Synthesis and structural characterization of iridium(I) com­plexes of 20-membered macrocyclic rings bearing chelating bis­(N-heterocyclic carbene) ligands

The reactivities of two 20-membered macrocyclic ligands, each containing two N-heterocyclic carbene (NHC) and two amine groups, towards [IrCl(COD)]₂ (COD is cyclo­octa-1,5-diene) were investigated. Macrocycles containing imidazolin-2-yl­idene groups formed the monometallic com­plex [(1,2,5,6-η)-cyclo­octa-1,5-diene](5,16-dibenzyl-1,5,9,12,16,20-hexa­aza­tri­cyclo­[18.2.1.1^9,12]tetra­cosa-10,21-dien-21,22-diyl­idene)iridium(I) bromide di­chloro­methane monosolvate, [Ir(C₈H₁₂)(C₃₂H₄₂N₆)]Br·CH₂Cl₂, 2a. The structure of iridium com­plex 2a at 100 K has triclinic P symmetry. The ligand in 2a coordinates to the Ir center through the NHC moieties in a cis fashion. Additionally, the ligand adopts an umbrella-like structure that appears to envelope the Ir center. The structure displays C—H...Br inter­actions. Macrocycles containing benzimidazolin-2-yl­idene groups formed the bimetallic com­plex [μ-5,20-dibenzyl-1,5,9,16,20,24-hexa­aza­penta­cyclo­[22.6.1.1^9,16.0^10,15.0^25,30]dotriaconta-10(15),11,13,25(30),26,28-hexa­ene-31,32-diyl­idene]bis­{bromido­[(1,2,5,6-η)-cyclo­octa-1,5-diene]iridium(I)}, [Ir₂Br₂(C₈H₁₂)₂(C₄₀H₄₆N₆)], 2b. The structure of com­plex 2b at 100 K has ortho­rhom­bic Pbca symmetry. Each NHC moiety in 2b coordinates in a monodentate fashion to an Ir(COD) fragment. The structure exhibits disorder of the main mol­ecule. This disorder is found in the portion of the macrocycle containing an amine group. This structure also displays C—H...Br inter­actions. Finally, the structure of the hexa­fluorophosphate salt of the imidazolin-2-yl­idene-containing macrocycle, namely 5,16-dibenzyl-1λ⁵,5,9,12λ⁵,16,20-hexa­aza­tri­cyclo­[18.2.1.1^9,12]tetra­cosa-1(23),10,12(24),21-tetra­ene-1,12-diium bis­(hexa­fluoro­phosphate), C₃₂H₄₄N₆²⁺·2PF₆⁻, 1c, was determined. The structure of macrocycle 1c at 100 K has triclinic P symmetry and was found to contain C—H...F inter­actions.

Computing details

Data collection: APEX3 (Bruker, 2016) for (1c), (2b); APEX2 (Bruker, 2010) for (2a). Cell refinement: SAINT (Bruker, 2016) for (1c), (2b); SAINT (Bruker, 2010) for (2a). Data reduction: SAINT (Bruker, 2016) for (1c), (2b); SAINT (Bruker, 2010) for (2a). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for (1c), (2b); SHELXS97 (Sheldrick 2008) for (2a). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) for (1c); SHELXL2018 (Sheldrick, 2015b) for (2a), (2b). Molecular graphics: Mercury (Macrae et al., 2008) for (1c), (2b); SHELXTL (Bruker, 2010) for (2a). Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) for (1c); SHELXTL (Bruker, 2010) for (2a); SHELXL2018 (Sheldrick, 2015b) for (2b).

5,16-Dibenzyl-1λ⁵,5,9,12λ⁵,16,20-hexaazatricyclo[18.2.1.1^9,12]tetracosa-1(23),10,12(24),21-tetraene-1,12-diium bis(hexafluorophosphate) (1c)

Crystal data

C32H44N6^2+·2PF6^−	Z = 2
Mr = 802.67	F(000) = 832
Triclinic, P1	Dx = 1.467 Mg m^−3
a = 9.290 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.228 (14) Å	Cell parameters from 4108 reflections
c = 18.00 (2) Å	θ = 2.3–21.7°
α = 95.133 (17)°	µ = 0.22 mm^−1
β = 97.423 (17)°	T = 100 K
γ = 100.660 (17)°	Plate, colourless
V = 1817 (4) Å^3	0.44 × 0.20 × 0.06 mm

Data collection

Bruker APEX CCD diffractometer	4809 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.080
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 27.9°, θmin = 1.2°
Tmin = 0.911, Tmax = 0.987	h = −11→12
28213 measured reflections	k = −14→14
8188 independent reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.060P)^2 + 0.4P] where P = (Fo^2 + 2Fc^2)/3
8188 reflections	(Δ/σ)max < 0.001
527 parameters	Δρmax = 0.30 e Å^−3
606 restraints	Δρmin = −0.47 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1A	0.89124 (8)	0.49942 (6)	0.13859 (4)	0.02751 (19)
F1A	0.93515 (19)	0.40643 (14)	0.07561 (10)	0.0397 (4)
F2A	1.02453 (19)	0.60386 (14)	0.12466 (10)	0.0402 (4)
F3A	1.00117 (19)	0.45528 (16)	0.20239 (9)	0.0410 (4)
F4A	0.84698 (19)	0.59085 (15)	0.20133 (9)	0.0401 (4)
F5A	0.75884 (19)	0.39347 (15)	0.15241 (11)	0.0469 (5)
F6A	0.7820 (2)	0.54278 (16)	0.07463 (9)	0.0429 (5)
P1B	0.2809 (4)	0.3187 (3)	0.40681 (18)	0.0355 (4)	0.588 (3)
F1B	0.1942 (4)	0.3796 (4)	0.34269 (18)	0.0615 (11)	0.588 (3)
F2B	0.4234 (5)	0.3430 (6)	0.3650 (4)	0.0474 (15)	0.588 (3)
F3B	0.3341 (5)	0.4503 (3)	0.4548 (2)	0.0716 (14)	0.588 (3)
F4B	0.3675 (5)	0.2594 (5)	0.4703 (2)	0.0743 (13)	0.588 (3)
F5B	0.1380 (4)	0.2983 (5)	0.4481 (2)	0.0707 (14)	0.588 (3)
F6B	0.2252 (5)	0.1911 (3)	0.3568 (2)	0.0643 (13)	0.588 (3)
P1B'	0.2955 (5)	0.3072 (4)	0.4129 (3)	0.0355 (4)	0.412 (3)
F1B'	0.1780 (6)	0.2663 (7)	0.3387 (3)	0.0765 (19)	0.412 (3)
F2B'	0.4206 (7)	0.3727 (8)	0.3673 (5)	0.052 (2)	0.412 (3)
F3B'	0.2360 (7)	0.4296 (5)	0.4282 (3)	0.0689 (17)	0.412 (3)
F4B'	0.4117 (5)	0.3480 (5)	0.4885 (2)	0.0535 (14)	0.412 (3)
F5B'	0.1784 (6)	0.2404 (5)	0.4617 (3)	0.0553 (16)	0.412 (3)
F6B'	0.3564 (6)	0.1851 (4)	0.3999 (3)	0.0645 (16)	0.412 (3)
N1C	0.6852 (3)	0.59409 (19)	−0.16046 (12)	0.0259 (5)
N2C	0.6234 (2)	0.42161 (19)	−0.11543 (12)	0.0253 (5)
N3C	0.3554 (2)	0.16032 (19)	0.05119 (12)	0.0244 (5)
C1C	0.7188 (3)	0.5293 (2)	−0.10417 (15)	0.0265 (6)
H1C	0.7969	0.5551	−0.0631	0.032*
C2C	0.5650 (3)	0.5261 (2)	−0.20876 (16)	0.0341 (7)
H2C	0.5180	0.5502	−0.2534	0.041*
C3C	0.5264 (3)	0.4187 (3)	−0.18072 (16)	0.0340 (7)
H3C	0.4472	0.3535	−0.2020	0.041*
C4C	0.6268 (3)	0.3208 (2)	−0.06793 (16)	0.0271 (6)
H4C1	0.7214	0.3380	−0.0329	0.033*
H4C2	0.6226	0.2441	−0.1006	0.033*
C5C	0.4978 (3)	0.3041 (2)	−0.02236 (16)	0.0276 (6)
H5C1	0.5224	0.3632	0.0238	0.033*
H5C2	0.4082	0.3203	−0.0527	0.033*
C6C	0.4664 (3)	0.1741 (2)	−0.00064 (15)	0.0259 (6)
H6C1	0.4298	0.1158	−0.0468	0.031*
H6C2	0.5594	0.1544	0.0239	0.031*
C7C	0.4309 (3)	0.1777 (3)	0.12941 (15)	0.0287 (6)
H7C1	0.5117	0.2506	0.1360	0.034*
H7C2	0.4764	0.1063	0.1386	0.034*
C8C	0.3287 (3)	0.1938 (2)	0.18845 (16)	0.0297 (7)
H8C1	0.2656	0.1137	0.1918	0.036*
H8C2	0.3901	0.2217	0.2383	0.036*
C9C	0.2294 (3)	0.2850 (2)	0.17063 (17)	0.0296 (7)
H9C1	0.1591	0.2523	0.1240	0.036*
H9C2	0.1709	0.2947	0.2122	0.036*
C10C	0.2464 (3)	0.0436 (2)	0.03440 (15)	0.0261 (6)
H10A	0.1721	0.0423	0.0693	0.031*
H10B	0.2978	−0.0249	0.0426	0.031*
C11C	0.1688 (3)	0.0272 (2)	−0.04618 (16)	0.0261 (6)
C12C	0.1140 (3)	0.1236 (2)	−0.07668 (16)	0.0318 (7)
H12C	0.1228	0.1987	−0.0459	0.038*
C13C	0.0469 (3)	0.1105 (3)	−0.15158 (17)	0.0372 (7)
H13C	0.0102	0.1764	−0.1715	0.045*
C14C	0.0335 (3)	0.0012 (3)	−0.19735 (17)	0.0375 (7)
H14C	−0.0119	−0.0076	−0.2485	0.045*
C15C	0.0870 (3)	−0.0950 (3)	−0.16770 (17)	0.0353 (7)
H15C	0.0778	−0.1699	−0.1987	0.042*
C16C	0.1540 (3)	−0.0826 (3)	−0.09267 (17)	0.0314 (7)
H16C	0.1898	−0.1491	−0.0730	0.038*
N1D	0.2132 (3)	0.60795 (19)	0.61588 (12)	0.0268 (5)
N2D	0.2782 (3)	0.7897 (2)	0.58365 (13)	0.0296 (6)
N3D	0.1621 (2)	0.77568 (19)	0.39090 (12)	0.0261 (5)
C1D	0.2717 (3)	0.6710 (2)	0.56360 (15)	0.0270 (6)
H1D	0.3032	0.6371	0.5197	0.032*
C2D	0.1831 (4)	0.6882 (3)	0.67106 (18)	0.0470 (9)
H2D	0.1417	0.6680	0.7150	0.056*
C3D	0.2236 (4)	0.8019 (3)	0.65106 (18)	0.0492 (10)
H3D	0.2157	0.8762	0.6784	0.059*
C4D	0.3327 (3)	0.8930 (2)	0.54139 (16)	0.0294 (7)
H4D1	0.3946	0.8656	0.5050	0.035*
H4D2	0.3958	0.9601	0.5773	0.035*
C5D	0.2054 (3)	0.9414 (2)	0.49846 (16)	0.0324 (7)
H5D1	0.1118	0.9078	0.5167	0.039*
H5D2	0.2242	1.0314	0.5098	0.039*
C6D	0.1871 (3)	0.9080 (2)	0.41322 (16)	0.0293 (6)
H6D1	0.1024	0.9399	0.3891	0.035*
H6D2	0.2772	0.9481	0.3944	0.035*
C7D	0.0051 (3)	0.7188 (2)	0.39140 (16)	0.0271 (6)
H7D1	−0.0554	0.7356	0.3455	0.033*
H7D2	−0.0295	0.7572	0.4357	0.033*
C8D	−0.0207 (3)	0.5808 (2)	0.39419 (16)	0.0280 (6)
H8D1	0.0245	0.5425	0.3538	0.034*
H8D2	0.0276	0.5634	0.4433	0.034*
C9D	−0.1862 (3)	0.5263 (2)	0.38405 (16)	0.0285 (6)
H9D1	−0.2305	0.5629	0.4254	0.034*
H9D2	−0.2348	0.5463	0.3358	0.034*
C10D	0.2002 (3)	0.7524 (3)	0.31425 (15)	0.0306 (7)
H10C	0.1437	0.7963	0.2793	0.037*
H10D	0.1695	0.6641	0.2968	0.037*
C11D	0.3640 (3)	0.7922 (2)	0.31069 (15)	0.0274 (6)
C12D	0.4693 (3)	0.7502 (2)	0.35836 (15)	0.0275 (6)
H12D	0.4377	0.6974	0.3940	0.033*
C13D	0.6198 (3)	0.7840 (2)	0.35473 (15)	0.0269 (6)
H13D	0.6902	0.7563	0.3886	0.032*
C14D	0.6672 (3)	0.8589 (2)	0.30094 (16)	0.0303 (7)
H14D	0.7697	0.8806	0.2974	0.036*
C15D	0.5637 (3)	0.9017 (2)	0.25261 (16)	0.0304 (7)
H15D	0.5956	0.9526	0.2161	0.036*
C16D	0.4136 (3)	0.8696 (2)	0.25793 (16)	0.0291 (6)
H16D	0.3437	0.9004	0.2255	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1A	0.0307 (4)	0.0248 (4)	0.0270 (4)	0.0042 (3)	0.0063 (3)	0.0035 (3)
F1A	0.0390 (10)	0.0333 (9)	0.0451 (11)	0.0095 (8)	0.0061 (8)	−0.0084 (8)
F2A	0.0436 (11)	0.0282 (9)	0.0490 (11)	−0.0008 (8)	0.0199 (9)	0.0035 (8)
F3A	0.0384 (10)	0.0516 (11)	0.0363 (10)	0.0138 (9)	0.0045 (8)	0.0142 (9)
F4A	0.0434 (11)	0.0441 (10)	0.0348 (10)	0.0120 (8)	0.0130 (8)	−0.0027 (8)
F5A	0.0353 (10)	0.0365 (10)	0.0678 (13)	−0.0029 (8)	0.0130 (9)	0.0132 (9)
F6A	0.0513 (12)	0.0483 (11)	0.0344 (10)	0.0248 (9)	0.0026 (9)	0.0069 (8)
P1B	0.0453 (7)	0.0385 (7)	0.0240 (6)	0.0076 (5)	0.0130 (5)	0.0013 (5)
F1B	0.068 (2)	0.085 (3)	0.046 (2)	0.043 (2)	0.0170 (17)	0.0145 (19)
F2B	0.043 (3)	0.062 (3)	0.035 (3)	0.0022 (19)	0.011 (2)	0.002 (2)
F3B	0.092 (3)	0.059 (2)	0.051 (2)	−0.015 (2)	0.029 (2)	−0.0220 (19)
F4B	0.090 (3)	0.103 (3)	0.034 (2)	0.020 (3)	0.003 (2)	0.036 (2)
F5B	0.053 (3)	0.104 (4)	0.043 (2)	−0.016 (2)	0.0239 (19)	−0.011 (2)
F6B	0.100 (3)	0.0347 (19)	0.050 (2)	−0.012 (2)	0.028 (2)	−0.0081 (17)
P1B'	0.0453 (7)	0.0385 (7)	0.0240 (6)	0.0076 (5)	0.0130 (5)	0.0013 (5)
F1B'	0.062 (3)	0.120 (5)	0.038 (3)	0.005 (3)	0.009 (2)	−0.014 (3)
F2B'	0.067 (4)	0.060 (4)	0.031 (4)	0.001 (3)	0.019 (3)	0.017 (3)
F3B'	0.083 (4)	0.061 (3)	0.076 (4)	0.046 (3)	0.014 (3)	0.011 (3)
F4B'	0.048 (3)	0.080 (4)	0.031 (2)	0.003 (3)	0.011 (2)	0.009 (2)
F5B'	0.056 (3)	0.074 (4)	0.041 (3)	0.009 (3)	0.028 (2)	0.012 (3)
F6B'	0.071 (3)	0.038 (2)	0.089 (4)	0.012 (2)	0.035 (3)	−0.002 (2)
N1C	0.0333 (14)	0.0219 (12)	0.0219 (12)	0.0012 (10)	0.0091 (10)	0.0014 (9)
N2C	0.0319 (13)	0.0217 (12)	0.0217 (12)	0.0026 (10)	0.0066 (10)	0.0021 (9)
N3C	0.0277 (13)	0.0205 (11)	0.0251 (12)	0.0017 (10)	0.0096 (10)	0.0013 (9)
C1C	0.0303 (16)	0.0241 (14)	0.0244 (15)	0.0015 (12)	0.0097 (12)	−0.0005 (12)
C2C	0.049 (2)	0.0263 (15)	0.0239 (16)	0.0012 (14)	0.0006 (14)	0.0031 (12)
C3C	0.0400 (18)	0.0265 (15)	0.0294 (16)	−0.0020 (13)	−0.0027 (14)	−0.0004 (13)
C4C	0.0314 (16)	0.0197 (14)	0.0315 (16)	0.0043 (12)	0.0093 (13)	0.0044 (12)
C5C	0.0306 (16)	0.0232 (14)	0.0311 (16)	0.0051 (12)	0.0122 (13)	0.0030 (12)
C6C	0.0287 (16)	0.0219 (14)	0.0273 (15)	0.0039 (12)	0.0089 (12)	0.0003 (11)
C7C	0.0339 (17)	0.0265 (15)	0.0254 (15)	0.0042 (12)	0.0055 (13)	0.0036 (12)
C8C	0.0367 (17)	0.0240 (14)	0.0287 (16)	0.0028 (13)	0.0115 (13)	0.0024 (12)
C9C	0.0355 (17)	0.0226 (14)	0.0314 (16)	0.0004 (12)	0.0152 (13)	0.0036 (12)
C10C	0.0291 (16)	0.0211 (14)	0.0281 (15)	0.0015 (12)	0.0089 (12)	0.0030 (11)
C11C	0.0244 (15)	0.0250 (14)	0.0284 (15)	0.0011 (12)	0.0078 (12)	0.0035 (12)
C12C	0.0404 (18)	0.0218 (14)	0.0311 (16)	0.0017 (13)	0.0047 (14)	0.0023 (12)
C13C	0.0397 (18)	0.0356 (17)	0.0338 (18)	−0.0004 (14)	0.0023 (14)	0.0111 (14)
C14C	0.0391 (18)	0.0445 (19)	0.0256 (16)	−0.0036 (15)	0.0082 (14)	0.0057 (14)
C15C	0.0347 (18)	0.0346 (17)	0.0322 (17)	−0.0054 (14)	0.0130 (14)	−0.0064 (13)
C16C	0.0306 (16)	0.0264 (15)	0.0378 (17)	0.0023 (13)	0.0141 (13)	0.0002 (13)
N1D	0.0365 (14)	0.0192 (11)	0.0252 (12)	0.0027 (10)	0.0115 (11)	0.0007 (10)
N2D	0.0383 (15)	0.0212 (12)	0.0275 (13)	0.0004 (10)	0.0087 (11)	−0.0007 (10)
N3D	0.0288 (13)	0.0239 (12)	0.0256 (12)	0.0018 (10)	0.0101 (10)	0.0010 (10)
C1D	0.0332 (16)	0.0244 (14)	0.0230 (15)	0.0028 (12)	0.0099 (12)	−0.0006 (11)
C2D	0.082 (3)	0.0261 (16)	0.0357 (18)	0.0042 (17)	0.0333 (18)	−0.0004 (14)
C3D	0.087 (3)	0.0240 (16)	0.041 (2)	0.0051 (17)	0.0398 (19)	−0.0034 (14)
C4D	0.0393 (17)	0.0195 (14)	0.0284 (16)	−0.0010 (12)	0.0120 (13)	0.0012 (12)
C5D	0.0424 (18)	0.0208 (14)	0.0328 (17)	0.0026 (13)	0.0098 (14)	−0.0025 (12)
C6D	0.0357 (17)	0.0223 (14)	0.0297 (16)	0.0038 (12)	0.0078 (13)	0.0020 (12)
C7D	0.0294 (16)	0.0215 (14)	0.0310 (16)	0.0044 (12)	0.0103 (12)	−0.0010 (12)
C8D	0.0309 (16)	0.0223 (14)	0.0302 (16)	0.0041 (12)	0.0044 (13)	0.0025 (12)
C9D	0.0376 (17)	0.0186 (13)	0.0290 (15)	0.0029 (12)	0.0098 (13)	0.0000 (11)
C10D	0.0352 (17)	0.0321 (16)	0.0236 (15)	0.0046 (13)	0.0069 (13)	−0.0019 (12)
C11D	0.0344 (17)	0.0256 (14)	0.0219 (14)	0.0056 (13)	0.0064 (12)	−0.0015 (11)
C12D	0.0359 (17)	0.0221 (14)	0.0252 (15)	0.0049 (12)	0.0107 (13)	−0.0002 (12)
C13D	0.0334 (17)	0.0225 (14)	0.0250 (15)	0.0064 (12)	0.0054 (12)	0.0000 (11)
C14D	0.0298 (16)	0.0246 (14)	0.0346 (17)	−0.0013 (12)	0.0085 (13)	0.0013 (12)
C15D	0.0400 (18)	0.0229 (14)	0.0298 (16)	0.0053 (13)	0.0113 (13)	0.0049 (12)
C16D	0.0356 (17)	0.0277 (15)	0.0252 (15)	0.0087 (13)	0.0044 (13)	0.0042 (12)

