Crystal structure of {(E)-2-[(3,4-di­meth­oxy­phenyl­imino)­meth­yl]phenolato-κ2N,O1}bis­[2-(pyridin-2-yl)phenyl-κ2C1,N]iridium(III) di­chloro­methane disolvate

Shee, N.K.; Hong, C.S.; Lee, W.R.; Kim, H.-J.

doi:10.1107/S2056989018009970

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Volume 74| Part 8| August 2018| Pages 1107-1110

https://doi.org/10.1107/S2056989018009970

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Crystal structure of {(E)-2-[(3,4-dimethoxyphenylimino)methyl]phenolato-κ²N,O¹}bis[2-(pyridin-2-yl)phenyl-κ²C¹,N]iridium(III) dichloromethane disolvate

Nirmal K. Shee,^a Chang Seop Hong,^b Woo Ram Lee ^c and Hee-Joon Kim ^a ^*

^aDepartment of Applied Chemistry, Kumoh National Institute of Technology, Gumi, 39177, Republic of Korea, ^bDepartment of Chemistry, Korea University, Seoul 02841, Republic of Korea, and ^cDepartment of Chemistry, Sejong University, Seoul 05006, Republic of Korea
^*Correspondence e-mail: hjk@kumoh.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 8 June 2018; accepted 11 July 2018; online 17 July 2018)

The asymmetric unit of the solvated title complex, [Ir(C₁₁H₈N)₂(C₁₅H₁₄NO₃)]·2CH₂Cl₂, consists of two complex molecules together with four dichloromethane solvent molecules, one of which is disordered. In each complex molecule, the Ir^III ion has a distorted octahedral coordination environment defined by two 2-phenylpyridine ligands, through two phenyl C and two pyridine N atoms, and by one N,O-bidentate 2-[(2,4-dimethoxyphenylimino)methyl]phenolate anion. The Ir^III ions lie almost in the equatorial planes with deviations of 0.0396 (17) and 0.0237 (17) Å, respectively, for the two complex molecules. In both complex molecules, the two 2-phenylpyridine ligands are nearly perpendicular to each other [dihedral angles between the least-squares-planes of 89.91 (11) and 85.13 (11)°]. In the crystal, intermolecular C—H⋯O interactions as well as intermolecular C—H⋯π interactions are present, leading to a three-dimensional network structure. One of the four dichlormethane solvent molecules shows disorder over two sets of sites [occupancy ratio 0.79 (2):0.21 (2)].

Keywords: crystal structure; cyclometalated iridium(III) complex; Schiff base ligand; C₂N₃O coordination set.

CCDC reference: 1846724

1. Chemical context

Heteroleptic iridium(III) complexes bearing a coordinating phenylpyridine ligand are of great interest because of their potential applications in the field of organic light-emitting diodes (OLEDs), as phosphorescence sensors and in photocatalysis (Evans et al., 2006 ; Maity et al., 2015 ; Alam et al., 2017 ). In particular, cyclometalated Ir^III complexes with imine-based ancillary ligands exhibit strong aggregation-induced phosphorescent emission (AIPE) in the solid state (Howarth et al., 2014 ; You et al., 2008 ). The photophysical properties of these complexes are governed mainly by the coordination environment around the metal ions and the ligand architecture. Hence a small change in the ligand moiety can alter the ground as well as excited states of the metal complexes, making it important to analyze in detail the coordination environment of iridium complexes to understand the origin of phosphorescence in the solid state (Pal & Singh, 2013 ; Goo et al., 2016 ).

Here we report the crystal structure of the title compound, [Ir(C₁₁H₈N)₂(C₁₅H₁₄NO₃)]·2CH₂Cl₂, a heteroleptic Ir^III complex containing a derivative of a salicylimine ligand.

2. Structural commentary

The asymmetric unit of the title complex consists of two iridium complexes together with four dichloromethane solvent molecules. One of the solvent molecules is disordered over two sets of sites. Each complex molecular unit (Fig. 1) consists of one Ir^III ion, two C,N-chelating 2-phenylpyridine ligands, and one N,O-chelating 2-((2,4-dimethoxyphenylimino)methyl)phenolate anion. Each Ir^III ion adopts a distorted octahedral coordination environment defined by two phenyl C, two pyridine N, and one imine and one phenolic O atoms. Selected bond lengths and angles are given in Table 1 for both complex molecules.

Table 1
Selected bond lengths (Å) and angles (°) for the title complex

Molecule 1 (Ir1)		Molecule 2 (Ir2)
Ir1—N1	2.028 (3)	Ir2—C38	2.000 (4)
Ir1—C11	1.998 (4)	Ir2—N4	2.030 (3)
Ir1—C12	1.996 (4)	Ir2—C49	2.010 (4)
Ir1—N2	2.036 (3)	Ir2—N5	2.037 (3)
Ir1—O1	2.147 (2)	Ir2—O4	2.151 (2)
Ir1—N3	2.149 (3)	Ir2—N6	2.146 (3)

C11—Ir1—N1	80.64 (14)	N4—Ir2—C38	80.63 (14)
C12—Ir1—N1	94.36 (14)	C49—Ir2—C38	86.71 (14)
C12—Ir1—C11	89.53 (14)	C49—Ir2—N4	96.13 (14)
N2—Ir1—N1	174.57 (12)	N5—Ir2—C38	97.04 (14)
N2—Ir1—C11	97.33 (13)	N5—Ir2—N4	176.06 (12)
N2—Ir1—C12	80.55 (14)	N5—Ir2—C49	80.52 (14)
O1—Ir1—N1	94.86 (11)	O4—Ir2—C38	174.17 (13)
O1—Ir1—C11	175.03 (13)	O4—Ir2—N4	95.39 (11)
O1—Ir1—C12	88.70 (12)	O4—Ir2—C49	89.50 (12)
O1—Ir1—N2	86.97 (10)	O4—Ir2—N5	86.69 (11)
N3—Ir1—N1	86.66 (11)	N6—Ir2—C38	97.25 (13)
N3—Ir1—C11	96.53 (13)	N6—Ir2—N4	86.08 (12)
N3—Ir1—C12	173.93 (12)	N6—Ir2—C49	175.75 (12)
N3—Ir1—N2	98.60 (12)	N6—Ir2—N5	97.40 (12)
N3—Ir1—O1	85.25 (10)	N6—Ir2—O4	86.67 (10)

Figure 1
View of the asymmetric unit of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Purple and green dashed lines represent intra- and intermolecular C—H⋯π interactions, respectively. Solvent molecules are omitted for clarity.

In complex molecule 1 (Ir1), the equatorial plane is defined by atoms O1/N3/C11/C12, the mean deviation from the least-squares plane being 0.044 Å. The Ir1^III ion is displaced by 0.0396 (17) Å from the equatorial plane towards the axial N1 atom. The two 2-phenylpyridine ligands are nearly planar, with dihedral angles between the aromatic rings of 1.42 (13)° (between rings C6–C11 and N1–C5) and 0.60 (13)° (between rings C12–C17 and N2–C22). The 2-phenylpyridine ligands are perpendicular to each other, with a dihedral angle between the least-squares planes of 89.91 (11)°. The coordinating C atoms (C11, C12) are trans to the phenolic O1 atom and the imine N3 atom of the anionic ligand, and the two pyridine N atoms (N1 and N2) are also trans to each other.

