μ-Oxido-bis­­[hydridotris(tri­methyl­phosphane-κP)iridium(III)](Ir—Ir) bis­­(tetra­fluorido­borate) dihydrate

The title compound, [Ir₂H₂O(C₃H₉P)₆](BF₄)₂·2H₂O, was isolated from the reaction between [Ir(COD)(PMe₃)₃]BF₄ and H₂ in water (COD is cyclo­octa-1,5-diene). The asymmetric unit consists of one Ir^III atom bonded to three PMe₃ groups, one hydride ligand and half an oxide ligand, in addition to a BF₄⁻ counter-ion and one water molecule of hydration. The single oxide ligand bridging two Ir^III atoms is disordered across an inversion center with each O atom having a 50% site occupancy. Each Ir^III atom has three PMe₃ groups occupying facial positions, with the half-occupancy O atoms, a hydride ligand and an Ir—Ir bond completing the coordination sphere. The Ir—Ir distance is 2.8614 (12) Å, comparable to other iridium(III) metal–metal bonds. Two water mol­ecules hydrogen bond to two BF₄⁻ anions in the unit cell.

Related literature

For previous work on the aqueous chemistry of Ir(H)₂(Cl)(PMe₃)₃, see: Merola et al. (2012). For the synthesis of [Ir(COD)(PMe₃)₃]BF₄, see: Frazier & Merola (1992). For an Ir—Ir bond bridged only by an oxide, see: McGhee et al. (1988). For Ir—Ir bonds bridged by hydroxide and methoxide ligands, see: Fujita et al. (2000) (CCDC deposition numbers 146417–146418). For an Ir—Ir bond bridged by a phenoxide group, see: Lee et al. (2009) (CCDC deposition number 729562). For an Ir—Ir bond bridged by an oxide and a phenyl­imido group, see: Dobbs & Bergman (1994) (CCDC deposition number 645882). For a classic discussion of the trans effect and trans influence, see: Hartley (1973). For a description of the Cambridge Crystallographic Database, see: Groom & Allen (2014).

Experimental

Crystal data

• [Ir₂H₂O(C₃H₉P)₆](BF₄)₂·2H₂O

• M_r = 1068.50

• Triclinic,

• a = 9.2686 (19) Å

• b = 9.6491 (19) Å

• c = 11.082 (2) Å

• α = 96.48 (3)°

• β = 97.81 (3)°

• γ = 97.97 (3)°

• V = 963.6 (3) ų

• Z = 1

• Mo Kα radiation

• μ = 7.21 mm⁻¹

• T = 298 K

• 0.5 × 0.3 × 0.2 mm

Data collection

• Siemens P4 diffractometer

• Absorption correction: ψ scan (North et al., 1968) T_min = 0.293, T_max = 0.420

• 4707 measured reflections

• 4430 independent reflections

• 3949 reflections with I > 2σ(I)

• R_int = 0.015

• 3 standard reflections every 300 reflections intensity decay: 0.0 (1)

Refinement

• R[F² > 2σ(F²)] = 0.034

• wR(F²) = 0.086

• S = 1.10

• 4430 reflections

• 196 parameters

• 1 restraint

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

• Δρ_max = 1.04 e Å⁻³

• Δρ_min = −1.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯F1^i	0.85	2.08	2.856 (15)	152
O2—H2B⋯F4^ii	0.85	1.96	2.804 (18)	170
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z-1.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.

Supporting information

S1. Comment

Our studies of the aqueous catalysis of iridium trimethylphosphine complexes led us to a detailed study of the solution behavior and catalytic chemistry of H₂Ir(PMe₃)₃Cl in water (Merola et al., 2012). H₂Ir(PMe₃)₃Cl is formed by the reaction between [Ir(COD)(PMe₃)₃]Cl and H₂ in water (COD = 1,5-cyclooctadiene). The reaction of H₂ with [Ir(COD)(PMe₃)₃][BF₄] (Frazier & Merola, 1992) was investigated to see how a poorly coordinating anion will affect that system. The reaction of hydrogen gas with the BF₄^- salt did not lead to a clean product, but to a yellow solid that, according to its ¹H NMR spectrum, is a very complex mixture of products. The hydride region of the spectrum was particularly complicated with many hydride resonances from δ -10 to -40 p.p.m.. Slow cooling of an aqueous solution of the reaction mixture produced a few crystals suitable for X-ray diffraction. The title compound is a dinuclear iridium complex with an iridium—iridium bond bridged by a single oxo bridge. Iridium hydride hydrogen atoms were located via a difference map and set at a fixed Ir—H distance of 1.55 Å with U_iso set at 1.5 the U_eq of iridium. The oxo bridge is disordered about the inversion center. The Ir—P bond distances are 2.2524 (19), 2.258 (2), and 2.4001 (17) Å with the longer bond length for P trans to H which has a large trans influence (Hartley, 1973). The dinuclear iridium fragment is a dication charge balanced by two BF₄^- ions that show the large thermal ellipsoids common for fluorinated anions. There are two waters of hydration in the crystal lattice that are hydrogen-bonded to the BF₄^- ions.

