Synthesis, crystal structure and Hirshfeld surface analysis of [bis­(di­phenyl­phosphan­yl)methane-κP]chloridobis­[2-(pyridin-2-yl)phenyl-κ2N,C1]iridium(III)

Klaimanee, E.; Sangwisut, P.; Saithong, S.; Leesakul, N.

doi:10.1107/S2056989021000955

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 3| March 2021| Pages 217-221

https://doi.org/10.1107/S2056989021000955

Open

access

Synthesis, crystal structure and Hirshfeld surface analysis of [bis(diphenylphosphanyl)methane-κP]chloridobis[2-(pyridin-2-yl)phenyl-κ²N,C¹]iridium(III)

Ekkapong Klaimanee,^a Peerapong Sangwisut,^a Saowanit Saithong ^a and Nararak Leesakul ^a ^*

^aDivision of Physical Science and Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla, 90112, Thailand
^*Correspondence e-mail: nararak.le@psu.ac.th

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 January 2021; accepted 27 January 2021; online 2 February 2021)

The title Ir^III complex, [Ir(C₁₁H₈N)₂Cl(C₂₅H₂₂P₂)], was synthesized from the substitution reaction between the (ppy)₂Ir(μ-Cl)₂Ir(ppy)₂ (ppy = deprotonated 2-phenylpyridine, C₁₁H₈N⁻) dimer and 1,1-bis(diphenylphosphanyl)methane (dppm, C₂₅H₂₂P₂) under an argon gas atmosphere for 20 h. The Ir^III atom is coordinated by two C,N-bidentate ppy anions, a unidentate dppm ligand and a chloride anion in a distorted octahedral IrC₂N₂PCl arrangement. The N donor atoms of the ppy ligands are mutually trans while the C atoms are cis. Intramolecular aromatic π–π stacking between the phenyl rings of ppy and dppm, and C—H⋯Cl interactions are observed. In the crystal, C—H⋯Cl and C—H⋯π contacts link the molecules into a three-dimensional network. A Hirshfeld surface analysis was carried out to further quantify the intermolecular interactions, and indicated that H⋯H contacts (63.9%) dominate the packing.

Keywords: crystal structure; iridium; 2-phenylpyridine; diphenylphosphanylmethane.

CCDC reference: 2058995

1. Chemical context

Iridium(III) complexes have been investigated for decades because of their stability (Jian et al., 2011 ; Lee et al., 2009 ; Tsuboyama et al., 2003 ), promising luminescent properties (Lin et al., 2011 ; Lowry et al., 2004 ; Tamayo et al., 2003 ) and medicinal applications, especially as anticancer agents (Hearn et al., 2018 ; Rubio et al., 2020 ; Xiao et al., 2018 ). The syntheses of cyclometallated iridium(III) complexes have mainly focused on the 2-phenylpyridine (ppy) ligand and its derivatives. The octahedral geometry of bis-complexes is commonly selected as the main backbone accompanied by various types of ancillary ligands. Most of them are N-donor ligands (Chi & Chou, 2010 ; Goldsmith et al., 2005 ; Lin et al., 2011) owing to the strong binding of the borderline acid metal and basic ligand. However, there are fewer reports of P-donor ancillary ligands. In this present work, we report the synthesis and characterization of the title photoactive complex, (I), obtained by the reaction between (ppy)₂Ir(μ-Cl)₂Ir(ppy)₂) dimer (ppy = deprotonated 2-phenylpyridine, C₁₁H₈N⁻) with 1,1-bis(diphenylphosphanyl)methane under an inert gas atmosphere.

2. Structural commentary

The asymmetric unit of (I) shows a distorted octahedral molecular structure to overcome steric hindrance between the ligands (Fig. 1) in space group P2₁/n. The Ir^III atom is linked to two C,N-bidentate 2-phenylpyridine (ppy) anions through five-membered chelate rings where the N1 and N2 atoms of the ppy pyridine rings exist in a trans orientation to each other [N1—Ir1—N2 = 170.97 (9)°] and C11 and C22 are in cis orientation [C11—Ir1—C22 = 91.12 (11)°]. The bond lengths of Ir1—N1, Ir1—N2, Ir1—C11 and Ir1—C22 are 2.051 (2), 2.062 (2), 2.004 (3) and 2.032 (3) Å, respectively. As expected, the averaged Ir–C and Ir—N bond lengths are much shorter than the Ir—Cl and Ir—P bonds, based on the sizes of the different species.

Figure 1
The molecular structure of the title compound, including atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

The averaged Ir—N and Ir—C distances in (I) are both slightly shorter than those in [Ir(ppy)₂(dppm)]PF₆ (Hao et al., 2019 ). However, the averaged Ir—N distance is a little longer, but the Ir—C bond lengths are relatively shorter than those of related Ir^III complexes bonded with ppy ligands (Chen et al., 2015 ; Shen et al., 2011 ; Wang et al., 2005 )

Although bis(diphenylphosphanyl)methane (dppm) often occurs as a bidentate ligand (e.g., Hao et al., 2019), in (I) it is unidentate [Ir1—P1 = 2.4241 (7) Å]. This Ir—P distance is somewhat longer than that in the [Ir(ppy)₂(dppm)](PF₆) (Hao et al., 2019) complex. The Ir—Cl bond distances in chlorobis[2-(2-pyridyl)phenyl-κ²N,C](triphenylphosphine-κP)iridium(III) are reported to be 2.503 (19) (Wang et al., 2005) and 2.505 (16) (Shen et al., 2011) Å, which are slightly longer than that in (I) [Ir1—Cl1 = 2.4866 (8) Å]. The cis bond angles in (I) all deviate from the ideal value of 90° [80.07 (10)–95.27 (7)°] and likewise, the trans bond angles deviate from the ideal 180° [170.97 (9)–175.37 (8)°], similar to related compounds (Shen et al., 2011; Wang et al., 2005). The dihedral angle between the mean planes of the ppy rings is 77.98 (4)°, indicating the cis-form of the chelate rings. Key geometrical data are given in Table 1.

