Synthesis and crystal structure of (1,8-naphth-yridine-κ2 N,N')[2-(1H-pyrazol-1-yl)phenyl-κ2 N 2,C 1]iridium(III) hexa-fluorido-phosphate di-chloro-methane monosolvate.

The solvated title salt, [Ir(C9H7N2)2(C8H6N2)]PF6·CH2Cl2, was obtained from the reaction between 1,8-naphthyridine (NAP) and an orthometalated iridium(III) precursor containing a 1-phenyl-pyrazole (ppz) ligand. The asymmetric unit comprises one [Ir(ppz)2(NAP)]+ cation, one PF6 - counter-ion and one CH2Cl2 solvent mol-ecule. The central IrIII atom of the [Ir(ppz)2(NAP)]+ cation is distorted-octa-hedrally coordinated by four N atoms and two C atoms, whereby two N atoms stem from the NAP ligand while the ppz ligands ligate through one N and one C atom each. In the crystal, the [Ir(ppz)2(NAP)]+ cations and PF6 - counter-ions are connected with each other through weak inter-molecular C-H⋯F hydrogen bonds. Together with an additional C-H⋯F inter-action involving the solvent mol-ecule, a three-dimensional network structure is formed. © Ye et al. 2020.

Chemical context

Over the past two decades, transition-metal complexes have attracted considerable attention in both academia and industry (Dixon et al., 2000 ▸). For example, d 6 iridium complexes with pseudo-octa­hedral coordination environments have been widely used in electroluminescent devices (sensors and light-emitting instruments) or photocatalysis because of their long excited-state lifetime, high quantum efficiency, luminescent colour adjustment and thermal stability (Lee et al., 2013 ▸; Fan et al., 2013 ▸). Among various iridium complexes, cyclo­metalated iridium(III) complexes are particularly attractive for the wide-range tunability of electronic structures via the rational mol­ecular design of different components (Zhu et al., 2016 ▸). According to the set-up of cyclo­metalated iridium(III) cations with general formula [(NN)Ir(CN)2]+ in which NN refers to a di­imine ligand and CN refers to a cyclo­metalated ligand, the combination and variation of NN and CN ligands provides the opportunity to modulate the properties of the target complexes (Goswami et al., 2014 ▸; Radwan et al., 2015 ▸).

In our laboratory, a key motivation for studies in this area arises from our inter­est in cyclo­metalated iridium(III) complexes, which exhibit a strong conjugated system with a high degree of delocalized π-electrons. Thus, one can enhance the non-linear optical properties of a system through the inter­action between the d orbitals of IrIII and the π-orbitals of an organic conjugated system (Liu et al., 2018 ▸). Here we report the crystal structure of a solvated cyclo­metalated iridium(III) complex, [Ir(C9H7N2)2(C8H6N2)](PF6)·CH2Cl2, obtained from the reaction between an orthometalated iridium precursor ({(ppz)2Ir(μ-Cl)}2) (ppz = 1-phenyl­pyrazole) and 1,8-naphthyridine (NAP) as an auxiliary ligand.

Structural commentary

The asymmetric unit of the title cyclo­metalated iridium(III) complex is composed of one [Ir(ppz)2(NAP)]+ cation, one PF6 − counter-ion and one CH2Cl2 solvent mol­ecule. As shown in Fig. 1 ▸, the IrIII atom is coordinated by four N and two C atoms in the form of a pseudo-octa­hedral [IrN4C2] polyhedron. The axial positions are occupied by two N atoms from two ppz ligands, while the equatorial plane is defined by two N atoms from the NAP ligand and two C atoms from the ppz ligands.

Figure 1

The structures of the mol­ecular entities in the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by spheres of arbitrary radius.

The bond lengths and angles related to the ppz ligand are normal and agree with the values in other cyclo­metalated iridium(III) compounds based on this ligand (see Database survey for details).