Geometric parameters (Å, º)

P1A—F2A	1.602 (2)	C12C—C13C	1.393 (4)
P1A—F4A	1.602 (2)	C12C—H12C	0.9500
P1A—F6A	1.604 (2)	C13C—C14C	1.391 (4)
P1A—F5A	1.606 (2)	C13C—H13C	0.9500
P1A—F3A	1.610 (2)	C14C—C15C	1.390 (4)
P1A—F1A	1.615 (2)	C14C—H14C	0.9500
P1B—F4B	1.579 (4)	C15C—C16C	1.396 (4)
P1B—F6B	1.583 (4)	C15C—H15C	0.9500
P1B—F5B	1.594 (4)	C16C—H16C	0.9500
P1B—F1B	1.597 (4)	N1D—C1D	1.338 (3)
P1B—F2B	1.598 (4)	N1D—C2D	1.372 (4)
P1B—F3B	1.601 (4)	N1D—C9D^ii	1.482 (4)
P1B'—F1B'	1.587 (5)	N2D—C1D	1.337 (4)
P1B'—F6B'	1.587 (5)	N2D—C3D	1.380 (4)
P1B'—F3B'	1.588 (5)	N2D—C4D	1.490 (4)
P1B'—F4B'	1.597 (5)	N3D—C6D	1.471 (4)
P1B'—F5B'	1.606 (5)	N3D—C10D	1.481 (4)
P1B'—F2B'	1.614 (5)	N3D—C7D	1.482 (4)
N1C—C1C	1.337 (4)	C1D—H1D	0.9500
N1C—C2C	1.379 (4)	C2D—C3D	1.356 (4)
N1C—C9C^i	1.479 (4)	C2D—H2D	0.9500
N2C—C1C	1.342 (4)	C3D—H3D	0.9500
N2C—C3C	1.380 (4)	C4D—C5D	1.539 (4)
N2C—C4C	1.480 (3)	C4D—H4D1	0.9900
N3C—C7C	1.469 (4)	C4D—H4D2	0.9900
N3C—C6C	1.474 (3)	C5D—C6D	1.526 (4)
N3C—C10C	1.480 (4)	C5D—H5D1	0.9900
C1C—H1C	0.9500	C5D—H5D2	0.9900
C2C—C3C	1.354 (4)	C6D—H6D1	0.9900
C2C—H2C	0.9500	C6D—H6D2	0.9900
C3C—H3C	0.9500	C7D—C8D	1.530 (4)
C4C—C5C	1.531 (4)	C7D—H7D1	0.9900
C4C—H4C1	0.9900	C7D—H7D2	0.9900
C4C—H4C2	0.9900	C8D—C9D	1.527 (4)
C5C—C6C	1.530 (4)	C8D—H8D1	0.9900
C5C—H5C1	0.9900	C8D—H8D2	0.9900
C5C—H5C2	0.9900	C9D—N1D^ii	1.482 (4)
C6C—H6C1	0.9900	C9D—H9D1	0.9900
C6C—H6C2	0.9900	C9D—H9D2	0.9900
C7C—C8C	1.534 (4)	C10D—C11D	1.516 (4)
C7C—H7C1	0.9900	C10D—H10C	0.9900
C7C—H7C2	0.9900	C10D—H10D	0.9900
C8C—C9C	1.528 (4)	C11D—C12D	1.393 (4)
C8C—H8C1	0.9900	C11D—C16D	1.408 (4)
C8C—H8C2	0.9900	C12D—C13D	1.391 (4)
C9C—N1C^i	1.479 (4)	C12D—H12D	0.9500
C9C—H9C1	0.9900	C13D—C14D	1.400 (4)
C9C—H9C2	0.9900	C13D—H13D	0.9500
C10C—C11C	1.513 (4)	C14D—C15D	1.393 (4)
C10C—H10A	0.9900	C14D—H14D	0.9500
C10C—H10B	0.9900	C15D—C16D	1.392 (4)
C11C—C16C	1.401 (4)	C15D—H15D	0.9500
C11C—C12C	1.404 (4)	C16D—H16D	0.9500
F2A—P1A—F4A	90.54 (12)	C11C—C10C—H10A	109.4
F2A—P1A—F6A	90.12 (13)	N3C—C10C—H10B	109.4
F4A—P1A—F6A	90.22 (12)	C11C—C10C—H10B	109.4
F2A—P1A—F5A	179.29 (10)	H10A—C10C—H10B	108.0
F4A—P1A—F5A	90.04 (12)	C16C—C11C—C12C	118.5 (3)
F6A—P1A—F5A	90.30 (13)	C16C—C11C—C10C	121.1 (2)
F2A—P1A—F3A	89.88 (12)	C12C—C11C—C10C	120.4 (3)
F4A—P1A—F3A	90.15 (12)	C13C—C12C—C11C	120.7 (3)
F6A—P1A—F3A	179.63 (10)	C13C—C12C—H12C	119.6
F5A—P1A—F3A	89.69 (12)	C11C—C12C—H12C	119.6
F2A—P1A—F1A	89.87 (12)	C14C—C13C—C12C	120.3 (3)
F4A—P1A—F1A	179.57 (10)	C14C—C13C—H13C	119.8
F6A—P1A—F1A	89.91 (12)	C12C—C13C—H13C	119.8
F5A—P1A—F1A	89.56 (12)	C15C—C14C—C13C	119.5 (3)
F3A—P1A—F1A	89.71 (12)	C15C—C14C—H14C	120.3
F4B—P1B—F6B	91.8 (3)	C13C—C14C—H14C	120.3
F4B—P1B—F5B	90.2 (3)	C14C—C15C—C16C	120.5 (3)
F6B—P1B—F5B	91.3 (3)	C14C—C15C—H15C	119.7
F4B—P1B—F1B	179.6 (3)	C16C—C15C—H15C	119.7
F6B—P1B—F1B	88.5 (3)	C15C—C16C—C11C	120.5 (3)
F5B—P1B—F1B	90.0 (3)	C15C—C16C—H16C	119.8
F4B—P1B—F2B	91.0 (3)	C11C—C16C—H16C	119.8
F6B—P1B—F2B	89.8 (3)	C1D—N1D—C2D	108.9 (2)
F5B—P1B—F2B	178.4 (3)	C1D—N1D—C9D^ii	126.4 (2)
F1B—P1B—F2B	88.7 (3)	C2D—N1D—C9D^ii	124.7 (2)
F4B—P1B—F3B	90.5 (3)	C1D—N2D—C3D	108.2 (2)
F6B—P1B—F3B	177.8 (3)	C1D—N2D—C4D	127.0 (2)
F5B—P1B—F3B	88.9 (3)	C3D—N2D—C4D	124.7 (2)
F1B—P1B—F3B	89.2 (3)	C6D—N3D—C10D	109.6 (2)
F2B—P1B—F3B	90.0 (3)	C6D—N3D—C7D	110.4 (2)
F1B'—P1B'—F6B'	90.3 (4)	C10D—N3D—C7D	109.4 (2)
F1B'—P1B'—F3B'	91.0 (4)	N2D—C1D—N1D	108.5 (2)
F6B'—P1B'—F3B'	178.6 (4)	N2D—C1D—H1D	125.8
F1B'—P1B'—F4B'	179.1 (4)	N1D—C1D—H1D	125.8
F6B'—P1B'—F4B'	90.0 (3)	C3D—C2D—N1D	107.0 (3)
F3B'—P1B'—F4B'	88.6 (3)	C3D—C2D—H2D	126.5
F1B'—P1B'—F5B'	90.1 (4)	N1D—C2D—H2D	126.5
F6B'—P1B'—F5B'	89.9 (3)	C2D—C3D—N2D	107.4 (3)
F3B'—P1B'—F5B'	89.5 (4)	C2D—C3D—H3D	126.3
F4B'—P1B'—F5B'	89.1 (4)	N2D—C3D—H3D	126.3
F1B'—P1B'—F2B'	92.7 (4)	N2D—C4D—C5D	112.4 (2)
F6B'—P1B'—F2B'	88.4 (4)	N2D—C4D—H4D1	109.1
F3B'—P1B'—F2B'	92.1 (4)	C5D—C4D—H4D1	109.1
F4B'—P1B'—F2B'	88.1 (4)	N2D—C4D—H4D2	109.1
F5B'—P1B'—F2B'	176.7 (4)	C5D—C4D—H4D2	109.1
C1C—N1C—C2C	108.5 (2)	H4D1—C4D—H4D2	107.8
C1C—N1C—C9C^i	124.8 (2)	C6D—C5D—C4D	112.9 (2)
C2C—N1C—C9C^i	126.5 (2)	C6D—C5D—H5D1	109.0
C1C—N2C—C3C	108.4 (2)	C4D—C5D—H5D1	109.0
C1C—N2C—C4C	125.7 (2)	C6D—C5D—H5D2	109.0
C3C—N2C—C4C	125.9 (2)	C4D—C5D—H5D2	109.0
C7C—N3C—C6C	109.5 (2)	H5D1—C5D—H5D2	107.8
C7C—N3C—C10C	111.7 (2)	N3D—C6D—C5D	113.0 (2)
C6C—N3C—C10C	113.6 (2)	N3D—C6D—H6D1	109.0
N1C—C1C—N2C	108.5 (2)	C5D—C6D—H6D1	109.0
N1C—C1C—H1C	125.8	N3D—C6D—H6D2	109.0
N2C—C1C—H1C	125.8	C5D—C6D—H6D2	109.0
C3C—C2C—N1C	107.3 (3)	H6D1—C6D—H6D2	107.8
C3C—C2C—H2C	126.3	N3D—C7D—C8D	113.6 (2)
N1C—C2C—H2C	126.3	N3D—C7D—H7D1	108.8
C2C—C3C—N2C	107.3 (3)	C8D—C7D—H7D1	108.8
C2C—C3C—H3C	126.4	N3D—C7D—H7D2	108.8
N2C—C3C—H3C	126.4	C8D—C7D—H7D2	108.8
N2C—C4C—C5C	112.1 (2)	H7D1—C7D—H7D2	107.7
N2C—C4C—H4C1	109.2	C9D—C8D—C7D	110.6 (2)
C5C—C4C—H4C1	109.2	C9D—C8D—H8D1	109.5
N2C—C4C—H4C2	109.2	C7D—C8D—H8D1	109.5
C5C—C4C—H4C2	109.2	C9D—C8D—H8D2	109.5
H4C1—C4C—H4C2	107.9	C7D—C8D—H8D2	109.5
C6C—C5C—C4C	110.4 (2)	H8D1—C8D—H8D2	108.1
C6C—C5C—H5C1	109.6	N1D^ii—C9D—C8D	111.3 (2)
C4C—C5C—H5C1	109.6	N1D^ii—C9D—H9D1	109.4
C6C—C5C—H5C2	109.6	C8D—C9D—H9D1	109.4
C4C—C5C—H5C2	109.6	N1D^ii—C9D—H9D2	109.4
H5C1—C5C—H5C2	108.1	C8D—C9D—H9D2	109.4
N3C—C6C—C5C	111.3 (2)	H9D1—C9D—H9D2	108.0
N3C—C6C—H6C1	109.4	N3D—C10D—C11D	113.2 (2)
C5C—C6C—H6C1	109.4	N3D—C10D—H10C	108.9
N3C—C6C—H6C2	109.4	C11D—C10D—H10C	108.9
C5C—C6C—H6C2	109.4	N3D—C10D—H10D	108.9
H6C1—C6C—H6C2	108.0	C11D—C10D—H10D	108.9
N3C—C7C—C8C	113.9 (2)	H10C—C10D—H10D	107.8
N3C—C7C—H7C1	108.8	C12D—C11D—C16D	118.3 (3)
C8C—C7C—H7C1	108.8	C12D—C11D—C10D	120.7 (3)
N3C—C7C—H7C2	108.8	C16D—C11D—C10D	121.0 (3)
C8C—C7C—H7C2	108.8	C13D—C12D—C11D	121.3 (3)
H7C1—C7C—H7C2	107.7	C13D—C12D—H12D	119.3
C9C—C8C—C7C	113.3 (2)	C11D—C12D—H12D	119.3
C9C—C8C—H8C1	108.9	C12D—C13D—C14D	119.8 (3)
C7C—C8C—H8C1	108.9	C12D—C13D—H13D	120.1
C9C—C8C—H8C2	108.9	C14D—C13D—H13D	120.1
C7C—C8C—H8C2	108.9	C15D—C14D—C13D	119.8 (3)
H8C1—C8C—H8C2	107.7	C15D—C14D—H14D	120.1
N1C^i—C9C—C8C	112.5 (2)	C13D—C14D—H14D	120.1
N1C^i—C9C—H9C1	109.1	C16D—C15D—C14D	119.9 (3)
C8C—C9C—H9C1	109.1	C16D—C15D—H15D	120.0
N1C^i—C9C—H9C2	109.1	C14D—C15D—H15D	120.0
C8C—C9C—H9C2	109.1	C15D—C16D—C11D	120.9 (3)
H9C1—C9C—H9C2	107.8	C15D—C16D—H16D	119.6
N3C—C10C—C11C	111.1 (2)	C11D—C16D—H16D	119.6
N3C—C10C—H10A	109.4
C2C—N1C—C1C—N2C	0.2 (3)	C3D—N2D—C1D—N1D	0.6 (4)
C9C^i—N1C—C1C—N2C	−176.1 (2)	C4D—N2D—C1D—N1D	−178.7 (3)
C3C—N2C—C1C—N1C	−0.2 (3)	C2D—N1D—C1D—N2D	−0.6 (3)
C4C—N2C—C1C—N1C	176.9 (2)	C9D^ii—N1D—C1D—N2D	−179.9 (2)
C1C—N1C—C2C—C3C	−0.1 (3)	C1D—N1D—C2D—C3D	0.4 (4)
C9C^i—N1C—C2C—C3C	176.2 (2)	C9D^ii—N1D—C2D—C3D	179.7 (3)
N1C—C2C—C3C—N2C	−0.1 (3)	N1D—C2D—C3D—N2D	0.0 (4)
C1C—N2C—C3C—C2C	0.2 (3)	C1D—N2D—C3D—C2D	−0.4 (4)
C4C—N2C—C3C—C2C	−176.9 (2)	C4D—N2D—C3D—C2D	178.9 (3)
C1C—N2C—C4C—C5C	109.7 (3)	C1D—N2D—C4D—C5D	102.2 (3)
C3C—N2C—C4C—C5C	−73.6 (3)	C3D—N2D—C4D—C5D	−76.9 (4)
N2C—C4C—C5C—C6C	156.8 (2)	N2D—C4D—C5D—C6D	−108.0 (3)
C7C—N3C—C6C—C5C	−95.3 (3)	C10D—N3D—C6D—C5D	−159.2 (2)
C10C—N3C—C6C—C5C	139.1 (2)	C7D—N3D—C6D—C5D	80.2 (3)
C4C—C5C—C6C—N3C	172.9 (2)	C4D—C5D—C6D—N3D	57.3 (3)
C6C—N3C—C7C—C8C	167.1 (2)	C6D—N3D—C7D—C8D	−161.3 (2)
C10C—N3C—C7C—C8C	−66.2 (3)	C10D—N3D—C7D—C8D	78.0 (3)
N3C—C7C—C8C—C9C	−47.1 (3)	N3D—C7D—C8D—C9D	−172.5 (2)
C7C—C8C—C9C—N1C^i	−55.5 (3)	C7D—C8D—C9D—N1D^ii	178.2 (2)
C7C—N3C—C10C—C11C	179.6 (2)	C6D—N3D—C10D—C11D	66.7 (3)
C6C—N3C—C10C—C11C	−55.9 (3)	C7D—N3D—C10D—C11D	−172.1 (2)
N3C—C10C—C11C—C16C	132.1 (3)	N3D—C10D—C11D—C12D	54.3 (3)
N3C—C10C—C11C—C12C	−45.8 (3)	N3D—C10D—C11D—C16D	−127.5 (3)
C16C—C11C—C12C—C13C	−0.2 (4)	C16D—C11D—C12D—C13D	0.4 (4)
C10C—C11C—C12C—C13C	177.8 (3)	C10D—C11D—C12D—C13D	178.7 (2)
C11C—C12C—C13C—C14C	−0.1 (4)	C11D—C12D—C13D—C14D	−1.8 (4)
C12C—C13C—C14C—C15C	0.3 (4)	C12D—C13D—C14D—C15D	1.6 (4)
C13C—C14C—C15C—C16C	−0.1 (4)	C13D—C14D—C15D—C16D	0.0 (4)
C14C—C15C—C16C—C11C	−0.2 (4)	C14D—C15D—C16D—C11D	−1.3 (4)
C12C—C11C—C16C—C15C	0.4 (4)	C12D—C11D—C16D—C15D	1.1 (4)
C10C—C11C—C16C—C15C	−177.6 (2)	C10D—C11D—C16D—C15D	−177.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1C—H1C···F1A^iii	0.95	2.49	3.126 (5)	124
C1C—H1C···F6A	0.95	2.52	3.181 (5)	127
C2C—H2C···F2B^i	0.95	2.50	3.292 (7)	141
C2C—H2C···F2B′^i	0.95	2.39	3.175 (8)	140
C4C—H4C1···F1A	0.99	2.55	3.525 (5)	168
C5C—H5C2···F6A^i	0.99	2.56	3.451 (4)	149
C7C—H7C1···F5A	0.99	2.51	3.476 (5)	165
C8C—H8C2···F2B	0.99	2.50	3.385 (8)	149
C9C—H9C2···F3A^iv	0.99	2.61	3.177 (4)	117
C9C—H9C2···F1B	0.99	2.42	3.260 (5)	142
C9C—H9C2···F1B′	0.99	2.32	3.142 (7)	140
C1D—H1D···F3B	0.95	2.39	3.204 (5)	143
C1D—H1D···F3B′	0.95	2.65	3.417 (7)	138
C1D—H1D···F4B′^v	0.95	2.65	3.239 (7)	121
C2D—H2D···F3A^v	0.95	2.47	3.370 (4)	159
C2D—H2D···F5A^v	0.95	2.64	3.390 (5)	136
C5D—H5D2···F5B′^vi	0.99	2.66	3.526 (8)	146
C6D—H6D2···F6B′^vi	0.99	2.61	3.260 (6)	123
C7D—H7D2···F5B^ii	0.99	2.52	3.339 (6)	140
C7D—H7D2···F5B′^ii	0.99	2.45	3.368 (6)	154
C8D—H8D1···F1B	0.99	2.64	3.424 (5)	137
C8D—H8D2···F3B′	0.99	2.69	3.202 (6)	113
C9D—H9D1···F3B^ii	0.99	2.48	3.376 (6)	151
C9D—H9D1···F5B^ii	0.99	2.59	3.386 (6)	137
C9D—H9D1···F4B′^ii	0.99	2.69	3.660 (6)	166
C9D—H9D2···F4A^iv	0.99	2.69	3.470 (5)	136