In complex molecule 2 (Ir2), a similar bonding situation is observed, with the phenyl C atoms C38 and C49 trans to the O4 and N6 atoms of the 2-[(2,4-dimethoxyphenylimino)methyl]phenolate anion. The equatorial plane is formed by atoms O4/C49/C38/N6. The mean deviation from the least-squares plane is 0.055 Å and the Ir2^III ion is displaced by 0.0237 (17) Å from the equatorial plane towards the axial N4 atom. The deviation from a perpendicular arrangement of the two 2-phenylpyridine ligands is slightly higher than in complex 1 [the dihedral angle between the least-squares planes is 85.13 (11)°], likewise the deviation from planarity with dihedral angles of 1.69 (13)° (between rings C49–C54 and N5–C59) and 3.36 (13)° (between rings C38–C43 and N4–C48), respectively.

The configurations in both complexes are stabilised by intramolecular C—H⋯O interactions between the phenolic O1 and O4 atoms as acceptors and the phenyl C1—H1 and C48—H48 groups as donors (Fig. 1, Table 2), as well as by intramolecular C—H⋯π interactions between H13 with Cg1 and H50 with Cg2 (Cg1 and Cg2 are the centroids of the N1/C1–C5 and N4/C44–C48 rings, respectively).

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N4/C44–C48 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1	0.95	2.51	3.112 (5)	121
C13—H13⋯Cg1	0.95	3.06	3.83 (4)	139
C74—H74a⋯Cg1	0.98	3.40	4.12 (5)	132
C48—H48⋯O4	0.95	2.56	3.155 (5)	121
C36—H36c⋯Cg2	0.98	3.47	4.18 (5)	131
C50—H50⋯Cg2	0.95	3.22	3.98 (4)	138
C29—H29⋯O2ⁱ	0.95	2.60	3.152 (5)	118
C29—H29⋯O3ⁱ	0.95	2.52	3.463 (5)	172
C58—H58⋯O6ⁱⁱ	0.95	2.39	3.330 (5)	170
C75—H75a⋯O4ⁱⁱⁱ	0.99	2.35	3.310 (7)	165
C77—H77a⋯O1^iv	0.99	2.19	3.172 (7)	172
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z+1; (iii) x+1, y, z; (iv) x-1, y, z.

The Ir—C, Ir—N, and Ir—O bond lengths, as shown in Table 1, are consistent with values reported in the literature, e.g. for {(E)-2-[(2,6-diisopropylphenylimino)methyl]phenolato-κ²N,O}bis(2-phenylpyridine-κ²C,N)iridium(III) (Howarth et al., 2014), {(E)-2-[(phenylimino)methyl]phenolato-κ²N,O}bis[2-(2,4-difluorophenyl)pyridine-κ²C,N]iridium(III) (You et al., 2008) or {(E)-2-[(phenylimino)methyl]phenolato-κ²N,O}bis[2-(pyridin-2-yl)phenyl-κ²C,N]iridium(III) (Goo et al., 2016).

3. Supramolecular features

In the crystal, the molecules are linked by non-classical C—H⋯O hydrogen-bonds as well as C—H⋯π interactions (Figs. 1 and 2, Table 2). Intermolecular C—H⋯O interactions are present between aromatic and methyl donor groups (also involving solvent molecules) and phenolic and methoxy O atoms. Additional C—H⋯π interactions (Table 2) are present between H74a with Cg1 and H36c with Cg2. The crystal packing lacks any π–π interactiosn (negligible above 3.8 Å), although the title compound is very similar to a previously reported compound (Goo et al., 2016) where this packing feature is present.

Figure 2
Packing plot of the molecular components in the title compound. Cyan lines represent intermolecular short contact. Solvent molecules are omitted for clarity.

4. Synthesis and crystallization

The title compound was prepared according to a reported procedure (Goo et al., 2016), using 2-[(2,4-dimethoxyphenylimino)methyl]phenol instead of 2-[(phenylimino)methyl]phenol. Single crystals suitable for X-ray diffrection were obtained by direct diffusion of n-hexane (5 mL) into a dichloromethane (5 mL) solution of the title compound (6 mg; 8.0 × 10⁻³ mmol) at room temperature.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined using a riding-model approximation: C—H = 0.95 Å for Csp²—H and 0.99 Å for methylene C—H with U_iso(H) = 1.2U_eq(C); C—H = 0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms. One of the four dichloromethane solvent molecules shows disorder over two sets of sites [occupancy ratio 0.79 (2):0.21 (2)].

Table 3
Experimental details

Crystal data
Chemical formula	2[Ir(C₁₁H₈N)₂(C₁₅H₁₄NO₃)]·4CH₂Cl₂
M_r	1853.49
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	130
a, b, c (Å)	12.4000 (5), 14.5371 (6), 21.3502 (8)
α, β, γ (°)	90.112 (1), 106.092 (1), 92.697 (1)
V (Å³)	3693.2 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.95
Crystal size (mm)	0.25 × 0.14 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.439, 0.827
No. of measured, independent and observed [I ≥ 2σ(I)] reflections	51940, 17551, 13646
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.066, 1.03
No. of reflections	17551
No. of parameters	921
No. of restraints	14
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	1.25, −1.23
Computer programs: APEX2 and SAINT (Bruker, 2013 ), olex2.solve and olex2.refine (Bourhis et al., 2015 ), OLEX2 (Dolomanov et al., 2009 ) and DIAMOND (Brandenburg, 2010 ).

Supporting information

CCDC reference: 1846724

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009970/wm5449sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009970/wm5449Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

{(E)-2-[(3,4-Dimethoxyphenylimino)methyl]phenolato-κ²N,O¹}bis[2-(pyridin-2-yl)phenyl-κ²C¹,N]iridium(III) dichloromethane disolvate top

Crystal data top

2[Ir(C₁₁H₈N)₂(C₁₅H₁₄NO₃)]·4CH₂Cl₂	Z = 2
M_r = 1853.49	F(000) = 1829.2575
Triclinic, P1	D_x = 1.667 Mg m⁻³
a = 12.4000 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.5371 (6) Å	Cell parameters from 9867 reflections
c = 21.3502 (8) Å	θ = 2.2–28.4°
α = 90.112 (1)°	µ = 3.95 mm⁻¹
β = 106.092 (1)°	T = 130 K
γ = 92.697 (1)°	Plate, orange
V = 3693.2 (3) Å³	0.25 × 0.14 × 0.05 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	13646 reflections with I ≥ 2σ(I)
ω scans	R_int = 0.038
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.3°, θ_min = 1.0°
T_min = 0.439, T_max = 0.827	h = −16→16
51940 measured reflections	k = −17→19
17551 independent reflections	l = −27→26

