(2-Benzoyl-1-phenyl­ethenolato-κ2O,O′)bis­[2-(1-phenyl-1H-benzimidazol-2-yl)phenyl-κC1]iridium(III) di­chloro­methane disolvate

Bezzubov, S.I.; Doljenko, V.D.; Kurnosov, N.M.; Zharinova, I.S.; Kovalenko, I.V.; Kiselev, Y.M.

doi:10.1107/S2414314616019155

metal-organic compounds

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ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161915

https://doi.org/10.1107/S2414314616019155

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(2-Benzoyl-1-phenylethenolato-κ²O,O′)bis[2-(1-phenyl-1H-benzimidazol-2-yl)phenyl-κC¹]iridium(III) dichloromethane disolvate

Stanislav I. Bezzubov,^a ^* Vladimir D. Doljenko,^b Nikon M. Kurnosov,^b Irina S. Zharinova,^b Ilya V. Kovalenko ^b and Yuri M. Kiselev ^b

^aInstitute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii prosp. 31, Moscow 119991, Russian Federation, and ^bDepartment of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russian Federation
^*Correspondence e-mail: bezzubov@igic.ras.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 23 November 2016; accepted 1 December 2016; online 9 December 2016)

We present here synthesis and crystal structure of a neutral Ir^III complex, [Ir(C₁₉H₁₃N₂)₂(C₁₅H₁₁O₂)]·2CH₂Cl₂ or [Ir(C^N)₂O^O]·2CH₂Cl₂, where C^N is 1,2-diphenyl-1H-benzimidazole and O^O is 2-benzoyl-1-phenylethenolate. The coordination sphere of the Ir^III atom, located on a twofold rotation axis, is that of a slighlty distorted C₂N₂O₂ octahedron, with the N atoms in a trans configuration. In the crystal, complex molecules assemble through weak C—H⋯π interactions in the range 2.699 (3)–2.892 (3) Å. The solvent CH₂Cl₂ molecules reside in channels aligned along the a axis and are connected to the complex molecules by C—H⋯O interactions.

Keywords: crystal structure; iridium complexes; dibenzoylmethane; benzimidazole; trans effect.

CCDC reference: 1517541

Structure description

Cyclometalated Ir^III complexes with benzimidazole derivatives demonstrate unique optical properties, which have been intensively used in creating promising Ir^III-based luminescent and antitumor agents, as well as effective photosensitizers (Huang et al., 2004 ; Yellol et al., 2015 ). The title complex was synthesized in this context. Its molecular structure exhibits point-group symmetry C2, with the Ir^III ion situated on the twofold rotation axis. The central ion shows a distorted octahedral C₂N₂O₂ coordination set formed by two bidentate C^N ligands and one bidentate O^O ligand (Fig. 1). The N atoms adopt a trans configuration other in this octahedron. The Ir—C [1.999 (4) Å] and Ir—N [2.041 (3) Å] bond lengths are significantly shorter than the Ir—O bond length [2.176 (3) Å], which is due to the trans effect exerted by the C-donor atoms of the coordinating C^N ligands. The dihedral angle between the planes of the benzimidazolyl and phenyl units of the C^N ligand is 2.6 (3)°, whereas the plane of the N-phenyl ring is inclined to the 2-phenyl-1H-benzimidazole plane by 80.3 (3)°. There are large channels in the crystal structure passing parallel to the a axis, which are filled by solvent CH₂Cl₂ molecules. These molecules form weak C—H⋯O hydrogen bonds with O atoms of the Ir^III complex molecules with an almost ideal D—H⋯A angle of 179° (Table 1). Other intermolecular interactions between complex molecules include weak C—H⋯π interactions [range 2.699 (3)–2.892 (3) Å] involving phenyl H atoms and the centroids of the benzimidazole rings. The packing of the molecules is displayed in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C31—H31A⋯O1ⁱ	0.99	2.39	3.377 (6)	179
Symmetry code: (i) $[-x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of [Ir(C^N)₂(O^O)]. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. The suffix A in atom labels indicates the symmetry operator (−x, −y, z). The solvent molecule is not shown.

Figure 2
The crystal packing of the title complex.

The structures of similar benzimidazole-based Ir^III complexes have been reported by Bezzubov et al. (2014 , 2016 ).