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

[(1,2,5,6-η)-Cycloocta-1,5-diene](5,16-dibenzyl-1,5,9,12,16,20-hexaazatricyclo[18.2.1.1^9,12]tetracosa-10,21-dien-21,22-diylidene)iridium(I) bromide dichloromethane monosolvate (2a)

Crystal data

[Ir(C8H12)(C32H42N6)]Br·CH2Cl2	Z = 2
Mr = 991.92	F(000) = 996
Triclinic, P1	Dx = 1.575 Mg m^−3
a = 10.3943 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.6413 (6) Å	Cell parameters from 9731 reflections
c = 15.8517 (7) Å	θ = 2.3–36.4°
α = 91.6088 (18)°	µ = 4.31 mm^−1
β = 95.5859 (19)°	T = 100 K
γ = 110.4270 (16)°	Plate, yellow
V = 2091.66 (15) Å^3	0.26 × 0.17 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer	11240 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.038
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 29.6°, θmin = 2.1°
Tmin = 0.517, Tmax = 0.747	h = −14→14
44172 measured reflections	k = −18→18
11734 independent reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.180	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.120P)^2 + 22.P] where P = (Fo^2 + 2Fc^2)/3
11734 reflections	(Δ/σ)max = 0.001
433 parameters	Δρmax = 2.71 e Å^−3
6 restraints	Δρmin = −4.38 e Å^−3

Special details

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

Refinement. Disordered dichloromethane was best modeled with SQUEEZE

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

	x	y	z	Uiso*/Ueq
Ir1	0.31659 (2)	0.66192 (2)	0.37793 (2)	0.01202 (8)
N1	0.5935 (5)	0.7660 (4)	0.4907 (3)	0.0132 (9)
N2	0.6145 (5)	0.8084 (4)	0.3622 (3)	0.0145 (9)
N3	0.4540 (8)	0.8589 (6)	0.1151 (4)	0.0323 (15)
N4	0.2067 (6)	0.8387 (4)	0.3300 (4)	0.0168 (10)
N5	0.1938 (6)	0.8119 (4)	0.4622 (3)	0.0157 (10)
N6	0.3580 (6)	0.7177 (4)	0.6990 (3)	0.0159 (10)
C1	0.5192 (6)	0.7534 (5)	0.4131 (4)	0.0141 (10)
C2	0.7313 (6)	0.8282 (5)	0.4881 (4)	0.0166 (11)
H2	0.802634	0.848114	0.534276	0.020*
C3	0.7435 (6)	0.8547 (5)	0.4069 (4)	0.0163 (11)
H3	0.825194	0.897112	0.384965	0.020*
C4	0.5832 (7)	0.8023 (5)	0.2692 (4)	0.0180 (11)
H4A	0.482178	0.782439	0.254892	0.022*
H4AB	0.610550	0.746082	0.244386	0.022*
C5	0.6550 (9)	0.9031 (6)	0.2291 (5)	0.0300 (16)
H5A	0.756204	0.919657	0.237067	0.036*
H5AB	0.635068	0.961413	0.256692	0.036*
C6	0.6042 (10)	0.8914 (8)	0.1344 (6)	0.040 (2)
H6A	0.647599	0.959327	0.109508	0.048*
H6AB	0.635448	0.839211	0.106506	0.048*
C7	0.4162 (10)	0.8260 (8)	0.0246 (5)	0.039 (2)
H7A	0.466870	0.780237	0.008507	0.046*
H7AB	0.445238	0.888720	−0.008829	0.046*
C8	0.2635 (9)	0.7681 (7)	0.0023 (5)	0.0301 (16)
C9	0.1952 (9)	0.6876 (7)	0.0502 (5)	0.0315 (17)
H9	0.244433	0.670745	0.097850	0.038*
C10	0.0546 (11)	0.6304 (7)	0.0296 (6)	0.041 (2)
H10	0.008953	0.574635	0.062954	0.050*
C11	−0.0180 (10)	0.6548 (8)	−0.0388 (6)	0.040 (2)
H11	−0.113927	0.616614	−0.052820	0.048*
C12	0.0510 (11)	0.7362 (8)	−0.0872 (6)	0.039 (2)
H12	0.002104	0.753317	−0.134893	0.047*
C13	0.1889 (9)	0.7917 (7)	−0.0666 (5)	0.0303 (16)
H13	0.234427	0.847437	−0.100002	0.036*
C14	0.3989 (10)	0.9387 (7)	0.1378 (5)	0.0353 (19)
H14A	0.317622	0.931335	0.096553	0.042*
H14B	0.469502	1.008317	0.132166	0.042*
C15	0.3556 (9)	0.9357 (6)	0.2271 (5)	0.0309 (17)
H15A	0.436939	0.944009	0.268576	0.037*
H15B	0.326144	0.996152	0.237714	0.037*
C16	0.2397 (8)	0.8361 (5)	0.2428 (4)	0.0230 (13)
H16A	0.156553	0.828185	0.203074	0.028*
H16B	0.267522	0.774968	0.231991	0.028*
C17	0.2401 (6)	0.7815 (4)	0.3920 (4)	0.0132 (10)
C18	0.1421 (7)	0.9027 (5)	0.3630 (5)	0.0225 (13)
H18	0.109909	0.950121	0.332436	0.027*
C19	0.1337 (7)	0.8864 (5)	0.4429 (4)	0.0178 (11)
H19	0.093871	0.919244	0.481190	0.021*
C20	0.2087 (6)	0.7761 (5)	0.5474 (4)	0.0151 (11)
H20A	0.224270	0.708595	0.543359	0.018*
H20B	0.122144	0.763988	0.573542	0.018*
C21	0.3292 (6)	0.8562 (5)	0.6040 (4)	0.0169 (11)
H21A	0.316291	0.924738	0.605723	0.020*
H21B	0.416596	0.865347	0.579717	0.020*
C22	0.3386 (7)	0.8202 (5)	0.6945 (4)	0.0188 (12)
H22A	0.416816	0.873954	0.729499	0.023*
H22B	0.252961	0.815266	0.719315	0.023*
C23	0.2773 (7)	0.6563 (5)	0.7633 (4)	0.0199 (12)
H23A	0.187258	0.666614	0.760107	0.024*
H23B	0.326956	0.683850	0.820328	0.024*
C24	0.2510 (7)	0.5399 (5)	0.7534 (4)	0.0185 (12)
C25	0.2467 (8)	0.4898 (6)	0.6755 (5)	0.0239 (13)
H25	0.270605	0.529564	0.627481	0.029*
C26	0.2070 (8)	0.3798 (6)	0.6674 (5)	0.0233 (13)
H26	0.205186	0.345810	0.613918	0.028*
C27	0.1705 (8)	0.3206 (6)	0.7369 (5)	0.0245 (14)
H27	0.140929	0.246329	0.730834	0.029*
C28	0.1779 (9)	0.3717 (6)	0.8161 (5)	0.0294 (16)
H28	0.155904	0.332426	0.864636	0.035*
C29	0.2174 (8)	0.4800 (6)	0.8231 (5)	0.0260 (14)
H29	0.221668	0.514177	0.876860	0.031*
C30	0.5038 (6)	0.7297 (5)	0.7179 (4)	0.0182 (11)
H30A	0.509987	0.659914	0.726880	0.022*
H30B	0.541841	0.773700	0.771605	0.022*
C31	0.5926 (6)	0.7793 (5)	0.6483 (4)	0.0175 (11)
H31A	0.593311	0.851405	0.641732	0.021*
H31B	0.688852	0.783210	0.664169	0.021*
C32	0.5349 (6)	0.7140 (5)	0.5653 (4)	0.0156 (11)
H32A	0.552599	0.647454	0.568978	0.019*
H32B	0.433494	0.696473	0.557173	0.019*
C33	0.3610 (6)	0.5194 (5)	0.3994 (4)	0.0160 (11)
H33	0.446606	0.530729	0.439082	0.019*
C34	0.3867 (7)	0.5480 (5)	0.3164 (4)	0.0195 (12)
H34	0.486744	0.575143	0.307610	0.023*
C35	0.2885 (8)	0.4986 (7)	0.2362 (5)	0.0293 (16)
H35A	0.316704	0.544733	0.189068	0.035*
H35B	0.297115	0.430549	0.220461	0.035*
C36	0.1388 (8)	0.4807 (6)	0.2461 (5)	0.0269 (15)
H36A	0.097249	0.412608	0.271057	0.032*
H36B	0.087629	0.477207	0.189392	0.032*
C37	0.1237 (7)	0.5672 (5)	0.3023 (4)	0.0182 (12)
H37	0.071405	0.608294	0.273400	0.022*
C38	0.1083 (6)	0.5557 (5)	0.3897 (4)	0.0168 (11)
H38	0.046831	0.590262	0.412035	0.020*
C39	0.1144 (7)	0.4632 (5)	0.4365 (5)	0.0212 (13)
H39A	0.027325	0.403418	0.420014	0.025*
H39B	0.119777	0.480378	0.498155	0.025*
C40	0.2352 (7)	0.4290 (5)	0.4208 (5)	0.0211 (12)
H40A	0.205375	0.374343	0.373337	0.025*
H40B	0.261794	0.397615	0.472109	0.025*
Br1	−0.00120 (8)	0.11762 (7)	0.32409 (5)	0.03063 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.00950 (12)	0.00964 (12)	0.01628 (12)	0.00284 (8)	0.00113 (8)	−0.00128 (8)
N1	0.007 (2)	0.014 (2)	0.019 (2)	0.0033 (17)	0.0035 (17)	−0.0014 (18)
N2	0.013 (2)	0.011 (2)	0.015 (2)	0.0007 (18)	0.0004 (18)	−0.0028 (17)
N3	0.036 (4)	0.032 (4)	0.020 (3)	0.002 (3)	0.002 (3)	0.006 (3)
N4	0.015 (2)	0.015 (2)	0.022 (3)	0.0088 (19)	−0.0012 (19)	−0.0034 (19)
N5	0.016 (2)	0.015 (2)	0.019 (2)	0.0104 (19)	−0.0011 (19)	−0.0022 (19)
N6	0.016 (2)	0.014 (2)	0.017 (2)	0.0053 (19)	0.0036 (19)	−0.0007 (18)
C1	0.010 (2)	0.013 (2)	0.018 (3)	0.003 (2)	0.002 (2)	−0.001 (2)
C2	0.012 (3)	0.016 (3)	0.020 (3)	0.003 (2)	0.001 (2)	0.000 (2)
C3	0.011 (2)	0.015 (3)	0.021 (3)	0.002 (2)	0.001 (2)	−0.001 (2)
C4	0.017 (3)	0.016 (3)	0.017 (3)	0.001 (2)	0.001 (2)	0.000 (2)
C5	0.031 (4)	0.023 (3)	0.027 (4)	0.000 (3)	−0.003 (3)	0.005 (3)
C6	0.032 (4)	0.045 (5)	0.030 (4)	−0.003 (4)	0.001 (3)	0.011 (4)
C7	0.035 (4)	0.049 (5)	0.021 (3)	0.000 (4)	0.003 (3)	0.005 (3)
C8	0.033 (4)	0.033 (4)	0.019 (3)	0.006 (3)	−0.001 (3)	−0.003 (3)
C9	0.031 (4)	0.036 (4)	0.020 (3)	0.003 (3)	0.006 (3)	−0.006 (3)
C10	0.042 (5)	0.031 (4)	0.036 (4)	−0.006 (4)	0.009 (4)	−0.010 (3)
C11	0.030 (4)	0.046 (5)	0.041 (5)	0.011 (4)	0.002 (3)	−0.017 (4)
C12	0.045 (5)	0.042 (5)	0.035 (4)	0.024 (4)	−0.006 (4)	−0.014 (4)
C13	0.039 (4)	0.029 (4)	0.025 (3)	0.017 (3)	−0.001 (3)	−0.008 (3)
C14	0.049 (5)	0.025 (4)	0.022 (3)	0.001 (3)	0.001 (3)	0.008 (3)
C15	0.042 (4)	0.021 (3)	0.022 (3)	0.001 (3)	0.004 (3)	0.001 (3)
C16	0.025 (3)	0.016 (3)	0.020 (3)	0.000 (2)	−0.002 (2)	0.002 (2)
C17	0.010 (2)	0.010 (2)	0.019 (3)	0.0020 (19)	0.0022 (19)	−0.003 (2)
C18	0.019 (3)	0.013 (3)	0.040 (4)	0.013 (2)	−0.005 (3)	−0.004 (3)
C19	0.0163 (18)	0.0160 (18)	0.0261 (19)	0.0127 (15)	0.0007 (15)	−0.0010 (15)
C20	0.010 (2)	0.012 (2)	0.023 (3)	0.004 (2)	0.003 (2)	−0.001 (2)
C21	0.015 (3)	0.015 (3)	0.019 (3)	0.003 (2)	0.000 (2)	0.002 (2)
C22	0.021 (3)	0.015 (3)	0.020 (3)	0.007 (2)	−0.001 (2)	−0.001 (2)
C23	0.026 (3)	0.015 (3)	0.019 (3)	0.007 (2)	0.007 (2)	−0.002 (2)
C24	0.014 (3)	0.018 (3)	0.024 (3)	0.005 (2)	0.002 (2)	0.003 (2)
C25	0.032 (4)	0.017 (3)	0.023 (3)	0.010 (3)	0.005 (3)	0.001 (2)
C26	0.026 (3)	0.019 (3)	0.028 (3)	0.012 (3)	0.004 (3)	0.000 (3)
C27	0.023 (3)	0.018 (3)	0.034 (4)	0.008 (3)	0.005 (3)	0.003 (3)
C28	0.034 (4)	0.025 (3)	0.034 (4)	0.012 (3)	0.013 (3)	0.012 (3)
C29	0.024 (3)	0.030 (4)	0.022 (3)	0.006 (3)	0.007 (3)	0.003 (3)
C30	0.012 (3)	0.023 (3)	0.018 (3)	0.005 (2)	0.000 (2)	0.001 (2)
C31	0.012 (3)	0.018 (3)	0.020 (3)	0.004 (2)	0.002 (2)	0.000 (2)
C32	0.015 (3)	0.014 (3)	0.015 (3)	0.003 (2)	0.002 (2)	0.001 (2)
C33	0.014 (3)	0.016 (3)	0.020 (3)	0.008 (2)	0.003 (2)	0.001 (2)
C34	0.021 (3)	0.021 (3)	0.018 (3)	0.007 (2)	0.009 (2)	−0.004 (2)
C35	0.026 (4)	0.030 (4)	0.031 (4)	0.010 (3)	0.007 (3)	−0.013 (3)
C36	0.028 (4)	0.025 (3)	0.024 (3)	0.007 (3)	−0.004 (3)	−0.012 (3)
C37	0.015 (3)	0.016 (3)	0.019 (3)	0.002 (2)	−0.003 (2)	−0.005 (2)
C38	0.010 (2)	0.013 (3)	0.024 (3)	0.001 (2)	0.003 (2)	−0.004 (2)
C39	0.017 (3)	0.015 (3)	0.031 (3)	0.003 (2)	0.008 (2)	0.004 (2)
C40	0.022 (3)	0.012 (3)	0.031 (3)	0.008 (2)	0.007 (3)	0.006 (2)
Br1	0.0221 (3)	0.0335 (4)	0.0371 (4)	0.0124 (3)	−0.0002 (3)	−0.0056 (3)