Refinement top

Refinement on F²	14 restraints
Least-squares matrix: full	122 constraints
R[F² > 2σ(F²)] = 0.032	All H-atom parameters refined
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0222P)² + 3.8204P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.042
17551 reflections	Δρ_max = 1.25 e Å⁻³
921 parameters	Δρ_min = −1.23 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ir1	0.787612 (11)	0.424026 (9)	0.236018 (7)	0.01822 (4)
N1	0.7554 (2)	0.5519 (2)	0.26199 (14)	0.0212 (7)
C1	0.8299 (3)	0.6244 (3)	0.2692 (2)	0.0305 (9)
H1	0.8991 (3)	0.6170 (3)	0.2593 (2)	0.0366 (11)*
C2	0.8080 (4)	0.7088 (3)	0.2907 (2)	0.0422 (11)
H2	0.8618 (4)	0.7590 (3)	0.2964 (2)	0.0507 (14)*
C3	0.7060 (4)	0.7195 (3)	0.3040 (2)	0.0391 (11)
H3	0.6892 (4)	0.7773 (3)	0.3188 (2)	0.0469 (13)*
C4	0.6294 (4)	0.6463 (3)	0.2956 (2)	0.0347 (10)
H4	0.5589 (4)	0.6534 (3)	0.3041 (2)	0.0416 (12)*
C5	0.6551 (3)	0.5614 (3)	0.27463 (19)	0.0255 (8)
C6	0.5848 (3)	0.4760 (3)	0.26520 (18)	0.0237 (8)
C7	0.4773 (3)	0.4692 (3)	0.2740 (2)	0.0329 (10)
H7	0.4459 (3)	0.5219 (3)	0.2870 (2)	0.0395 (12)*
C8	0.4164 (3)	0.3854 (3)	0.2636 (2)	0.0368 (11)
H8	0.3436 (3)	0.3803 (3)	0.2702 (2)	0.0441 (13)*
C9	0.4616 (3)	0.3096 (3)	0.24380 (19)	0.0319 (10)
H9	0.4193 (3)	0.2524 (3)	0.23635 (19)	0.0383 (12)*
C10	0.5682 (3)	0.3158 (3)	0.23460 (18)	0.0250 (8)
H10	0.5980 (3)	0.2626 (3)	0.22123 (18)	0.0300 (10)*
C11	0.6326 (3)	0.3987 (3)	0.24456 (17)	0.0218 (8)
C12	0.8508 (3)	0.3837 (3)	0.32767 (18)	0.0231 (8)
C13	0.8650 (3)	0.4342 (3)	0.38602 (19)	0.0285 (9)
H13	0.8377 (3)	0.4944 (3)	0.38418 (19)	0.0342 (11)*
C14	0.9177 (3)	0.3981 (3)	0.4458 (2)	0.0347 (10)
H14	0.9262 (3)	0.4339 (3)	0.4843 (2)	0.0417 (12)*
C15	0.9584 (4)	0.3104 (3)	0.4506 (2)	0.0381 (11)
H15	0.9953 (4)	0.2865 (3)	0.4920 (2)	0.0457 (13)*
C16	0.9449 (4)	0.2579 (3)	0.3945 (2)	0.0361 (10)
H16	0.9718 (4)	0.1976 (3)	0.3974 (2)	0.0433 (12)*
C17	0.8913 (3)	0.2940 (3)	0.33371 (19)	0.0254 (8)
C18	0.8737 (3)	0.2435 (3)	0.2723 (2)	0.0263 (9)
C19	0.9052 (4)	0.1548 (3)	0.2643 (2)	0.0379 (11)
H19	0.9423 (4)	0.1211 (3)	0.3015 (2)	0.0455 (13)*
C20	0.8837 (4)	0.1150 (3)	0.2035 (2)	0.0418 (11)
H20	0.9068 (4)	0.0547 (3)	0.1984 (2)	0.0502 (14)*
C21	0.8282 (4)	0.1638 (3)	0.1498 (2)	0.0353 (10)
H21	0.8113 (4)	0.1373 (3)	0.1072 (2)	0.0424 (12)*
C22	0.7977 (3)	0.2517 (3)	0.15916 (19)	0.0274 (9)
H22	0.7595 (3)	0.2854 (3)	0.12220 (19)	0.0328 (11)*
N2	0.8201 (2)	0.2918 (2)	0.21864 (15)	0.0224 (7)
O1	0.9555 (2)	0.46108 (18)	0.23268 (12)	0.0253 (6)
C23	0.9886 (3)	0.4459 (2)	0.18083 (18)	0.0213 (8)
C24	1.1033 (3)	0.4290 (2)	0.18814 (19)	0.0244 (8)
H24	1.1536 (3)	0.4286 (2)	0.23077 (19)	0.0293 (10)*
C25	1.1437 (3)	0.4134 (3)	0.1361 (2)	0.0304 (9)
H25	1.2207 (3)	0.4009 (3)	0.1433 (2)	0.0365 (11)*
C26	1.0738 (3)	0.4154 (3)	0.0725 (2)	0.0354 (10)
H26	1.1022 (3)	0.4036 (3)	0.0364 (2)	0.0425 (12)*
C27	0.9633 (3)	0.4349 (3)	0.0631 (2)	0.0312 (9)
H27	0.9156 (3)	0.4380 (3)	0.0199 (2)	0.0375 (11)*
C28	0.9189 (3)	0.4504 (3)	0.11611 (19)	0.0238 (8)
C29	0.8038 (3)	0.4767 (3)	0.10017 (19)	0.0253 (8)
H29	0.7739 (3)	0.5015 (3)	0.05814 (19)	0.0304 (10)*
N3	0.7377 (2)	0.4700 (2)	0.13701 (15)	0.0214 (7)
C30	0.6300 (3)	0.5092 (3)	0.11168 (17)	0.0215 (8)
C31	0.6223 (3)	0.6030 (3)	0.10533 (19)	0.0276 (9)
H31	0.6882 (3)	0.6426 (3)	0.11735 (19)	0.0332 (10)*
C32	0.5164 (3)	0.6400 (3)	0.08095 (19)	0.0302 (9)
H32	0.5106 (3)	0.7047 (3)	0.07703 (19)	0.0362 (11)*
C33	0.4212 (3)	0.5831 (3)	0.06279 (18)	0.0274 (9)
C34	0.4293 (3)	0.4871 (3)	0.06999 (18)	0.0249 (8)
C35	0.5330 (3)	0.4508 (3)	0.09482 (17)	0.0217 (8)
H35	0.5387 (3)	0.3863 (3)	0.10047 (17)	0.0260 (9)*
O2	0.3141 (2)	0.6130 (2)	0.03783 (14)	0.0360 (7)
C36	0.3044 (4)	0.7090 (3)	0.0242 (2)	0.0449 (12)
H36a	0.349 (2)	0.7266 (5)	−0.0057 (12)	0.0673 (18)*
H36b	0.2254 (5)	0.7213 (5)	0.0041 (14)	0.0673 (18)*
H36c	0.332 (2)	0.7448 (3)	0.0649 (3)	0.0673 (18)*
O3	0.3305 (2)	0.43578 (19)	0.05053 (13)	0.0300 (6)
C37	0.3382 (3)	0.3381 (3)	0.0546 (2)	0.0332 (10)
H37a	0.3872 (18)	0.3180 (4)	0.0287 (11)	0.0498 (15)*
H37b	0.370 (2)	0.3211 (3)	0.1002 (3)	0.0498 (15)*
H37c	0.2632 (4)	0.3083 (3)	0.0376 (12)	0.0498 (15)*