Synthesis and crystallization

The title complex was synthesized by a two-step procedure. (i) IrCl₃·3H₂O (80 mg, 0.25 mmol) and 1,2-diphenylbenzimidazole (259 mg, 0.96 mmol) in a mixture of 2-ethoxyethanol and water (3:1 v/v, 10 ml) were refluxed for 20 h under an argon atmosphere and cooled to room temperature. Distilled water (3 ml) was added and the precipitate which formed was collected by filtration, washed several times with water, ethanol and acetone, and dried in vacuo for 12 h. (ii) The crude μ-chlorido-bridged iridium dimer (70 mg, 0.046 mmol), dibenzoylmethane (20.6 mg, 0.092 mmol) and Na₂CO₃ (50 mg, 0.47 mmol) in 2-ethoxyethanol (5 ml) were refluxed under an argon atmosphere for 12 h and cooled to room temperature. Distilled water (2 ml) was added and the precipitate which formed was collected by filtration, washed several times with water and dried in vacuo. The orange solid was extracted with CH₂Cl₂ and the extract was purified by column chromatography (SiO₂, CH₂Cl₂/hexane 1:1 v/v) (yield: 47 mg, 54%). Single crystals of the desired complex were grown by slow evaporation of the solvent from a solution of the complex in CH₂Cl₂.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95–1.00 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise.

Table 2
Experimental details

Crystal data
Chemical formula	[Ir(C₁₉H₁₃N₂)₂(C₁₅H₁₁O₂)]·2CH₂Cl₂
M_r	1123.92
Crystal system, space group	Orthorhombic, Aba2
Temperature (K)	150
a, b, c (Å)	13.9159 (7), 25.5352 (12), 13.0898 (6)
V (Å³)	4651.4 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.15
Crystal size (mm)	0.40 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
No. of measured, independent and observed [I > 2σ(I)] reflections	21901, 6169, 5029
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.043, 1.07
No. of reflections	6169
No. of parameters	299
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.46
Absolute structure	Flack x determined using 2201 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.007 (3)
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1517541

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019155/wm4034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019155/wm4034Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(2-Benzoyl-1-phenylethenolato-κ²O,O')bis[2-(1-phenyl-1H-benzimidazol-2-yl)phenyl-κC¹]iridium(III) dichloromethane disolvate top

Crystal data top

[Ir(C₁₉H₁₃N₂)₂(C₁₅H₁₁O₂)]·2CH₂Cl₂	D_x = 1.605 Mg m⁻³
M_r = 1123.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Aba2	Cell parameters from 9873 reflections
a = 13.9159 (7) Å	θ = 2.2–30.5°
b = 25.5352 (12) Å	µ = 3.15 mm⁻¹
c = 13.0898 (6) Å	T = 150 K
V = 4651.4 (4) Å³	Plate, orange
Z = 4	0.40 × 0.25 × 0.15 mm
F(000) = 2240

