Di-[mu]-chloro-bis­{bis­[2,5-bis­(4-methoxy­phenyl)-1,3,4-oxadiazole-[kappa]²C^2',N]iridium(III)] dichloro­methane disolvate

In the title compound, [Ir₂(C₁₆H₁₃N₂O₃)₄Cl₂]·2CH₂Cl₂, the two Ir atoms, 3.7075 (6) Å apart, are bridged by two Cl atoms which straddle a twofold axis of rotation through the two Ir atoms. Each Ir centre resides in a distorted octa­hedral environment completed by two chelating 2,5-bis­(4-methoxy­phenyl)-1,3,4-oxadiazole ligands, with trans-N-N and cis-C-C dispositions. In the stacking structure, there are two types of hydrogen bonds, involving the meth­oxy substitutent, an N atom of the oxadiazole ring and the dichloro­methane solvent mol­ecules.

S1. Comment

In recent decades, luminescent metal complexes have attracted considerable attention, due to their intriguing photophysical, photochemical and excited-state redox properties, and their potential applications in photonic and photoelectronic devices (King et al., 1985; King & Watts, 1987). In particular, iridium(III) complexes with cyclometallated ligands show intense phosphorescence at room temperature and very promising behaviour as phosphor dyes in OLEDs (Baldo et al., 1998; Lamansky et al., 2001). On the other hand, oxadiazole derivatives have played a very important role in the field of electroactive and photoactive materials, due to their high electron affinities, which makes them good candidates for electron injection and transportation (Gregory & Martin, 2005). However, oxadiazole-based metal complexes are very scarce. To our knowledge, there have not been any reports of oxadiazole-based cyclometallated iridium complexes. In addition, although many structures of mononuclear cyclometallated iridium complexes have been determined (Lamansky et al., 2001), there are very limited reports on the structures of dinuclear iridium complexes. In this paper, a new dinuclear iridium complex, (I), with 2,5-bis(4-methoxyphenyl)-1,3,4-oxadiazole as the cyclometallated ligand, is presented.

In compound (I), which is a methylene chloride solvate, the Ir atoms, 3.7075 (6) Å apart on a twofold axis of rotation, are bridged by two Cl atoms. The Ir—C bond exerts a significant trans effect which favours the formation of bridged Ir—Cl bonds trans to the Ir—C bonds. Each Ir centre sits in a distorted octahedral environment formed by two chelating ligands with trans-N—N and cis-C—C dispositions. The molecules take the racemate form, rather than the meso form, owing to the interligand steric interactions (see scheme). This conformation is consistent with a similar dirhodium complex (Sprouse et al., 1984).

The Ir1—Cl, Ir1—C and Ir1—N bond distances are slightly different from the corresponding distances involving Ir2 (Table 1). These values are, in general, similar to those in the analogous complex [(ppy)₂IrCl]₂ (ppy = phenylpridine) [Ir—Cl 2.500 (10), Ir—C 2.020 (2) and Ir—N 2.090 (10) Å; Garces et al., 1993]. The oxadiazole plane and metallated 4-methoxyphenyl ring are coplanar, due to the formation of a five-membered chelate ring by the coordination of Ir with a C atom of the 4-methoxyphenyl and an N atom of the oxadiazole. Each free 4-methoxyphenyl ring is twisted out of the oxadiazole plane by rotation of the C—C single bond. The dihedral angles between them are 10.3 (12)° with respect to Ir1 and 13.7 (11)° with respect to Ir2.

In the stacking structure of compound (I), there are two types of weak hydrogen bonds (Table 2) between atom O3 of the methoxy substitute and an H atom on C26, and between atom N4 of oxadiazole ring and H atoms of the CH₂Cl₂ solvent molecule (Fig. 2).

The absorption and photoluminescence (PL) spectra of the dimer in CH₂Cl₂ solution were investigated (Fig. 3). In the absorption spectrum, intense absorptions are observed in the UV region of the spectrum, between 250 and 320 nm, which can be assigned to the spin-allowed π–π* transition from the cyclometallated ligands. The weaker absorption bands in the range 320–450 nm can probably be assigned to metal-to-ligand charge transfer (MLCT) and 3π–π* transition (Sprouse et al., 1984). The PL spectrum of the dimer shows two major peaks at 503 and 540 nm. The vibronic fine structures in the PL spectrum imply that the emissions predominantly result from ligand-based 3π–π* transition.