Ir2	0.231563 (11)	0.938616 (9)	0.272341 (7)	0.01839 (4)
C38	0.3875 (3)	0.9561 (3)	0.26341 (18)	0.0237 (8)
C39	0.4595 (3)	1.0350 (3)	0.27746 (19)	0.0297 (9)
H39	0.4368 (3)	1.0878 (3)	0.29586 (19)	0.0356 (11)*
C40	0.5638 (3)	1.0374 (3)	0.2649 (2)	0.0381 (11)
H40	0.6121 (3)	1.0912 (3)	0.2761 (2)	0.0457 (13)*
C41	0.5984 (3)	0.9630 (3)	0.2366 (2)	0.0422 (12)
H41	0.6694 (3)	0.9657 (3)	0.2277 (2)	0.0506 (14)*
C42	0.5286 (3)	0.8846 (3)	0.2214 (2)	0.0375 (11)
H42	0.5514 (3)	0.8333 (3)	0.2014 (2)	0.0450 (13)*
C43	0.4243 (3)	0.8800 (3)	0.23504 (19)	0.0270 (9)
C44	0.3462 (3)	0.7992 (3)	0.22164 (18)	0.0276 (9)
C45	0.3637 (4)	0.7133 (3)	0.1975 (2)	0.0367 (10)
H45	0.4327 (4)	0.7031 (3)	0.1881 (2)	0.0441 (12)*
C46	0.2824 (4)	0.6441 (3)	0.1874 (2)	0.0437 (12)
H46	0.2938 (4)	0.5863 (3)	0.1701 (2)	0.0524 (14)*
C47	0.1832 (4)	0.6590 (3)	0.2025 (2)	0.0404 (11)
H47	0.1259 (4)	0.6114 (3)	0.1963 (2)	0.0484 (13)*
C48	0.1688 (3)	0.7437 (3)	0.2267 (2)	0.0323 (10)
H48	0.1007 (3)	0.7538 (3)	0.2373 (2)	0.0388 (11)*
N4	0.2477 (2)	0.8125 (2)	0.23585 (15)	0.0238 (7)
C49	0.1800 (3)	1.0004 (3)	0.18569 (18)	0.0233 (8)
C50	0.1597 (3)	0.9617 (3)	0.12341 (19)	0.0294 (9)
H50	0.1723 (3)	0.8984 (3)	0.11877 (19)	0.0353 (11)*
C51	0.1214 (3)	1.0141 (3)	0.0681 (2)	0.0364 (10)
H51	0.1082 (3)	0.9861 (3)	0.0262 (2)	0.0436 (12)*
C52	0.1024 (4)	1.1062 (3)	0.0730 (2)	0.0401 (11)
H52	0.0756 (4)	1.1412 (3)	0.0349 (2)	0.0481 (13)*
C53	0.1225 (4)	1.1470 (3)	0.1339 (2)	0.0364 (10)
H53	0.1108 (4)	1.2107 (3)	0.1379 (2)	0.0436 (12)*
C54	0.1603 (3)	1.0941 (3)	0.18968 (19)	0.0265 (9)
C55	0.1824 (3)	1.1316 (3)	0.2562 (2)	0.0274 (9)
C56	0.1672 (4)	1.2216 (3)	0.2727 (2)	0.0395 (11)
H56	0.1420 (4)	1.2653 (3)	0.2395 (2)	0.0474 (13)*
C57	0.1888 (4)	1.2474 (3)	0.3373 (2)	0.0389 (11)
H57	0.1789 (4)	1.3090 (3)	0.3489 (2)	0.0467 (13)*
C58	0.2248 (3)	1.1832 (3)	0.3851 (2)	0.0343 (10)
H58	0.2395 (3)	1.1996 (3)	0.4299 (2)	0.0411 (12)*
C59	0.2389 (3)	1.0951 (3)	0.3665 (2)	0.0272 (9)
H59	0.2641 (3)	1.0508 (3)	0.3993 (2)	0.0327 (10)*
N5	0.2183 (2)	1.0690 (2)	0.30361 (15)	0.0217 (7)
O4	0.05898 (19)	0.91397 (17)	0.27204 (12)	0.0236 (6)
C60	0.0248 (3)	0.9107 (2)	0.32446 (19)	0.0224 (8)
C61	−0.0876 (3)	0.9321 (2)	0.3194 (2)	0.0257 (9)
H61	−0.1340 (3)	0.9504 (2)	0.2785 (2)	0.0308 (10)*
C62	−0.1314 (3)	0.9272 (3)	0.3716 (2)	0.0297 (9)
H62	−0.2069 (3)	0.9429 (3)	0.3661 (2)	0.0357 (11)*
C63	−0.0676 (3)	0.8998 (3)	0.4325 (2)	0.0332 (10)
H63	−0.0983 (3)	0.8965 (3)	0.4686 (2)	0.0398 (12)*
C64	0.0417 (3)	0.8775 (3)	0.4387 (2)	0.0283 (9)
H64	0.0857 (3)	0.8571 (3)	0.4796 (2)	0.0340 (11)*
C65	0.0906 (3)	0.8838 (2)	0.38691 (19)	0.0216 (8)
C66	0.2063 (3)	0.8577 (2)	0.40021 (18)	0.0227 (8)
H66	0.2343 (3)	0.8234 (2)	0.43865 (18)	0.0273 (10)*
N6	0.2751 (2)	0.8754 (2)	0.36617 (14)	0.0197 (6)
C67	0.3841 (3)	0.8369 (2)	0.39048 (17)	0.0203 (8)
C68	0.4788 (3)	0.8960 (2)	0.41121 (17)	0.0200 (8)
H68	0.4718 (3)	0.9607 (2)	0.40859 (17)	0.0240 (9)*
C69	0.5831 (3)	0.8604 (2)	0.43559 (18)	0.0211 (8)
C70	0.5937 (3)	0.7647 (3)	0.43798 (18)	0.0231 (8)
C71	0.4995 (3)	0.7068 (3)	0.41701 (18)	0.0243 (8)
H71	0.5065 (3)	0.6420 (3)	0.41879 (18)	0.0291 (10)*
C72	0.3937 (3)	0.7425 (2)	0.39314 (18)	0.0237 (8)
H72	0.3288 (3)	0.7023 (2)	0.37881 (18)	0.0284 (10)*
O5	0.6809 (2)	0.91291 (18)	0.45896 (13)	0.0290 (6)
C73	0.6730 (3)	1.0102 (3)	0.4541 (2)	0.0318 (10)
H73a	0.638 (2)	1.0262 (3)	0.4087 (3)	0.0476 (14)*
H73b	0.6272 (18)	1.0313 (3)	0.4816 (10)	0.0476 (14)*
H73c	0.7485 (4)	1.0401 (3)	0.4688 (12)	0.0476 (14)*
O6	0.7018 (2)	0.73717 (18)	0.46183 (13)	0.0286 (6)
C74	0.7146 (4)	0.6413 (3)	0.4727 (2)	0.0379 (11)
H74a	0.685 (2)	0.6073 (3)	0.4313 (3)	0.0569 (16)*
H74b	0.7944 (4)	0.6299 (4)	0.4908 (13)	0.0569 (16)*
H74c	0.6731 (19)	0.6206 (5)	0.5035 (11)	0.0569 (16)*
C75	0.8953 (4)	0.8577 (4)	0.1249 (3)	0.0675 (17)
H75a	0.9343 (4)	0.8666 (4)	0.1718 (3)	0.10 (2)*
H75b	0.9312 (4)	0.9013 (4)	0.1002 (3)	0.15 (4)*
Cl1	0.91048 (13)	0.74443 (12)	0.10109 (8)	0.0808 (5)
Cl2	0.75576 (15)	0.88210 (15)	0.11117 (12)	0.1191 (8)
C76	0.4050 (4)	0.0541 (3)	0.0954 (3)	0.0478 (12)
H76a	0.4118 (4)	0.0338 (3)	0.1406 (3)	0.078 (19)*