The average Ir—NC (CN refers to the ppz ligand) and Ir—C bond lengths are 2.013 and 2.008 Å, respectively, while the average Ir—NN (NN refers to the NAP ligand) bond length is much longer at 2.208 Å. The bond angles around the IrIII atom involving cis-arranged ligand atoms deviate clearly from 90° and range from 60.74 (10)° (the bite angle of the NAP ligand) to 110.71 (12)°, except for N1—Ir1—N5 with a value of 90.63 (11)°. Likewise, the bond angles N3—Ir1—N1, C1—Ir1—N6 and C10—Ir1—N5 of trans-oriented atoms are 173.28 (13), 170.06 (13) and 161.07 (13)°, respectively, and indicate a distortion from the ideal octa­hedral arrangement. The planes of the two planar ppz ligands (C1–C6/C7–C9/N1/N2, r.m.s. deviation of 0.0097 Å; C10–C15/C16–C18/N3/N4, r.m.s. deviation of 0.0562 Å) and the NAP ligand (r.m.s. deviation 0.389 Å) are 76.26 (8) and 70.63 (9)°, respectively, and thus deviate significantly from a perpendicular arrangement.

Supra­molecular features

In the crystal, the [Ir(ppz)2(NAP)]+ cations and PF6 − counter-ions are linked by six charge-assisted and partly bifurcated C—H⋯F hydrogen bonds (C16—H16A⋯F5i, C16—H16A⋯F6i, C9—H9A⋯F1, C9—H9A⋯F4, C7—H7A⋯F5ii, C25—H25A⋯F5iii; Table 1 ▸) into a three-dimensional supra­molecular network, as shown in Fig. 2 ▸. In addition, a similar hydrogen bond between the CH2Cl2 solvent mol­ecule and the PF6 −counter-ion (C27—H27A⋯F2iv) consolidates this arrangement.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯F1	0.93	2.47	3.239 (4)	140
C9—H9A⋯F4	0.93	2.48	3.386 (5)	164
C16—H16A⋯F5i	0.93	2.46	3.018 (5)	118
C16—H16A⋯F6i	0.93	2.51	3.418 (6)	167
C7—H7A⋯F5ii	0.93	2.46	3.201 (5)	136
C25—H25A⋯F5iii	0.93	2.32	3.215 (4)	160
C27—H27A⋯F2iv	0.97	2.52	3.370 (13)	146

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 2

A packing diagram of the title compound in a view along the a axis, showing the three-dimensional supra­molecular network structure. C—H⋯F hydrogen bonds are shown as dashed lines.

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.39, updated November 2017; Groom et al., 2016 ▸) for complexes containing an iridium(III) atom together with 1-phenyl­pyrazole ligand fragments yielded 36 hits. Among these, eight crystallize in the monoclinic system like the title compound. Five of them have similar chelating N,N′-ligands, viz. XAHXIP (Jiang et al., 2010 ▸), KISYOC/KISZIX (Davies et al., 2014 ▸), ROFZET (Sauvageot et al., 2014 ▸) and JUPTIZ (Howarth et al., 2015 ▸). Two compounds contain the same tetra­dentate ligand, N,N′-bis­(3,5-bis­(tri­fluoro­meth­yl)benzo­yl)hydrazide, and are meso and rac diastereomers, viz. NASQEG and NASQIK (Congrave et al., 2017 ▸), and one compound is constructed solely by the 1-phenyl­pyrazole ligand, viz. OHUZAS (Tamayo et al., 2003 ▸).

Synthesis and crystallization

The iridium dichloride bridge compound, [(ppz)2Ir(μ-Cl)]2, was synthesized following a reported literature procedure (Kwon et al., 2005 ▸) by heating IrCl3·3H2O (1 equiv.) and 1-phenyl­pyrazole (2.3 equiv.) in a mixed solution of 2-eth­oxy­ethanol and water (v/v = 3/1) at 408 K.