S2. Experimental

Iridium trichloride hydrate was purchased and used without further purification. 2,5-bis(4-methoxyphenyl)-1,3,4-oxadiazole was prepared following the published procedure of Sun & Wang (2001). Iridium trichloride hydrate (0.352 g, 1.0 mmol) was combined with 2.5 equivalents of the cyclometallating ligand, 2,5-bis(4-methoxyphenyl)-1,3,4-oxadiazole (0.705 g, 2.5 mmol), dissolved in a mixture of 2-ethoxyethanol (30 ml) and water (10 ml), and then refluxed for 24 h. The solution was cooled to room temperature and the resulting yellow precipitate was collected on a glass filter frit. The crude product was washed with water, ethanol and hexane. The residue was dried under vacuum and recrystallized from dichloromethane–hexane (1:1, v/v. (yield 0.515 g, 65.2%). Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 7.84 (d, J = 8.4 Hz, 8H), 7.43 (d, J = 8.4 Hz, 4H), 6.64 (d, J = 8.4 Hz, 8H), 6.42 (d, J = 8.1 Hz, 4H), 6.01 (s, 4H), 3.84 (s, 12H), 3.50 (s, 12H). Analysis, calculated for C₆₄H₅₂O₁₂N₈Cl₂Ir·2CH₂Cl₂: C 45.29, H 3.22, N 6.40%; found: C 45.23, H 3.10, N 6.21%.

S3. Refinement

Atoms O1 and C1 of the ligand were found to be disordered over two positions (O1/O1' and C1/C1'), with refined occupancies of 0.62(s.u.?) and 0.38(s.u.?) and anisotropic displacement parameters. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms. The H atoms bonded to C10, C11 and C12 [No H atoms on C10. Should it be C11, C12 and C14?] were constrained with C—H distances of 0.90 Å [0.93 Å in CIF tables?] and with U_iso(H) = 1.2U_eq(C). The other H atoms bonded to C and O atoms [No H atoms on O atoms?] were placed in calculated positions, with C—H distances of 0.96 Å and O—H distances of 0.85 ° [Remove this phrase?], and with U_iso(H) = 1.5U_eq(C). [Please check added text]

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Please provide reference); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms and solvent molecules have been omitted for clarity.
	Fig. 2. The packing structure of compound (I). Hydrogen bonds are indicated by dashed lines.
	Fig. 3. The absorption and photoluminescence spectra of the dimer in CH2Cl2 solution.

Di-µ-chloro-bis{bis[2,5-bis(4-methoxyphenyl)-1,3,4-oxadiazole- κ²C₂,N]iridium(III)] dichloromethane disolvate

Crystal data

[Ir2(C16H13N2O3)4Cl2]·2CH2Cl2	F(000) = 3440
Mr = 1750.29	Dx = 1.726 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 3335 reflections
a = 11.5352 (10) Å	θ = 2.2–20.4°
b = 23.390 (2) Å	µ = 4.25 mm^−1
c = 25.239 (2) Å	T = 292 K
β = 98.423 (2)°	Plate, yellow
V = 6736.4 (10) Å^3	0.28 × 0.20 × 0.08 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	6526 independent reflections
Radiation source: fine-focus sealed tube	4696 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ϕ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
Tmin = 0.321, Tmax = 0.712	k = −28→28
17436 measured reflections	l = −31→23