H76b	0.3336 (4)	0.0856 (3)	0.0799 (3)	0.11 (2)*
Cl3	0.51784 (13)	0.13247 (10)	0.09582 (8)	0.0679 (4)
Cl4	0.40064 (15)	−0.04258 (11)	0.04579 (8)	0.0792 (5)
C77	0.1228 (3)	0.5166 (3)	0.3705 (2)	0.0361 (10)
H77a	0.0712 (3)	0.4932 (3)	0.3288 (2)	0.039 (12)*
H77b	0.1072 (3)	0.4795 (3)	0.4061 (2)	0.057 (15)*
Cl5	0.26333 (9)	0.50318 (7)	0.36926 (6)	0.0393 (3)
Cl6	0.09709 (9)	0.63296 (8)	0.38213 (6)	0.0427 (3)
C78	0.6216 (4)	0.3251 (3)	0.4127 (2)	0.0524 (13)
H78a	0.5855 (4)	0.3514 (3)	0.3697 (2)	0.0629 (16)*	0.21 (2)
H78b	0.6987 (4)	0.3098 (3)	0.4129 (2)	0.0629 (16)*	0.21 (2)
H78c	0.6104 (4)	0.3378 (3)	0.3658 (2)	0.0629 (16)*	0.79 (2)
H78d	0.7029 (4)	0.3183 (3)	0.4330 (2)	0.0629 (16)*	0.79 (2)
Cl8A	0.6309 (11)	0.4091 (9)	0.4729 (6)	0.047 (4)	0.21 (2)
Cl8B	0.5743 (11)	0.41843 (18)	0.4508 (4)	0.108 (3)	0.79 (2)
Cl7	0.54746 (15)	0.22451 (9)	0.42112 (7)	0.0723 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01840 (7)	0.01837 (8)	0.01894 (8)	0.00189 (5)	0.00675 (6)	0.00085 (6)
N1	0.0242 (15)	0.0217 (16)	0.0175 (16)	0.0041 (13)	0.0048 (13)	0.0007 (13)
C1	0.031 (2)	0.024 (2)	0.037 (3)	−0.0007 (17)	0.0106 (19)	−0.0019 (18)
C2	0.047 (3)	0.022 (2)	0.056 (3)	0.0007 (19)	0.011 (2)	−0.003 (2)
C3	0.052 (3)	0.026 (2)	0.039 (3)	0.013 (2)	0.010 (2)	−0.0028 (19)
C4	0.039 (2)	0.040 (3)	0.026 (2)	0.017 (2)	0.0085 (19)	−0.0025 (19)
C5	0.0276 (19)	0.028 (2)	0.023 (2)	0.0105 (16)	0.0093 (16)	0.0057 (16)
C6	0.0206 (18)	0.034 (2)	0.018 (2)	0.0039 (16)	0.0070 (15)	0.0046 (16)
C7	0.027 (2)	0.042 (3)	0.032 (2)	0.0144 (18)	0.0112 (18)	0.010 (2)
C8	0.0196 (19)	0.056 (3)	0.039 (3)	0.0042 (19)	0.0143 (18)	0.010 (2)
C9	0.026 (2)	0.038 (2)	0.030 (2)	−0.0064 (18)	0.0056 (18)	0.0085 (19)
C10	0.0251 (19)	0.028 (2)	0.024 (2)	0.0018 (16)	0.0099 (16)	0.0035 (16)
C11	0.0222 (18)	0.028 (2)	0.0167 (19)	0.0025 (15)	0.0066 (15)	0.0035 (15)
C12	0.0204 (18)	0.027 (2)	0.024 (2)	0.0006 (15)	0.0095 (16)	0.0011 (16)
C13	0.028 (2)	0.031 (2)	0.027 (2)	0.0009 (17)	0.0088 (17)	0.0009 (17)
C14	0.041 (2)	0.041 (3)	0.020 (2)	−0.012 (2)	0.0086 (19)	−0.0018 (19)
C15	0.038 (2)	0.044 (3)	0.027 (2)	−0.004 (2)	0.0024 (19)	0.013 (2)
C16	0.044 (2)	0.029 (2)	0.034 (3)	0.0051 (19)	0.007 (2)	0.0089 (19)
C17	0.0257 (19)	0.025 (2)	0.023 (2)	0.0010 (16)	0.0035 (16)	0.0060 (16)
C18	0.0258 (19)	0.0197 (19)	0.032 (2)	0.0008 (15)	0.0060 (17)	0.0038 (17)
C19	0.049 (3)	0.022 (2)	0.041 (3)	0.0091 (19)	0.008 (2)	0.0039 (19)
C20	0.049 (3)	0.021 (2)	0.058 (3)	0.003 (2)	0.020 (2)	−0.002 (2)
C21	0.042 (2)	0.029 (2)	0.039 (3)	−0.0005 (19)	0.019 (2)	−0.0092 (19)
C22	0.029 (2)	0.027 (2)	0.027 (2)	0.0011 (16)	0.0088 (17)	−0.0063 (17)
N2	0.0205 (15)	0.0220 (16)	0.0270 (18)	−0.0008 (12)	0.0108 (13)	−0.0013 (14)
O1	0.0189 (13)	0.0331 (15)	0.0237 (15)	−0.0014 (11)	0.0063 (11)	−0.0043 (12)
C23	0.0232 (18)	0.0164 (18)	0.025 (2)	−0.0020 (14)	0.0078 (16)	0.0004 (15)
C24	0.0208 (18)	0.023 (2)	0.029 (2)	−0.0001 (15)	0.0070 (16)	0.0044 (16)
C25	0.028 (2)	0.029 (2)	0.040 (3)	0.0079 (17)	0.0178 (19)	0.0076 (19)
C26	0.035 (2)	0.045 (3)	0.034 (3)	0.0120 (19)	0.020 (2)	0.011 (2)
C27	0.030 (2)	0.041 (2)	0.027 (2)	0.0071 (18)	0.0142 (18)	0.0082 (19)
C28	0.0233 (18)	0.024 (2)	0.026 (2)	0.0034 (15)	0.0092 (16)	0.0066 (16)
C29	0.0262 (19)	0.028 (2)	0.022 (2)	0.0043 (16)	0.0063 (16)	0.0027 (16)
N3	0.0192 (15)	0.0221 (16)	0.0236 (18)	0.0037 (12)	0.0067 (13)	0.0009 (13)
C30	0.0211 (18)	0.030 (2)	0.0153 (19)	0.0077 (15)	0.0062 (15)	0.0006 (15)
C31	0.027 (2)	0.031 (2)	0.024 (2)	0.0018 (17)	0.0063 (17)	0.0008 (17)
C32	0.036 (2)	0.027 (2)	0.029 (2)	0.0101 (18)	0.0110 (18)	0.0021 (17)
C33	0.0233 (19)	0.044 (2)	0.016 (2)	0.0130 (17)	0.0066 (16)	0.0038 (17)
C34	0.0252 (19)	0.035 (2)	0.017 (2)	0.0047 (16)	0.0097 (16)	0.0016 (16)
C35	0.0221 (18)	0.028 (2)	0.0166 (19)	0.0038 (15)	0.0072 (15)	0.0036 (15)
O2	0.0288 (15)	0.0420 (18)	0.0354 (17)	0.0163 (13)	0.0036 (13)	0.0015 (14)
C36	0.041 (3)	0.048 (3)	0.042 (3)	0.025 (2)	0.001 (2)	0.007 (2)
O3	0.0178 (13)	0.0398 (17)	0.0314 (16)	0.0031 (11)	0.0048 (12)	0.0043 (13)
C37	0.027 (2)	0.039 (2)	0.034 (3)	−0.0031 (18)	0.0095 (18)	−0.0030 (19)