Geometric parameters (Å, º)

Ir1—C1	2.049 (6)	C16—H16A	0.9900
Ir1—C17	2.065 (6)	C16—H16B	0.9900
Ir1—C38	2.174 (6)	C18—C19	1.298 (11)
Ir1—C33	2.177 (6)	C18—H18	0.9500
Ir1—C34	2.178 (6)	C19—H19	0.9500
Ir1—C37	2.182 (6)	C20—C21	1.529 (8)
N1—C1	1.360 (8)	C20—H20A	0.9900
N1—C2	1.392 (8)	C20—H20B	0.9900
N1—C32	1.468 (8)	C21—C22	1.534 (9)
N2—C1	1.366 (8)	C21—H21A	0.9900
N2—C3	1.377 (8)	C21—H21B	0.9900
N2—C4	1.471 (8)	C22—H22A	0.9900
N3—C14	1.447 (13)	C22—H22B	0.9900
N3—C7	1.464 (10)	C23—C24	1.516 (9)
N3—C6	1.464 (12)	C23—H23A	0.9900
N4—C17	1.363 (8)	C23—H23B	0.9900
N4—C18	1.393 (8)	C24—C25	1.384 (10)
N4—C16	1.458 (9)	C24—C29	1.392 (10)
N5—C17	1.365 (8)	C25—C26	1.409 (10)
N5—C19	1.393 (7)	C25—H25	0.9500
N5—C20	1.462 (8)	C26—C27	1.388 (10)
N6—C30	1.466 (8)	C26—H26	0.9500
N6—C23	1.472 (8)	C27—C28	1.401 (11)
N6—C22	1.484 (8)	C27—H27	0.9500
C2—C3	1.353 (9)	C28—C29	1.386 (11)
C2—H2	0.9500	C28—H28	0.9500
C3—H3	0.9500	C29—H29	0.9500
C4—C5	1.510 (10)	C30—C31	1.527 (9)
C4—H4A	0.9900	C30—H30A	0.9900
C4—H4AB	0.9900	C30—H30B	0.9900
C5—C6	1.527 (11)	C31—C32	1.514 (9)
C5—H5A	0.9900	C31—H31A	0.9900
C5—H5AB	0.9900	C31—H31B	0.9900
C6—H6A	0.9900	C32—H32A	0.9900
C6—H6AB	0.9900	C32—H32B	0.9900
C7—C8	1.506 (12)	C33—C34	1.407 (9)
C7—H7A	0.9900	C33—C40	1.526 (9)
C7—H7AB	0.9900	C33—H33	1.0000
C8—C9	1.376 (12)	C34—C35	1.527 (10)
C8—C13	1.388 (11)	C34—H34	1.0000
C9—C10	1.396 (12)	C35—C36	1.513 (11)
C9—H9	0.9500	C35—H35A	0.9900
C10—C11	1.376 (15)	C35—H35B	0.9900
C10—H10	0.9500	C36—C37	1.519 (10)
C11—C12	1.391 (15)	C36—H36A	0.9900
C11—H11	0.9500	C36—H36B	0.9900
C12—C13	1.368 (13)	C37—C38	1.417 (9)
C12—H12	0.9500	C37—H37	1.0000
C13—H13	0.9500	C38—C39	1.498 (9)
C14—C15	1.525 (11)	C38—H38	1.0000
C14—H14A	0.9900	C39—C40	1.523 (10)
C14—H14B	0.9900	C39—H39A	0.9900
C15—C16	1.514 (10)	C39—H39B	0.9900
C15—H15A	0.9900	C40—H40A	0.9900
C15—H15B	0.9900	C40—H40B	0.9900
C1—Ir1—C17	95.5 (2)	N5—C19—H19	126.3
C1—Ir1—C38	159.0 (3)	N5—C20—C21	111.4 (5)
C17—Ir1—C38	86.3 (2)	N5—C20—H20A	109.3
C1—Ir1—C33	91.4 (2)	C21—C20—H20A	109.3
C17—Ir1—C33	161.0 (2)	N5—C20—H20B	109.3
C38—Ir1—C33	81.1 (2)	C21—C20—H20B	109.3
C1—Ir1—C34	88.8 (2)	H20A—C20—H20B	108.0
C17—Ir1—C34	159.7 (3)	C20—C21—C22	110.8 (5)
C38—Ir1—C34	96.9 (2)	C20—C21—H21A	109.5
C33—Ir1—C34	37.7 (2)	C22—C21—H21A	109.5
C1—Ir1—C37	162.4 (3)	C20—C21—H21B	109.5
C17—Ir1—C37	89.8 (2)	C22—C21—H21B	109.5
C38—Ir1—C37	38.0 (2)	H21A—C21—H21B	108.1
C33—Ir1—C37	88.9 (2)	N6—C22—C21	113.8 (5)
C34—Ir1—C37	80.7 (3)	N6—C22—H22A	108.8
C1—N1—C2	111.3 (5)	C21—C22—H22A	108.8
C1—N1—C32	123.2 (5)	N6—C22—H22B	108.8
C2—N1—C32	125.4 (5)	C21—C22—H22B	108.8
C1—N2—C3	111.8 (5)	H22A—C22—H22B	107.7
C1—N2—C4	122.0 (5)	N6—C23—C24	114.0 (5)
C3—N2—C4	125.6 (5)	N6—C23—H23A	108.7
C14—N3—C7	110.4 (7)	C24—C23—H23A	108.7
C14—N3—C6	113.9 (8)	N6—C23—H23B	108.7
C7—N3—C6	108.9 (7)	C24—C23—H23B	108.7
C17—N4—C18	110.2 (6)	H23A—C23—H23B	107.6
C17—N4—C16	124.6 (6)	C25—C24—C29	118.8 (7)
C18—N4—C16	125.2 (6)	C25—C24—C23	122.0 (6)
C17—N5—C19	110.6 (5)	C29—C24—C23	118.9 (6)
C17—N5—C20	125.8 (5)	C24—C25—C26	120.1 (7)
C19—N5—C20	123.5 (5)	C24—C25—H25	120.0
C30—N6—C23	110.0 (5)	C26—C25—H25	120.0
C30—N6—C22	112.1 (5)	C27—C26—C25	120.5 (7)
C23—N6—C22	110.1 (5)	C27—C26—H26	119.7
N1—C1—N2	103.7 (5)	C25—C26—H26	119.7
N1—C1—Ir1	128.2 (4)	C26—C27—C28	119.3 (7)
N2—C1—Ir1	127.9 (4)	C26—C27—H27	120.4
C3—C2—N1	106.5 (5)	C28—C27—H27	120.4
C3—C2—H2	126.8	C29—C28—C27	119.4 (7)
N1—C2—H2	126.8	C29—C28—H28	120.3
C2—C3—N2	106.7 (5)	C27—C28—H28	120.3
C2—C3—H3	126.6	C28—C29—C24	121.8 (7)
N2—C3—H3	126.6	C28—C29—H29	119.1
N2—C4—C5	113.9 (5)	C24—C29—H29	119.1
N2—C4—H4A	108.8	N6—C30—C31	113.8 (5)
C5—C4—H4A	108.8	N6—C30—H30A	108.8
N2—C4—H4AB	108.8	C31—C30—H30A	108.8
C5—C4—H4AB	108.8	N6—C30—H30B	108.8
H4A—C4—H4AB	107.7	C31—C30—H30B	108.8
C4—C5—C6	109.5 (6)	H30A—C30—H30B	107.7
C4—C5—H5A	109.8	C32—C31—C30	109.7 (5)
C6—C5—H5A	109.8	C32—C31—H31A	109.7
C4—C5—H5AB	109.8	C30—C31—H31A	109.7
C6—C5—H5AB	109.8	C32—C31—H31B	109.7
H5A—C5—H5AB	108.2	C30—C31—H31B	109.7
N3—C6—C5	114.3 (7)	H31A—C31—H31B	108.2
N3—C6—H6A	108.7	N1—C32—C31	114.0 (5)
C5—C6—H6A	108.7	N1—C32—H32A	108.8
N3—C6—H6AB	108.7	C31—C32—H32A	108.8
C5—C6—H6AB	108.7	N1—C32—H32B	108.8
H6A—C6—H6AB	107.6	C31—C32—H32B	108.8
N3—C7—C8	112.9 (7)	H32A—C32—H32B	107.7
N3—C7—H7A	109.0	C34—C33—C40	124.2 (6)
C8—C7—H7A	109.0	C34—C33—Ir1	71.2 (4)
N3—C7—H7AB	109.0	C40—C33—Ir1	112.6 (4)
C8—C7—H7AB	109.0	C34—C33—H33	113.8
H7A—C7—H7AB	107.8	C40—C33—H33	113.8
C9—C8—C13	118.4 (8)	Ir1—C33—H33	113.8
C9—C8—C7	119.5 (8)	C33—C34—C35	125.0 (6)
C13—C8—C7	122.1 (8)	C33—C34—Ir1	71.1 (4)
C8—C9—C10	120.9 (9)	C35—C34—Ir1	109.0 (5)
C8—C9—H9	119.6	C33—C34—H34	114.4
C10—C9—H9	119.6	C35—C34—H34	114.4
C11—C10—C9	120.1 (9)	Ir1—C34—H34	114.4
C11—C10—H10	120.0	C36—C35—C34	113.4 (6)
C9—C10—H10	120.0	C36—C35—H35A	108.9
C10—C11—C12	119.1 (9)	C34—C35—H35A	108.9
C10—C11—H11	120.5	C36—C35—H35B	108.9
C12—C11—H11	120.5	C34—C35—H35B	108.9
C13—C12—C11	120.4 (9)	H35A—C35—H35B	107.7
C13—C12—H12	119.8	C35—C36—C37	112.0 (6)
C11—C12—H12	119.8	C35—C36—H36A	109.2
C12—C13—C8	121.2 (9)	C37—C36—H36A	109.2
C12—C13—H13	119.4	C35—C36—H36B	109.2
C8—C13—H13	119.4	C37—C36—H36B	109.2
N3—C14—C15	115.1 (7)	H36A—C36—H36B	107.9
N3—C14—H14A	108.5	C38—C37—C36	121.6 (6)
C15—C14—H14A	108.5	C38—C37—Ir1	70.7 (3)
N3—C14—H14B	108.5	C36—C37—Ir1	113.0 (5)
C15—C14—H14B	108.5	C38—C37—H37	114.7
H14A—C14—H14B	107.5	C36—C37—H37	114.7
C16—C15—C14	114.3 (6)	Ir1—C37—H37	114.7
C16—C15—H15A	108.7	C37—C38—C39	124.5 (6)
C14—C15—H15A	108.7	C37—C38—Ir1	71.3 (4)
C16—C15—H15B	108.7	C39—C38—Ir1	109.7 (4)
C14—C15—H15B	108.7	C37—C38—H38	114.4
H15A—C15—H15B	107.6	C39—C38—H38	114.4
N4—C16—C15	110.8 (6)	Ir1—C38—H38	114.4
N4—C16—H16A	109.5	C38—C39—C40	114.8 (5)
C15—C16—H16A	109.5	C38—C39—H39A	108.6
N4—C16—H16B	109.5	C40—C39—H39A	108.6
C15—C16—H16B	109.5	C38—C39—H39B	108.6
H16A—C16—H16B	108.1	C40—C39—H39B	108.6
N4—C17—N5	103.8 (5)	H39A—C39—H39B	107.5
N4—C17—Ir1	127.5 (4)	C39—C40—C33	112.8 (5)
N5—C17—Ir1	128.1 (5)	C39—C40—H40A	109.0
C19—C18—N4	108.1 (6)	C33—C40—H40A	109.0
C19—C18—H18	126.0	C39—C40—H40B	109.0
N4—C18—H18	126.0	C33—C40—H40B	109.0
C18—C19—N5	107.4 (6)	H40A—C40—H40B	107.8
C18—C19—H19	126.3
C2—N1—C1—N2	0.6 (7)	C17—N4—C18—C19	−0.5 (8)
C32—N1—C1—N2	−175.8 (5)	C16—N4—C18—C19	−177.9 (6)
C2—N1—C1—Ir1	175.3 (5)	N4—C18—C19—N5	0.4 (8)
C32—N1—C1—Ir1	−1.1 (9)	C17—N5—C19—C18	−0.2 (8)
C3—N2—C1—N1	−0.7 (7)	C20—N5—C19—C18	177.5 (6)
C4—N2—C1—N1	170.3 (5)	C17—N5—C20—C21	99.7 (7)
C3—N2—C1—Ir1	−175.4 (5)	C19—N5—C20—C21	−77.6 (7)
C4—N2—C1—Ir1	−4.4 (9)	N5—C20—C21—C22	176.9 (5)
C1—N1—C2—C3	−0.2 (7)	C30—N6—C22—C21	95.8 (6)
C32—N1—C2—C3	176.0 (6)	C23—N6—C22—C21	−141.4 (6)
N1—C2—C3—N2	−0.2 (7)	C20—C21—C22—N6	59.1 (7)
C1—N2—C3—C2	0.6 (7)	C30—N6—C23—C24	−75.2 (7)
C4—N2—C3—C2	−170.0 (6)	C22—N6—C23—C24	160.8 (5)
C1—N2—C4—C5	146.6 (7)	N6—C23—C24—C25	−26.9 (9)
C3—N2—C4—C5	−43.7 (9)	N6—C23—C24—C29	159.3 (6)
N2—C4—C5—C6	−174.3 (7)	C29—C24—C25—C26	0.9 (11)
C14—N3—C6—C5	70.0 (10)	C23—C24—C25—C26	−173.0 (7)
C7—N3—C6—C5	−166.3 (8)	C24—C25—C26—C27	0.7 (11)
C4—C5—C6—N3	55.0 (11)	C25—C26—C27—C28	−2.0 (11)
C14—N3—C7—C8	−67.6 (10)	C26—C27—C28—C29	1.9 (12)
C6—N3—C7—C8	166.7 (8)	C27—C28—C29—C24	−0.4 (12)
N3—C7—C8—C9	−48.5 (13)	C25—C24—C29—C28	−1.0 (11)
N3—C7—C8—C13	132.8 (9)	C23—C24—C29—C28	173.0 (7)
C13—C8—C9—C10	0.6 (13)	C23—N6—C30—C31	172.1 (5)
C7—C8—C9—C10	−178.2 (9)	C22—N6—C30—C31	−65.1 (7)
C8—C9—C10—C11	−0.6 (14)	N6—C30—C31—C32	−57.7 (7)
C9—C10—C11—C12	0.6 (14)	C1—N1—C32—C31	−145.3 (6)
C10—C11—C12—C13	−0.5 (14)	C2—N1—C32—C31	38.9 (8)
C11—C12—C13—C8	0.5 (13)	C30—C31—C32—N1	167.4 (5)
C9—C8—C13—C12	−0.5 (13)	C40—C33—C34—C35	4.7 (11)
C7—C8—C13—C12	178.2 (9)	Ir1—C33—C34—C35	−100.4 (7)
C7—N3—C14—C15	146.2 (7)	C40—C33—C34—Ir1	105.1 (6)
C6—N3—C14—C15	−91.0 (9)	C33—C34—C35—C36	42.5 (10)
N3—C14—C15—C16	−62.6 (11)	Ir1—C34—C35—C36	−37.3 (8)
C17—N4—C16—C15	−106.6 (8)	C34—C35—C36—C37	35.7 (10)
C18—N4—C16—C15	70.4 (9)	C35—C36—C37—C38	−97.1 (8)
C14—C15—C16—N4	178.8 (7)	C35—C36—C37—Ir1	−16.3 (8)
C18—N4—C17—N5	0.4 (7)	C36—C37—C38—C39	4.2 (10)
C16—N4—C17—N5	177.8 (6)	Ir1—C37—C38—C39	−101.5 (6)
C18—N4—C17—Ir1	172.4 (4)	C36—C37—C38—Ir1	105.7 (6)
C16—N4—C17—Ir1	−10.1 (9)	C37—C38—C39—C40	47.0 (9)
C19—N5—C17—N4	−0.2 (7)	Ir1—C38—C39—C40	−33.5 (7)
C20—N5—C17—N4	−177.8 (5)	C38—C39—C40—C33	28.7 (9)
C19—N5—C17—Ir1	−172.1 (4)	C34—C33—C40—C39	−91.4 (8)
C20—N5—C17—Ir1	10.2 (9)	Ir1—C33—C40—C39	−9.4 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br1^i	0.95	2.81	3.753 (6)	173
C18—H18···Br1^ii	0.95	2.90	3.764 (6)	152
C20—H20B···Br1^iii	0.99	2.91	3.711 (6)	138
C22—H22B···Br1^iii	0.99	3.08	3.872 (7)	137
C31—H31B···Br1^i	0.99	3.03	3.955 (6)	155