There were some issues with making correct assignments for the title compound in the absence of clear spectral identification. One must be cautious in the assignment of hydrogen attached to a heavy metal such as iridium, but the presence of iridium hydrides is consistent with one set of resonances found in the ¹H NMR spectrum at δ -11 p.p.m. as a doublet of triplets due to coupling to the hydrogen from one trans P atom (larger doublet coupling) and two cis P atoms (smaller triplet coupling). The larger Ir—P bond distance for one of the PMe₃ ligands is also consistent with a hydride ligand situated trans to it. That the bridging ligand is a single oxo bridge may be inferred by the fact that the iridium fragment is a dication - two oxo bridges would make the fragment neutral. Attempts were made to solve and refine the structure in P1 to try and resolve the issue of the disordered oxo group, but working in P1 led to a significantly poorer structure model. In addition, models with bridging hydroxides were attempted and also found to be unsatisfactory.

There are 783 structures in the CSD with Ir—Ir bonds, but when limited to those also bridged by oxygen, there are only 6 entries (Groom & Allen, 2014). Two of the structures contained bridging hydroxide and methoxide (Fujita et al., 2000) with Ir—Ir distances of 2.953 (1) and 2.933 (4) Å respectively. An Ir—Ir bond bridged by a phenoxide ligand had an Ir—Ir distance of 2.902 (4) Å (Lee et al., 2009). An Ir—Ir bond with a bridging oxide with no other bridging ligand displayed an Ir—Ir bond of 2.6172 (4) Å (McGhee et al., 1988) and two iridium atoms bridged with both an oxide and a phenylimido ligand showed an Ir—Ir distance of 2.7220 (2) Å (Dobbs & Bergman, 1994). The Ir—Ir distance in the title compound of 2.8614 (12) Å is consistent with a single metal-metal bond bridged by an oxide rather than an alkoxide or hydroxide.

Related literature

For previous work on the aqueous chemistry of Ir(H)₂(Cl)(PMe₃)₃, see: Merola et al. (2012). For the synthesis of [Ir(COD)(PMe₃)₃]BF₄, see: Frazier & Merola (1992). For an Ir—Ir bond bridged only by an oxide, see: McGhee et al. (1988). For Ir—Ir bonds bridged by hydroxide and methoxide ligands, see: Fujita et al. (2000) (CCDC deposition numbers 146417–146418). For an Ir—Ir bond bridged by a phenoxide group, see: Lee et al. (2009) (CCDC deposition number 729562). For an Ir—Ir bond bridged by an oxide and a phenylimido group, see: Dobbs & Bergman (1994) (CCDC deposition number 645882). For a classic discussion of the trans effect and the trans influence, see: Hartley (1973). A description of the Cambridge Crystallographic Database may be found in: Groom & Allen (2014).

S2. Experimental

[Ir(COD)(PMe₃)₃][BF₄] (0.100 g) (Frazier & Merola, 1992) was dissolved in 10 ml of degassed, distilled H₂O and heated to reflux while bubbling H₂ through the solution. At the end of 2 h reflux, the reaction mixture was a yellow, homogeneous solution. Removal of the solvent under reduced pressure yielded 0.062 g of a yellow powder with complicated NMR spectra indicating the presence of multiple products. Dissolving the yellow powder in water and allowing for the slow evaporation of the solution yielded a few crystals suitable for X-ray diffraction. Screening 3 of the dozen or so crytals all showed the same unit cell.