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0562P)^2] where P = (Fo^2 + 2Fc^2)/3
6526 reflections	(Δ/σ)max = 0.017
437 parameters	Δρmax = 1.84 e Å^−3
26 restraints	Δρmin = −0.69 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	0.5000	0.440885 (16)	0.7500	0.03954 (14)
Ir2	0.5000	0.282376 (15)	0.7500	0.03824 (14)
N1	0.2310 (6)	0.4305 (3)	0.6952 (3)	0.0528 (18)
N2	0.3471 (5)	0.4505 (2)	0.6986 (3)	0.0450 (15)
N3	0.3321 (5)	0.2738 (2)	0.7119 (2)	0.0424 (15)
N4	0.2632 (6)	0.2967 (2)	0.6674 (2)	0.0477 (16)
C1	−0.3612 (15)	0.4824 (10)	0.5404 (8)	0.118 (8)	0.623 (9)
H1A	−0.3539	0.5221	0.5497	0.177*	0.623 (9)
H1B	−0.4424	0.4730	0.5304	0.177*	0.623 (9)
H1C	−0.3196	0.4748	0.5109	0.177*	0.623 (9)
O1	−0.3120 (8)	0.4479 (5)	0.5861 (5)	0.088 (3)	0.623 (9)
C2	−0.1849 (11)	0.4574 (5)	0.5937 (6)	0.107 (4)
C3	−0.1489 (10)	0.4281 (5)	0.6398 (6)	0.102 (4)
H3	−0.2022	0.4082	0.6571	0.122*
C4	−0.0285 (8)	0.4288 (4)	0.6608 (5)	0.082 (3)
H4	−0.0021	0.4086	0.6919	0.099*
C5	0.0495 (8)	0.4589 (3)	0.6359 (4)	0.068 (3)
C6	0.0079 (9)	0.4891 (4)	0.5891 (5)	0.109 (4)
H6	0.0600	0.5103	0.5721	0.131*
C7	−0.1126 (11)	0.4878 (5)	0.5673 (6)	0.113 (4)
H7	−0.1406	0.5073	0.5359	0.136*
C8	0.1732 (7)	0.4605 (3)	0.6575 (4)	0.060 (2)
C9	0.3505 (7)	0.4907 (3)	0.6630 (3)	0.051 (2)
C10	0.4566 (7)	0.5216 (3)	0.6621 (3)	0.051 (2)
C11	0.4737 (8)	0.5665 (4)	0.6277 (4)	0.069 (3)
H11	0.4129	0.5778	0.6014	0.083*
C12	0.5804 (8)	0.5940 (4)	0.6325 (4)	0.075 (3)
H12	0.5919	0.6249	0.6106	0.090*
C13	0.6702 (8)	0.5744 (4)	0.6709 (4)	0.064 (2)
C14	0.6545 (7)	0.5300 (3)	0.7052 (3)	0.055 (2)
H14	0.7165	0.5182	0.7306	0.066*
C15	0.5458 (6)	0.5027 (3)	0.7018 (3)	0.0411 (17)
C16	0.8720 (8)	0.5816 (4)	0.7069 (4)	0.080 (3)
H16A	0.8556	0.5828	0.7431	0.121*
H16B	0.9394	0.6047	0.7039	0.121*
H16C	0.8871	0.5428	0.6975	0.121*
C17	−0.2700 (10)	0.3374 (5)	0.4850 (4)	0.106 (4)
H17A	−0.2333	0.3744	0.4881	0.158*
H17B	−0.3502	0.3414	0.4687	0.158*
H17C	−0.2294	0.3131	0.4632	0.158*
C18	−0.1552 (8)	0.3047 (4)	0.5659 (4)	0.062 (2)
C19	−0.0522 (8)	0.3220 (4)	0.5501 (3)	0.063 (2)
H19	−0.0521	0.3403	0.5174	0.075*
C20	0.0509 (8)	0.3120 (4)	0.5835 (4)	0.063 (2)
H20	0.1211	0.3243	0.5734	0.076*
C21	0.0526 (7)	0.2841 (3)	0.6316 (3)	0.053 (2)
C22	−0.0545 (7)	0.2663 (4)	0.6452 (4)	0.067 (3)
H22	−0.0552	0.2461	0.6768	0.081*
C23	−0.1585 (8)	0.2776 (4)	0.6135 (4)	0.074 (3)
H23	−0.2294	0.2671	0.6241	0.089*