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

\ [µ-5,20-dibenzyl-1,5,9,16,20,24-hexaazapentacyclo[22.6.1.1^9,16.0^10,15.\ 0^{25,30]dotriaconta-10(15),11,13,25(30),26,28-hexaene-31,32-diylidene]\ bis{bromido[(1,2,5,6-η)-cycloocta-1,5-diene]iridium(I)} (2b)}

Crystal data

[Ir2Br2(C8H12)2(C40H46N6)]	Dx = 1.752 Mg m^−3
Mr = 1371.40	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9077 reflections
a = 12.6186 (5) Å	θ = 2.3–28.8°
b = 27.2390 (11) Å	µ = 6.70 mm^−1
c = 30.2461 (11) Å	T = 100 K
V = 10396.1 (7) Å^3	Block, yellow
Z = 8	0.31 × 0.19 × 0.08 mm
F(000) = 5376

Data collection

Bruker Photon II cpad diffractometer	8220 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.051
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 26.7°, θmin = 2.2°
Tmin = 0.414, Tmax = 0.746	h = −15→15
58196 measured reflections	k = −34→34
11002 independent reflections	l = −38→38

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.237	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.1P)^2 + 300.P] where P = (Fo^2 + 2Fc^2)/3
11002 reflections	(Δ/σ)max = 0.003
777 parameters	Δρmax = 1.68 e Å^−3
1671 restraints	Δρmin = −3.42 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ir1	0.08096 (5)	0.40237 (2)	0.68885 (2)	0.03899 (17)
Ir2	0.34273 (5)	0.14044 (2)	0.53830 (2)	0.04385 (19)
Br1	−0.01115 (15)	0.33038 (6)	0.65619 (6)	0.0582 (4)
Br2	0.21703 (17)	0.20247 (10)	0.56866 (6)	0.0831 (7)
N1	0.2870 (10)	0.3906 (4)	0.6396 (4)	0.039 (2)
N2	0.2930 (10)	0.3470 (4)	0.7000 (4)	0.038 (2)
N3	0.3539 (13)	0.2157 (7)	0.7203 (5)	0.071 (2)	0.746 (18)
N3'	0.352 (2)	0.2144 (16)	0.7202 (5)	0.071 (3)	0.254 (18)
N4	0.5252 (11)	0.1711 (4)	0.5977 (4)	0.041 (2)
N5	0.5174 (9)	0.2187 (4)	0.5406 (4)	0.0378 (17)
N6	0.3054 (11)	0.3676 (6)	0.5145 (4)	0.0402 (15)	0.681 (9)
N6'	0.299 (2)	0.3406 (11)	0.5253 (8)	0.0402 (16)	0.319 (9)
C1	0.2264 (11)	0.3768 (5)	0.6737 (4)	0.036 (2)
C2	0.3884 (12)	0.3707 (5)	0.6423 (4)	0.040 (3)
C3	0.4786 (14)	0.3759 (6)	0.6143 (6)	0.056 (4)
H3	0.477136	0.394516	0.587736	0.067*
C4	0.5686 (13)	0.3518 (6)	0.6290 (5)	0.049 (3)
H4	0.630815	0.354155	0.611446	0.059*
C5	0.5741 (13)	0.3245 (6)	0.6674 (5)	0.053 (3)
H5	0.638795	0.309192	0.675652	0.064*
C6	0.4839 (11)	0.3194 (5)	0.6945 (4)	0.039 (3)
H6	0.484655	0.300266	0.720739	0.046*
C7	0.3937 (12)	0.3440 (5)	0.6803 (5)	0.039 (3)
C8	0.2565 (13)	0.3196 (5)	0.7389 (5)	0.044 (3)
H8A	0.208210	0.340557	0.756452	0.053*
H8AB	0.318171	0.311261	0.757666	0.053*
C9	0.1985 (15)	0.2722 (6)	0.7259 (5)	0.054 (3)
H9A	0.177886	0.254492	0.753120	0.065*
H9AB	0.132679	0.281001	0.709913	0.065*
C10	0.2641 (16)	0.2377 (6)	0.6968 (5)	0.065 (4)
H10A	0.217655	0.211166	0.685543	0.077*
H10B	0.290984	0.256245	0.670942	0.077*
C11	0.4327 (18)	0.1955 (7)	0.6897 (5)	0.075 (5)
H11A	0.454379	0.222523	0.669827	0.090*
H11B	0.495740	0.186865	0.707623	0.090*
C12	0.410 (2)	0.1538 (7)	0.6622 (5)	0.080 (6)
H12A	0.348042	0.162293	0.643670	0.096*
H12B	0.388221	0.126535	0.681756	0.096*
C13	0.4948 (17)	0.1345 (5)	0.6319 (5)	0.058 (4)
H13A	0.558071	0.125656	0.649529	0.070*
H13B	0.468845	0.104297	0.617178	0.070*
C14	0.4669 (12)	0.1804 (5)	0.5609 (4)	0.038 (2)
C15	0.6125 (13)	0.2025 (5)	0.6007 (4)	0.041 (3)
C16	0.6958 (15)	0.2056 (6)	0.6307 (5)	0.054 (3)
H16	0.700134	0.184491	0.655557	0.065*
C17	0.7726 (15)	0.2413 (6)	0.6224 (5)	0.058 (4)
H17	0.830267	0.245099	0.642331	0.070*
C18	0.7656 (14)	0.2710 (6)	0.5859 (5)	0.053 (3)
H18	0.819566	0.294744	0.581200	0.063*
C19	0.6845 (11)	0.2679 (5)	0.5560 (5)	0.041 (3)
H19	0.682500	0.288561	0.530649	0.049*
C20	0.6060 (11)	0.2339 (5)	0.5638 (4)	0.040 (3)
C21	0.4695 (17)	0.2511 (6)	0.5066 (6)	0.0393 (17)	0.681 (9)
H21A	0.408801	0.234103	0.492648	0.047*	0.681 (9)
H21B	0.522586	0.257974	0.483251	0.047*	0.681 (9)
C22	0.4317 (15)	0.2995 (6)	0.5265 (6)	0.0399 (17)	0.681 (9)
H22A	0.392960	0.292875	0.554338	0.048*	0.681 (9)
H22B	0.493724	0.320324	0.533616	0.048*	0.681 (9)
C23	0.3594 (15)	0.3266 (7)	0.4944 (6)	0.0400 (15)	0.681 (9)
H23A	0.402087	0.338613	0.469140	0.048*	0.681 (9)
H23B	0.306081	0.303294	0.482622	0.048*	0.681 (9)
C24	0.2269 (17)	0.3514 (6)	0.5461 (6)	0.0406 (17)	0.681 (9)
H24A	0.261009	0.328651	0.567301	0.049*	0.681 (9)
H24B	0.171297	0.332786	0.530184	0.049*	0.681 (9)
C25	0.1747 (12)	0.3930 (5)	0.5718 (4)	0.0413 (18)	0.681 (9)
H25A	0.143925	0.416686	0.550567	0.050*	0.681 (9)
H25B	0.115911	0.379355	0.589651	0.050*	0.681 (9)
C21'	0.489 (4)	0.2353 (12)	0.4953 (7)	0.0388 (19)	0.319 (9)
H21C	0.433132	0.213912	0.482825	0.047*	0.319 (9)
H21D	0.551916	0.233669	0.475766	0.047*	0.319 (9)
C22'	0.449 (3)	0.2880 (12)	0.4988 (13)	0.0395 (17)	0.319 (9)
H22C	0.503869	0.308180	0.513761	0.047*	0.319 (9)
H22D	0.439339	0.301392	0.468637	0.047*	0.319 (9)
C23'	0.345 (3)	0.2920 (11)	0.5242 (13)	0.0399 (17)	0.319 (9)
H23C	0.293464	0.269287	0.510687	0.048*	0.319 (9)
H23D	0.357666	0.281038	0.554936	0.048*	0.319 (9)
C24'	0.211 (3)	0.3428 (7)	0.5555 (14)	0.0406 (17)	0.319 (9)
H24C	0.229450	0.322803	0.581808	0.049*	0.319 (9)
H24D	0.149864	0.326682	0.541084	0.049*	0.319 (9)
C25'	0.1747 (12)	0.3930 (5)	0.5718 (4)	0.0413 (18)	0.319 (9)
H25C	0.161092	0.413958	0.545677	0.050*	0.319 (9)
H25D	0.106475	0.388786	0.587498	0.050*	0.319 (9)
C26	0.2505 (14)	0.4201 (5)	0.6023 (5)	0.046 (3)
H26A	0.312779	0.430969	0.584926	0.056*
H26B	0.214700	0.449831	0.613766	0.056*
C27	0.3185 (16)	0.1754 (7)	0.7515 (4)	0.072 (2)	0.746 (18)
H27A	0.255662	0.187220	0.767951	0.087*	0.746 (18)
H27B	0.295770	0.146851	0.733574	0.087*	0.746 (18)
C28	0.3966 (13)	0.1588 (5)	0.7831 (4)	0.073 (2)	0.746 (18)
C29	0.4555 (15)	0.1920 (7)	0.8078 (5)	0.074 (2)	0.746 (18)
H29	0.444106	0.226226	0.803759	0.089*	0.746 (18)
C30	0.5300 (16)	0.1765 (7)	0.8380 (6)	0.075 (2)	0.746 (18)
H30	0.569256	0.200024	0.854511	0.090*	0.746 (18)
C31	0.5480 (18)	0.1271 (6)	0.8445 (6)	0.075 (3)	0.746 (18)
H31	0.599265	0.116330	0.865294	0.090*	0.746 (18)
C32	0.4903 (16)	0.0936 (7)	0.8202 (6)	0.075 (3)	0.746 (18)
H32	0.502068	0.059497	0.824296	0.090*	0.746 (18)
C33	0.4156 (15)	0.1092 (6)	0.7900 (6)	0.074 (2)	0.746 (18)
H33	0.376426	0.085619	0.773644	0.089*	0.746 (18)
C27'	0.304 (2)	0.1746 (16)	0.7488 (6)	0.072 (2)	0.254 (18)
H27C	0.232967	0.185105	0.758961	0.087*	0.254 (18)
H27D	0.295671	0.144229	0.731239	0.087*	0.254 (18)
C28'	0.371 (2)	0.1648 (11)	0.7868 (7)	0.074 (2)	0.254 (18)
C29'	0.444 (3)	0.1990 (12)	0.8017 (12)	0.074 (2)	0.254 (18)
H29'	0.450342	0.229539	0.786786	0.089*	0.254 (18)
C30'	0.507 (3)	0.1896 (15)	0.8379 (13)	0.075 (3)	0.254 (18)
H30'	0.556415	0.213688	0.847388	0.090*	0.254 (18)
C31'	0.500 (3)	0.1458 (15)	0.8606 (14)	0.075 (3)	0.254 (18)
H31'	0.543879	0.139315	0.885481	0.090*	0.254 (18)
C32'	0.428 (4)	0.1116 (15)	0.8459 (12)	0.075 (3)	0.254 (18)
H32'	0.421156	0.081179	0.860955	0.090*	0.254 (18)
C33'	0.364 (3)	0.1208 (12)	0.8097 (11)	0.074 (2)	0.254 (18)
H33'	0.314823	0.096533	0.800318	0.089*	0.254 (18)
C34	0.2517 (12)	0.3938 (6)	0.4765 (5)	0.0407 (16)	0.681 (9)
H34A	0.224693	0.368338	0.455959	0.049*	0.681 (9)
H34B	0.189161	0.411126	0.488580	0.049*	0.681 (9)
C35	0.3114 (10)	0.4288 (5)	0.4506 (4)	0.0405 (16)	0.681 (9)
C36	0.2719 (12)	0.4469 (5)	0.4110 (4)	0.0417 (17)	0.681 (9)
H36	0.204601	0.436080	0.400793	0.050*	0.681 (9)
C37	0.3284 (11)	0.4802 (5)	0.3861 (5)	0.0421 (18)	0.681 (9)
H37	0.299724	0.492020	0.359081	0.051*	0.681 (9)
C38	0.4262 (12)	0.4967 (6)	0.4000 (5)	0.0414 (18)	0.681 (9)
H38	0.465050	0.519778	0.382995	0.050*	0.681 (9)
C39	0.4664 (12)	0.4788 (5)	0.4393 (5)	0.0405 (18)	0.681 (9)
H39	0.533744	0.489738	0.449288	0.049*	0.681 (9)
C40	0.4101 (11)	0.4454 (5)	0.4642 (5)	0.0404 (17)	0.681 (9)
H40	0.439258	0.433626	0.491143	0.048*	0.681 (9)
C34'	0.271 (2)	0.3607 (10)	0.4802 (8)	0.0402 (16)	0.319 (9)
H34C	0.285128	0.333948	0.458797	0.048*	0.319 (9)
H34D	0.193036	0.365462	0.480358	0.048*	0.319 (9)
C35'	0.3155 (16)	0.4048 (9)	0.4610 (6)	0.0406 (15)	0.319 (9)
C36'	0.2624 (18)	0.4306 (9)	0.4283 (8)	0.0410 (17)	0.319 (9)
H36'	0.195531	0.419107	0.418149	0.049*	0.319 (9)