S3. Refinement

Trimethylphosphine H atoms were placed at calculated positions and refined using a model in which the H atoms ride on the carbon atom to which it is attached with U_iso(H) = 1.5U_eq(C). The metal hydride hydrogen atoms were placed based on electron density from a difference map, the distance fixed to 1.55 Å and Uiso(H)=1.5Ueq(Ir) but the coordinates were allowed to refine. Hydrogen atoms on water were placed based on hydrogen-bonding vectors, U_iso(H) = 1.5U_eq(O) and the water was treated as a rigid group in refinement.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. Thermal ellipsoid plot of the structure with ellipsoids drawn at the 50% probability level. Atoms are labeled with superscripts to indicate the symmetry operator that generated them. A^1: –X,-Y,2-Z, A^2: 1-X,1-Y,1-Z, A^3: -1+X,+Y,1+Z, A^4: 1-X,-Y,1-Z.
	Fig. 2. The hydrogen-bonding between water and the tetrafluoroborate anion in the title compound. Ellipsoids are drawn at the 50% probability level and atoms are labeled with supercripts to indicate the symmetry operator that generated them. A^1: –X,-Y,2-Z, A^2: 1-X,1-Y,1-Z, A^3: -1+X,+Y,1+Z, A^4: 1-X,-Y,1-Z.

µ-Oxido-bis[hydridotris(trimethylphosphane-κP)iridium(III)](Ir—Ir) bis(tetrafluoridoborate) dihydrate

Crystal data

[Ir2H2O(C3H9P)6](BF4)2·2H2O	Z = 1
Mr = 1068.50	F(000) = 518
Triclinic, P1	Dx = 1.841 Mg m^−3
a = 9.2686 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6491 (19) Å	Cell parameters from 35 reflections
c = 11.082 (2) Å	θ = 2–22°
α = 96.48 (3)°	µ = 7.21 mm^−1
β = 97.81 (3)°	T = 298 K
γ = 97.97 (3)°	Prism, clear light yellow
V = 963.6 (3) Å^3	0.5 × 0.3 × 0.2 mm

Data collection

Siemens P4 diffractometer	3949 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Siemens P4	Rint = 0.015
Graphite monochromator	θmax = 27.5°, θmin = 1.9°
ω scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.293, Tmax = 0.420	l = −14→14
4707 measured reflections	3 standard reflections every 300 reflections
4430 independent reflections	intensity decay: 0.0(1)

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 1.2979P] where P = (Fo^2 + 2Fc^2)/3
4430 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 1.04 e Å^−3
1 restraint	Δρmin = −1.45 e Å^−3