C24	0.1623 (7)	0.2745 (3)	0.6675 (3)	0.050 (2)
C25	0.2693 (6)	0.2382 (3)	0.7347 (3)	0.0437 (18)
C26	0.3900 (9)	0.1461 (4)	0.5615 (4)	0.072 (3)
H26A	0.3419	0.1341	0.5874	0.108*
H26B	0.3673	0.1258	0.5285	0.108*
H26C	0.3801	0.1864	0.5552	0.108*
C27	0.5620 (8)	0.1602 (3)	0.6275 (3)	0.051 (2)
C28	0.5031 (7)	0.1995 (3)	0.6561 (3)	0.0452 (18)
H28	0.4256	0.2093	0.6439	0.054*
C29	0.5622 (6)	0.2242 (3)	0.7033 (3)	0.0395 (17)
C30	0.6809 (6)	0.2081 (3)	0.7187 (3)	0.0441 (18)
C31	0.7352 (7)	0.1677 (3)	0.6902 (3)	0.054 (2)
H31	0.8123	0.1571	0.7020	0.064*
C32	0.6758 (8)	0.1437 (3)	0.6449 (4)	0.060 (2)
H32	0.7118	0.1164	0.6260	0.072*
C33	0.0881 (14)	0.1582 (7)	0.4344 (5)	0.153 (6)
H33A	0.1220	0.1802	0.4079	0.183*
H33B	0.0069	0.1505	0.4202	0.183*
Cl1	0.0943 (4)	0.19664 (17)	0.49094 (17)	0.1556 (15)
Cl2	0.1639 (3)	0.09341 (16)	0.44599 (16)	0.1371 (14)
Cl3	0.43577 (17)	0.36129 (7)	0.80491 (8)	0.0443 (4)
O2	0.2436 (5)	0.4994 (2)	0.6354 (2)	0.0607 (15)
O3	0.7747 (6)	0.6027 (3)	0.6722 (3)	0.0795 (19)
O4	−0.2657 (6)	0.3134 (3)	0.5356 (3)	0.088 (2)
O5	0.1579 (4)	0.2363 (2)	0.7094 (2)	0.0509 (13)
O6	0.5094 (6)	0.1343 (2)	0.5811 (2)	0.0656 (16)
C1'	−0.372 (2)	0.4455 (17)	0.5717 (14)	0.118 (8)	0.377 (9)
H1'1	−0.3495	0.4097	0.5888	0.177*	0.377 (9)
H1'2	−0.4401	0.4398	0.5452	0.177*	0.377 (9)
H1'3	−0.3907	0.4724	0.5980	0.177*	0.377 (9)
O1'	−0.2778 (13)	0.4673 (9)	0.5463 (7)	0.088 (3)	0.377 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0377 (2)	0.0362 (2)	0.0444 (3)	0.000	0.00477 (19)	0.000
Ir2	0.0423 (3)	0.0351 (2)	0.0379 (3)	0.000	0.00791 (19)	0.000
N1	0.040 (4)	0.050 (4)	0.066 (5)	−0.004 (3)	0.000 (4)	−0.014 (3)
N2	0.035 (3)	0.047 (4)	0.051 (4)	0.001 (3)	0.000 (3)	−0.004 (3)
N3	0.043 (4)	0.038 (3)	0.047 (4)	0.003 (3)	0.008 (3)	0.003 (3)
N4	0.056 (4)	0.045 (4)	0.040 (4)	−0.002 (3)	0.001 (3)	0.004 (3)
C1	0.042 (8)	0.19 (2)	0.109 (19)	0.025 (12)	−0.035 (11)	−0.007 (13)
O1	0.033 (5)	0.105 (8)	0.117 (11)	−0.005 (5)	−0.016 (6)	−0.003 (7)
C2	0.091 (7)	0.091 (7)	0.130 (8)	0.020 (6)	−0.012 (7)	−0.035 (6)
C3	0.070 (6)	0.106 (7)	0.127 (8)	−0.001 (5)	0.007 (6)	−0.039 (6)
C4	0.054 (5)	0.079 (6)	0.109 (7)	−0.006 (4)	−0.002 (5)	−0.023 (5)
C5	0.052 (5)	0.046 (5)	0.097 (8)	0.012 (4)	−0.017 (5)	−0.022 (5)
C6	0.079 (7)	0.059 (6)	0.166 (12)	0.011 (5)	−0.055 (8)	−0.006 (7)
C7	0.104 (7)	0.088 (7)	0.132 (8)	0.015 (6)	−0.032 (7)	0.002 (6)