Ir2	0.01743 (7)	0.01797 (8)	0.01981 (8)	0.00181 (5)	0.00509 (6)	0.00010 (6)
C38	0.0217 (18)	0.029 (2)	0.020 (2)	0.0039 (15)	0.0057 (15)	0.0069 (16)
C39	0.0246 (19)	0.036 (2)	0.028 (2)	−0.0015 (17)	0.0071 (17)	0.0077 (18)
C40	0.025 (2)	0.049 (3)	0.036 (3)	−0.0076 (19)	0.0025 (19)	0.014 (2)
C41	0.023 (2)	0.065 (3)	0.043 (3)	0.007 (2)	0.015 (2)	0.017 (2)
C42	0.031 (2)	0.053 (3)	0.032 (2)	0.015 (2)	0.0134 (19)	0.009 (2)
C43	0.0234 (19)	0.036 (2)	0.022 (2)	0.0097 (17)	0.0055 (16)	0.0072 (17)
C44	0.029 (2)	0.034 (2)	0.019 (2)	0.0118 (17)	0.0040 (16)	0.0016 (17)
C45	0.043 (3)	0.039 (3)	0.029 (2)	0.020 (2)	0.008 (2)	−0.0014 (19)
C46	0.059 (3)	0.029 (2)	0.039 (3)	0.015 (2)	0.004 (2)	−0.005 (2)
C47	0.045 (3)	0.024 (2)	0.045 (3)	−0.0012 (19)	0.001 (2)	−0.008 (2)
C48	0.032 (2)	0.026 (2)	0.036 (3)	0.0020 (17)	0.0057 (19)	−0.0025 (18)
N4	0.0247 (16)	0.0226 (17)	0.0227 (18)	0.0027 (13)	0.0040 (13)	0.0021 (13)
C49	0.0184 (17)	0.027 (2)	0.025 (2)	0.0013 (15)	0.0067 (16)	0.0019 (16)
C50	0.0239 (19)	0.038 (2)	0.025 (2)	0.0020 (17)	0.0048 (17)	−0.0008 (18)
C51	0.034 (2)	0.051 (3)	0.022 (2)	0.000 (2)	0.0056 (18)	0.001 (2)
C52	0.039 (2)	0.051 (3)	0.027 (3)	0.009 (2)	0.004 (2)	0.013 (2)
C53	0.042 (2)	0.033 (2)	0.033 (3)	0.0073 (19)	0.006 (2)	0.0130 (19)
C54	0.0247 (19)	0.027 (2)	0.028 (2)	0.0035 (16)	0.0063 (17)	0.0041 (17)
C55	0.027 (2)	0.0190 (19)	0.036 (2)	0.0009 (16)	0.0077 (18)	0.0044 (17)
C56	0.051 (3)	0.020 (2)	0.044 (3)	0.0065 (19)	0.008 (2)	0.0079 (19)
C57	0.053 (3)	0.019 (2)	0.044 (3)	0.0058 (19)	0.012 (2)	−0.0057 (19)
C58	0.041 (2)	0.028 (2)	0.032 (3)	0.0017 (18)	0.007 (2)	−0.0066 (18)
C59	0.031 (2)	0.024 (2)	0.028 (2)	−0.0018 (16)	0.0105 (17)	−0.0005 (17)
N5	0.0243 (16)	0.0177 (15)	0.0231 (18)	0.0022 (12)	0.0063 (13)	−0.0008 (13)
O4	0.0152 (12)	0.0297 (14)	0.0251 (15)	0.0003 (10)	0.0045 (11)	−0.0017 (11)
C60	0.0194 (17)	0.0161 (18)	0.034 (2)	−0.0007 (14)	0.0106 (16)	−0.0034 (16)
C61	0.0213 (18)	0.022 (2)	0.033 (2)	0.0044 (15)	0.0059 (17)	0.0019 (17)
C62	0.0186 (18)	0.028 (2)	0.045 (3)	0.0024 (16)	0.0122 (18)	−0.0024 (19)
C63	0.032 (2)	0.037 (2)	0.037 (3)	0.0011 (18)	0.022 (2)	0.003 (2)
C64	0.0243 (19)	0.030 (2)	0.032 (2)	−0.0013 (16)	0.0115 (17)	0.0013 (18)
C65	0.0182 (17)	0.0153 (18)	0.031 (2)	0.0000 (14)	0.0061 (16)	0.0016 (15)
C66	0.0237 (18)	0.0206 (19)	0.022 (2)	−0.0025 (15)	0.0043 (16)	−0.0005 (15)
N6	0.0169 (14)	0.0203 (16)	0.0217 (17)	0.0021 (12)	0.0048 (13)	0.0016 (13)
C67	0.0180 (17)	0.025 (2)	0.019 (2)	0.0055 (14)	0.0063 (15)	0.0042 (15)
C68	0.0221 (18)	0.0197 (18)	0.019 (2)	0.0025 (14)	0.0076 (15)	−0.0015 (15)
C69	0.0181 (17)	0.026 (2)	0.020 (2)	−0.0009 (15)	0.0081 (15)	−0.0013 (15)
C70	0.0212 (18)	0.028 (2)	0.022 (2)	0.0083 (15)	0.0075 (15)	0.0006 (16)
C71	0.0274 (19)	0.0192 (19)	0.027 (2)	0.0042 (15)	0.0086 (17)	0.0020 (16)
C72	0.0223 (18)	0.0226 (19)	0.027 (2)	0.0025 (15)	0.0086 (16)	−0.0013 (16)
O5	0.0200 (13)	0.0282 (15)	0.0367 (17)	−0.0006 (11)	0.0045 (12)	0.0001 (12)
C73	0.0225 (19)	0.032 (2)	0.039 (3)	−0.0049 (17)	0.0066 (18)	−0.0071 (19)
O6	0.0207 (13)	0.0293 (15)	0.0337 (16)	0.0078 (11)	0.0034 (12)	0.0008 (12)
C74	0.036 (2)	0.032 (2)	0.042 (3)	0.0153 (19)	0.003 (2)	0.007 (2)
C75	0.045 (3)	0.084 (4)	0.067 (4)	−0.006 (3)	0.007 (3)	−0.024 (3)
Cl1	0.0607 (9)	0.0871 (11)	0.0785 (11)	0.0087 (8)	−0.0081 (8)	−0.0318 (9)
Cl2	0.0603 (10)	0.1180 (16)	0.161 (2)	0.0132 (10)	−0.0006 (12)	−0.0604 (15)
C76	0.044 (3)	0.052 (3)	0.047 (3)	−0.004 (2)	0.014 (2)	−0.006 (2)
Cl3	0.0760 (10)	0.0577 (9)	0.0758 (10)	−0.0187 (7)	0.0347 (8)	−0.0137 (7)
Cl4	0.0976 (12)	0.0687 (10)	0.0833 (12)	−0.0258 (9)	0.0503 (10)	−0.0310 (9)
C77	0.034 (2)	0.035 (2)	0.039 (3)	−0.0043 (19)	0.010 (2)	−0.001 (2)
Cl5	0.0349 (5)	0.0344 (6)	0.0472 (7)	−0.0012 (4)	0.0095 (5)	−0.0049 (5)
Cl6	0.0409 (6)	0.0405 (6)	0.0466 (7)	0.0017 (5)	0.0120 (5)	−0.0076 (5)
C78	0.051 (3)	0.056 (3)	0.049 (3)	−0.012 (2)	0.014 (3)	0.004 (3)
Cl8A	0.066 (8)	0.046 (4)	0.027 (5)	−0.035 (4)	0.015 (4)	−0.013 (4)
Cl8B	0.239 (7)	0.0434 (13)	0.051 (3)	−0.030 (2)	0.062 (4)	−0.0124 (12)
Cl7	0.1229 (13)	0.0366 (7)	0.0646 (10)	−0.0190 (8)	0.0417 (9)	−0.0050 (6)