Table 1
Selected geometric parameters (Å, °)

Ir1—C11	2.004 (3)	Ir1—N2	2.062 (2)
Ir1—C22	2.032 (3)	Ir1—P1	2.4241 (7)
Ir1—N1	2.051 (2)	Ir1—Cl1	2.4866 (8)

C11—Ir1—C22	91.12 (11)	N1—Ir1—P1	85.83 (6)
C11—Ir1—N1	80.35 (10)	N2—Ir1—P1	101.93 (6)
C22—Ir1—N1	92.62 (10)	C11—Ir1—Cl1	175.37 (8)
C11—Ir1—N2	94.40 (10)	C22—Ir1—Cl1	87.54 (8)
C22—Ir1—N2	80.07 (10)	N1—Ir1—Cl1	95.27 (7)
N1—Ir1—N2	170.97 (9)	N2—Ir1—Cl1	89.74 (7)
C11—Ir1—P1	93.75 (8)	P1—Ir1—Cl1	87.41 (3)
C22—Ir1—P1	174.57 (8)

Intramolecular π–π stacking interactions are observed for (I). The π–π stackings are found between two phenyl rings (C6–C11 and C23–C28) of the ppy and dppm ligands, Cg5⋯Cg7 = 3.621 (1) Å and between the phenyl rings of the dppm molecule (C29–C34 and C36–C41), Cg8⋯Cg9 = 3.997 (1) Å (Fig. 2). Three weak intramolecular hydrogen-bonding interactions, viz. C1—H1⋯Cl1 [C⋯Cl = 3.357 (3) Å], C30—H30⋯Cl1 [C⋯Cl = 3.664 (4) Å] and C35—H35A⋯Cl1 [C35⋯Cl = 3.460 (3) Å] (Fig. 3 and Table 2) are observed.

Table 2
Hydrogen-bond geometry (Å, °)

Cg6, Cg8 and Cg10 are the centroids of the C17–C22, C29–C34 and C42–C47 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1	0.93	2.73	3.357 (3)	126
C14—H14⋯Cl1ⁱ	0.93	2.77	3.548 (4)	142
C30—H30⋯Cl1	0.93	2.84	3.664 (4)	148
C35—H35A⋯Cl1	0.97	2.83	3.460 (3)	124
C3—H3⋯Cg6ⁱⁱ	0.93	2.83	3.572 (4)	137
C26—H26⋯Cg10ⁱⁱⁱ	0.93	2.79	3.575 (5)	143
C38—H38⋯C10ⁱⁱⁱ	0.93	2.81	3.659 (5)	153
C40—H40⋯Cg8^iv	0.93	2.95	3.711 (5)	140
Symmetry codes: (i) ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

Figure 2
Intramolecular π–π interactions occurred between the phenyl rings of the complex (H atoms are omitted).

Figure 3
The intramolecular C—H⋯Cl interactions in the title compound

3. Supramolecular features

Several weak C—H⋯π (ring) interactions are found in the crystal packing (Fig. 4). The interactions are observed between any two adjacent molecules of ppy via the C3—H3 grouping of the pyridine ring and the centroid (Cg6) of the C17–C22 phenyl ring (H3⋯Cg6 = 2.83 Å). In addition, C—H⋯π(ring) interactions are also found between the dppm phenyl rings of neighbouring molecules: C26—H26 ⋯Cg10 (H26⋯Cg10 = 2.79 Å; Cg10 is the centroid of the C42–C47 ring), C38—H38⋯Cg10 (H38⋯Cg10 = 2.81 Å) and C40—H40⋯Cg8 (H40⋯Cg8 = 2.95 Å). In addition, pairwise intermolecular hydrogen bonds are observed between C14—H14 of the pyridine ring of the ppy ring and Cl1 (Table 2).

Figure 4
The intermolecular C—H⋯·π interactions in the title compound.

4. Hirshfeld surface analysis

Additional insights into the weak intermolecular contacts in the crystal packing of (I) were gained from Hirshfeld surface analysis and the two-dimensional fingerprint plots (McKinnon et al., 2004 ; 2007 ; Spackman & Jayatilaka, 2009 ) generated using Crystal Explorer 17.5 program (Turner et al., 2017 ). The Hirshfeld surfaces were mapped over the normalized contact distance (d_norm) with the functions d_e and d_i, which are the distances from an indicated area on the Hirshfeld surface to the nearest atoms outside and inside the surface, respectively. The white, red, and blue areas on the d_norm-mapped Hirshfeld surfaces show intermolecular contacts that are equal to, shorter than, and longer than the sum of their van der Waals (vdW) radii, respectively. A pair of intermolecular contacts are shown as red spots on the Hirshfeld surface close to the Cl1 atom of the adjoining molecule and the H14 atom of the associated pyridine ring. The spots indicate hydrogen-bond donor-to-acceptor interactions of C14—H14⋯Cl1 and vice versa (Fig. 5). The relative contributions of the various types of contacts to the total of intermolecular interactions across the Hirshfeld surface are represented in two-dimensional fingerprint plots. Total intermolecular interactions (100%) are shown in Fig. 6(a) while Fig. 6(b)–(d) depict the contacts of the H⋯H (63.9%), C⋯H/H⋯C (29.5%) and H⋯Cl/Cl⋯H (4.4%) interactions, respectively.

Figure 5
Hirshfeld surface plot showing the C—H⋯·Cl interactions.

Figure 6
Fingerprint plots corresponding to intermolecular contacts in the crystal: (a) all interactions, (b) H⋯H contacts, (c) H⋯C/C⋯H and (d) H⋯Cl/Cl⋯H.

5. Database survey

A search of the SciFinder (SciFinder, 2020 ) database for phosphorescent complexes of ppy with iridium(III) diphosphine (dpp) reveals eight structures closely related to the title compound. Hao et al. (2019) report the crystal structure of an ionic complex of the [Ir(ppy)₂(dppm)]⁺; dppm = bis(diphenylphosphanyl)methane bidentate ligand. However, none of the remaining publications describe a monomeric Ir^III complex similar to the title compound. The seven hits include the octahedral crystal structures of Ir^III complexes with a bis(2-phenylpyridine)iridium(III) backbone and ancillary ligands of both N-donor, P-donor and O-donor ligands. There are a tris-complex of Ir(ppy)₃ (Huynh et al., 2005 ), [Ir(ppy)₂(dppel)]; dppel = 1,2-bis(diphenylphosphanyl)ethylene, [Ir(ppy)₂(dppp)]; dppp = 1,3-bis(diphenylphosphanyl)propane and [Ir(ppy)₂(dppe)]; dppe = 1,2-bis(diphenylphosphanyl) ethane] (Alam et al., 2013 ), [Ir(ppy)₂L₂]⁺ (L₂ = substituted 2,2′-bipyridine, dppe and 1,10-phenanthroline; Lowry & Bernhard, 2006 ), [Ir(ppy)₂(P^N)]PF₆, [Ir(dfppy)₂(P^N)]PF₆ and [Ir(dfmppy)₂(P^N)]PF₆ where P^N = 2-[(diphenylphosphanyl) methyl]pyridine, dfppy = 2-(2,4-difuorophenyl)pyridine and dfmppy = 2-(2,4-difluorophenyl)-4-methylpyridine (Ma et al., 2009 ), [Ir(ppy)₂(biq)]PF₆ (biq = 2,2-biquinoline; Nishikitani et al., 2018 ) and Ir(dppy)₂(acac) (dppy = 2,5-diphenylpyridyl and acac = acetylacetonate; Xu et al., 2005 ). There are four other related complexes, Ir(ppy)₂(L) [L = 1,2-bis(diphenylphosphanyl)ethane, 1,2-bis (diphenylphosphanyl)propane, 1,2-bis(diphenylphos phino)benzene and 1,8-bis(diphenylphos phino)naphthalene; Liu et al., 2019 ; Luo et al., 2013 ] and Ir(ppy)₂(PPh₃)Cl (Wang et al., 2005).