C8	0.045 (5)	0.042 (4)	0.086 (7)	0.007 (4)	−0.010 (5)	−0.008 (4)
C9	0.053 (5)	0.046 (4)	0.052 (5)	0.018 (4)	−0.005 (4)	0.002 (4)
C10	0.045 (5)	0.045 (4)	0.059 (5)	0.004 (3)	−0.004 (4)	0.003 (4)
C11	0.067 (6)	0.071 (6)	0.069 (6)	0.023 (5)	0.006 (5)	0.029 (5)
C12	0.060 (6)	0.070 (6)	0.096 (8)	0.005 (5)	0.016 (5)	0.038 (6)
C13	0.066 (6)	0.055 (5)	0.075 (7)	0.003 (4)	0.024 (5)	0.023 (5)
C14	0.057 (5)	0.042 (4)	0.069 (6)	0.007 (4)	0.014 (4)	0.015 (4)
C15	0.043 (4)	0.038 (4)	0.044 (4)	0.007 (3)	0.011 (3)	0.004 (3)
C16	0.064 (6)	0.074 (6)	0.107 (9)	−0.008 (5)	0.024 (6)	0.016 (6)
C17	0.105 (9)	0.119 (9)	0.083 (8)	0.009 (8)	−0.018 (7)	0.020 (7)
C18	0.057 (6)	0.073 (6)	0.053 (6)	0.000 (4)	0.000 (5)	0.008 (5)
C19	0.079 (7)	0.067 (6)	0.042 (5)	0.005 (5)	0.007 (5)	0.008 (4)
C20	0.059 (6)	0.072 (6)	0.058 (6)	0.002 (4)	0.004 (5)	0.008 (5)
C21	0.057 (5)	0.049 (5)	0.054 (6)	0.003 (4)	0.007 (4)	0.000 (4)
C22	0.053 (6)	0.077 (6)	0.068 (6)	−0.013 (5)	−0.003 (5)	0.018 (5)
C23	0.060 (6)	0.089 (7)	0.067 (7)	−0.012 (5)	−0.009 (5)	0.024 (5)
C24	0.051 (5)	0.052 (5)	0.048 (5)	−0.009 (4)	0.009 (4)	−0.003 (4)
C25	0.049 (5)	0.034 (4)	0.049 (5)	−0.003 (3)	0.007 (4)	0.006 (3)
C26	0.072 (7)	0.081 (7)	0.061 (6)	−0.017 (5)	0.000 (5)	−0.010 (5)
C27	0.072 (6)	0.043 (4)	0.041 (5)	−0.011 (4)	0.018 (4)	−0.007 (4)
C28	0.057 (5)	0.038 (4)	0.041 (5)	0.001 (3)	0.012 (4)	0.002 (3)
C29	0.039 (4)	0.036 (4)	0.045 (5)	0.002 (3)	0.009 (3)	0.008 (3)
C30	0.050 (5)	0.032 (4)	0.050 (5)	0.000 (3)	0.008 (4)	0.000 (3)
C31	0.058 (5)	0.041 (4)	0.064 (6)	0.002 (4)	0.016 (5)	−0.003 (4)
C32	0.066 (6)	0.049 (5)	0.069 (6)	0.005 (4)	0.021 (5)	−0.007 (4)
C33	0.187 (16)	0.201 (15)	0.074 (9)	0.076 (13)	0.032 (10)	0.035 (10)
Cl1	0.209 (4)	0.110 (3)	0.140 (3)	0.013 (3)	0.000 (3)	−0.015 (2)
Cl2	0.126 (3)	0.137 (3)	0.144 (3)	0.006 (2)	0.004 (2)	−0.054 (3)
Cl3	0.0489 (10)	0.0407 (9)	0.0455 (11)	−0.0001 (8)	0.0148 (9)	−0.0021 (8)
O2	0.056 (3)	0.055 (3)	0.066 (4)	0.012 (3)	−0.012 (3)	0.003 (3)
O3	0.075 (4)	0.071 (4)	0.093 (5)	−0.013 (3)	0.014 (4)	0.038 (4)
O4	0.084 (5)	0.106 (5)	0.065 (5)	0.012 (4)	−0.018 (4)	0.017 (4)
O5	0.051 (3)	0.054 (3)	0.046 (3)	−0.009 (3)	0.003 (3)	0.009 (3)
O6	0.083 (5)	0.065 (4)	0.049 (4)	−0.001 (3)	0.013 (3)	−0.016 (3)
C1'	0.042 (8)	0.19 (2)	0.109 (19)	0.025 (12)	−0.035 (11)	−0.007 (13)
O1'	0.033 (5)	0.105 (8)	0.117 (11)	−0.005 (5)	−0.016 (6)	−0.003 (7)