Special details

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	0.44635 (2)	0.39247 (2)	0.397713 (19)	0.04330 (8)
H	0.502 (7)	0.285 (6)	0.477 (5)	0.065*
P1	0.30869 (19)	0.54619 (17)	0.29012 (15)	0.0545 (4)
P2	0.26109 (19)	0.20850 (19)	0.36625 (17)	0.0573 (4)
P3	0.5672 (2)	0.3085 (2)	0.24848 (19)	0.0650 (5)
O1	0.6514 (12)	0.5458 (12)	0.4336 (9)	0.071 (3)	0.50
C11	0.1914 (11)	0.4787 (10)	0.1441 (8)	0.091 (3)
H11A	0.2482	0.4349	0.0888	0.137*
H11B	0.1530	0.5552	0.1092	0.137*
H11C	0.1113	0.4104	0.1572	0.137*
C12	0.4183 (10)	0.6996 (8)	0.2485 (7)	0.077 (2)
H12A	0.4619	0.7628	0.3215	0.115*
H12B	0.3563	0.7471	0.1960	0.115*
H12C	0.4947	0.6699	0.2059	0.115*
C13	0.1780 (9)	0.6263 (9)	0.3741 (8)	0.076 (2)
H13A	0.1068	0.5534	0.3938	0.114*
H13B	0.1284	0.6857	0.3241	0.114*
H13C	0.2300	0.6819	0.4486	0.114*
C21	0.2986 (10)	0.0608 (9)	0.4459 (10)	0.089 (3)
H21A	0.3734	0.0170	0.4114	0.133*
H21B	0.2101	−0.0068	0.4370	0.133*
H21C	0.3321	0.0936	0.5315	0.133*
C22	0.0959 (11)	0.2463 (12)	0.4220 (15)	0.133 (5)
H22A	0.1169	0.2749	0.5092	0.200*
H22B	0.0224	0.1633	0.4043	0.200*
H22C	0.0600	0.3210	0.3823	0.200*
C23	0.1925 (15)	0.1187 (14)	0.2126 (10)	0.153 (6)
H23A	0.1346	0.1767	0.1678	0.230*
H23B	0.1325	0.0306	0.2172	0.230*
H23C	0.2741	0.1012	0.1713	0.230*
C31	0.6143 (17)	0.1367 (12)	0.2590 (11)	0.136 (6)
H31A	0.6139	0.1158	0.3416	0.203*
H31B	0.7107	0.1338	0.2372	0.203*
H31C	0.5435	0.0681	0.2038	0.203*
C32	0.7546 (11)	0.4063 (16)	0.2693 (13)	0.139 (5)
H32A	0.7517	0.5056	0.2861	0.208*
H32B	0.7968	0.3878	0.1958	0.208*
H32C	0.8137	0.3769	0.3369	0.208*
C33	0.5107 (14)	0.3194 (16)	0.0923 (9)	0.129 (5)
H33A	0.4247	0.2506	0.0615	0.194*
H33B	0.5886	0.3015	0.0466	0.194*
H33C	0.4881	0.4122	0.0834	0.194*
F1	0.1765 (12)	0.0878 (10)	0.8932 (9)	0.183 (4)
F2	0.0995 (18)	0.1122 (13)	0.7112 (9)	0.239 (6)
F3	0.2533 (12)	0.2732 (13)	0.8167 (16)	0.276 (8)
F4	0.0302 (11)	0.2307 (12)	0.8445 (11)	0.195 (5)
B1	0.1475 (12)	0.1797 (12)	0.8151 (11)	0.082 (3)
O2	0.8397 (15)	0.1785 (12)	0.0159 (12)	0.152 (4)
H2A	0.8300	0.0897	0.0167	0.227*
H2B	0.9030	0.2028	−0.0295	0.227*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.04201 (12)	0.03886 (12)	0.04581 (13)	0.01001 (8)	−0.00422 (8)	0.00061 (8)
P1	0.0565 (9)	0.0488 (8)	0.0551 (9)	0.0168 (7)	−0.0087 (7)	0.0040 (7)
P2	0.0473 (8)	0.0595 (9)	0.0631 (10)	0.0015 (7)	0.0047 (7)	0.0133 (8)
P3	0.0593 (10)	0.0768 (12)	0.0724 (11)	0.0272 (9)	0.0252 (9)	0.0294 (9)
O1	0.073 (6)	0.078 (7)	0.054 (5)	0.013 (5)	−0.004 (5)	−0.001 (5)
C11	0.091 (6)	0.092 (6)	0.080 (5)	0.032 (5)	−0.034 (5)	−0.003 (5)
C12	0.087 (6)	0.072 (5)	0.069 (5)	0.014 (4)	−0.005 (4)	0.019 (4)
C13	0.061 (4)	0.081 (5)	0.088 (5)	0.033 (4)	0.000 (4)	0.008 (4)
C21	0.083 (6)	0.062 (5)	0.122 (8)	0.005 (4)	0.009 (5)	0.031 (5)
C22	0.069 (6)	0.111 (8)	0.252 (17)	0.032 (6)	0.075 (8)	0.078 (10)
C23	0.159 (12)	0.161 (11)	0.088 (7)	−0.101 (10)	−0.029 (7)	0.012 (7)
C31	0.215 (15)	0.115 (8)	0.129 (9)	0.105 (10)	0.103 (10)	0.044 (7)
C32	0.065 (6)	0.221 (16)	0.147 (11)	0.021 (8)	0.041 (7)	0.066 (11)
C33	0.139 (10)	0.215 (14)	0.064 (5)	0.094 (10)	0.036 (6)	0.040 (7)
F1	0.223 (10)	0.145 (7)	0.182 (8)	0.062 (7)	−0.027 (7)	0.050 (6)
F2	0.349 (18)	0.228 (12)	0.105 (6)	−0.025 (12)	0.014 (8)	−0.015 (7)
F3	0.136 (8)	0.222 (12)	0.46 (2)	−0.071 (8)	0.055 (11)	0.102 (14)
F4	0.173 (8)	0.227 (11)	0.245 (11)	0.118 (8)	0.097 (8)	0.110 (9)
B1	0.077 (6)	0.080 (6)	0.086 (7)	0.003 (5)	0.013 (5)	0.003 (5)
O2	0.179 (10)	0.139 (8)	0.165 (9)	0.073 (8)	0.071 (7)	0.027 (7)