Data collection top

Bruker SMART APEXII diffractometer	5029 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
ω scans	θ_max = 29.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −18→18
	k = −34→34
21901 measured reflections	l = −17→17
6169 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.018	w = 1/[σ²(F_o²) + (0.0163P)² + 6.3016P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.043	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 1.07 e Å⁻³
6169 reflections	Δρ_min = −0.46 e Å⁻³
299 parameters	Absolute structure: Flack x determined using 2201 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.007 (3)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ir1	0.0000	0.0000	0.87622 (4)	0.01596 (4)
O1	−0.0422 (2)	0.05472 (12)	0.7569 (2)	0.0202 (6)
N1	−0.12555 (19)	−0.04069 (10)	0.8901 (2)	0.0173 (6)
N2	−0.2133 (2)	−0.10159 (12)	0.9688 (2)	0.0202 (6)
C1	0.0377 (3)	−0.05237 (16)	0.9825 (3)	0.0169 (8)
C2	0.1284 (3)	−0.06017 (15)	1.0264 (3)	0.0206 (7)
H6A	0.1799	−0.0378	1.0070	0.025*
C3	0.1456 (3)	−0.09984 (15)	1.0979 (3)	0.0250 (8)
H5A	0.2084	−0.1044	1.1250	0.030*
C4	0.0721 (3)	−0.13256 (18)	1.1296 (3)	0.0261 (10)
H4A	0.0839	−0.1586	1.1798	0.031*
C5	−0.0197 (3)	−0.12704 (16)	1.0873 (3)	0.0238 (8)
H3A	−0.0704	−0.1496	1.1076	0.029*
C6	−0.0357 (3)	−0.08776 (15)	1.0147 (3)	0.0199 (7)
C7	−0.1252 (3)	−0.07847 (14)	0.9607 (3)	0.0187 (7)
C8	−0.2463 (3)	−0.14125 (14)	1.0383 (3)	0.0209 (7)
C9	−0.2713 (3)	−0.12733 (17)	1.1363 (3)	0.0312 (10)
H15A	−0.2627	−0.0923	1.1591	0.037*
C10	−0.3093 (3)	−0.16477 (19)	1.2019 (3)	0.0385 (11)
H16A	−0.3261	−0.1556	1.2699	0.046*
C11	−0.3226 (3)	−0.21529 (18)	1.1675 (4)	0.0346 (10)
H17A	−0.3492	−0.2409	1.2119	0.042*
C12	−0.2977 (4)	−0.22885 (18)	1.0693 (4)	0.0403 (11)
H19A	−0.3065	−0.2638	1.0464	0.048*
C13	−0.2600 (3)	−0.19165 (17)	1.0038 (3)	0.0360 (10)
H18A	−0.2437	−0.2008	0.9356	0.043*
C14	−0.2745 (3)	−0.07636 (14)	0.8998 (2)	0.0208 (8)
C15	−0.3710 (2)	−0.08408 (13)	0.8788 (4)	0.0246 (6)
H12A	−0.4077	−0.1102	0.9127	0.029*
C16	−0.4109 (3)	−0.05164 (17)	0.8058 (3)	0.0271 (8)
H11A	−0.4769	−0.0555	0.7889	0.033*
C17	−0.3568 (3)	−0.01333 (15)	0.7562 (3)	0.0244 (8)
H10A	−0.3870	0.0079	0.7060	0.029*
C18	−0.2600 (3)	−0.00515 (14)	0.7776 (3)	0.0219 (7)
H9A	−0.2237	0.0213	0.7441	0.026*
C19	−0.2191 (2)	−0.03793 (14)	0.8509 (2)	0.0179 (7)
C20	0.0000	0.0000	0.6161 (4)	0.0263 (11)
H21A	0.0000	0.0000	0.5435	0.032*
C21	−0.0349 (3)	0.04551 (14)	0.6622 (3)	0.0194 (7)
C22	−0.0652 (3)	0.08839 (15)	0.5905 (3)	0.0213 (7)
C23	−0.0429 (3)	0.13971 (18)	0.6134 (3)	0.0290 (10)
H24A	−0.0113	0.1478	0.6759	0.035*
C24	−0.0662 (4)	0.17976 (18)	0.5457 (4)	0.0381 (11)
H25A	−0.0493	0.2149	0.5614	0.046*
C25	−0.1137 (3)	0.16867 (17)	0.4558 (3)	0.0362 (10)
H26A	−0.1301	0.1961	0.4100	0.043*
C26	−0.1373 (3)	0.11718 (17)	0.4325 (3)	0.0294 (9)
H27A	−0.1708	0.1094	0.3711	0.035*