Geometric parameters (Å, º)

Ir1—C15	2.010 (7)	C14—H14	0.9300
Ir1—C15^i	2.010 (7)	C16—O3	1.410 (10)
Ir1—N2^i	2.043 (6)	C16—H16A	0.9600
Ir1—N2	2.043 (6)	C16—H16B	0.9600
Ir1—Cl3	2.4974 (18)	C16—H16C	0.9600
Ir1—Cl3^i	2.4975 (18)	C17—O4	1.389 (11)
Ir2—C29	2.001 (7)	C17—H17A	0.9600
Ir2—C29^i	2.001 (7)	C17—H17B	0.9600
Ir2—N3^i	2.042 (6)	C17—H17C	0.9600
Ir2—N3	2.042 (6)	C18—C23	1.364 (12)
Ir2—Cl3^i	2.4854 (17)	C18—C19	1.369 (11)
Ir2—Cl3	2.4854 (17)	C18—O4	1.403 (10)
N1—C8	1.286 (10)	C19—C20	1.374 (11)
N1—N2	1.408 (8)	C19—H19	0.9300
N2—C9	1.307 (9)	C20—C21	1.377 (11)
N3—C25	1.292 (8)	C20—H20	0.9300
N3—N4	1.385 (8)	C21—C22	1.392 (11)
N4—C24	1.276 (9)	C21—C24	1.461 (11)
C1—O1	1.453 (16)	C22—C23	1.366 (12)
C1—H1A	0.9600	C22—H22	0.9300
C1—H1B	0.9600	C23—H23	0.9300
C1—H1C	0.9600	C24—O5	1.389 (9)
O1—C2	1.468 (14)	C25—O5	1.350 (8)
C2—C7	1.344 (17)	C25—C30^i	1.418 (10)
C2—C3	1.363 (16)	C26—O6	1.421 (11)
C2—O1'	1.501 (17)	C26—H26A	0.9600
C3—C4	1.411 (14)	C26—H26B	0.9600
C3—H3	0.9300	C26—H26C	0.9600
C4—C5	1.365 (13)	C27—C32	1.377 (12)
C4—H4	0.9300	C27—O6	1.379 (9)
C5—C6	1.399 (14)	C27—C28	1.404 (10)
C5—C8	1.452 (11)	C28—C29	1.406 (10)
C6—C7	1.419 (14)	C28—H28	0.9300
C6—H6	0.9300	C29—C30	1.419 (9)
C7—H7	0.9300	C30—C31	1.391 (10)
C8—O2	1.389 (10)	C30—C25^i	1.418 (10)
C9—O2	1.340 (8)	C31—C32	1.364 (11)
C9—C10	1.425 (10)	C31—H31	0.9300
C10—C11	1.395 (11)	C32—H32	0.9300
C10—C15	1.397 (10)	C33—Cl1	1.679 (14)
C11—C12	1.379 (12)	C33—Cl2	1.753 (13)
C11—H11	0.9300	C33—H33A	0.9700
C12—C13	1.390 (12)	C33—H33B	0.9700
C12—H12	0.9300	C1'—O1'	1.44 (2)
C13—O3	1.371 (10)	C1'—H1'1	0.9600
C13—C14	1.379 (11)	C1'—H1'2	0.9600
C14—C15	1.399 (10)	C1'—H1'3	0.9600
C15—Ir1—C15^i	88.0 (4)	C10—C15—Ir1	115.5 (5)
C15—Ir1—N2^i	91.5 (3)	C14—C15—Ir1	127.2 (5)
C15^i—Ir1—N2^i	79.4 (3)	O3—C16—H16A	109.5
C15—Ir1—N2	79.4 (3)	O3—C16—H16B	109.5
C15^i—Ir1—N2	91.5 (3)	H16A—C16—H16B	109.5
N2^i—Ir1—N2	167.4 (3)	O3—C16—H16C	109.5
C15—Ir1—Cl3	176.4 (2)	H16A—C16—H16C	109.5
C15^i—Ir1—Cl3	94.3 (2)	H16B—C16—H16C	109.5
N2^i—Ir1—Cl3	91.60 (17)	O4—C17—H17A	109.5
N2—Ir1—Cl3	97.78 (18)	O4—C17—H17B	109.5
C15—Ir1—Cl3^i	94.29 (19)	H17A—C17—H17B	109.5
C15^i—Ir1—Cl3^i	176.4 (2)	O4—C17—H17C	109.5
N2^i—Ir1—Cl3^i	97.78 (18)	H17A—C17—H17C	109.5
N2—Ir1—Cl3^i	91.60 (17)	H17B—C17—H17C	109.5
Cl3—Ir1—Cl3^i	83.59 (8)	C23—C18—C19	122.2 (9)
C29—Ir2—C29^i	94.2 (4)	C23—C18—O4	114.1 (8)
C29—Ir2—N3^i	79.2 (3)	C19—C18—O4	123.7 (8)
C29^i—Ir2—N3^i	93.0 (3)	C18—C19—C20	118.7 (8)
C29—Ir2—N3	93.0 (3)	C18—C19—H19	120.6
C29^i—Ir2—N3	79.2 (3)	C20—C19—H19	120.6
N3^i—Ir2—N3	168.7 (3)	C19—C20—C21	121.4 (8)
C29—Ir2—Cl3^i	90.86 (19)	C19—C20—H20	119.3
C29^i—Ir2—Cl3^i	174.55 (19)	C21—C20—H20	119.3
N3^i—Ir2—Cl3^i	89.77 (16)	C20—C21—C22	117.4 (8)
N3—Ir2—Cl3^i	98.62 (17)	C20—C21—C24	121.2 (8)
C29—Ir2—Cl3	174.55 (19)	C22—C21—C24	121.4 (8)