1,8-Naphthyridine was synthesized by a slight modification of a reported procedure (Majewicz & Caluwe, 1975 ▸). The reaction of 1,3-cyclo­hexa­nedione and an excess of 2-amino­nicotinaldehyde in refluxing ethanol, which contains a few drops of methano­lic KOH, resulted in the 1,8-naphthyridine ligand.

The cyclo­metalated iridium(III) title complex (I) was synthesized from the reaction of [(ppz)2Ir(μ-Cl)]2 with 1,8-naphthyridine in a mixed solution of di­chloro­methane (CH2Cl2) and methanol (MeOH) (v/v = 2/1) at 358 K with KPF6 as counter-ion through metathesis. The reaction process was monitored by thin layer chromatography. After the reaction was complete, the mixture was dried under vacuum and separated by column chromatography on silica gel with CH2Cl2/petroleum ether (v/v = 4/1) as eluent. The pure product of the cyclo­metalated iridium(III) complex was obtained as a dark-yellow solid. Single crystals were grown by inter-diffusion between n-hexane and a di­chloro­methane solution of the pure solid with CH2Cl2/hexane (v/v = 1/1) as buffer solution at room temperature. Compared to the direct benign/inert solvents reaction system, here the inter-diffusion method was applied as a mild way for the crystallization of the title complex. The use of the buffer solution ensures stable conditions for the crystallization of co-responsive constituents (Nie et al., 2019 ▸). Therefore, well-shaped crystals of complex(I) can be obtained from the buffer area.

Elemental analysis for C27H22Cl2F6IrN6P (found): C, 36.86; H, 2.63; N, 10.19%; (calculated): C, 37.65; H, 2.62; N, 10.12%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 Å for [Ir(ppz)2(NAP)]+ cation, C—H = 0.97 Å for CH2Cl2 solvent mol­ecule) and were included in the refinement in the riding-model approximation, with U iso(H) set to 1.2U eq(C).

Table 2

Experimental details

Crystal data
Chemical formula	[Ir(C9H7N2)2(C8H6N2)]PF6·CH2Cl2
M r	838.57
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	293
a, b, c (Å)	12.1222 (3), 15.5510 (4), 17.1579 (5)
β (°)	105.313 (1)
V (Å3)	3119.64 (14)
Z	4
Radiation type	Mo Kα
μ (mm−1)	4.57
Crystal size (mm)	0.20 × 0.18 × 0.15
Data collection
Diffractometer	APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2016 ▸)
T min, T max	0.417, 0.504
No. of measured, independent and observed [I > 2σ(I)] reflections	36216, 6387, 5528
R int	0.032
(sin θ/λ)max (Å−1)	0.626
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.024, 0.062, 1.04
No. of reflections	6387
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	1.29, −1.04

Computer programs: APEX3 and SAINT (Bruker, 2016 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019016773/wm5533sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019016773/wm5533Isup3.hkl

CCDC reference: 1874317

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ir(C9H7N2)2(C8H6N2)]PF6·CH2Cl2	F(000) = 1624
Mr = 838.57	Dx = 1.785 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1222 (3) Å	Cell parameters from 9905 reflections
b = 15.5510 (4) Å	θ = 2.9–26.4°
c = 17.1579 (5) Å	µ = 4.57 mm−1
β = 105.313 (1)°	T = 293 K
V = 3119.64 (14) Å3	Block, red
Z = 4	0.20 × 0.18 × 0.15 mm

APEXII CCD area detector diffractometer	5528 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 26.4°, θmin = 2.9°
Tmin = 0.417, Tmax = 0.504	h = −15→15
36216 measured reflections	k = −19→19
6387 independent reflections	l = −21→21