C37'	0.305 (2)	0.4726 (9)	0.4101 (10)	0.0414 (17)	0.319 (9)
H37'	0.267343	0.489723	0.387706	0.050*	0.319 (9)
C38'	0.402 (2)	0.4900 (12)	0.4242 (9)	0.0412 (18)	0.319 (9)
H38'	0.431265	0.518988	0.411658	0.049*	0.319 (9)
C39'	0.456 (2)	0.4648 (9)	0.4567 (10)	0.0407 (19)	0.319 (9)
H39'	0.522409	0.476368	0.466702	0.049*	0.319 (9)
C40'	0.4129 (19)	0.4228 (9)	0.4749 (8)	0.0405 (18)	0.319 (9)
H40'	0.450801	0.405838	0.497350	0.049*	0.319 (9)
C41	−0.0597 (7)	0.4454 (4)	0.6791 (5)	0.047 (3)
H41	−0.111630	0.429540	0.658640	0.057*
C42	−0.0621 (7)	0.4261 (6)	0.7208 (4)	0.050 (3)
H42	−0.115705	0.399337	0.724595	0.059*
C43	−0.0456 (11)	0.4566 (5)	0.7617 (4)	0.049 (3)
H43A	−0.093825	0.445097	0.785389	0.059*
H43B	−0.062843	0.491318	0.755241	0.059*
C44	0.0693 (10)	0.4528 (6)	0.7775 (4)	0.049 (3)
H44A	0.087573	0.482858	0.794193	0.059*
H44B	0.075453	0.424596	0.798051	0.059*
C45	0.1481 (9)	0.4462 (5)	0.7406 (3)	0.042 (3)
H45	0.220184	0.435587	0.750433	0.050*
C46	0.1467 (10)	0.4741 (3)	0.6989 (5)	0.048 (3)
H46	0.218207	0.478730	0.685320	0.057*
C47	0.0697 (12)	0.5148 (5)	0.6888 (6)	0.060 (4)
H47A	0.105141	0.539337	0.669719	0.073*
H47B	0.049889	0.531315	0.716753	0.073*
C48	−0.0312 (13)	0.4969 (5)	0.6657 (5)	0.059 (4)
H48A	−0.090487	0.519199	0.673155	0.070*
H48B	−0.020579	0.498070	0.633287	0.070*
C49	0.4436 (8)	0.0777 (3)	0.5302 (5)	0.038 (3)
H49	0.512373	0.079872	0.546541	0.046*
C50	0.4406 (9)	0.1056 (5)	0.4895 (4)	0.048 (3)
H50	0.507576	0.123669	0.482628	0.058*
C51	0.3770 (15)	0.0910 (7)	0.4495 (5)	0.078 (5)
H51A	0.409413	0.061347	0.436355	0.094*
H51B	0.381509	0.117676	0.427379	0.094*
C52	0.2599 (16)	0.0804 (9)	0.4589 (7)	0.106 (7)
H52A	0.216987	0.091432	0.433332	0.127*
H52B	0.249949	0.044536	0.462079	0.127*
C53	0.2208 (11)	0.1056 (7)	0.5000 (6)	0.082 (5)
H53	0.157658	0.127036	0.494820	0.099*
C54	0.2226 (9)	0.0848 (4)	0.5412 (9)	0.081 (5)
H54	0.160358	0.093184	0.560253	0.098*
C55	0.2737 (12)	0.0362 (6)	0.5517 (9)	0.092 (8)
H55A	0.229352	0.009868	0.538839	0.110*
H55B	0.273375	0.031851	0.584148	0.110*
C56	0.3874 (10)	0.0293 (4)	0.5352 (5)	0.048 (3)
H56A	0.426816	0.008413	0.556319	0.057*
H56B	0.386192	0.012233	0.506270	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0414 (3)	0.0313 (3)	0.0443 (3)	−0.0005 (2)	0.0011 (2)	−0.0007 (2)
Ir2	0.0368 (3)	0.0475 (3)	0.0472 (3)	0.0020 (2)	0.0050 (2)	0.0225 (3)
Br1	0.0612 (10)	0.0452 (8)	0.0683 (10)	−0.0091 (7)	−0.0093 (9)	0.0005 (7)
Br2	0.0720 (13)	0.1227 (19)	0.0546 (10)	0.0440 (13)	0.0193 (9)	0.0360 (11)
N1	0.046 (5)	0.031 (5)	0.038 (5)	0.002 (4)	−0.003 (4)	−0.004 (4)
N2	0.039 (5)	0.041 (6)	0.034 (5)	0.001 (4)	−0.002 (4)	−0.006 (4)
N3	0.103 (6)	0.060 (5)	0.051 (4)	0.007 (4)	0.013 (4)	0.001 (4)
N3'	0.103 (6)	0.060 (5)	0.051 (5)	0.006 (5)	0.013 (4)	0.001 (4)
N4	0.068 (7)	0.027 (5)	0.030 (5)	0.009 (4)	0.005 (4)	0.003 (4)
N5	0.042 (4)	0.038 (4)	0.034 (3)	0.001 (3)	0.005 (3)	0.011 (3)
N6	0.043 (3)	0.041 (3)	0.036 (3)	−0.003 (3)	0.000 (3)	0.009 (3)
N6'	0.044 (3)	0.041 (3)	0.036 (3)	−0.002 (3)	0.001 (3)	0.009 (3)
C1	0.042 (6)	0.043 (6)	0.023 (5)	−0.004 (5)	−0.013 (4)	−0.015 (4)
C2	0.044 (5)	0.041 (7)	0.034 (6)	−0.002 (5)	−0.005 (4)	−0.006 (5)
C3	0.058 (7)	0.048 (9)	0.063 (9)	−0.002 (6)	0.016 (6)	−0.005 (7)
C4	0.048 (7)	0.058 (9)	0.042 (6)	−0.002 (6)	0.019 (6)	−0.017 (5)
C5	0.048 (7)	0.065 (10)	0.046 (7)	−0.001 (7)	0.007 (6)	−0.014 (6)
C6	0.040 (6)	0.043 (7)	0.033 (6)	0.003 (5)	−0.004 (5)	−0.009 (5)
C7	0.041 (5)	0.040 (7)	0.037 (6)	0.005 (5)	0.002 (4)	−0.003 (5)
C8	0.059 (9)	0.034 (6)	0.040 (6)	0.001 (6)	0.005 (6)	−0.004 (5)
C9	0.070 (9)	0.043 (7)	0.049 (8)	−0.007 (5)	−0.010 (7)	−0.001 (6)
C10	0.114 (10)	0.036 (7)	0.044 (7)	−0.004 (7)	−0.002 (7)	−0.010 (5)
C11	0.130 (14)	0.053 (9)	0.041 (8)	0.019 (8)	0.021 (8)	0.007 (6)
C12	0.147 (18)	0.051 (9)	0.044 (8)	0.011 (10)	0.035 (10)	0.010 (6)
C13	0.119 (14)	0.028 (6)	0.029 (6)	0.000 (7)	0.017 (7)	0.005 (5)
C14	0.052 (7)	0.029 (5)	0.033 (5)	0.007 (5)	0.013 (4)	0.006 (4)
C15	0.062 (7)	0.038 (6)	0.023 (5)	0.010 (5)	0.007 (4)	−0.007 (4)
C16	0.075 (9)	0.054 (8)	0.034 (6)	0.013 (6)	−0.003 (6)	−0.012 (6)
C17	0.069 (9)	0.061 (9)	0.044 (7)	0.008 (6)	−0.012 (7)	−0.012 (6)
C18	0.053 (8)	0.058 (9)	0.047 (7)	0.002 (6)	−0.002 (6)	−0.010 (6)
C19	0.041 (6)	0.046 (7)	0.036 (6)	−0.001 (5)	0.009 (5)	−0.006 (5)
C20	0.042 (6)	0.041 (6)	0.037 (6)	0.006 (4)	0.008 (4)	0.002 (5)
C21	0.043 (4)	0.040 (3)	0.035 (3)	0.000 (3)	0.002 (3)	0.010 (3)
C22	0.043 (4)	0.041 (4)	0.036 (3)	0.000 (3)	0.001 (3)	0.008 (3)
C23	0.043 (3)	0.041 (3)	0.036 (3)	−0.002 (3)	0.001 (3)	0.009 (3)
C24	0.044 (4)	0.042 (3)	0.036 (3)	−0.003 (3)	0.001 (3)	0.009 (3)
C25	0.045 (4)	0.042 (4)	0.037 (4)	−0.001 (3)	0.002 (3)	0.008 (3)
C21'	0.043 (4)	0.039 (4)	0.034 (4)	0.000 (3)	0.003 (3)	0.010 (3)
C22'	0.043 (4)	0.040 (3)	0.035 (3)	−0.001 (3)	0.002 (3)	0.009 (3)
C23'	0.043 (3)	0.041 (3)	0.036 (3)	−0.001 (3)	0.002 (3)	0.009 (3)
C24'	0.044 (4)	0.042 (4)	0.036 (3)	−0.003 (3)	0.001 (3)	0.008 (3)
C25'	0.045 (4)	0.042 (4)	0.037 (4)	−0.001 (3)	0.002 (3)	0.008 (3)
C26	0.060 (8)	0.035 (6)	0.044 (6)	0.001 (5)	−0.003 (5)	0.006 (4)
C27	0.103 (6)	0.061 (5)	0.052 (4)	0.005 (4)	0.012 (4)	0.001 (4)
C28	0.104 (6)	0.062 (5)	0.053 (4)	0.003 (4)	0.011 (4)	0.002 (3)
C29	0.105 (6)	0.063 (5)	0.055 (4)	0.002 (4)	0.011 (4)	0.002 (4)
C30	0.105 (6)	0.064 (5)	0.056 (4)	0.001 (5)	0.010 (4)	0.002 (4)
C31	0.105 (6)	0.064 (5)	0.056 (4)	0.002 (5)	0.009 (4)	0.002 (4)
C32	0.106 (6)	0.064 (5)	0.056 (4)	0.002 (5)	0.009 (4)	0.002 (4)
C33	0.105 (6)	0.063 (5)	0.055 (4)	0.002 (4)	0.009 (4)	0.002 (4)
C27'	0.104 (6)	0.061 (5)	0.052 (4)	0.005 (4)	0.012 (4)	0.001 (4)
C28'	0.104 (6)	0.062 (5)	0.054 (4)	0.003 (4)	0.011 (4)	0.002 (4)
C29'	0.105 (6)	0.063 (5)	0.055 (4)	0.002 (4)	0.011 (4)	0.002 (4)
C30'	0.105 (6)	0.063 (5)	0.055 (4)	0.002 (5)	0.010 (4)	0.002 (4)
C31'	0.105 (6)	0.064 (5)	0.056 (4)	0.002 (5)	0.009 (4)	0.002 (4)
C32'	0.105 (6)	0.063 (5)	0.056 (4)	0.002 (5)	0.009 (4)	0.002 (4)
C33'	0.105 (6)	0.063 (5)	0.055 (4)	0.002 (5)	0.010 (4)	0.002 (4)
C34	0.043 (3)	0.043 (3)	0.036 (3)	−0.004 (3)	−0.001 (3)	0.009 (3)
C35	0.042 (3)	0.043 (3)	0.036 (3)	−0.004 (3)	0.000 (3)	0.010 (3)
C36	0.043 (4)	0.045 (4)	0.037 (3)	−0.005 (3)	0.000 (3)	0.010 (3)
C37	0.043 (4)	0.046 (4)	0.037 (4)	−0.005 (3)	0.000 (3)	0.010 (3)
C38	0.043 (4)	0.045 (4)	0.037 (4)	−0.005 (3)	0.001 (3)	0.009 (3)
C39	0.041 (4)	0.044 (4)	0.036 (4)	−0.004 (3)	0.000 (3)	0.009 (3)
C40	0.041 (3)	0.043 (4)	0.037 (3)	−0.004 (3)	0.000 (3)	0.009 (3)
C34'	0.043 (3)	0.042 (3)	0.036 (3)	−0.003 (3)	0.000 (3)	0.009 (3)
C35'	0.043 (3)	0.043 (3)	0.036 (3)	−0.004 (3)	0.000 (3)	0.009 (3)
C36'	0.043 (4)	0.043 (4)	0.037 (3)	−0.005 (3)	0.000 (3)	0.010 (3)
C37'	0.043 (4)	0.044 (4)	0.037 (3)	−0.005 (3)	0.000 (3)	0.010 (3)
C38'	0.042 (4)	0.044 (4)	0.037 (4)	−0.005 (3)	0.000 (3)	0.010 (3)
C39'	0.042 (4)	0.044 (4)	0.037 (4)	−0.004 (3)	0.000 (3)	0.009 (3)
C40'	0.042 (4)	0.043 (4)	0.036 (4)	−0.004 (3)	0.000 (3)	0.009 (3)
C41	0.034 (7)	0.055 (7)	0.053 (6)	0.014 (5)	0.003 (6)	0.009 (6)
C42	0.044 (7)	0.056 (8)	0.049 (6)	0.003 (6)	0.007 (5)	0.006 (5)
C43	0.050 (7)	0.041 (7)	0.055 (7)	0.006 (6)	0.006 (6)	0.004 (6)
C44	0.050 (7)	0.052 (9)	0.045 (7)	0.004 (6)	0.005 (5)	−0.004 (6)
C45	0.043 (6)	0.041 (7)	0.042 (6)	−0.003 (6)	0.000 (5)	−0.011 (5)
C46	0.054 (7)	0.039 (7)	0.051 (7)	−0.009 (5)	0.003 (6)	−0.005 (5)
C47	0.078 (10)	0.045 (8)	0.058 (9)	0.005 (6)	0.012 (7)	0.006 (7)
C48	0.068 (9)	0.058 (8)	0.051 (9)	0.012 (7)	0.011 (7)	0.017 (7)
C49	0.023 (5)	0.041 (6)	0.050 (7)	−0.004 (5)	0.000 (5)	0.005 (5)
C50	0.059 (8)	0.038 (7)	0.047 (7)	−0.003 (6)	0.005 (6)	0.003 (5)
C51	0.120 (13)	0.063 (11)	0.051 (8)	−0.019 (10)	−0.018 (8)	0.008 (8)
C52	0.108 (13)	0.081 (15)	0.128 (14)	−0.022 (12)	−0.052 (11)	0.011 (12)
C53	0.036 (7)	0.079 (12)	0.132 (12)	−0.008 (8)	−0.035 (8)	0.033 (9)
C54	0.032 (7)	0.066 (10)	0.147 (14)	−0.001 (6)	−0.005 (9)	0.045 (11)
C55	0.048 (9)	0.061 (11)	0.16 (2)	−0.003 (7)	0.015 (11)	0.047 (12)
C56	0.037 (7)	0.042 (7)	0.064 (9)	−0.008 (5)	−0.013 (6)	0.008 (6)