C29^i—Ir2—Cl3	90.87 (19)	C23—C22—C21	122.2 (9)
N3^i—Ir2—Cl3	98.63 (17)	C23—C22—H22	118.9
N3—Ir2—Cl3	89.77 (16)	C21—C22—H22	118.9
Cl3^i—Ir2—Cl3	84.09 (8)	C18—C23—C22	118.0 (9)
C8—N1—N2	104.5 (7)	C18—C23—H23	121.0
C9—N2—N1	108.7 (6)	C22—C23—H23	121.0
C9—N2—Ir1	113.9 (5)	N4—C24—O5	113.5 (7)
N1—N2—Ir1	136.7 (5)	N4—C24—C21	130.0 (8)
C25—N3—N4	108.5 (6)	O5—C24—C21	116.4 (7)
C25—N3—Ir2	114.1 (5)	N3—C25—O5	111.6 (6)
N4—N3—Ir2	137.4 (5)	N3—C25—C30^i	120.2 (7)
C24—N4—N3	104.8 (6)	O5—C25—C30^i	128.2 (6)
C1—O1—C2	106.6 (12)	O6—C26—H26A	109.5
C7—C2—C3	123.8 (13)	O6—C26—H26B	109.5
C7—C2—O1	134.1 (13)	H26A—C26—H26B	109.5
C3—C2—O1	102.0 (12)	O6—C26—H26C	109.5
C7—C2—O1'	86.9 (12)	H26A—C26—H26C	109.5
C3—C2—O1'	148.2 (14)	H26B—C26—H26C	109.5
O1—C2—O1'	48.5 (9)	C32—C27—O6	115.3 (7)
C2—C3—C4	118.3 (13)	C32—C27—C28	122.1 (8)
C2—C3—H3	120.8	O6—C27—C28	122.6 (8)
C4—C3—H3	120.8	C27—C28—C29	119.5 (7)
C5—C4—C3	120.8 (12)	C27—C28—H28	120.2
C5—C4—H4	119.6	C29—C28—H28	120.2
C3—C4—H4	119.6	C28—C29—C30	116.9 (6)
C4—C5—C6	118.7 (9)	C28—C29—Ir2	127.3 (5)
C4—C5—C8	121.3 (9)	C30—C29—Ir2	115.7 (5)
C6—C5—C8	120.0 (10)	C31—C30—C25^i	127.5 (7)
C5—C6—C7	120.8 (12)	C31—C30—C29	121.8 (7)
C5—C6—H6	119.6	C25^i—C30—C29	110.7 (6)
C7—C6—H6	119.6	C32—C31—C30	120.3 (8)
C2—C7—C6	117.5 (13)	C32—C31—H31	119.8
C2—C7—H7	121.2	C30—C31—H31	119.8
C6—C7—H7	121.2	C31—C32—C27	119.3 (8)
N1—C8—O2	112.6 (7)	C31—C32—H32	120.4
N1—C8—C5	129.6 (9)	C27—C32—H32	120.4
O2—C8—C5	117.8 (8)	Cl1—C33—Cl2	111.3 (7)
N2—C9—O2	110.4 (7)	Cl1—C33—H33A	109.4
N2—C9—C10	119.2 (7)	Cl2—C33—H33A	109.4
O2—C9—C10	130.0 (7)	Cl1—C33—H33B	109.4
C11—C10—C15	121.9 (7)	Cl2—C33—H33B	109.4
C11—C10—C9	126.2 (7)	H33A—C33—H33B	108.0
C15—C10—C9	111.9 (7)	Ir2—Cl3—Ir1	96.16 (6)
C12—C11—C10	120.1 (8)	C9—O2—C8	103.9 (6)
C12—C11—H11	120.0	C13—O3—C16	117.4 (6)
C10—C11—H11	120.0	C17—O4—C18	117.9 (8)
C11—C12—C13	118.2 (8)	C25—O5—C24	101.6 (6)
C11—C12—H12	120.9	C27—O6—C26	119.7 (7)
C13—C12—H12	120.9	O1'—C1'—H1'1	109.5
O3—C13—C14	123.1 (8)	O1'—C1'—H1'2	109.5
O3—C13—C12	114.8 (7)	H1'1—C1'—H1'2	109.5
C14—C13—C12	122.2 (8)	O1'—C1'—H1'3	109.5
C13—C14—C15	120.3 (8)	H1'1—C1'—H1'3	109.5
C13—C14—H14	119.9	H1'2—C1'—H1'3	109.5
C15—C14—H14	119.9	C1'—O1'—C2	95.2 (17)
C10—C15—C14	117.3 (7)
C8—N1—N2—C9	0.0 (8)	N2—Ir1—C15—C10	2.5 (5)
C8—N1—N2—Ir1	169.3 (6)	C15^i—Ir1—C15—C14	87.8 (7)
C15—Ir1—N2—C9	−2.4 (5)	N2^i—Ir1—C15—C14	8.4 (7)
C15^i—Ir1—N2—C9	85.2 (6)	N2—Ir1—C15—C14	179.7 (7)
Cl3—Ir1—N2—C9	179.8 (5)	C23—C18—C19—C20	−0.3 (14)
Cl3^i—Ir1—N2—C9	−96.5 (5)	O4—C18—C19—C20	178.9 (8)
C15—Ir1—N2—N1	−171.3 (7)	C18—C19—C20—C21	1.2 (13)
C15^i—Ir1—N2—N1	−83.7 (7)	C19—C20—C21—C22	0.1 (13)
N2^i—Ir1—N2—N1	−127.0 (6)	C19—C20—C21—C24	−178.9 (8)
Cl3—Ir1—N2—N1	10.9 (7)	C20—C21—C22—C23	−2.5 (14)
Cl3^i—Ir1—N2—N1	94.6 (6)	C24—C21—C22—C23	176.5 (8)
C29—Ir2—N3—C25	94.7 (5)	C19—C18—C23—C22	−1.9 (15)