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024	H-atom parameters constrained
wR(F2) = 0.062	w = 1/[σ2(Fo2) + (0.0254P)2 + 8.5285P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.002
6387 reflections	Δρmax = 1.29 e Å−3
388 parameters	Δρmin = −1.03 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ir1	0.69497 (2)	0.12122 (2)	0.36803 (2)	0.02071 (5)
N1	0.5244 (3)	0.11978 (17)	0.35308 (18)	0.0227 (6)
N2	0.4908 (3)	0.11594 (18)	0.42268 (19)	0.0279 (7)
N3	0.8666 (3)	0.12796 (19)	0.3960 (2)	0.0324 (7)
N4	0.9109 (3)	0.2077 (2)	0.4177 (3)	0.0446 (10)
N5	0.6867 (3)	−0.00707 (18)	0.30844 (17)	0.0231 (6)
N6	0.6822 (3)	0.11475 (18)	0.23884 (18)	0.0229 (6)
C1	0.6907 (3)	0.1083 (2)	0.4841 (2)	0.0272 (8)
C2	0.7798 (4)	0.1025 (3)	0.5545 (3)	0.0423 (11)
H2A	0.8550	0.1019	0.5508	0.051*
C3	0.7581 (6)	0.0977 (3)	0.6303 (3)	0.0552 (15)
H3A	0.8190	0.0936	0.6763	0.066*
C4	0.6483 (6)	0.0990 (3)	0.6380 (3)	0.0541 (15)
H4A	0.6355	0.0960	0.6891	0.065*
C5	0.5570 (5)	0.1046 (3)	0.5705 (3)	0.0435 (11)
H5A	0.4822	0.1053	0.5749	0.052*
C6	0.5806 (4)	0.1092 (2)	0.4952 (2)	0.0295 (8)
C7	0.3761 (4)	0.1172 (3)	0.4054 (3)	0.0379 (10)
H7A	0.3329	0.1153	0.4428	0.045*
C8	0.3336 (4)	0.1219 (3)	0.3234 (3)	0.0389 (10)
H8A	0.2572	0.1237	0.2943	0.047*
C9	0.4292 (3)	0.1233 (2)	0.2927 (2)	0.0301 (8)
H9A	0.4269	0.1262	0.2381	0.036*
C10	0.7152 (3)	0.2476 (2)	0.3880 (2)	0.0280 (8)
C11	0.6328 (4)	0.3117 (2)	0.3775 (2)	0.0296 (8)
H11A	0.5559	0.2964	0.3638	0.036*
C12	0.6627 (4)	0.3982 (3)	0.3869 (3)	0.0387 (10)
H12A	0.6058	0.4399	0.3784	0.046*
C13	0.7757 (5)	0.4221 (3)	0.4087 (3)	0.0512 (13)
H13A	0.7950	0.4800	0.4149	0.061*
C14	0.8604 (5)	0.3609 (3)	0.4213 (4)	0.0572 (14)
H14A	0.9371	0.3767	0.4369	0.069*
C15	0.8290 (4)	0.2753 (3)	0.4102 (3)	0.0383 (10)
C16	1.0249 (4)	0.2038 (3)	0.4437 (4)	0.0682 (18)
H16A	1.0740	0.2498	0.4615	0.082*
C17	1.0564 (4)	0.1195 (3)	0.4393 (4)	0.0653 (17)
H17A	1.1302	0.0973	0.4536	0.078*
C18	0.9556 (4)	0.0745 (3)	0.4092 (3)	0.0451 (11)
H18A	0.9506	0.0156	0.3996	0.054*
C19	0.6751 (3)	0.1585 (2)	0.1718 (2)	0.0290 (8)
H19A	0.6762	0.2183	0.1736	0.035*
C20	0.6659 (4)	0.1168 (3)	0.0978 (2)	0.0353 (9)
H20A	0.6611	0.1492	0.0515	0.042*
C21	0.6641 (4)	0.0293 (3)	0.0932 (2)	0.0369 (9)
H21A	0.6585	0.0019	0.0441	0.044*
C22	0.6709 (3)	−0.0195 (2)	0.1641 (2)	0.0292 (8)
C23	0.6710 (4)	−0.1098 (3)	0.1724 (3)	0.0398 (10)
H23A	0.6657	−0.1451	0.1278	0.048*
C24	0.6790 (4)	−0.1446 (3)	0.2465 (3)	0.0420 (11)
H24A	0.6796	−0.2041	0.2526	0.050*
C25	0.6864 (4)	−0.0915 (2)	0.3141 (2)	0.0303 (8)
H25A	0.6913	−0.1167	0.3640	0.036*
C26	0.6794 (3)	0.0278 (2)	0.2341 (2)	0.0231 (7)
P1	0.33055 (9)	0.18918 (6)	0.06223 (6)	0.0258 (2)
F1	0.42475 (18)	0.23551 (13)	0.13286 (12)	0.0291 (5)
F2	0.2498 (2)	0.17991 (17)	0.12174 (15)	0.0450 (6)
F3	0.4115 (2)	0.20007 (16)	0.00312 (14)	0.0392 (6)
F4	0.3873 (2)	0.09807 (14)	0.09090 (15)	0.0417 (6)
F5	0.2744 (2)	0.28140 (14)	0.03324 (14)	0.0372 (5)
F6	0.2350 (2)	0.14372 (16)	−0.00851 (15)	0.0435 (6)
Cl1	−0.0040 (4)	0.7352 (5)	0.2789 (3)	0.279 (3)
Cl2	0.0137 (4)	0.5589 (5)	0.3252 (4)	0.302 (3)
C27	0.0177 (11)	0.6755 (13)	0.3551 (10)	0.214 (8)
H27A	−0.0402	0.6863	0.3836	0.256*
H27B	0.0918	0.6888	0.3915	0.256*