Geometric parameters (Å, º)

Ir1—Ir1^i	2.8614 (12)	C13—H13C	0.9600
Ir1—H	1.53 (2)	C21—H21A	0.9600
Ir1—P1	2.4000 (17)	C21—H21B	0.9600
Ir1—P2	2.2524 (19)	C21—H21C	0.9600
Ir1—P3	2.258 (2)	C22—H22A	0.9600
Ir1—O1^i	2.242 (10)	C22—H22B	0.9600
Ir1—O1	2.200 (11)	C22—H22C	0.9600
P1—C11	1.820 (8)	C23—H23A	0.9600
P1—C12	1.817 (8)	C23—H23B	0.9600
P1—C13	1.827 (8)	C23—H23C	0.9600
P2—C21	1.808 (8)	C31—H31A	0.9600
P2—C22	1.794 (9)	C31—H31B	0.9600
P2—C23	1.809 (11)	C31—H31C	0.9600
P3—C31	1.784 (9)	C32—H32A	0.9600
P3—C32	1.830 (11)	C32—H32B	0.9600
P3—C33	1.759 (10)	C32—H32C	0.9600
O1—Ir1^i	2.242 (10)	C33—H33A	0.9600
C11—H11A	0.9600	C33—H33B	0.9600
C11—H11B	0.9600	C33—H33C	0.9600
C11—H11C	0.9600	F1—B1	1.336 (14)
C12—H12A	0.9600	F2—B1	1.249 (14)
C12—H12B	0.9600	F3—B1	1.234 (13)
C12—H12C	0.9600	F4—B1	1.318 (13)
C13—H13A	0.9600	O2—H2A	0.8500
C13—H13B	0.9600	O2—H2B	0.8499
Ir1^i—Ir1—H	88 (3)	H12B—C12—H12C	109.5
P1—Ir1—Ir1^i	92.32 (5)	P1—C13—H13A	109.5
P1—Ir1—H	167 (3)	P1—C13—H13B	109.5
P2—Ir1—Ir1^i	132.22 (5)	P1—C13—H13C	109.5
P2—Ir1—H	75 (3)	H13A—C13—H13B	109.5
P2—Ir1—P1	95.38 (7)	H13A—C13—H13C	109.5
P2—Ir1—P3	95.89 (8)	H13B—C13—H13C	109.5
P3—Ir1—Ir1^i	128.86 (6)	P2—C21—H21A	109.5
P3—Ir1—H	89 (3)	P2—C21—H21B	109.5
P3—Ir1—P1	100.31 (7)	P2—C21—H21C	109.5
O1—Ir1—Ir1^i	50.6 (3)	H21A—C21—H21B	109.5
O1^i—Ir1—Ir1^i	49.2 (3)	H21A—C21—H21C	109.5
O1^i—Ir1—H	81 (3)	H21B—C21—H21C	109.5
O1—Ir1—H	97 (3)	P2—C22—H22A	109.5
O1—Ir1—P1	93.5 (3)	P2—C22—H22B	109.5
O1^i—Ir1—P1	89.5 (3)	P2—C22—H22C	109.5
O1—Ir1—P2	170.5 (3)	H22A—C22—H22B	109.5
O1^i—Ir1—P2	83.7 (3)	H22A—C22—H22C	109.5
O1^i—Ir1—P3	170.2 (3)	H22B—C22—H22C	109.5
O1—Ir1—P3	79.2 (3)	P2—C23—H23A	109.5
O1—Ir1—O1^i	99.8 (4)	P2—C23—H23B	109.5
C11—P1—Ir1	120.0 (3)	P2—C23—H23C	109.5
C11—P1—C13	100.5 (4)	H23A—C23—H23B	109.5
C12—P1—Ir1	115.3 (3)	H23A—C23—H23C	109.5
C12—P1—C11	100.7 (4)	H23B—C23—H23C	109.5
C12—P1—C13	102.1 (4)	P3—C31—H31A	109.5
C13—P1—Ir1	115.4 (3)	P3—C31—H31B	109.5
C21—P2—Ir1	114.9 (3)	P3—C31—H31C	109.5
C21—P2—C23	100.6 (6)	H31A—C31—H31B	109.5
C22—P2—Ir1	114.6 (4)	H31A—C31—H31C	109.5