Geometric parameters (Å, º) top

Ir1—N1	2.028 (3)	Ir2—N6	2.146 (3)
Ir1—C11	1.998 (4)	C38—C39	1.398 (5)
Ir1—C12	1.996 (4)	C38—C43	1.413 (5)
Ir1—N2	2.036 (3)	C39—C40	1.390 (5)
Ir1—O1	2.147 (2)	C40—C41	1.380 (6)
Ir1—N3	2.149 (3)	C41—C42	1.380 (6)
N1—C1	1.347 (5)	C42—C43	1.402 (5)
N1—C5	1.357 (5)	C43—C44	1.462 (5)
C1—C2	1.374 (5)	C44—C45	1.398 (5)
C2—C3	1.386 (6)	C44—N4	1.360 (5)
C3—C4	1.370 (6)	C45—C46	1.363 (6)
C4—C5	1.392 (5)	C46—C47	1.381 (6)
C5—C6	1.464 (5)	C47—C48	1.372 (5)
C6—C7	1.396 (5)	C48—N4	1.341 (5)
C6—C11	1.419 (5)	C49—C50	1.395 (5)
C7—C8	1.387 (6)	C49—C54	1.402 (5)
C8—C9	1.376 (6)	C50—C51	1.389 (6)
C9—C10	1.389 (5)	C51—C52	1.379 (6)
C10—C11	1.395 (5)	C52—C53	1.381 (6)
C12—C13	1.409 (5)	C53—C54	1.400 (5)
C12—C17	1.413 (5)	C54—C55	1.468 (6)
C13—C14	1.379 (5)	C55—C56	1.389 (5)
C14—C15	1.387 (6)	C55—N5	1.358 (5)
C15—C16	1.383 (6)	C56—C57	1.378 (6)
C16—C17	1.400 (5)	C57—C58	1.378 (6)
C17—C18	1.458 (5)	C58—C59	1.374 (5)
C18—C19	1.388 (5)	C59—N5	1.345 (5)
C18—N2	1.369 (5)	O4—C60	1.303 (4)
C19—C20	1.372 (6)	C60—C61	1.416 (5)
C20—C21	1.379 (6)	C60—C65	1.423 (5)
C21—C22	1.380 (5)	C61—C62	1.368 (5)
C22—N2	1.348 (5)	C62—C63	1.393 (6)
O1—C23	1.304 (4)	C63—C64	1.379 (5)
C23—C24	1.421 (5)	C64—C65	1.401 (5)
C23—C28	1.416 (5)	C65—C66	1.452 (5)
C24—C25	1.361 (5)	C66—N6	1.283 (4)
C25—C26	1.396 (6)	N6—C67	1.447 (4)
C26—C27	1.371 (5)	C67—C68	1.388 (5)
C27—C28	1.412 (5)	C67—C72	1.382 (5)
C28—C29	1.442 (5)	C68—C69	1.379 (5)
C29—N3	1.285 (5)	C69—C70	1.403 (5)
N3—C30	1.439 (4)	C69—O5	1.371 (4)
C30—C31	1.376 (5)	C70—C71	1.374 (5)
C30—C35	1.399 (5)	C70—O6	1.375 (4)
C31—C32	1.405 (5)	C71—C72	1.394 (5)
C32—C33	1.371 (5)	O5—C73	1.425 (4)
C33—C34	1.409 (5)	O6—C74	1.423 (5)
C33—O2	1.378 (4)	C75—Cl1	1.757 (6)
C34—C35	1.378 (5)	C75—Cl2	1.727 (6)
C34—O3	1.364 (4)	C76—Cl3	1.761 (5)
O2—C36	1.430 (5)	C76—Cl4	1.748 (5)
O3—C37	1.429 (5)	C77—Cl5	1.770 (4)
Ir2—C38	2.000 (4)	C77—Cl6	1.766 (4)
Ir2—N4	2.030 (3)	C78—Cl8A	1.748 (5)
Ir2—C49	2.010 (4)	C78—Cl8B	1.784 (4)
Ir2—N5	2.037 (3)	C78—Cl7	1.727 (5)
Ir2—O4	2.151 (2)