C29^i—Ir2—N3—C25	1.0 (5)	O4—C18—C23—C22	178.7 (8)
Cl3^i—Ir2—N3—C25	−173.9 (5)	C21—C22—C23—C18	3.4 (15)
Cl3—Ir2—N3—C25	−90.0 (5)	N3—N4—C24—O5	−1.1 (8)
C29—Ir2—N3—N4	−86.6 (7)	N3—N4—C24—C21	177.2 (8)
C29^i—Ir2—N3—N4	179.7 (7)	C20—C21—C24—N4	14.4 (13)
N3^i—Ir2—N3—N4	−132.9 (6)	C22—C21—C24—N4	−164.6 (9)
Cl3^i—Ir2—N3—N4	4.8 (7)	C20—C21—C24—O5	−167.4 (7)
Cl3—Ir2—N3—N4	88.8 (6)	C22—C21—C24—O5	13.6 (11)
C25—N3—N4—C24	1.9 (8)	N4—N3—C25—O5	−2.1 (8)
Ir2—N3—N4—C24	−176.9 (6)	Ir2—N3—C25—O5	177.0 (4)
C1—O1—C2—C7	−3 (2)	N4—N3—C25—C30^i	179.4 (6)
C1—O1—C2—C3	174.4 (13)	Ir2—N3—C25—C30^i	−1.5 (9)
C1—O1—C2—O1'	−19.0 (15)	C32—C27—C28—C29	1.6 (11)
C7—C2—C3—C4	−1.1 (19)	O6—C27—C28—C29	179.8 (6)
O1—C2—C3—C4	−178.5 (9)	C27—C28—C29—C30	1.3 (10)
O1'—C2—C3—C4	162 (2)	C27—C28—C29—Ir2	178.3 (5)
C2—C3—C4—C5	1.1 (16)	C29^i—Ir2—C29—C28	90.3 (6)
C3—C4—C5—C6	0.0 (14)	N3^i—Ir2—C29—C28	−177.4 (6)
C3—C4—C5—C8	179.2 (9)	N3—Ir2—C29—C28	10.9 (6)
C4—C5—C6—C7	−1.0 (15)	C29^i—Ir2—C29—C30	−92.6 (5)
C8—C5—C6—C7	179.7 (9)	N3^i—Ir2—C29—C30	−0.3 (5)
C3—C2—C7—C6	0 (2)	N3—Ir2—C29—C30	−172.1 (5)
O1—C2—C7—C6	176.4 (12)	C28—C29—C30—C31	−3.2 (10)
O1'—C2—C7—C6	−171.3 (13)	Ir2—C29—C30—C31	179.4 (6)
C5—C6—C7—C2	1.0 (17)	C28—C29—C30—C25^i	177.1 (6)
N2—N1—C8—O2	0.1 (9)	Ir2—C29—C30—C25^i	−0.3 (8)
N2—N1—C8—C5	179.7 (8)	C25^i—C30—C31—C32	−178.0 (8)
C4—C5—C8—N1	11.0 (14)	C29—C30—C31—C32	2.3 (11)
C6—C5—C8—N1	−169.8 (9)	C30—C31—C32—C27	0.6 (12)
C4—C5—C8—O2	−169.4 (8)	O6—C27—C32—C31	179.1 (7)
C6—C5—C8—O2	9.8 (12)	C28—C27—C32—C31	−2.5 (12)
N1—N2—C9—O2	−0.1 (8)	N3^i—Ir2—Cl3—Ir1	88.86 (17)
Ir1—N2—C9—O2	−172.0 (5)	N3—Ir2—Cl3—Ir1	−98.70 (17)
N1—N2—C9—C10	173.9 (6)	Cl3^i—Ir2—Cl3—Ir1	0.0
Ir1—N2—C9—C10	2.0 (9)	N2^i—Ir1—Cl3—Ir2	−97.65 (18)
N2—C9—C10—C11	−178.4 (8)	N2—Ir1—Cl3—Ir2	90.75 (17)
O2—C9—C10—C11	−5.7 (14)	Cl3^i—Ir1—Cl3—Ir2	0.0
N2—C9—C10—C15	0.2 (11)	N2—C9—O2—C8	0.1 (8)
O2—C9—C10—C15	172.8 (7)	C10—C9—O2—C8	−173.0 (8)
C15—C10—C11—C12	−0.7 (14)	N1—C8—O2—C9	−0.1 (9)
C9—C10—C11—C12	177.7 (9)	C5—C8—O2—C9	−179.8 (7)
C10—C11—C12—C13	2.4 (15)	C14—C13—O3—C16	5.8 (13)
C11—C12—C13—O3	178.0 (9)	C12—C13—O3—C16	−174.5 (9)
C11—C12—C13—C14	−2.3 (15)	C23—C18—O4—C17	−175.9 (9)
O3—C13—C14—C15	−179.8 (8)	C19—C18—O4—C17	4.7 (14)
C12—C13—C14—C15	0.5 (14)	N3—C25—O5—C24	1.3 (8)
C11—C10—C15—C14	−1.1 (12)	C30^i—C25—O5—C24	179.7 (7)
C9—C10—C15—C14	−179.7 (7)	N4—C24—O5—C25	−0.1 (8)
C11—C10—C15—Ir1	176.4 (7)	C21—C24—O5—C25	−178.6 (6)
C9—C10—C15—Ir1	−2.3 (9)	C32—C27—O6—C26	176.6 (7)
C13—C14—C15—C10	1.2 (12)	C28—C27—O6—C26	−1.8 (11)
C13—C14—C15—Ir1	−175.9 (6)	C7—C2—O1'—C1'	−170 (2)
C15^i—Ir1—C15—C10	−89.4 (6)	C3—C2—O1'—C1'	24 (3)
N2^i—Ir1—C15—C10	−168.7 (6)	O1—C2—O1'—C1'	−2 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C33—H33A···N4^ii	0.97	2.53	3.456 (16)	160
C26—H26A···O3^iii	0.96	2.49	3.419 (12)	163

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