6. Synthesis and crystallization

The title complex was synthesized from the reaction between (ppy)₂Ir(μ-Cl)2Ir(ppy)₂ (0.5 mmol) and bis(diphenylphosphanyl)methane (1.25 mmol) in CH₂Cl₂ solution. The reaction was carried out by refluxing the mixture under Ar gas for 20 h. The solution mixture was then cooled to room temperature and the solvent was evaporated. The crude yellow product thus obtained was washed with diethyl ether to remove excess ligands and impurities, and the complex was crystallized and recrystallized in mixed solvents of dichloromethane:diethyl ether (9:1) at room temperature three times, yielding yellowish crystals (yield = 30%), m.p. = 488–489 K IR (KBr, cm⁻¹): ν(C—H), 3054; ν(C=C), 1436, 2367; ν(C—N), 1030; ν(C=N), 1613; ν(P—Ph), 1098; ν(Ir—P), 760; ν(Ir—N), 733; ν(Ir—Cl), 510. Analysis (%): found C 61.01, H 4.38, N 2.77; calculated C 61.33, H 4.16, N 3.04.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were included in calculated positions [C—H = 0.93 (aromatic) or 0.97 Å (Csp²)] and refined as riding with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Ir(C₁₁H₈N)₂Cl(C₂₅H₂₂P₂)]
M_r	920.38
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.4506 (5), 15.4490 (5), 17.8532 (6)
β (°)	103.044 (1)
V (Å³)	3882.8 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.63
Crystal size (mm)	0.19 × 0.09 × 0.06

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.800, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	35153, 9248, 7758
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.062, 1.05
No. of reflections	9248
No. of parameters	478
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.33
Computer programs: SMART and SAINT (Bruker, 2003), SHELXT2014 (Sheldrick, 2015a ), ShelXle (Hübschle et al., 2011 ), SHELXL2014/7 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ), WinGX publication routines (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2058995

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021000955/hb7961sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021000955/hb7961Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021000955/hb7961Isup3.mol

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: ShelXle (Hübschle et al., 2011), SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010).

[Bis(diphenylphosphanyl)methane-κP]chloridobis[2-(pyridin-2-yl)phenyl-κ²N,C¹]iridium(III) top