C27	−0.1123 (3)	0.07730 (16)	0.4986 (3)	0.0243 (8)
H28A	−0.1272	0.0421	0.4815	0.029*
C31	0.1018 (3)	0.32965 (17)	0.3649 (4)	0.0386 (11)
H31A	0.0838	0.3634	0.3331	0.046*
H31B	0.1283	0.3370	0.4336	0.046*
Cl1	−0.00094 (11)	0.28980 (5)	0.3765 (3)	0.0586 (3)
Cl2	0.18966 (10)	0.29873 (7)	0.28987 (11)	0.0620 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01740 (7)	0.01518 (7)	0.01531 (6)	0.00053 (8)	0.000	0.000
O1	0.0239 (16)	0.0183 (16)	0.0183 (13)	0.0011 (12)	0.0007 (12)	0.0014 (12)
N1	0.0189 (12)	0.0176 (13)	0.0153 (17)	0.0023 (10)	−0.0004 (11)	0.0010 (12)
N2	0.0207 (15)	0.0215 (15)	0.0184 (14)	−0.0016 (12)	−0.0006 (12)	0.0039 (12)
C1	0.023 (2)	0.015 (2)	0.0127 (16)	0.0016 (16)	0.0002 (15)	−0.0030 (14)
C2	0.0211 (17)	0.0209 (18)	0.0200 (17)	0.0011 (14)	−0.0008 (14)	−0.0009 (14)
C3	0.0244 (19)	0.026 (2)	0.0248 (19)	0.0071 (15)	−0.0053 (15)	−0.0015 (15)
C4	0.029 (2)	0.029 (2)	0.0205 (18)	0.0084 (17)	−0.0044 (16)	0.0054 (16)
C5	0.025 (2)	0.025 (2)	0.0208 (17)	0.0004 (14)	0.0028 (14)	0.0046 (15)
C6	0.0203 (16)	0.0210 (19)	0.0183 (17)	0.0030 (15)	−0.0001 (14)	0.0001 (14)
C7	0.0212 (17)	0.0172 (17)	0.0177 (17)	0.0007 (13)	−0.0001 (13)	−0.0006 (14)
C8	0.0178 (16)	0.0234 (18)	0.0214 (17)	−0.0011 (14)	0.0006 (13)	0.0050 (15)
C9	0.039 (3)	0.030 (2)	0.025 (2)	−0.0131 (17)	0.0054 (19)	−0.0043 (17)
C10	0.045 (3)	0.050 (3)	0.0197 (19)	−0.016 (2)	0.0026 (18)	0.0027 (19)
C11	0.035 (2)	0.034 (2)	0.035 (2)	−0.0056 (18)	0.0003 (19)	0.0153 (19)
C12	0.056 (3)	0.019 (2)	0.047 (3)	−0.003 (2)	0.011 (2)	0.0046 (19)
C13	0.048 (3)	0.025 (2)	0.034 (2)	−0.0034 (19)	0.016 (2)	−0.0020 (18)
C14	0.0225 (17)	0.0207 (17)	0.019 (2)	0.0036 (13)	−0.0003 (12)	0.0006 (12)
C15	0.0214 (15)	0.0263 (16)	0.0261 (16)	−0.0036 (12)	0.003 (2)	0.003 (2)
C16	0.0193 (18)	0.033 (2)	0.029 (2)	0.0011 (16)	−0.0023 (15)	0.0007 (17)
C17	0.0247 (18)	0.026 (2)	0.0222 (17)	0.0053 (14)	−0.0022 (15)	0.0028 (14)
C18	0.0244 (17)	0.0218 (19)	0.0195 (15)	0.0015 (15)	0.0016 (13)	0.0014 (15)
C19	0.0184 (16)	0.0188 (16)	0.0166 (17)	0.0016 (13)	−0.0006 (11)	−0.0004 (12)
C20	0.034 (3)	0.028 (3)	0.017 (2)	0.008 (3)	0.000	0.000
C21	0.0167 (15)	0.0215 (18)	0.0202 (16)	0.0004 (14)	0.0001 (14)	0.0021 (14)
C22	0.0217 (17)	0.0227 (19)	0.0196 (16)	0.0022 (14)	0.0011 (14)	0.0035 (14)
C23	0.035 (2)	0.026 (2)	0.026 (2)	−0.0007 (19)	−0.0047 (19)	−0.0026 (18)
C24	0.055 (3)	0.021 (2)	0.038 (2)	−0.0029 (19)	−0.007 (2)	0.0073 (18)
C25	0.045 (3)	0.028 (2)	0.036 (2)	0.0024 (19)	−0.006 (2)	0.0135 (19)
C26	0.032 (2)	0.034 (2)	0.0227 (19)	0.0030 (18)	−0.0063 (16)	0.0050 (16)
C27	0.0248 (19)	0.0247 (19)	0.0235 (19)	0.0007 (15)	−0.0011 (15)	0.0016 (15)
C31	0.049 (2)	0.033 (2)	0.034 (3)	0.0042 (17)	−0.008 (2)	−0.007 (2)
Cl1	0.0683 (7)	0.0556 (6)	0.0518 (6)	−0.0168 (7)	−0.0125 (7)	0.0098 (18)
Cl2	0.0531 (8)	0.0838 (11)	0.0490 (7)	0.0266 (8)	−0.0111 (6)	−0.0246 (7)