	U11	U22	U33	U12	U13	U23
Ir1	0.02483 (8)	0.01435 (7)	0.02045 (8)	−0.00010 (5)	0.00159 (5)	−0.00110 (5)
N1	0.0284 (16)	0.0174 (14)	0.0222 (15)	0.0003 (12)	0.0064 (12)	0.0015 (11)
N2	0.0368 (18)	0.0195 (15)	0.0300 (17)	0.0019 (13)	0.0133 (14)	0.0004 (12)
N3	0.0291 (17)	0.0183 (15)	0.046 (2)	−0.0023 (13)	0.0033 (15)	−0.0015 (14)
N4	0.0296 (19)	0.0245 (17)	0.070 (3)	−0.0053 (15)	−0.0045 (18)	−0.0040 (17)
N5	0.0264 (16)	0.0185 (14)	0.0221 (15)	−0.0024 (12)	0.0025 (12)	−0.0014 (11)
N6	0.0253 (15)	0.0186 (14)	0.0250 (15)	0.0012 (12)	0.0071 (12)	0.0016 (11)
C1	0.038 (2)	0.0158 (16)	0.0241 (18)	0.0026 (15)	0.0014 (16)	−0.0021 (13)
C2	0.059 (3)	0.028 (2)	0.030 (2)	0.0075 (19)	−0.007 (2)	−0.0012 (16)
C3	0.102 (5)	0.031 (2)	0.021 (2)	0.012 (3)	−0.004 (2)	0.0003 (17)
C4	0.110 (5)	0.028 (2)	0.026 (2)	0.012 (3)	0.021 (3)	0.0009 (17)
C5	0.078 (3)	0.027 (2)	0.033 (2)	0.008 (2)	0.026 (2)	0.0020 (17)
C6	0.049 (2)	0.0155 (17)	0.0236 (18)	0.0025 (16)	0.0089 (17)	−0.0006 (13)
C7	0.033 (2)	0.030 (2)	0.056 (3)	0.0010 (17)	0.021 (2)	0.0007 (18)
C8	0.027 (2)	0.029 (2)	0.058 (3)	0.0014 (17)	0.0057 (19)	0.0043 (19)
C9	0.029 (2)	0.0230 (18)	0.034 (2)	0.0001 (15)	0.0000 (16)	0.0030 (15)
C10	0.041 (2)	0.0170 (17)	0.0242 (18)	0.0010 (15)	0.0048 (16)	−0.0019 (13)
C11	0.043 (2)	0.0205 (18)	0.0253 (19)	0.0011 (16)	0.0093 (17)	−0.0020 (14)
C12	0.058 (3)	0.0200 (19)	0.038 (2)	0.0073 (18)	0.013 (2)	−0.0022 (16)
C13	0.062 (3)	0.018 (2)	0.071 (3)	−0.005 (2)	0.012 (3)	−0.007 (2)
C14	0.051 (3)	0.029 (2)	0.085 (4)	−0.013 (2)	0.008 (3)	−0.009 (2)
