125—C126—H126	120.4	C233—C234—C235	108.4 (7)
C132—C131—C135	106.8 (6)	C233—C234—H234	125.8
C132—C131—P1	128.4 (5)	C235—C234—H234	125.8
C135—C131—P1	124.6 (5)	C234—C235—C231	108.7 (7)
C133—C132—C131	109.4 (7)	C234—C235—H235	125.7
C133—C132—H132	125.3	C231—C235—H235	125.7
C131—C132—H132	125.3	C242—C241—C245	109.8 (8)
C132—C133—C134	107.1 (7)	C242—C241—H241	125.1
C132—C133—H133	126.4	C245—C241—H241	125.1
C134—C133—H133	126.4	C241—C242—C243	106.6 (8)
C135—C134—C133	109.1 (7)	C241—C242—H242	126.7
C135—C134—H134	125.4	C243—C242—H242	126.7
C133—C134—H134	125.4	C244—C243—C242	107.3 (9)
C134—C135—C131	107.4 (7)	C244—C243—H243	126.3
C134—C135—H135	126.3	C242—C243—H243	126.3
C131—C135—H135	126.3	C245—C244—C243	108.8 (9)
C142—C141—C145	109.1 (8)	C245—C244—H244	125.6
C142—C141—H141	125.5	C243—C244—H244	125.6
C145—C141—H141	125.5	C244—C245—C241	107.4 (8)
C141—C142—C143	107.1 (8)	C244—C245—H245	126.3
C141—C142—H142	126.5	C241—C245—H245	126.3
C143—C142—H142	126.5	Cl4—C3—Cl3	138.4 (19)
C144—C143—C142	108.0 (9)	Cl4—C3—H3A	102.5
C144—C143—H143	126.0	Cl3—C3—H3A	102.5
C142—C143—H143	126.0	Cl4—C3—H3B	102.5
C143—C144—C145	108.2 (9)	Cl3—C3—H3B	102.5
C143—C144—H144	125.9	H3A—C3—H3B	104.9
Ir1—P1—C131—C141	−49.5 (3)	C132—C131—C135—C134	−1.3 (7)
Ir2—P2—C231—C241	−42.2 (3)	P1—C131—C135—C134	−177.1 (5)
Ir1—Cl1A—C1A—O1A	156 (4)	C145—C141—C142—C143	1.6 (9)
P1^i—Ir1—Cl1B—O1B	−63 (5)	C141—C142—C143—C144	−1.7 (9)
P1—Ir1—Cl1B—O1B	117 (5)	C142—C143—C144—C145	1.3 (10)
Ir1—Cl1B—C1B—O1B	−167 (5)	C143—C144—C145—C141	−0.3 (9)
O1B—Cl1B—C1B—Ir1	167 (5)	C142—C141—C145—C144	−0.8 (9)
C1B—Ir1—P1—C131	−55.9 (10)	P2^ii—Ir2—Cl2—O2	−112 (3)
C1B^i—Ir1—P1—C131	124.1 (10)	P2—Ir2—Cl2—O2	68 (3)
C1A—Ir1—P1—C131	−35.2 (9)	Ir2—Cl2—O2—C2	−1 (2)
C1A^i—Ir1—P1—C131	144.8 (9)	C2^ii—Ir2—P2—C231	−29.0 (7)
Cl1A—Ir1—P1—C131	−42.9 (3)	C2—Ir2—P2—C231	151.0 (7)
Cl1A^i—Ir1—P1—C131	137.1 (3)	Cl2^ii—Ir2—P2—C231	−32.4 (3)
Cl1B—Ir1—P1—C131	−60.3 (3)	Cl2—Ir2—P2—C231	147.6 (3)
Cl1B^i—Ir1—P1—C131	119.7 (3)	C2^ii—Ir2—P2—C221	−151.3 (7)
C1B—Ir1—P1—C111	−178.5 (10)	C2—Ir2—P2—C221	28.7 (7)
C1B^i—Ir1—P1—C111	1.5 (10)	Cl2^ii—Ir2—P2—C221	−154.6 (3)
C1A—Ir1—P1—C111	−157.8 (9)	Cl2—Ir2—P2—C221	25.4 (3)
Cl1A—Ir1—P1—C111	−165.5 (3)	C2^ii—Ir2—P2—C211	93.1 (7)
Cl1B—Ir1—P1—C111	177.0 (3)	C2—Ir2—P2—C211	−86.9 (7)
Cl1B^i—Ir1—P1—C111	−3.0 (3)	Cl2—Ir2—P2—C211	−90.2 (3)
C1B—Ir1—P1—C121	63.4 (10)	C231—P2—C211—C212	177.9 (6)
C1B^i—Ir1—P1—C121	−116.6 (10)	C221—P2—C211—C212	−77.3 (6)
C1A—Ir1—P1—C121	84.1 (9)	Ir2—P2—C211—C212	44.9 (6)
C1A^i—Ir1—P1—C121	−95.9 (9)	C231—P2—C211—C216	−1.0 (7)