Geometric parameters (Å, º) top

Ir1—C1ⁱ	1.999 (4)	C12—H19A	0.9500
Ir1—C1	1.999 (4)	C13—H18A	0.9500
Ir1—N1ⁱ	2.041 (3)	C14—C15	1.386 (5)
Ir1—N1	2.041 (3)	C14—C19	1.402 (5)
Ir1—O1ⁱ	2.176 (3)	C15—C16	1.381 (6)
Ir1—O1	2.176 (3)	C15—H12A	0.9500
O1—C21	1.267 (5)	C16—C17	1.395 (6)
N1—C7	1.337 (4)	C16—H11A	0.9500
N1—C19	1.400 (4)	C17—C18	1.392 (5)
N2—C7	1.365 (5)	C17—H10A	0.9500
N2—C14	1.398 (4)	C18—C19	1.395 (5)
N2—C8	1.436 (5)	C18—H9A	0.9500
C1—C2	1.402 (6)	C20—C21ⁱ	1.397 (4)
C1—C6	1.427 (6)	C20—C21	1.397 (4)
C2—C3	1.400 (5)	C20—H21A	0.9500
C2—H6A	0.9500	C21—C22	1.502 (5)
C3—C4	1.385 (6)	C22—C23	1.380 (6)
C3—H5A	0.9500	C22—C27	1.400 (5)
C4—C5	1.399 (5)	C23—C24	1.392 (6)
C4—H4A	0.9500	C23—H24A	0.9500
C5—C6	1.400 (5)	C24—C25	1.379 (6)
C5—H3A	0.9500	C24—H25A	0.9500
C6—C7	1.451 (5)	C25—C26	1.389 (6)
C8—C9	1.377 (5)	C25—H26A	0.9500
C8—C13	1.377 (5)	C26—C27	1.380 (5)
C9—C10	1.389 (6)	C26—H27A	0.9500
C9—H15A	0.9500	C27—H28A	0.9500
C10—C11	1.379 (7)	C31—Cl2	1.755 (5)
C10—H16A	0.9500	C31—Cl1	1.762 (5)
C11—C12	1.375 (7)	C31—H31A	0.9900
C11—H17A	0.9500	C31—H31B	0.9900
C12—C13	1.383 (6)