Crystal data top

[Ir(C₁₁H₈N)₂Cl(C₂₅H₂₂P₂)]	F(000) = 1832
M_r = 920.38	D_x = 1.574 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.4506 (5) Å	Cell parameters from 9441 reflections
b = 15.4490 (5) Å	θ = 2.3–25.6°
c = 17.8532 (6) Å	µ = 3.63 mm⁻¹
β = 103.044 (1)°	T = 293 K
V = 3882.8 (2) Å³	Block, light yellow
Z = 4	0.19 × 0.09 × 0.06 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	9248 independent reflections
Radiation source: fine-focus sealed tube	7758 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Frames, each covering 0.3 ° in ω scans	θ_max = 27.9°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −19→18
T_min = 0.800, T_max = 1.000	k = −20→20
35153 measured reflections	l = −23→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0298P)² + 0.328P] where P = (F_o² + 2F_c²)/3
9248 reflections	(Δ/σ)_max = 0.004
478 parameters	Δρ_max = 0.90 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻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	0.68717 (2)	0.18203 (2)	0.91417 (2)	0.02951 (4)
Cl1	0.53215 (5)	0.24293 (5)	0.92683 (4)	0.04323 (17)
P1	0.76225 (5)	0.28142 (5)	1.01468 (4)	0.03235 (16)
P2	0.76117 (6)	0.48320 (5)	1.05116 (4)	0.03587 (17)
N1	0.71230 (16)	0.27466 (14)	0.83889 (12)	0.0322 (5)
N2	0.66418 (17)	0.07508 (14)	0.97668 (13)	0.0345 (5)
C1	0.6505 (2)	0.33752 (19)	0.80720 (17)	0.0414 (7)
H1	0.5898	0.3378	0.8167	0.050*
C2	0.6752 (3)	0.4012 (2)	0.76128 (18)	0.0492 (8)
H2	0.6313	0.4433	0.7395	0.059*
C3	0.7646 (3)	0.4020 (2)	0.74807 (19)	0.0528 (9)
H3	0.7830	0.4458	0.7187	0.063*
C4	0.8269 (3)	0.3377 (2)	0.77858 (18)	0.0466 (8)
H4	0.8880	0.3380	0.7700	0.056*
C5	0.7996 (2)	0.27145 (18)	0.82245 (15)	0.0353 (6)
C6	0.8552 (2)	0.19571 (18)	0.85264 (17)	0.0374 (7)
C7	0.9445 (2)	0.1771 (2)	0.8388 (2)	0.0494 (8)
H7	0.9729	0.2159	0.8111	0.059*
C8	0.9905 (3)	0.1019 (2)	0.8659 (2)	0.0575 (9)
H8	1.0506	0.0901	0.8577	0.069*
C9	0.9467 (3)	0.0438 (2)	0.9055 (2)	0.0556 (9)
H9	0.9766	−0.0082	0.9224	0.067*
C10	0.8589 (2)	0.0618 (2)	0.92042 (18)	0.0449 (7)
H10	0.8312	0.0217	0.9474	0.054*
C11	0.8109 (2)	0.13846 (18)	0.89610 (15)	0.0338 (6)
C12	0.7031 (2)	0.06046 (19)	1.05128 (17)	0.0469 (8)
H12	0.7442	0.1017	1.0785	0.056*
C13	0.6849 (3)	−0.0130 (2)	1.0891 (2)	0.0598 (10)
H13	0.7127	−0.0209	1.1409	0.072*
C14	0.6251 (3)	−0.0741 (2)	1.0492 (2)	0.0656 (11)
H14	0.6112	−0.1240	1.0736	0.079*
C15	0.5859 (3)	−0.0609 (2)	0.9727 (2)	0.0543 (9)
H15	0.5446	−0.1019	0.9453	0.065*
C16	0.6071 (2)	0.01343 (18)	0.93549 (17)	0.0373 (6)
C17	0.5754 (2)	0.03060 (18)	0.85349 (16)	0.0366 (6)
C18	0.5151 (2)	−0.0240 (2)	0.80214 (19)	0.0457 (7)
H18	0.4890	−0.0725	0.8203	0.055*
C19	0.4945 (2)	−0.0059 (2)	0.72503 (19)	0.0520 (8)
H19	0.4546	−0.0424	0.6907	0.062*
C20	0.5328 (2)	0.0662 (2)	0.69845 (18)	0.0488 (8)
H20	0.5194	0.0778	0.6460	0.059*
C21	0.5910 (2)	0.1216 (2)	0.74885 (16)	0.0409 (7)
H21	0.6159	0.1701	0.7296	0.049*
C22	0.61342 (19)	0.10635 (17)	0.82804 (15)	0.0324 (6)
C23	0.8897 (2)	0.2899 (2)	1.02168 (16)	0.0381 (7)
C24	0.9480 (2)	0.2230 (2)	1.0551 (2)	0.0531 (8)
H24	0.9226	0.1784	1.0793	0.064*
C25	1.0427 (3)	0.2207 (3)	1.0535 (2)	0.0675 (11)
H25	1.0807	0.1751	1.0767	0.081*
C26	1.0814 (3)	0.2856 (3)	1.0178 (3)	0.0708 (12)
H26	1.1452	0.2839	1.0160	0.085*
C27	1.0251 (3)	0.3526 (3)	0.9848 (2)	0.0621 (10)
H27	1.0513	0.3969	0.9610	0.074*
C28	0.9301 (2)	0.3557 (2)	0.98620 (18)	0.0460 (7)
H28	0.8929	0.4019	0.9634	0.055*
C29	0.7500 (2)	0.27335 (18)	1.11445 (16)	0.0388 (7)
C30	0.6630 (3)	0.2510 (2)	1.12801 (19)	0.0529 (8)
H30	0.6141	0.2342	1.0872	0.063*
C31	0.6477 (3)	0.2534 (3)	1.2018 (2)	0.0694 (11)
H31	0.5884	0.2392	1.2104	0.083*
C32	0.7209 (4)	0.2769 (3)	1.2625 (2)	0.0792 (13)
H32	0.7108	0.2784	1.3121	0.095*
C33	0.8081 (4)	0.2980 (3)	1.2500 (2)	0.0743 (13)
H33	0.8572	0.3133	1.2912	0.089*
C34	0.8234 (3)	0.2965 (2)	1.17625 (19)	0.0551 (9)
H34	0.8827	0.3110	1.1679	0.066*
C35	0.7142 (2)	0.38963 (17)	0.98911 (16)	0.0381 (7)
H35A	0.6463	0.3870	0.9857	0.046*
H35B	0.7227	0.4023	0.9379	0.046*
C36	0.6829 (2)	0.49398 (19)	1.11822 (17)	0.0395 (7)
C37	0.5910 (3)	0.4657 (2)	1.1068 (2)	0.0625 (10)
H37	0.5653	0.4332	1.0632	0.075*
C38	0.5354 (3)	0.4842 (3)	1.1587 (3)	0.0831 (14)
H38	0.4734	0.4636	1.1504	0.100*
C39	0.5727 (3)	0.5334 (3)	1.2227 (2)	0.0721 (12)
H39	0.5361	0.5458	1.2580	0.086*
C40	0.6627 (3)	0.5638 (3)	1.2342 (2)	0.0699 (12)
H40	0.6869	0.5988	1.2764	0.084*
C41	0.7188 (3)	0.5429 (2)	1.18332 (19)	0.0565 (9)
H41	0.7815	0.5619	1.1930	0.068*
C42	0.7121 (2)	0.56941 (18)	0.98220 (17)	0.0383 (7)
C43	0.6538 (3)	0.6345 (2)	0.9985 (2)	0.0520 (8)
H43	0.6357	0.6344	1.0453	0.062*
C44	0.6223 (3)	0.6995 (2)	0.9458 (2)	0.0659 (11)
H44	0.5827	0.7424	0.9574	0.079*
C45	0.6479 (3)	0.7019 (3)	0.8779 (2)	0.0673 (11)
H45	0.6269	0.7467	0.8434	0.081*
C46	0.7056 (3)	0.6376 (3)	0.8596 (2)	0.0594 (10)
H46	0.7224	0.6381	0.8123	0.071*
C47	0.7380 (2)	0.5729 (2)	0.91164 (18)	0.0468 (8)
H47	0.7780	0.5306	0.8996	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.03490 (7)	0.02715 (6)	0.02633 (6)	−0.00467 (4)	0.00662 (4)	−0.00016 (4)
Cl1	0.0386 (4)	0.0438 (4)	0.0497 (4)	−0.0044 (3)	0.0150 (3)	−0.0041 (3)
P1	0.0393 (4)	0.0284 (3)	0.0293 (4)	−0.0065 (3)	0.0075 (3)	−0.0017 (3)
P2	0.0401 (4)	0.0312 (4)	0.0358 (4)	−0.0056 (3)	0.0074 (3)	−0.0042 (3)
N1	0.0393 (13)	0.0303 (12)	0.0270 (11)	−0.0046 (10)	0.0074 (10)	0.0011 (9)
N2	0.0420 (14)	0.0295 (12)	0.0320 (12)	−0.0061 (10)	0.0085 (11)	0.0011 (10)
C1	0.0457 (18)	0.0408 (17)	0.0376 (16)	0.0004 (13)	0.0090 (14)	0.0047 (13)
C2	0.063 (2)	0.0413 (18)	0.0418 (17)	0.0032 (16)	0.0096 (16)	0.0115 (14)
C3	0.072 (2)	0.0458 (18)	0.0463 (19)	−0.0085 (17)	0.0247 (18)	0.0100 (15)
C4	0.053 (2)	0.0519 (19)	0.0410 (17)	−0.0136 (15)	0.0233 (16)	−0.0014 (14)
C5	0.0417 (17)	0.0379 (16)	0.0279 (13)	−0.0059 (12)	0.0110 (12)	−0.0045 (12)
C6	0.0394 (16)	0.0397 (16)	0.0334 (15)	−0.0049 (12)	0.0092 (13)	−0.0067 (12)
C7	0.0446 (19)	0.059 (2)	0.0473 (19)	−0.0043 (16)	0.0167 (16)	−0.0086 (16)
C8	0.047 (2)	0.069 (2)	0.057 (2)	0.0124 (18)	0.0130 (17)	−0.0148 (19)
C9	0.057 (2)	0.050 (2)	0.055 (2)	0.0152 (17)	0.0033 (18)	−0.0123 (17)
C10	0.0518 (19)	0.0372 (17)	0.0446 (17)	0.0032 (14)	0.0089 (15)	−0.0021 (13)
C11	0.0378 (16)	0.0347 (15)	0.0274 (13)	−0.0005 (12)	0.0039 (12)	−0.0074 (11)
C12	0.067 (2)	0.0370 (17)	0.0339 (15)	−0.0143 (15)	0.0066 (15)	0.0024 (13)
C13	0.088 (3)	0.048 (2)	0.0401 (18)	−0.0137 (19)	0.0080 (18)	0.0123 (15)
C14	0.090 (3)	0.0412 (19)	0.064 (2)	−0.0216 (19)	0.014 (2)	0.0167 (17)
C15	0.068 (2)	0.0337 (17)	0.057 (2)	−0.0173 (16)	0.0066 (18)	0.0020 (15)
C16	0.0403 (16)	0.0297 (14)	0.0410 (16)	−0.0047 (12)	0.0072 (13)	−0.0019 (12)
C17	0.0378 (16)	0.0342 (15)	0.0379 (15)	−0.0024 (12)	0.0084 (13)	−0.0078 (12)
C18	0.0412 (17)	0.0392 (17)	0.055 (2)	−0.0065 (13)	0.0065 (15)	−0.0099 (14)
C19	0.0437 (19)	0.054 (2)	0.051 (2)	−0.0006 (16)	−0.0045 (16)	−0.0211 (16)
C20	0.0482 (19)	0.059 (2)	0.0335 (16)	0.0087 (16)	−0.0022 (14)	−0.0101 (15)
C21	0.0437 (17)	0.0437 (17)	0.0348 (15)	0.0045 (13)	0.0075 (14)	0.0008 (13)
C22	0.0303 (14)	0.0344 (14)	0.0319 (14)	0.0002 (11)	0.0057 (12)	−0.0064 (11)
C23	0.0407 (17)	0.0386 (15)	0.0343 (15)	−0.0089 (13)	0.0071 (13)	−0.0098 (12)
C24	0.049 (2)	0.0446 (19)	0.062 (2)	−0.0051 (16)	0.0060 (17)	−0.0013 (16)
C25	0.046 (2)	0.065 (3)	0.083 (3)	0.0051 (19)	−0.001 (2)	−0.011 (2)
C26	0.042 (2)	0.079 (3)	0.093 (3)	−0.014 (2)	0.018 (2)	−0.027 (3)
C27	0.057 (2)	0.071 (3)	0.065 (2)	−0.027 (2)	0.026 (2)	−0.018 (2)
C28	0.0501 (19)	0.0464 (18)	0.0431 (17)	−0.0130 (15)	0.0137 (15)	−0.0107 (14)
C29	0.0549 (19)	0.0316 (15)	0.0297 (14)	−0.0039 (13)	0.0093 (14)	−0.0023 (12)
C30	0.058 (2)	0.060 (2)	0.0440 (18)	−0.0061 (17)	0.0199 (17)	−0.0005 (16)
C31	0.082 (3)	0.076 (3)	0.062 (2)	−0.003 (2)	0.039 (2)	0.001 (2)
C32	0.116 (4)	0.089 (3)	0.041 (2)	0.001 (3)	0.034 (3)	−0.004 (2)
C33	0.101 (4)	0.086 (3)	0.0325 (19)	−0.008 (3)	0.006 (2)	−0.0113 (19)
C34	0.064 (2)	0.059 (2)	0.0387 (18)	−0.0119 (18)	0.0044 (17)	−0.0041 (15)
C35	0.0490 (18)	0.0304 (14)	0.0326 (14)	−0.0048 (13)	0.0044 (13)	−0.0031 (12)
C36	0.0453 (18)	0.0354 (15)	0.0380 (16)	0.0017 (13)	0.0100 (14)	0.0043 (13)
C37	0.059 (2)	0.058 (2)	0.075 (3)	−0.0176 (18)	0.023 (2)	−0.0163 (19)
C38	0.063 (3)	0.078 (3)	0.126 (4)	−0.016 (2)	0.057 (3)	−0.009 (3)
C39	0.080 (3)	0.081 (3)	0.068 (3)	0.014 (2)	0.042 (2)	0.018 (2)
C40	0.075 (3)	0.094 (3)	0.0402 (19)	0.023 (2)	0.0102 (19)	−0.005 (2)
C41	0.048 (2)	0.077 (2)	0.0423 (18)	0.0061 (18)	0.0049 (16)	−0.0139 (17)
C42	0.0420 (17)	0.0328 (15)	0.0411 (16)	−0.0066 (12)	0.0113 (14)	−0.0014 (12)
C43	0.069 (2)	0.0363 (17)	0.057 (2)	0.0033 (16)	0.0286 (18)	0.0051 (15)
C44	0.076 (3)	0.049 (2)	0.079 (3)	0.0178 (19)	0.032 (2)	0.0156 (19)
C45	0.072 (3)	0.064 (2)	0.071 (3)	0.013 (2)	0.026 (2)	0.034 (2)
C46	0.063 (2)	0.067 (2)	0.051 (2)	−0.007 (2)	0.0206 (18)	0.0163 (18)
C47	0.050 (2)	0.0455 (18)	0.0477 (19)	−0.0042 (15)	0.0173 (16)	0.0002 (14)