Geometric parameters (Å, º)

Ir1—C1	2.017 (14)	C25'—H25D	0.9900
Ir1—C45	2.144 (6)	C26—H26A	0.9900
Ir1—C46	2.144 (6)	C26—H26B	0.9900
Ir1—C41	2.147 (6)	C27—C28	1.446 (18)
Ir1—C42	2.147 (6)	C27—H27A	0.9900
Ir1—Br1	2.4843 (17)	C27—H27B	0.9900
Ir2—C14	2.027 (15)	C28—C33	1.388 (12)
Ir2—C50	2.144 (6)	C28—C29	1.388 (12)
Ir2—C49	2.145 (6)	C29—C30	1.378 (9)
Ir2—C54	2.146 (6)	C29—H29	0.9500
Ir2—C53	2.147 (6)	C30—C31	1.379 (9)
Ir2—Br2	2.493 (2)	C30—H30	0.9500
N1—C1	1.338 (18)	C31—C32	1.379 (9)
N1—C2	1.391 (18)	C31—H31	0.9500
N1—C26	1.461 (17)	C32—C33	1.379 (9)
N2—C7	1.406 (19)	C32—H32	0.9500
N2—C1	1.413 (17)	C33—H33	0.9500
N2—C8	1.467 (18)	C27'—C28'	1.446 (18)
N3—C10	1.465 (15)	C27'—H27C	0.9900
N3—C11	1.466 (15)	C27'—H27D	0.9900
N3—C27	1.516 (15)	C28'—C33'	1.388 (12)
N3'—C10	1.465 (16)	C28'—C29'	1.388 (12)
N3'—C11	1.465 (16)	C29'—C30'	1.379 (9)
N3'—C27'	1.515 (15)	C29'—H29'	0.9500
N4—C14	1.356 (18)	C30'—C31'	1.379 (9)
N4—C15	1.40 (2)	C30'—H30'	0.9500
N4—C13	1.488 (17)	C31'—C32'	1.379 (9)
N5—C14	1.369 (17)	C31'—H31'	0.9500
N5—C20	1.383 (19)	C32'—C33'	1.379 (9)
N5—C21	1.486 (18)	C32'—H32'	0.9500
N5—C21'	1.486 (18)	C33'—H33'	0.9500
N6—C23	1.443 (16)	C34—C35	1.447 (18)
N6—C24	1.444 (16)	C34—H34A	0.9900
N6—C34	1.515 (15)	C34—H34B	0.9900
N6'—C24'	1.444 (16)	C35—C40	1.388 (12)
N6'—C23'	1.444 (16)	C35—C36	1.388 (12)
N6'—C34'	1.515 (15)	C36—C37	1.378 (9)
C2—C7	1.36 (2)	C36—H36	0.9500
C2—C3	1.43 (2)	C37—C38	1.378 (9)
C3—C4	1.39 (2)	C37—H37	0.9500
C3—H3	0.9500	C38—C39	1.379 (9)
C4—C5	1.38 (2)	C38—H38	0.9500
C4—H4	0.9500	C39—C40	1.379 (9)
C5—C6	1.41 (2)	C39—H39	0.9500
C5—H5	0.9500	C40—H40	0.9500
C6—C7	1.39 (2)	C34'—C35'	1.45 (2)
C6—H6	0.9500	C34'—H34C	0.9900
C8—C9	1.53 (2)	C34'—H34D	0.9900
C8—H8A	0.9900	C35'—C40'	1.388 (12)
C8—H8AB	0.9900	C35'—C36'	1.388 (12)
C9—C10	1.53 (2)	C36'—C37'	1.379 (9)
C9—H9A	0.9900	C36'—H36'	0.9500
C9—H9AB	0.9900	C37'—C38'	1.379 (9)
C10—H10A	0.9900	C37'—H37'	0.9500
C10—H10B	0.9900	C38'—C39'	1.379 (9)
C11—C12	1.44 (3)	C38'—H38'	0.9500
C11—H11A	0.9900	C39'—C40'	1.379 (9)
C11—H11B	0.9900	C39'—H39'	0.9500
C12—C13	1.50 (2)	C40'—H40'	0.9500
C12—H12A	0.9900	C41—C42	1.37 (2)
C12—H12B	0.9900	C41—C48	1.505 (8)
C13—H13A	0.9900	C41—H41	1.0000
C13—H13B	0.9900	C42—C43	1.506 (8)
C15—C16	1.39 (2)	C42—H42	1.0000
C15—C20	1.406 (19)	C43—C44	1.531 (13)
C16—C17	1.39 (3)	C43—H43A	0.9900
C16—H16	0.9500	C43—H43B	0.9900
C17—C18	1.37 (2)	C44—C45	1.505 (8)
C17—H17	0.9500	C44—H44A	0.9900
C18—C19	1.37 (2)	C44—H44B	0.9900
C18—H18	0.9500	C45—C46	1.473 (19)
C19—C20	1.38 (2)	C45—H45	1.0000
C19—H19	0.9500	C46—C47	1.505 (8)
C21—C22	1.525 (13)	C46—H46	1.0000
C21—H21A	0.9900	C47—C48	1.531 (13)
C21—H21B	0.9900	C47—H47A	0.9900
C22—C23	1.524 (13)	C47—H47B	0.9900
C22—H22A	0.9900	C48—H48A	0.9900
C22—H22B	0.9900	C48—H48B	0.9900
C23—H23A	0.9900	C49—C50	1.448 (19)
C23—H23B	0.9900	C49—C56	1.505 (8)
C24—C25	1.525 (13)	C49—H49	1.0000
C24—H24A	0.9900	C50—C51	1.505 (8)
C24—H24B	0.9900	C50—H50	1.0000
C25—C26	1.52 (2)	C51—C52	1.531 (13)
C25—H25A	0.9900	C51—H51A	0.9900
C25—H25B	0.9900	C51—H51B	0.9900
C21'—C22'	1.525 (13)	C52—C53	1.505 (8)
C21'—H21C	0.9900	C52—H52A	0.9900
C21'—H21D	0.9900	C52—H52B	0.9900
C22'—C23'	1.525 (13)	C53—C54	1.37 (3)
C22'—H22C	0.9900	C53—H53	1.0000
C22'—H22D	0.9900	C54—C55	1.505 (8)
C23'—H23C	0.9900	C54—H54	1.0000
C23'—H23D	0.9900	C55—C56	1.531 (13)
C24'—C25'	1.524 (13)	C55—H55A	0.9900
C24'—H24C	0.9900	C55—H55B	0.9900
C24'—H24D	0.9900	C56—H56A	0.9900
C25'—C26	1.52 (2)	C56—H56B	0.9900
C25'—H25C	0.9900
C1—Ir1—C45	89.9 (5)	N1—C26—H26A	108.9
C1—Ir1—C46	89.7 (5)	C25—C26—H26A	108.9
C45—Ir1—C46	40.2 (5)	N1—C26—H26B	108.9
C1—Ir1—C41	155.5 (5)	C25—C26—H26B	108.9
C45—Ir1—C41	97.0 (6)	H26A—C26—H26B	107.7
C46—Ir1—C41	80.9 (5)	C28—C27—N3	115.9 (11)
C1—Ir1—C42	166.4 (5)	C28—C27—H27A	108.3
C45—Ir1—C42	80.6 (5)	N3—C27—H27A	108.3
C46—Ir1—C42	89.3 (6)	C28—C27—H27B	108.3
C41—Ir1—C42	37.1 (5)	N3—C27—H27B	108.3
C1—Ir1—Br1	93.6 (3)	H27A—C27—H27B	107.4
C45—Ir1—Br1	156.2 (4)	C33—C28—C29	117.5 (18)
C46—Ir1—Br1	163.0 (4)	C33—C28—C27	121.4 (10)
C41—Ir1—Br1	89.4 (4)	C29—C28—C27	121.1 (10)
C42—Ir1—Br1	91.3 (4)	C30—C29—C28	121.5 (15)
C14—Ir2—C50	91.4 (5)	C30—C29—H29	119.3
C14—Ir2—C49	90.4 (5)	C28—C29—H29	119.3
C50—Ir2—C49	39.4 (5)	C29—C30—C31	120.3 (18)
C14—Ir2—C54	155.7 (7)	C29—C30—H30	119.8
C50—Ir2—C54	97.0 (8)	C31—C30—H30	119.8
C49—Ir2—C54	82.0 (5)	C30—C31—C32	119 (2)
C14—Ir2—C53	166.8 (7)	C30—C31—H31	120.5
C50—Ir2—C53	81.2 (7)	C32—C31—H31	120.5
C49—Ir2—C53	90.7 (6)	C31—C32—C33	120.6 (18)
C54—Ir2—C53	37.2 (8)	C31—C32—H32	119.7
C14—Ir2—Br2	90.2 (4)	C33—C32—H32	119.7
C50—Ir2—Br2	156.8 (4)	C32—C33—C28	121.1 (15)
C49—Ir2—Br2	163.7 (4)	C32—C33—H33	119.4
C54—Ir2—Br2	90.8 (5)	C28—C33—H33	119.4
C53—Ir2—Br2	92.4 (5)	C28'—C27'—N3'	110.6 (16)
C1—N1—C2	111.8 (12)	C28'—C27'—H27C	109.5
C1—N1—C26	124.7 (12)	N3'—C27'—H27C	109.5
C2—N1—C26	123.4 (12)	C28'—C27'—H27D	109.5
C7—N2—C1	109.4 (11)	N3'—C27'—H27D	109.5
C7—N2—C8	126.4 (12)	H27C—C27'—H27D	108.1
C1—N2—C8	123.9 (12)	C33'—C28'—C29'	117.2 (19)
C10—N3—C11	111.9 (14)	C33'—C28'—C27'	121.4 (10)
C10—N3—C27	111.7 (15)	C29'—C28'—C27'	121.4 (10)
C11—N3—C27	108.6 (13)	C30'—C29'—C28'	121.3 (16)
C10—N3'—C11	111.9 (14)	C30'—C29'—H29'	119.4
C10—N3'—C27'	106 (2)	C28'—C29'—H29'	119.4
C11—N3'—C27'	113 (2)	C29'—C30'—C31'	121 (3)
C14—N4—C15	111.5 (11)	C29'—C30'—H30'	119.3
C14—N4—C13	123.7 (14)	C31'—C30'—H30'	119.3
C15—N4—C13	124.7 (13)	C30'—C31'—C32'	118 (3)
C14—N5—C20	112.1 (11)	C30'—C31'—H31'	121.2
C14—N5—C21	125.1 (14)	C32'—C31'—H31'	121.2
C20—N5—C21	120.2 (13)	C31'—C32'—C33'	121 (3)
C14—N5—C21'	122 (2)	C31'—C32'—H32'	119.3
C20—N5—C21'	125 (2)	C33'—C32'—H32'	119.3
C23—N6—C24	111.5 (15)	C32'—C33'—C28'	121.2 (16)
C23—N6—C34	104.8 (12)	C32'—C33'—H33'	119.4
C24—N6—C34	109.8 (14)	C28'—C33'—H33'	119.4
C24'—N6'—C23'	111 (2)	C35—C34—N6	119.3 (10)
C24'—N6'—C34'	112 (3)	C35—C34—H34A	107.5
C23'—N6'—C34'	114 (3)	N6—C34—H34A	107.5
N1—C1—N2	104.8 (12)	C35—C34—H34B	107.5
N1—C1—Ir1	126.8 (10)	N6—C34—H34B	107.5
N2—C1—Ir1	127.7 (10)	H34A—C34—H34B	107.0
C7—C2—N1	107.6 (13)	C40—C35—C36	117.6 (16)
C7—C2—C3	121.0 (15)	C40—C35—C34	121.5 (9)
N1—C2—C3	131.3 (14)	C36—C35—C34	121.0 (8)
C4—C3—C2	114.6 (15)	C37—C36—C35	121.3 (13)
C4—C3—H3	122.7	C37—C36—H36	119.4
C2—C3—H3	122.7	C35—C36—H36	119.4
C5—C4—C3	124.5 (15)	C36—C37—C38	120.7 (14)
C5—C4—H4	117.8	C36—C37—H37	119.7
C3—C4—H4	117.8	C38—C37—H37	119.7
C4—C5—C6	120.1 (16)	C37—C38—C39	118.5 (17)
C4—C5—H5	120.0	C37—C38—H38	120.7
C6—C5—H5	120.0	C39—C38—H38	120.7
C7—C6—C5	115.8 (14)	C38—C39—C40	120.9 (14)
C7—C6—H6	122.1	C38—C39—H39	119.5
C5—C6—H6	122.1	C40—C39—H39	119.5
C2—C7—C6	124.0 (14)	C39—C40—C35	121.0 (13)
C2—C7—N2	106.4 (12)	C39—C40—H40	119.5
C6—C7—N2	129.7 (13)	C35—C40—H40	119.5
N2—C8—C9	111.9 (12)	C35'—C34'—N6'	124.5 (18)
N2—C8—H8A	109.2	C35'—C34'—H34C	106.2
C9—C8—H8A	109.2	N6'—C34'—H34C	106.2
N2—C8—H8AB	109.2	C35'—C34'—H34D	106.2
C9—C8—H8AB	109.2	N6'—C34'—H34D	106.2
H8A—C8—H8AB	107.9	H34C—C34'—H34D	106.4
C10—C9—C8	114.0 (15)	C40'—C35'—C36'	117.7 (19)
C10—C9—H9A	108.8	C40'—C35'—C34'	121.1 (10)
C8—C9—H9A	108.8	C36'—C35'—C34'	121.2 (10)
C10—C9—H9AB	108.8	C37'—C36'—C35'	121.0 (13)
C8—C9—H9AB	108.8	C37'—C36'—H36'	119.5
H9A—C9—H9AB	107.7	C35'—C36'—H36'	119.5
N3—C10—C9	112.9 (14)	C38'—C37'—C36'	121 (2)
N3'—C10—C9	113.4 (15)	C38'—C37'—H37'	119.7
N3—C10—H10A	109.0	C36'—C37'—H37'	119.7
C9—C10—H10A	109.0	C39'—C38'—C37'	119 (3)
N3—C10—H10B	109.0	C39'—C38'—H38'	120.5
C9—C10—H10B	109.0	C37'—C38'—H38'	120.5
H10A—C10—H10B	107.8	C40'—C39'—C38'	120 (2)
C12—C11—N3'	120 (3)	C40'—C39'—H39'	119.8
C12—C11—N3	122 (2)	C38'—C39'—H39'	119.8
C12—C11—H11A	106.9	C39'—C40'—C35'	121.2 (13)
N3—C11—H11A	106.9	C39'—C40'—H40'	119.4
C12—C11—H11B	106.9	C35'—C40'—H40'	119.4
N3—C11—H11B	106.9	C42—C41—C48	127.9 (15)
H11A—C11—H11B	106.7	C42—C41—Ir1	71.5 (3)
C11—C12—C13	119 (2)	C48—C41—Ir1	110.4 (9)
C11—C12—H12A	107.5	C42—C41—H41	113.0
C13—C12—H12A	107.5	C48—C41—H41	113.0
C11—C12—H12B	107.5	Ir1—C41—H41	113.0
C13—C12—H12B	107.5	C41—C42—C43	122.9 (14)
H12A—C12—H12B	107.0	C41—C42—Ir1	71.4 (3)
N4—C13—C12	111.8 (13)	C43—C42—Ir1	114.8 (8)
N4—C13—H13A	109.3	C41—C42—H42	113.7
C12—C13—H13A	109.3	C43—C42—H42	113.7
N4—C13—H13B	109.3	Ir1—C42—H42	113.7
C12—C13—H13B	109.3	C42—C43—C44	110.5 (11)
H13A—C13—H13B	107.9	C42—C43—H43A	109.6
N4—C14—N5	104.9 (13)	C44—C43—H43A	109.6