C1ⁱ—Ir1—C1	91.9 (2)	C11—C12—C13	120.1 (4)
C1ⁱ—Ir1—N1ⁱ	79.76 (15)	C11—C12—H19A	119.9
C1—Ir1—N1ⁱ	93.11 (15)	C13—C12—H19A	119.9
C1ⁱ—Ir1—N1	93.11 (15)	C8—C13—C12	119.4 (4)
C1—Ir1—N1	79.76 (15)	C8—C13—H18A	120.3
N1ⁱ—Ir1—N1	169.81 (18)	C12—C13—H18A	120.3
C1ⁱ—Ir1—O1ⁱ	177.96 (17)	C15—C14—N2	130.7 (4)
C1—Ir1—O1ⁱ	89.94 (10)	C15—C14—C19	122.8 (3)
N1ⁱ—Ir1—O1ⁱ	99.17 (12)	N2—C14—C19	106.4 (3)
N1—Ir1—O1ⁱ	88.17 (12)	C16—C15—C14	116.2 (4)
C1ⁱ—Ir1—O1	89.94 (10)	C16—C15—H12A	121.9
C1—Ir1—O1	177.96 (17)	C14—C15—H12A	121.9
N1ⁱ—Ir1—O1	88.17 (12)	C15—C16—C17	121.7 (4)
N1—Ir1—O1	99.17 (12)	C15—C16—H11A	119.1
O1ⁱ—Ir1—O1	88.29 (16)	C17—C16—H11A	119.1
C21—O1—Ir1	124.2 (3)	C18—C17—C16	122.3 (4)
C7—N1—C19	107.0 (3)	C18—C17—H10A	118.9
C7—N1—Ir1	115.2 (2)	C16—C17—H10A	118.9
C19—N1—Ir1	137.5 (2)	C17—C18—C19	116.3 (3)
C7—N2—C14	107.3 (3)	C17—C18—H9A	121.8
C7—N2—C8	129.8 (3)	C19—C18—H9A	121.8
C14—N2—C8	122.6 (3)	C18—C19—N1	131.4 (3)
C2—C1—C6	115.7 (4)	C18—C19—C14	120.6 (3)
C2—C1—Ir1	128.1 (3)	N1—C19—C14	108.0 (3)
C6—C1—Ir1	116.2 (3)	C21ⁱ—C20—C21	128.8 (5)
C3—C2—C1	122.1 (4)	C21ⁱ—C20—H21A	115.6
C3—C2—H6A	119.0	C21—C20—H21A	115.6
C1—C2—H6A	119.0	O1—C21—C20	127.3 (4)
C4—C3—C2	120.7 (4)	O1—C21—C22	117.0 (3)
C4—C3—H5A	119.6	C20—C21—C22	115.8 (3)
C2—C3—H5A	119.6	C23—C22—C27	119.0 (4)
C3—C4—C5	119.7 (4)	C23—C22—C21	119.5 (4)
C3—C4—H4A	120.2	C27—C22—C21	121.4 (3)
C5—C4—H4A	120.2	C22—C23—C24	120.4 (4)
C4—C5—C6	119.1 (4)	C22—C23—H24A	119.8
C4—C5—H3A	120.4	C24—C23—H24A	119.8
C6—C5—H3A	120.4	C25—C24—C23	120.3 (4)
C5—C6—C1	122.7 (4)	C25—C24—H25A	119.9
C5—C6—C7	125.8 (4)	C23—C24—H25A	119.9
C1—C6—C7	111.5 (3)	C24—C25—C26	119.7 (4)
N1—C7—N2	111.2 (3)	C24—C25—H26A	120.2
N1—C7—C6	117.3 (3)	C26—C25—H26A	120.2
N2—C7—C6	131.5 (3)	C27—C26—C25	120.1 (4)
C9—C8—C13	120.8 (4)	C27—C26—H27A	119.9
C9—C8—N2	119.3 (3)	C25—C26—H27A	119.9
C13—C8—N2	119.7 (3)	C26—C27—C22	120.5 (4)
C8—C9—C10	119.6 (4)	C26—C27—H28A	119.8
C8—C9—H15A	120.2	C22—C27—H28A	119.8
C10—C9—H15A	120.2	Cl2—C31—Cl1	110.7 (3)
C11—C10—C9	119.6 (4)	Cl2—C31—H31A	109.5
C11—C10—H16A	120.2	Cl1—C31—H31A	109.5
C9—C10—H16A	120.2	Cl2—C31—H31B	109.5
C12—C11—C10	120.5 (4)	Cl1—C31—H31B	109.5
C12—C11—H17A	119.8	H31A—C31—H31B	108.1
C10—C11—H17A	119.8

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C31—H31A···O1ⁱⁱ	0.99	2.39	3.377 (6)	179

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

Acknowledgements

This work was supported by RFBR (project No. 16-33-00604 `mol-a').

References

Bezzubov, S. I., Doljenko, V. D., Troyanov, S. I. & Kiselev, Y. M. (2014). Inorg. Chim. Acta, 415, 22–30. CSD CrossRef CAS Google Scholar
Bezzubov, S. I., Kiselev, Y. M., Churakov, A. V., Kozyukhin, S. A., Sadovnikov, A. A., Grinberg, V. A., Emets, V. V. & Doljenko, V. D. (2016). Eur. J. Inorg. Chem. pp. 347–354. CSD CrossRef Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Huang, W. S., Lin, J. T., Chien, C. H., Tao, Y. T., Sun, S. S. & Wen, Y. S. (2004). Chem. Mater. 16, 2480–2488. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Yellol, G. S., Yellol, J. G., Kenche, V. B., Liu, X. M., Barnham, K. J., Donaire, A., Janiak, C. & Ruiz, J. (2015). Inorg. Chem. 54, 470–475. CSD CrossRef CAS Google Scholar

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