C22—P2—C21	100.8 (5)	H31B—C31—H31C	109.5
C22—P2—C23	102.8 (7)	P3—C32—H32A	109.5
C23—P2—Ir1	120.3 (4)	P3—C32—H32B	109.5
C31—P3—Ir1	115.4 (3)	P3—C32—H32C	109.5
C31—P3—C32	97.9 (7)	H32A—C32—H32B	109.5
C32—P3—Ir1	109.8 (5)	H32A—C32—H32C	109.5
C33—P3—Ir1	122.3 (4)	H32B—C32—H32C	109.5
C33—P3—C31	107.5 (6)	P3—C33—H33A	109.5
C33—P3—C32	100.0 (6)	P3—C33—H33B	109.5
Ir1—O1—Ir1^i	80.2 (4)	P3—C33—H33C	109.5
P1—C11—H11A	109.5	H33A—C33—H33B	109.5
P1—C11—H11B	109.5	H33A—C33—H33C	109.5
P1—C11—H11C	109.5	H33B—C33—H33C	109.5
H11A—C11—H11B	109.5	F2—B1—F1	108.4 (11)
H11A—C11—H11C	109.5	F2—B1—F4	102.0 (12)
H11B—C11—H11C	109.5	F3—B1—F1	112.7 (12)
P1—C12—H12A	109.5	F3—B1—F2	114.0 (13)
P1—C12—H12B	109.5	F3—B1—F4	112.5 (12)
P1—C12—H12C	109.5	F4—B1—F1	106.4 (10)
H12A—C12—H12B	109.5	H2A—O2—H2B	109.5
H12A—C12—H12C	109.5
Ir1^i—Ir1—P1—C11	−176.0 (4)	P2—Ir1—P3—C33	78.6 (6)
Ir1^i—Ir1—P1—C12	63.3 (3)	P3—Ir1—P1—C11	53.8 (4)
Ir1^i—Ir1—P1—C13	−55.5 (3)	P3—Ir1—P1—C12	−66.9 (3)
Ir1^i—Ir1—P2—C21	−75.3 (4)	P3—Ir1—P1—C13	174.3 (3)
Ir1^i—Ir1—P2—C22	40.9 (5)	P3—Ir1—P2—C21	85.6 (4)
Ir1^i—Ir1—P2—C23	164.2 (7)	P3—Ir1—P2—C22	−158.2 (5)
Ir1^i—Ir1—P3—C31	106.5 (6)	P3—Ir1—P2—C23	−34.8 (7)
Ir1^i—Ir1—P3—C32	−2.9 (5)	P3—Ir1—O1—Ir1^i	−170.1 (3)
Ir1^i—Ir1—P3—C33	−119.5 (6)	O1—Ir1—P1—C11	133.4 (5)
P1—Ir1—P2—C21	−173.4 (4)	O1^i—Ir1—P1—C11	−126.8 (5)
P1—Ir1—P2—C22	−57.2 (5)	O1^i—Ir1—P1—C12	112.5 (4)
P1—Ir1—P2—C23	66.2 (7)	O1—Ir1—P1—C12	12.7 (4)
P1—Ir1—P3—C31	−152.0 (6)	O1^i—Ir1—P1—C13	−6.3 (4)
P1—Ir1—P3—C32	98.6 (5)	O1—Ir1—P1—C13	−106.1 (4)
P1—Ir1—P3—C33	−18.0 (6)	O1^i—Ir1—P2—C21	−84.5 (5)
P1—Ir1—O1—Ir1^i	90.1 (2)	O1^i—Ir1—P2—C22	31.7 (6)
P2—Ir1—P1—C11	−43.2 (4)	O1^i—Ir1—P2—C23	155.1 (7)
P2—Ir1—P1—C12	−163.9 (3)	O1—Ir1—P3—C31	116.3 (7)
P2—Ir1—P1—C13	77.3 (3)	O1—Ir1—P3—C32	6.9 (5)
P2—Ir1—P3—C31	−55.4 (6)	O1—Ir1—P3—C33	−109.6 (7)
P2—Ir1—P3—C32	−164.9 (5)	O1^i—Ir1—O1—Ir1^i	0.0

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···F1^ii	0.85	2.08	2.856 (15)	152
O2—H2B···F4^iii	0.85	1.96	2.804 (18)	170

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