Cl1A—Ir1—P1—C121	76.4 (3)	C221—P2—C211—C216	103.8 (7)
Cl1A^i—Ir1—P1—C121	−103.6 (3)	Ir2—P2—C211—C216	−134.0 (6)
Cl1B—Ir1—P1—C121	59.0 (3)	C216—C211—C212—C213	−0.4 (12)
Cl1B^i—Ir1—P1—C121	−121.0 (3)	P2—C211—C212—C213	−179.3 (6)
C131—P1—C111—C116	92.1 (6)	C211—C212—C213—C214	0.6 (13)
C121—P1—C111—C116	−13.9 (7)	C212—C213—C214—C215	−0.8 (14)
Ir1—P1—C111—C116	−135.6 (6)	C213—C214—C215—C216	0.7 (15)
C131—P1—C111—C112	−84.0 (6)	C212—C211—C216—C215	0.3 (12)
C121—P1—C111—C112	169.9 (5)	P2—C211—C216—C215	179.2 (7)
Ir1—P1—C111—C112	48.2 (6)	C214—C215—C216—C211	−0.5 (15)
C116—C111—C112—C113	−0.3 (11)	C231—P2—C221—C222	93.6 (7)
P1—C111—C112—C113	176.1 (6)	C211—P2—C221—C222	−13.0 (7)
C111—C112—C113—C114	−0.1 (13)	Ir2—P2—C221—C222	−132.7 (6)
C112—C113—C114—C115	1.4 (14)	C231—P2—C221—C226	−84.7 (6)
C113—C114—C115—C116	−2.2 (14)	C211—P2—C221—C226	168.7 (6)
C114—C115—C116—C111	1.8 (13)	Ir2—P2—C221—C226	49.0 (6)
C112—C111—C116—C115	−0.5 (11)	C226—C221—C222—C223	−2.9 (12)
P1—C111—C116—C115	−176.8 (6)	P2—C221—C222—C223	178.8 (7)
C131—P1—C121—C122	168.8 (6)	C221—C222—C223—C224	4.5 (14)
C111—P1—C121—C122	−86.9 (6)	C222—C223—C224—C225	−3.0 (13)
Ir1—P1—C121—C122	39.5 (6)	C223—C224—C225—C226	0.1 (12)
C131—P1—C121—C126	−10.5 (6)	C224—C225—C226—C221	1.5 (11)
C111—P1—C121—C126	93.8 (6)	C222—C221—C226—C225	−0.1 (11)
Ir1—P1—C121—C126	−139.8 (5)	P2—C221—C226—C225	178.3 (6)
C126—C121—C122—C123	−2.0 (11)	C221—P2—C231—C235	176.5 (6)
P1—C121—C122—C123	178.7 (6)	C211—P2—C231—C235	−76.9 (6)
C121—C122—C123—C124	2.5 (12)	Ir2—P2—C231—C235	48.4 (7)
C122—C123—C124—C125	−1.5 (13)	C221—P2—C231—C232	−8.2 (6)
C123—C124—C125—C126	0.1 (14)	C211—P2—C231—C232	98.4 (6)
C122—C121—C126—C125	0.7 (11)	Ir2—P2—C231—C232	−136.3 (5)
P1—C121—C126—C125	179.9 (6)	C235—C231—C232—C233	−1.2 (8)
C124—C125—C126—C121	0.3 (12)	P2—C231—C232—C233	−177.3 (5)
C111—P1—C131—C132	171.5 (6)	C231—C232—C233—C234	1.3 (8)
C121—P1—C131—C132	−81.9 (6)	C232—C233—C234—C235	−0.8 (8)
Ir1—P1—C131—C132	41.0 (7)	C233—C234—C235—C231	0.1 (8)
C111—P1—C131—C135	−13.6 (6)	C232—C231—C235—C234	0.7 (8)
C121—P1—C131—C135	92.9 (6)	P2—C231—C235—C234	176.7 (5)
Ir1—P1—C131—C135	−144.1 (5)	C245—C241—C242—C243	−1.5 (9)
C135—C131—C132—C133	1.6 (8)	C241—C242—C243—C244	1.8 (9)
P1—C131—C132—C133	177.2 (5)	C242—C243—C244—C245	−1.5 (10)
C131—C132—C133—C134	−1.3 (8)	C243—C244—C245—C241	0.6 (10)
C132—C133—C134—C135	0.5 (9)	C242—C241—C245—C244	0.6 (9)
C133—C134—C135—C131	0.5 (8)

Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C125—H125···O2	0.95	2.56	3.349 (15)	141
C235—H235···Cl2^ii	0.95	2.64	3.286 (9)	126

Symmetry code: (ii) −x+1, −y+1, −z+1.