Geometric parameters (Å, º) top

Ir1—C11	2.004 (3)	C20—C21	1.381 (4)
Ir1—C22	2.032 (3)	C20—H20	0.9300
Ir1—N1	2.051 (2)	C21—C22	1.397 (4)
Ir1—N2	2.062 (2)	C21—H21	0.9300
Ir1—P1	2.4241 (7)	C23—C24	1.381 (5)
Ir1—Cl1	2.4866 (8)	C23—C28	1.394 (4)
P1—C23	1.822 (3)	C24—C25	1.377 (5)
P1—C35	1.828 (3)	C24—H24	0.9300
P1—C29	1.834 (3)	C25—C26	1.373 (6)
P2—C36	1.830 (3)	C25—H25	0.9300
P2—C42	1.844 (3)	C26—C27	1.365 (6)
P2—C35	1.854 (3)	C26—H26	0.9300
N1—C1	1.354 (4)	C27—C28	1.380 (5)
N1—C5	1.360 (4)	C27—H27	0.9300
N2—C12	1.343 (4)	C28—H28	0.9300
N2—C16	1.362 (3)	C29—C30	1.376 (4)
C1—C2	1.378 (4)	C29—C34	1.394 (4)
C1—H1	0.9300	C30—C31	1.384 (5)
C2—C3	1.365 (5)	C30—H30	0.9300
C2—H2	0.9300	C31—C32	1.381 (6)
C3—C4	1.369 (5)	C31—H31	0.9300
C3—H3	0.9300	C32—C33	1.367 (6)
C4—C5	1.398 (4)	C32—H32	0.9300
C4—H4	0.9300	C33—C34	1.384 (5)
C5—C6	1.453 (4)	C33—H33	0.9300
C6—C7	1.397 (4)	C34—H34	0.9300
C6—C11	1.421 (4)	C35—H35A	0.9700
C7—C8	1.372 (5)	C35—H35B	0.9700
C7—H7	0.9300	C36—C37	1.369 (4)
C8—C9	1.382 (5)	C36—C41	1.385 (4)
C8—H8	0.9300	C37—C38	1.387 (5)
C9—C10	1.382 (5)	C37—H37	0.9300
C9—H9	0.9300	C38—C39	1.376 (6)
C10—C11	1.391 (4)	C38—H38	0.9300
C10—H10	0.9300	C39—C40	1.353 (6)
C12—C13	1.376 (4)	C39—H39	0.9300
C12—H12	0.9300	C40—C41	1.386 (5)
C13—C14	1.367 (5)	C40—H40	0.9300
C13—H13	0.9300	C41—H41	0.9300
C14—C15	1.370 (5)	C42—C43	1.384 (4)
C14—H14	0.9300	C42—C47	1.394 (4)
C15—C16	1.395 (4)	C43—C44	1.382 (5)
C15—H15	0.9300	C43—H43	0.9300
C16—C17	1.456 (4)	C44—C45	1.344 (5)
C17—C18	1.397 (4)	C44—H44	0.9300
C17—C22	1.411 (4)	C45—C46	1.384 (5)
C18—C19	1.370 (4)	C45—H45	0.9300
C18—H18	0.9300	C46—C47	1.372 (5)
C19—C20	1.376 (5)	C46—H46	0.9300
C19—H19	0.9300	C47—H47	0.9300