N4—C14—Ir2	126.6 (10)	C42—C43—H43B	109.6
N5—C14—Ir2	128.2 (10)	C44—C43—H43B	109.6
C16—C15—N4	132.5 (14)	H43A—C43—H43B	108.1
C16—C15—C20	121.6 (15)	C45—C44—C43	113.7 (11)
N4—C15—C20	106.0 (12)	C45—C44—H44A	108.8
C15—C16—C17	116.8 (15)	C43—C44—H44A	108.8
C15—C16—H16	121.6	C45—C44—H44B	108.8
C17—C16—H16	121.6	C43—C44—H44B	108.8
C18—C17—C16	120.6 (16)	H44A—C44—H44B	107.7
C18—C17—H17	119.7	C46—C45—C44	124.5 (13)
C16—C17—H17	119.7	C46—C45—Ir1	69.9 (3)
C19—C18—C17	123.0 (17)	C44—C45—Ir1	110.3 (8)
C19—C18—H18	118.5	C46—C45—H45	114.5
C17—C18—H18	118.5	C44—C45—H45	114.5
C18—C19—C20	117.6 (15)	Ir1—C45—H45	114.5
C18—C19—H19	121.2	C45—C46—C47	124.2 (13)
C20—C19—H19	121.2	C45—C46—Ir1	69.9 (3)
C19—C20—N5	134.0 (13)	C47—C46—Ir1	113.1 (9)
C19—C20—C15	120.2 (14)	C45—C46—H46	114.0
N5—C20—C15	105.5 (12)	C47—C46—H46	114.0
N5—C21—C22	111.5 (14)	Ir1—C46—H46	114.0
N5—C21—H21A	109.3	C46—C47—C48	113.2 (12)
C22—C21—H21A	109.3	C46—C47—H47A	108.9
N5—C21—H21B	109.3	C48—C47—H47A	108.9
C22—C21—H21B	109.3	C46—C47—H47B	108.9
H21A—C21—H21B	108.0	C48—C47—H47B	108.9
C23—C22—C21	110.7 (14)	H47A—C47—H47B	107.7
C23—C22—H22A	109.5	C41—C48—C47	111.9 (12)
C21—C22—H22A	109.5	C41—C48—H48A	109.2
C23—C22—H22B	109.5	C47—C48—H48A	109.2
C21—C22—H22B	109.5	C41—C48—H48B	109.2
H22A—C22—H22B	108.1	C47—C48—H48B	109.2
N6—C23—C22	112.8 (14)	H48A—C48—H48B	107.9
N6—C23—H23A	109.0	C50—C49—C56	122.2 (12)
C22—C23—H23A	109.0	C50—C49—Ir2	70.3 (3)
N6—C23—H23B	109.0	C56—C49—Ir2	114.0 (7)
C22—C23—H23B	109.0	C50—C49—H49	114.3
H23A—C23—H23B	107.8	C56—C49—H49	114.3
N6—C24—C25	114.0 (15)	Ir2—C49—H49	114.3
N6—C24—H24A	108.8	C49—C50—C51	123.9 (13)
C25—C24—H24A	108.8	C49—C50—Ir2	70.3 (3)
N6—C24—H24B	108.8	C51—C50—Ir2	111.3 (10)
C25—C24—H24B	108.8	C49—C50—H50	114.4
H24A—C24—H24B	107.6	C51—C50—H50	114.4
C26—C25—C24	113.5 (14)	Ir2—C50—H50	114.4
C26—C25—H25A	108.9	C50—C51—C52	114.6 (15)
C24—C25—H25A	108.9	C50—C51—H51A	108.6
C26—C25—H25B	108.9	C52—C51—H51A	108.6
C24—C25—H25B	108.9	C50—C51—H51B	108.6
H25A—C25—H25B	107.7	C52—C51—H51B	108.6
N5—C21'—C22'	108 (2)	H51A—C51—H51B	107.6
N5—C21'—H21C	110.2	C53—C52—C51	112.5 (17)
C22'—C21'—H21C	110.2	C53—C52—H52A	109.1
N5—C21'—H21D	110.2	C51—C52—H52A	109.1
C22'—C21'—H21D	110.2	C53—C52—H52B	109.1
H21C—C21'—H21D	108.5	C51—C52—H52B	109.1
C23'—C22'—C21'	113 (3)	H52A—C52—H52B	107.8
C23'—C22'—H22C	109.1	C54—C53—C52	124.0 (19)
C21'—C22'—H22C	109.1	C54—C53—Ir2	71.4 (4)
C23'—C22'—H22D	109.1	C52—C53—Ir2	114.4 (12)
C21'—C22'—H22D	109.1	C54—C53—H53	113.4
H22C—C22'—H22D	107.8	C52—C53—H53	113.4
N6'—C23'—C22'	115 (3)	Ir2—C53—H53	113.4
N6'—C23'—H23C	108.5	C53—C54—C55	124 (2)
C22'—C23'—H23C	108.5	C53—C54—Ir2	71.4 (4)
N6'—C23'—H23D	108.5	C55—C54—Ir2	109.0 (9)
C22'—C23'—H23D	108.5	C53—C54—H54	114.6
H23C—C23'—H23D	107.5	C55—C54—H54	114.6
N6'—C24'—C25'	118 (2)	Ir2—C54—H54	114.6
N6'—C24'—H24C	107.7	C54—C55—C56	116.3 (13)
C25'—C24'—H24C	107.7	C54—C55—H55A	108.2
N6'—C24'—H24D	107.7	C56—C55—H55A	108.2
C25'—C24'—H24D	107.7	C54—C55—H55B	108.2
H24C—C24'—H24D	107.1	C56—C55—H55B	108.2
C26—C25'—C24'	116 (2)	H55A—C55—H55B	107.4
C26—C25'—H25C	108.2	C49—C56—C55	111.5 (11)
C24'—C25'—H25C	108.2	C49—C56—H56A	109.3
C26—C25'—H25D	108.2	C55—C56—H56A	109.3
C24'—C25'—H25D	108.2	C49—C56—H56B	109.3
H25C—C25'—H25D	107.4	C55—C56—H56B	109.3
N1—C26—C25'	113.5 (11)	H56A—C56—H56B	108.0
N1—C26—C25	113.5 (11)
C2—N1—C1—N2	0.8 (14)	C21'—C22'—C23'—N6'	−175 (3)
C26—N1—C1—N2	177.0 (11)	C23'—N6'—C24'—C25'	162 (3)
C2—N1—C1—Ir1	171.7 (9)	C34'—N6'—C24'—C25'	−70 (4)
C26—N1—C1—Ir1	−12.2 (18)	N6'—C24'—C25'—C26	−68 (4)
C7—N2—C1—N1	0.1 (14)	C1—N1—C26—C25'	−70.2 (17)
C8—N2—C1—N1	−173.5 (11)	C2—N1—C26—C25'	105.6 (15)
C7—N2—C1—Ir1	−170.6 (9)	C1—N1—C26—C25	−70.2 (17)
C8—N2—C1—Ir1	15.7 (17)	C2—N1—C26—C25	105.6 (15)
C1—N1—C2—C7	−1.4 (15)	C24'—C25'—C26—N1	−51 (2)
C26—N1—C2—C7	−177.7 (12)	C24—C25—C26—N1	−68.3 (17)
C1—N1—C2—C3	−178.7 (15)	C10—N3—C27—C28	−166.9 (11)
C26—N1—C2—C3	5 (2)	C11—N3—C27—C28	69.2 (16)
C7—C2—C3—C4	0 (2)	N3—C27—C28—C33	−132.7 (11)
N1—C2—C3—C4	177.3 (14)	N3—C27—C28—C29	47.4 (11)
C2—C3—C4—C5	0 (2)	C33—C28—C29—C30	0.0 (4)
C3—C4—C5—C6	1 (2)	C27—C28—C29—C30	180.0 (3)
C4—C5—C6—C7	−1 (2)	C28—C29—C30—C31	0.0 (6)
N1—C2—C7—C6	−178.9 (13)	C29—C30—C31—C32	0.0 (8)
C3—C2—C7—C6	−1 (2)	C30—C31—C32—C33	−0.2 (8)
N1—C2—C7—N2	1.4 (15)	C31—C32—C33—C28	0.2 (8)
C3—C2—C7—N2	179.0 (13)	C29—C28—C33—C32	−0.1 (6)
C5—C6—C7—C2	2 (2)	C27—C28—C33—C32	179.9 (4)
C5—C6—C7—N2	−178.6 (14)	C10—N3'—C27'—C28'	−153.9 (19)
C1—N2—C7—C2	−1.0 (15)	C11—N3'—C27'—C28'	83.2 (18)
C8—N2—C7—C2	172.5 (12)	N3'—C27'—C28'—C33'	−159 (2)
C1—N2—C7—C6	179.3 (14)	N3'—C27'—C28'—C29'	21 (2)
C8—N2—C7—C6	−7 (2)	C33'—C28'—C29'—C30'	0.0 (4)
C7—N2—C8—C9	−94.0 (17)	C27'—C28'—C29'—C30'	180.0 (3)
C1—N2—C8—C9	78.6 (16)	C28'—C29'—C30'—C31'	0.0 (6)
N2—C8—C9—C10	56.4 (18)	C29'—C30'—C31'—C32'	0.0 (8)
C11—N3—C10—C9	−162.6 (17)	C30'—C31'—C32'—C33'	0.1 (8)
C27—N3—C10—C9	75.3 (18)	C31'—C32'—C33'—C28'	−0.1 (8)
C11—N3'—C10—C9	−161 (2)	C29'—C28'—C33'—C32'	0.1 (6)
C27'—N3'—C10—C9	76 (2)	C27'—C28'—C33'—C32'	−179.9 (4)
C8—C9—C10—N3	69 (2)	C23—N6—C34—C35	−83.9 (15)
C8—C9—C10—N3'	70 (3)	C24—N6—C34—C35	156.2 (11)
C10—N3'—C11—C12	−70 (4)	N6—C34—C35—C40	−11.6 (12)
C27'—N3'—C11—C12	50 (2)	N6—C34—C35—C36	168.3 (12)
C10—N3—C11—C12	−67 (2)	C40—C35—C36—C37	−0.1 (4)
C27—N3—C11—C12	57 (2)	C34—C35—C36—C37	−180.0 (3)
N3'—C11—C12—C13	−178.7 (17)	C35—C36—C37—C38	−0.2 (6)
N3—C11—C12—C13	−179.4 (15)	C36—C37—C38—C39	0.3 (8)
C14—N4—C13—C12	−78.2 (19)	C37—C38—C39—C40	−0.2 (8)
C15—N4—C13—C12	97 (2)	C38—C39—C40—C35	0.0 (8)
C11—C12—C13—N4	−64 (2)	C36—C35—C40—C39	0.1 (6)
C15—N4—C14—N5	−0.8 (14)	C34—C35—C40—C39	−179.9 (4)
C13—N4—C14—N5	175.1 (12)	C24'—N6'—C34'—C35'	114 (2)
C15—N4—C14—Ir2	172.9 (9)	C23'—N6'—C34'—C35'	−119 (3)
C13—N4—C14—Ir2	−11.3 (19)	N6'—C34'—C35'—C40'	23 (3)
C20—N5—C14—N4	−0.2 (15)	N6'—C34'—C35'—C36'	−157 (3)
C21—N5—C14—N4	−162.0 (13)	C40'—C35'—C36'—C37'	0.0 (4)
C21'—N5—C14—N4	170 (2)	C34'—C35'—C36'—C37'	180.0 (3)
C20—N5—C14—Ir2	−173.7 (10)	C35'—C36'—C37'—C38'	0.0 (6)
C21—N5—C14—Ir2	25 (2)	C36'—C37'—C38'—C39'	0.0 (8)
C21'—N5—C14—Ir2	−4 (2)	C37'—C38'—C39'—C40'	−0.1 (8)
C14—N4—C15—C16	−176.8 (15)	C38'—C39'—C40'—C35'	0.1 (8)
C13—N4—C15—C16	7 (2)	C36'—C35'—C40'—C39'	−0.1 (6)
C14—N4—C15—C20	1.4 (15)	C34'—C35'—C40'—C39'	179.9 (4)
C13—N4—C15—C20	−174.5 (12)	C48—C41—C42—C43	6.3 (13)
N4—C15—C16—C17	177.9 (14)	Ir1—C41—C42—C43	108.1 (9)
C20—C15—C16—C17	0 (2)	C48—C41—C42—Ir1	−101.8 (10)
C15—C16—C17—C18	−1 (2)	C41—C42—C43—C44	−97.5 (12)
C16—C17—C18—C19	0 (3)	Ir1—C42—C43—C44	−14.4 (16)
C17—C18—C19—C20	1 (2)	C42—C43—C44—C45	32.4 (18)
C18—C19—C20—N5	−176.0 (15)	C43—C44—C45—C46	44.1 (16)
C18—C19—C20—C15	−2 (2)	C43—C44—C45—Ir1	−35.0 (16)
C14—N5—C20—C19	175.4 (15)	C44—C45—C46—C47	3.6 (13)
C21—N5—C20—C19	−22 (2)	Ir1—C45—C46—C47	104.9 (10)
C21'—N5—C20—C19	5 (3)	C44—C45—C46—Ir1	−101.3 (9)
C14—N5—C20—C15	1.0 (15)	C45—C46—C47—C48	−91.2 (14)
C21—N5—C20—C15	163.8 (13)	Ir1—C46—C47—C48	−10.5 (17)
C21'—N5—C20—C15	−168.9 (19)	C42—C41—C48—C47	46.1 (17)
C16—C15—C20—C19	2 (2)	Ir1—C41—C48—C47	−35.8 (16)
N4—C15—C20—C19	−176.7 (12)	C46—C47—C48—C41	30.6 (19)
C16—C15—C20—N5	177.0 (13)	C56—C49—C50—C51	3.7 (14)
N4—C15—C20—N5	−1.4 (14)	Ir2—C49—C50—C51	−102.9 (12)
C14—N5—C21—C22	99.4 (19)	C56—C49—C50—Ir2	106.6 (9)
C20—N5—C21—C22	−61 (2)	C49—C50—C51—C52	52 (2)
N5—C21—C22—C23	−165.9 (16)	Ir2—C50—C51—C52	−28 (2)
C24—N6—C23—C22	−69 (2)	C50—C51—C52—C53	24 (3)
C34—N6—C23—C22	171.8 (15)	C51—C52—C53—C54	−91 (2)
C21—C22—C23—N6	168.8 (17)	C51—C52—C53—Ir2	−8 (2)
C23—N6—C24—C25	174.3 (16)	C52—C53—C54—C55	6.5 (18)
C34—N6—C24—C25	−70 (2)	Ir2—C53—C54—C55	−100.8 (12)
N6—C24—C25—C26	−66 (2)	C52—C53—C54—Ir2	107.3 (14)
C14—N5—C21'—C22'	118 (3)	C53—C54—C55—C56	50 (3)
C20—N5—C21'—C22'	−73 (4)	Ir2—C54—C55—C56	−30 (3)
N5—C21'—C22'—C23'	−66 (4)	C50—C49—C56—C55	−89.4 (16)
C24'—N6'—C23'—C22'	−171 (4)	Ir2—C49—C56—C55	−8.4 (19)
C34'—N6'—C23'—C22'	62 (4)	C54—C55—C56—C49	26 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9AB···Br1	0.99	2.78	3.735 (17)	162
C12—H12A···Br2	0.99	3.01	3.96 (2)	161
C19—H19···Br2^i	0.95	3.04	3.876 (14)	147
C21—H21B···Br2^i	0.99	3.11	4.07 (2)	164
C25—H25B···Br1	0.99	2.90	3.863 (14)	165
C21′—H21D···Br2^i	0.99	3.03	3.86 (4)	142
C23′—H23C···Br2	0.99	2.70	3.22 (3)	113
C25′—H25D···Br1	0.99	3.01	3.863 (14)	145

Symmetry code: (i) x+1/2, −y+1/2, −z+1.