C11—Ir1—N1	80.64 (14)	C49—Ir2—N4	96.13 (14)
C12—Ir1—N1	94.36 (14)	N5—Ir2—C38	97.04 (14)
C12—Ir1—C11	89.53 (14)	N5—Ir2—N4	176.06 (12)
N2—Ir1—N1	174.57 (12)	N5—Ir2—C49	80.52 (14)
N2—Ir1—C11	97.33 (13)	O4—Ir2—C38	174.17 (13)
N2—Ir1—C12	80.55 (14)	O4—Ir2—N4	95.39 (11)
O1—Ir1—N1	94.86 (11)	O4—Ir2—C49	89.50 (12)
O1—Ir1—C11	175.03 (13)	O4—Ir2—N5	86.69 (11)
O1—Ir1—C12	88.70 (12)	N6—Ir2—C38	97.25 (13)
O1—Ir1—N2	86.97 (10)	N6—Ir2—N4	86.08 (12)
N3—Ir1—N1	86.66 (11)	N6—Ir2—C49	175.75 (12)
N3—Ir1—C11	96.53 (13)	N6—Ir2—N5	97.40 (12)
N3—Ir1—C12	173.93 (12)	N6—Ir2—O4	86.67 (10)
N3—Ir1—N2	98.60 (12)	C39—C38—Ir2	128.3 (3)
N3—Ir1—O1	85.26 (10)	C43—C38—Ir2	114.2 (3)
C1—N1—Ir1	123.0 (3)	C43—C38—C39	117.4 (3)
C5—N1—Ir1	116.7 (2)	C40—C39—C38	121.0 (4)
C5—N1—C1	120.3 (3)	C41—C40—C39	121.2 (4)
C2—C1—N1	121.5 (4)	C42—C41—C40	119.2 (4)
C3—C2—C1	118.9 (4)	C43—C42—C41	120.6 (4)
C4—C3—C2	119.8 (4)	C42—C43—C38	120.7 (4)
C5—C4—C3	119.8 (4)	C44—C43—C38	115.2 (3)
C4—C5—N1	119.8 (4)	C44—C43—C42	124.1 (4)
C6—C5—N1	113.4 (3)	C45—C44—C43	127.2 (4)
C6—C5—C4	126.8 (4)	N4—C44—C43	113.6 (3)
C7—C6—C5	123.8 (4)	N4—C44—C45	119.2 (4)
C11—C6—C5	115.1 (3)	C46—C45—C44	120.5 (4)
C11—C6—C7	121.1 (4)	C47—C46—C45	119.3 (4)
C8—C7—C6	119.8 (4)	C48—C47—C46	118.9 (4)
C9—C8—C7	119.9 (4)	N4—C48—C47	122.1 (4)
C10—C9—C8	120.7 (4)	C44—N4—Ir2	116.3 (3)
C11—C10—C9	121.4 (4)	C48—N4—Ir2	123.8 (3)
C6—C11—Ir1	114.2 (3)	C48—N4—C44	119.9 (3)
C10—C11—Ir1	128.7 (3)	C50—C49—Ir2	128.5 (3)
C10—C11—C6	117.1 (3)	C54—C49—Ir2	114.5 (3)
C13—C12—Ir1	128.6 (3)	C54—C49—C50	117.0 (4)
C17—C12—Ir1	114.7 (3)	C51—C50—C49	121.2 (4)
C17—C12—C13	116.6 (3)	C52—C51—C50	120.9 (4)
C14—C13—C12	121.4 (4)	C53—C52—C51	119.6 (4)
C15—C14—C13	121.1 (4)	C54—C53—C52	119.5 (4)
C16—C15—C14	119.4 (4)	C53—C54—C49	121.8 (4)
C17—C16—C15	119.9 (4)	C55—C54—C49	115.1 (3)
C16—C17—C12	121.6 (4)	C55—C54—C53	123.1 (4)
C18—C17—C12	114.9 (3)	C56—C55—C54	125.9 (4)
C18—C17—C16	123.5 (4)	N5—C55—C54	114.0 (3)
C19—C18—C17	126.8 (4)	N5—C55—C56	120.1 (4)
N2—C18—C17	113.8 (3)	C57—C56—C55	120.0 (4)
N2—C18—C19	119.4 (4)	C58—C57—C56	119.5 (4)
C20—C19—C18	121.0 (4)	C59—C58—C57	118.5 (4)
C21—C20—C19	119.1 (4)	N5—C59—C58	122.6 (4)
C22—C21—C20	118.6 (4)	C55—N5—Ir2	115.9 (3)
N2—C22—C21	122.6 (4)	C59—N5—Ir2	124.8 (3)
C18—N2—Ir1	115.8 (2)	C59—N5—C55	119.3 (3)
C22—N2—Ir1	125.0 (3)	C60—O4—Ir2	124.1 (2)
C22—N2—C18	119.2 (3)	C61—C60—O4	118.4 (3)
C23—O1—Ir1	121.7 (2)	C65—C60—O4	125.0 (3)
C24—C23—O1	119.1 (3)	C65—C60—C61	116.6 (3)
C28—C23—O1	124.4 (3)	C62—C61—C60	122.2 (4)
C28—C23—C24	116.4 (3)	C63—C62—C61	121.4 (4)
C25—C24—C23	122.2 (4)	C64—C63—C62	117.7 (4)
C26—C25—C24	121.0 (4)	C65—C64—C63	122.7 (4)
C27—C26—C25	118.7 (4)	C64—C65—C60	119.5 (3)
C28—C27—C26	121.5 (4)	C66—C65—C60	123.7 (3)
C27—C28—C23	120.1 (3)	C66—C65—C64	116.8 (3)
C29—C28—C23	123.3 (3)	N6—C66—C65	127.7 (3)
C29—C28—C27	116.5 (3)	C66—N6—Ir2	124.7 (2)
N3—C29—C28	126.7 (4)	C67—N6—Ir2	119.6 (2)
C29—N3—Ir1	124.0 (2)	C67—N6—C66	115.1 (3)
C30—N3—Ir1	119.8 (2)	C68—C67—N6	119.1 (3)
C30—N3—C29	115.6 (3)	C72—C67—N6	120.4 (3)
C31—C30—N3	120.4 (3)	C72—C67—C68	120.5 (3)
C35—C30—N3	119.2 (3)	C69—C68—C67	119.8 (3)
C35—C30—C31	120.4 (3)	C70—C69—C68	120.0 (3)
C32—C31—C30	119.5 (4)	O5—C69—C68	124.2 (3)
C33—C32—C31	120.4 (4)	O5—C69—C70	115.8 (3)
C34—C33—C32	119.9 (3)	C71—C70—C69	119.7 (3)
O2—C33—C32	124.4 (4)	O6—C70—C69	114.9 (3)
O2—C33—C34	115.7 (3)	O6—C70—C71	125.4 (3)
C35—C34—C33	119.8 (3)	C72—C71—C70	120.5 (3)
O3—C34—C33	115.9 (3)	C71—C72—C67	119.5 (3)
O3—C34—C35	124.3 (3)	C73—O5—C69	116.8 (3)
C34—C35—C30	119.9 (3)	C74—O6—C70	116.5 (3)
C36—O2—C33	116.8 (3)	Cl2—C75—Cl1	111.8 (3)
C37—O3—C34	116.4 (3)	Cl4—C76—Cl3	112.5 (3)
N4—Ir2—C38	80.63 (14)	Cl6—C77—Cl5	111.7 (2)
C49—Ir2—C38	86.71 (14)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N4/C44–C48 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1	0.95 (1)	2.51 (1)	3.112 (5)	121 (1)
C13—H13···Cg1	0.95 (1)	3.06 (4)	3.83 (4)	139 (1)
C74—H74a···Cg1	0.98 (1)	3.40 (17)	4.12 (5)	132 (2)
C48—H48···O4	0.95 (1)	2.56 (1)	3.155 (5)	121 (1)
C36—H36c···Cg2	0.98 (1)	3.47 (19)	4.18 (5)	131 (2)
C50—H50···Cg2	0.95 (1)	3.22 (4)	3.98 (4)	138 (1)
C29—H29···O2ⁱ	0.95 (1)	2.60 (1)	3.152 (5)	118 (1)
C29—H29···O3ⁱ	0.95 (1)	2.52 (1)	3.463 (5)	172 (1)
C58—H58···O6ⁱⁱ	0.95 (1)	2.39 (1)	3.330 (5)	170 (1)
C75—H75A···O4ⁱⁱⁱ	0.99 (1)	2.35 (1)	3.310 (7)	165 (1)
C77—H77A···O1^iv	0.99 (1)	2.19 (1)	3.172 (7)	172 (1)

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

Selected bond lengths (Å) and angles (°) for the title complex top

Molecule 1 (Ir1)		Molecule 2 (Ir2)

Ir1—N1	2.028 (3)	Ir2—C38	2.000 (4)
Ir1—C11	1.998 (4)	Ir2—N4	2.030 (3)
Ir1—C12	1.996 (4)	Ir2—C49	2.010 (4)
Ir1—N2	2.036 (3)	Ir2—N5	2.037 (3)
Ir1—O1	2.147 (2)	Ir2—O4	2.151 (2)
Ir1—N3	2.149 (3)	Ir2—N6	2.146 (3)

C11—Ir1—N1	80.64 (14)	N4—Ir2—C38	80.63 (14)
C12—Ir1—N1	94.36 (14)	C49—Ir2—C38	86.71 (14)
C12—Ir1—C11	89.53 (14)	C49—Ir2—N4	96.13 (14)
N2—Ir1—N1	174.57 (12)	N5—Ir2—C38	97.04 (14)
N2—Ir1—C11	97.33 (13)	N5—Ir2—N4	176.06 (12)
N2—Ir1—C12	80.55 (14)	N5—Ir2—C49	80.52 (14)
O1—Ir1—N1	94.86 (11)	O4—Ir2—C38	174.17 (13)
O1—Ir1—C11	175.03 (13)	O4—Ir2—N4	95.39 (11)
O1—Ir1—C12	88.70 (12)	O4—Ir2—C49	89.50 (12)
O1—Ir1—N2	86.97 (10)	O4—Ir2—N5	86.69 (11)
N3—Ir1—N1	86.66 (11)	N6—Ir2—C38	97.25 (13)
N3—Ir1—C11	96.53 (13)	N6—Ir2—N4	86.08 (12)
N3—Ir1—C12	173.93 (12)	N6—Ir2—C49	175.75 (12)
N3—Ir1—N2	98.60 (12)	N6—Ir2—N5	97.40 (12)
N3—Ir1—O1	85.25 (10)	N6—Ir2—O4	86.67 (10)

Funding information

This work was supported by Kumoh National Institute of Technology.

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