C11—Ir1—C22	91.12 (11)	C19—C20—C21	120.7 (3)
C11—Ir1—N1	80.35 (10)	C19—C20—H20	119.7
C22—Ir1—N1	92.62 (10)	C21—C20—H20	119.7
C11—Ir1—N2	94.40 (10)	C20—C21—C22	121.5 (3)
C22—Ir1—N2	80.07 (10)	C20—C21—H21	119.2
N1—Ir1—N2	170.97 (9)	C22—C21—H21	119.2
C11—Ir1—P1	93.75 (8)	C21—C22—C17	116.6 (3)
C22—Ir1—P1	174.57 (8)	C21—C22—Ir1	129.1 (2)
N1—Ir1—P1	85.83 (6)	C17—C22—Ir1	114.18 (19)
N2—Ir1—P1	101.93 (6)	C24—C23—C28	117.8 (3)
C11—Ir1—Cl1	175.37 (8)	C24—C23—P1	118.9 (2)
C22—Ir1—Cl1	87.54 (8)	C28—C23—P1	122.8 (3)
N1—Ir1—Cl1	95.27 (7)	C25—C24—C23	121.5 (3)
N2—Ir1—Cl1	89.74 (7)	C25—C24—H24	119.3
P1—Ir1—Cl1	87.41 (3)	C23—C24—H24	119.3
C23—P1—C35	105.78 (14)	C26—C25—C24	120.1 (4)
C23—P1—C29	104.84 (14)	C26—C25—H25	119.9
C35—P1—C29	100.97 (13)	C24—C25—H25	119.9
C23—P1—Ir1	111.90 (9)	C27—C26—C25	119.3 (4)
C35—P1—Ir1	108.25 (9)	C27—C26—H26	120.3
C29—P1—Ir1	123.42 (10)	C25—C26—H26	120.3
C36—P2—C42	99.77 (13)	C26—C27—C28	121.1 (4)
C36—P2—C35	105.37 (14)	C26—C27—H27	119.4
C42—P2—C35	97.50 (13)	C28—C27—H27	119.4
C1—N1—C5	119.5 (2)	C27—C28—C23	120.2 (3)
C1—N1—Ir1	125.2 (2)	C27—C28—H28	119.9
C5—N1—Ir1	115.23 (18)	C23—C28—H28	119.9
C12—N2—C16	119.0 (2)	C30—C29—C34	119.2 (3)
C12—N2—Ir1	126.07 (19)	C30—C29—P1	118.7 (2)
C16—N2—Ir1	114.83 (18)	C34—C29—P1	121.9 (3)
N1—C1—C2	121.7 (3)	C29—C30—C31	120.6 (4)
N1—C1—H1	119.1	C29—C30—H30	119.7
C2—C1—H1	119.1	C31—C30—H30	119.7
C3—C2—C1	119.5 (3)	C32—C31—C30	119.7 (4)
C3—C2—H2	120.3	C32—C31—H31	120.2
C1—C2—H2	120.3	C30—C31—H31	120.2
C2—C3—C4	119.2 (3)	C33—C32—C31	120.3 (4)
C2—C3—H3	120.4	C33—C32—H32	119.8
C4—C3—H3	120.4	C31—C32—H32	119.8
C3—C4—C5	120.7 (3)	C32—C33—C34	120.1 (4)
C3—C4—H4	119.6	C32—C33—H33	119.9
C5—C4—H4	119.6	C34—C33—H33	119.9
N1—C5—C4	119.1 (3)	C33—C34—C29	120.1 (4)
N1—C5—C6	114.3 (2)	C33—C34—H34	120.0
C4—C5—C6	126.5 (3)	C29—C34—H34	120.0
C7—C6—C11	121.1 (3)	P1—C35—P2	119.78 (16)
C7—C6—C5	123.8 (3)	P1—C35—H35A	107.4
C11—C6—C5	115.1 (3)	P2—C35—H35A	107.4
C8—C7—C6	120.4 (3)	P1—C35—H35B	107.4
C8—C7—H7	119.8	P2—C35—H35B	107.4
C6—C7—H7	119.8	H35A—C35—H35B	106.9
C7—C8—C9	119.2 (3)	C37—C36—C41	117.8 (3)
C7—C8—H8	120.4	C37—C36—P2	126.5 (3)
C9—C8—H8	120.4	C41—C36—P2	115.4 (2)
C8—C9—C10	121.0 (3)	C36—C37—C38	121.6 (4)
C8—C9—H9	119.5	C36—C37—H37	119.2
C10—C9—H9	119.5	C38—C37—H37	119.2
C9—C10—C11	121.7 (3)	C39—C38—C37	119.4 (4)
C9—C10—H10	119.1	C39—C38—H38	120.3
C11—C10—H10	119.1	C37—C38—H38	120.3
C10—C11—C6	116.5 (3)	C40—C39—C38	120.0 (4)
C10—C11—Ir1	129.5 (2)	C40—C39—H39	120.0
C6—C11—Ir1	114.0 (2)	C38—C39—H39	120.0
N2—C12—C13	122.8 (3)	C39—C40—C41	120.3 (4)
N2—C12—H12	118.6	C39—C40—H40	119.9
C13—C12—H12	118.6	C41—C40—H40	119.9
C14—C13—C12	118.8 (3)	C36—C41—C40	120.9 (4)
C14—C13—H13	120.6	C36—C41—H41	119.6
C12—C13—H13	120.6	C40—C41—H41	119.6
C13—C14—C15	119.2 (3)	C43—C42—C47	117.5 (3)
C13—C14—H14	120.4	C43—C42—P2	123.0 (2)
C15—C14—H14	120.4	C47—C42—P2	119.4 (2)
C14—C15—C16	120.8 (3)	C44—C43—C42	120.4 (3)
C14—C15—H15	119.6	C44—C43—H43	119.8
C16—C15—H15	119.6	C42—C43—H43	119.8
N2—C16—C15	119.3 (3)	C45—C44—C43	121.3 (4)
N2—C16—C17	115.5 (2)	C45—C44—H44	119.3
C15—C16—C17	125.2 (3)	C43—C44—H44	119.3
C18—C17—C22	121.3 (3)	C44—C45—C46	119.7 (3)
C18—C17—C16	123.9 (3)	C44—C45—H45	120.2
C22—C17—C16	114.7 (2)	C46—C45—H45	120.2
C19—C18—C17	119.9 (3)	C47—C46—C45	119.7 (3)
C19—C18—H18	120.0	C47—C46—H46	120.2
C17—C18—H18	120.0	C45—C46—H46	120.2
C18—C19—C20	119.9 (3)	C46—C47—C42	121.3 (3)
C18—C19—H19	120.1	C46—C47—H47	119.3
C20—C19—H19	120.1	C42—C47—H47	119.3

C5—N1—C1—C2	−3.1 (4)	C35—P1—C23—C28	−21.3 (3)
Ir1—N1—C1—C2	175.3 (2)	C29—P1—C23—C28	−127.5 (2)
N1—C1—C2—C3	−1.0 (5)	Ir1—P1—C23—C28	96.4 (2)
C1—C2—C3—C4	2.3 (5)	C28—C23—C24—C25	−0.2 (5)
C2—C3—C4—C5	0.3 (5)	P1—C23—C24—C25	171.8 (3)
C1—N1—C5—C4	5.6 (4)	C23—C24—C25—C26	−0.4 (6)
Ir1—N1—C5—C4	−172.9 (2)	C24—C25—C26—C27	0.8 (6)
C1—N1—C5—C6	−173.3 (3)	C25—C26—C27—C28	−0.6 (6)
Ir1—N1—C5—C6	8.1 (3)	C26—C27—C28—C23	0.0 (5)
C3—C4—C5—N1	−4.3 (4)	C24—C23—C28—C27	0.4 (5)
C3—C4—C5—C6	174.5 (3)	P1—C23—C28—C27	−171.3 (2)
N1—C5—C6—C7	176.2 (3)	C23—P1—C29—C30	−168.8 (3)
C4—C5—C6—C7	−2.6 (5)	C35—P1—C29—C30	81.4 (3)
N1—C5—C6—C11	−1.6 (4)	Ir1—P1—C29—C30	−39.2 (3)
C4—C5—C6—C11	179.6 (3)	C23—P1—C29—C34	17.0 (3)
C11—C6—C7—C8	1.2 (5)	C35—P1—C29—C34	−92.8 (3)
C5—C6—C7—C8	−176.5 (3)	Ir1—P1—C29—C34	146.5 (2)
C6—C7—C8—C9	1.5 (5)	C34—C29—C30—C31	1.5 (5)
C7—C8—C9—C10	−2.3 (5)	P1—C29—C30—C31	−172.9 (3)
C8—C9—C10—C11	0.3 (5)	C29—C30—C31—C32	−1.2 (6)
C9—C10—C11—C6	2.3 (4)	C30—C31—C32—C33	0.2 (7)
C9—C10—C11—Ir1	−177.0 (2)	C31—C32—C33—C34	0.5 (7)
C7—C6—C11—C10	−3.1 (4)	C32—C33—C34—C29	−0.2 (6)
C5—C6—C11—C10	174.9 (3)	C30—C29—C34—C33	−0.8 (5)
C7—C6—C11—Ir1	176.3 (2)	P1—C29—C34—C33	173.4 (3)
C5—C6—C11—Ir1	−5.8 (3)	C23—P1—C35—P2	−56.6 (2)
C16—N2—C12—C13	−2.7 (5)	C29—P1—C35—P2	52.4 (2)
Ir1—N2—C12—C13	−179.5 (3)	Ir1—P1—C35—P2	−176.66 (14)
N2—C12—C13—C14	0.4 (6)	C36—P2—C35—P1	−93.0 (2)
C12—C13—C14—C15	0.6 (6)	C42—P2—C35—P1	164.65 (18)
C13—C14—C15—C16	0.6 (6)	C42—P2—C36—C37	76.6 (3)
C12—N2—C16—C15	3.9 (4)	C35—P2—C36—C37	−24.0 (3)
Ir1—N2—C16—C15	−179.0 (2)	C42—P2—C36—C41	−97.0 (3)
C12—N2—C16—C17	−174.2 (3)	C35—P2—C36—C41	162.4 (2)
Ir1—N2—C16—C17	3.0 (3)	C41—C36—C37—C38	−0.6 (5)
C14—C15—C16—N2	−2.9 (5)	P2—C36—C37—C38	−174.1 (3)
C14—C15—C16—C17	174.9 (3)	C36—C37—C38—C39	1.0 (7)
N2—C16—C17—C18	−178.7 (3)	C37—C38—C39—C40	0.5 (7)
C15—C16—C17—C18	3.4 (5)	C38—C39—C40—C41	−2.4 (6)
N2—C16—C17—C22	3.7 (4)	C37—C36—C41—C40	−1.3 (5)
C15—C16—C17—C22	−174.2 (3)	P2—C36—C41—C40	172.9 (3)
C22—C17—C18—C19	2.3 (5)	C39—C40—C41—C36	2.8 (6)
C16—C17—C18—C19	−175.2 (3)	C36—P2—C42—C43	16.7 (3)
C17—C18—C19—C20	−0.4 (5)	C35—P2—C42—C43	123.8 (3)
C18—C19—C20—C21	−0.9 (5)	C36—P2—C42—C47	−166.7 (2)
C19—C20—C21—C22	0.4 (5)	C35—P2—C42—C47	−59.6 (3)
C20—C21—C22—C17	1.4 (4)	C47—C42—C43—C44	0.6 (5)
C20—C21—C22—Ir1	−174.3 (2)	P2—C42—C43—C44	177.3 (3)
C18—C17—C22—C21	−2.7 (4)	C42—C43—C44—C45	−0.6 (6)
C16—C17—C22—C21	175.0 (3)	C43—C44—C45—C46	1.0 (7)
C18—C17—C22—Ir1	173.6 (2)	C44—C45—C46—C47	−1.5 (6)
C16—C17—C22—Ir1	−8.7 (3)	C45—C46—C47—C42	1.5 (5)
C35—P1—C23—C24	167.1 (2)	C43—C42—C47—C46	−1.1 (5)
C29—P1—C23—C24	60.9 (3)	P2—C42—C47—C46	−177.9 (3)
Ir1—P1—C23—C24	−75.2 (3)

Hydrogen-bond geometry (Å, º) top

Cg6, Cg8 and Cg10 are the centroids of the C17–C22, C29–C34 and C42–C47 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl1	0.93	2.73	3.357 (3)	126
C14—H14···Cl1ⁱ	0.93	2.77	3.548 (4)	142
C30—H30···Cl1	0.93	2.84	3.664 (4)	148
C35—H35A···Cl1	0.97	2.83	3.460 (3)	124
C3—H3···Cg6ⁱⁱ	0.93	2.83	3.572 (4)	137
C26—H26···Cg10ⁱⁱⁱ	0.93	2.79	3.575 (5)	143
C38—H38···C10ⁱⁱⁱ	0.93	2.81	3.659 (5)	153
C40—H40···Cg8^iv	0.93	2.95	3.711 (5)	140

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+2, −y+1, −z+2; (iv) −x+3/2, y+1/2, −z+5/2.

Acknowledgements

We are grateful to the Division of Physical Science, Faculty of Science, Prince of Songkla University, for research facilities.

Funding information

NL acknowledges financial support from the Thailand Research Fund (TRF), Office of the Higher Education Commission and Prince of Songkla University under contract number MRG 5580109 as well as the financial support from the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Ministry of Higher Education, Science, Research and Innovation.

References

Alam, P., Laskar, I. R., Climent, C., Casanova, D., Alemany, P., Karanam, M., Choudhury, A. R. & Raymond Butcher, J. (2013). Polyhedron, 53, 286–294. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2003). SMART, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Z.-Q., Shen, X., Xu, J.-X., Zou, H., Wang, X., Xu, Y. & Zhu, D.-R. (2015). Inorg. Chem. Commun. 61, 152–156. Web of Science CSD CrossRef CAS Google Scholar
Chi, Y. & Chou, P. T. (2010). Chem. Soc. Rev. 39, 638–655. Web of Science CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Goldsmith, J. I., Hudson, W. R., Lowry, M. S., Anderson, T. H. & Bernhard, S. (2005). J. Am. Chem. Soc. 127, 7502–7510. Web of Science CrossRef PubMed CAS Google Scholar
Hao, L., Li, Z. W., Zhang, D. Y., He, L., Liu, W., Yang, J., Tan, C. P., Ji, L. N. & Mao, Z. W. (2019). Chem. Sci. 10, 1285–1293. Web of Science CSD CrossRef CAS PubMed Google Scholar
Hearn, J. M., Hughes, G. M., Romero-Canelón, I., Munro, A. F., Rubio-Ruiz, B., Liu, Z., Carragher, N. O. & Sadler, P. J. (2018). Metallomics, 10, 93–107. Web of Science CrossRef CAS PubMed Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Huynh, L., Wang, Z., Yang, J., Stoeva, V., Lough, A., Manners, I. & Winnik, M. A. (2005). Chem. Mater. 17, 4765–4773. Web of Science CSD CrossRef CAS Google Scholar
Jian, Y., Peng, S., Li, X., Wen, X., He, J., Jiang, L. & Dang, Y. (2011). Inorg. Chim. Acta, 368, 37–43. Web of Science CSD CrossRef CAS Google Scholar
Lee, S., Park, K.-M., Yang, K. & Kang, Y. (2009). Inorg. Chem. 48, 1030–1037. Web of Science CSD CrossRef PubMed CAS Google Scholar
Lin, C. H., Chi, Y., Chung, M. W., Chen, Y. J., Wang, K. W., Lee, G. H., Chou, P. T., Hung, W. Y. & Chiu, H. C. (2011). Dalton Trans. 40, 1132–1143. Web of Science CSD CrossRef CAS PubMed Google Scholar
Liu, Z., Li, J., Ge, X., Zhang, S., Xu, Z. & Gao, W. (2019). J. Inorg. Biochem. 197, 110703. Web of Science CSD CrossRef PubMed Google Scholar
Lowry, M. S. & Bernhard, S. (2006). Chem. Eur. J. 12, 7970–7977. Web of Science CrossRef PubMed CAS Google Scholar
Lowry, M. S., Hudson, W. R., Pascal, R. A. & Bernhard, S. (2004). J. Am. Chem. Soc. 126, 14129–14135. Web of Science CrossRef PubMed CAS Google Scholar
Luo, S.-X., Wei, L., Zhang, X.-H., Lim, M. H., Lin, K. X. V., Yeo, M. H. V., Zhang, W.-H., Liu, Z.-P., Young, D. J. & Hor, T. S. A. (2013). Organometallics, 32, 2908–2917. Web of Science CSD CrossRef CAS Google Scholar
Ma, A.-F., Seo, H.-J., Jin, S.-H., Ung, C., Yoon, M., Ho, H., Kang, S. & Kim, Y.-I. (2009). Bull. Korean Chem. Soc. 30, 2754–2758. CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
McKinnon, J. J., Spackman, M. A. & Mitchell, A. S. (2004). Acta Cryst. B60, 627–668. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nishikitani, Y., Cho, T., Uchida, S., Nishimura, S., Oyaizu, K. & Nishide, H. (2018). ChemPlusChem, 83, 463-469. Web of Science CrossRef CAS PubMed Google Scholar
Rubio, A. R., Fidalgo, J., Martin-Vargas, J., Pérez-Arnaiz, C., Alonso-Torre, S. R., Biver, T., Espino, G., Busto, N. & García, B. (2020). J. Inorg. Biochem. 203, 110885. Web of Science CrossRef PubMed Google Scholar
SciFinder (2020). Chemical Abstracts Service: Colombus, OH, 2010; RN 58-08-2 (accessed November 26, 2020). Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shen, X., Wang, F.-L., Sun, F., Zhao, R., Wang, X., Jing, S., Xu, Y. & Zhu, D.-R. (2011). Inorg. Chem. Commun. 14, 1511–1515. Web of Science CSD CrossRef CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Tamayo, A. B., Alleyne, B. D., Djurovich, P. I., Lamansky, S., Tsyba, I., Ho, N. N., Bau, R. & Thompson, M. E. (2003). Inorg. Chem. Commun. 125, 7377–7387. CAS Google Scholar
Tsuboyama, A., Iwawaki, H., Furugori, M., Mukaide, T., Kamatani, J., Igawa, S., Moriyama, T., Miura, S., Takiguchi, T., Okada, S., Hoshino, M. & Ueno, K. (2003). J. Am. Chem. Soc. 125, 12971–12979. Web of Science CSD CrossRef PubMed CAS Google Scholar
Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17.5. The University of Western Australia. Google Scholar
Wang, Y., Teng, F., Tang, A., Wang, Y. & Xu, X. (2005). Acta Cryst. E61, m778–m780. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xiao, Q., Zhao, Z., Lin, K. & Wang, J. (2018). Inorg. Chem. Commun. 94, 75–79. Web of Science CrossRef CAS Google Scholar
Xu, M., Li, W., An, Z., Zhou, Q. & Wang, G. (2005). Appl. Organomet. Chem. 19, 1225–1231. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.