C15	0.035 (2)	0.0201 (19)	0.052 (3)	−0.0029 (17)	−0.002 (2)	−0.0036 (17)
C16	0.031 (3)	0.039 (3)	0.119 (5)	−0.008 (2)	−0.008 (3)	−0.006 (3)
C17	0.027 (2)	0.045 (3)	0.111 (5)	0.004 (2)	−0.005 (3)	−0.002 (3)
C18	0.033 (2)	0.028 (2)	0.068 (3)	0.0030 (18)	0.003 (2)	−0.001 (2)
C19	0.032 (2)	0.0225 (18)	0.033 (2)	0.0021 (15)	0.0094 (17)	0.0082 (15)
C20	0.044 (2)	0.038 (2)	0.0251 (19)	0.0044 (19)	0.0111 (18)	0.0101 (16)
C21	0.050 (3)	0.037 (2)	0.0234 (19)	−0.0016 (19)	0.0101 (18)	−0.0004 (16)
C22	0.036 (2)	0.0276 (19)	0.0232 (18)	−0.0051 (16)	0.0061 (16)	−0.0022 (15)
C23	0.066 (3)	0.028 (2)	0.028 (2)	−0.008 (2)	0.015 (2)	−0.0095 (16)
C24	0.074 (3)	0.0171 (18)	0.036 (2)	−0.008 (2)	0.018 (2)	−0.0052 (16)
C25	0.045 (2)	0.0189 (17)	0.0273 (19)	−0.0042 (16)	0.0102 (18)	0.0030 (14)
C26	0.0269 (19)	0.0199 (17)	0.0215 (17)	−0.0008 (14)	0.0046 (14)	0.0018 (13)
P1	0.0312 (5)	0.0184 (4)	0.0244 (5)	0.0010 (4)	0.0015 (4)	−0.0036 (3)
F1	0.0335 (12)	0.0243 (11)	0.0242 (11)	−0.0019 (9)	−0.0015 (9)	−0.0027 (8)
F2	0.0416 (14)	0.0511 (16)	0.0445 (15)	−0.0082 (12)	0.0155 (12)	−0.0054 (12)
F3	0.0461 (15)	0.0417 (14)	0.0311 (12)	0.0004 (11)	0.0122 (11)	−0.0046 (10)
F4	0.0535 (16)	0.0168 (11)	0.0486 (15)	0.0020 (10)	0.0023 (12)	0.0010 (10)
F5	0.0427 (14)	0.0249 (11)	0.0362 (13)	0.0089 (10)	−0.0035 (11)	−0.0021 (9)
F6	0.0433 (14)	0.0369 (13)	0.0396 (14)	−0.0039 (11)	−0.0077 (11)	−0.0148 (11)
Cl1	0.177 (4)	0.470 (9)	0.169 (4)	−0.139 (5)	0.008 (3)	0.032 (5)
Cl2	0.106 (3)	0.407 (9)	0.381 (8)	−0.022 (4)	0.043 (4)	0.061 (7)
C27	0.116 (10)	0.34 (2)	0.197 (15)	0.054 (13)	0.065 (10)	0.096 (17)

Ir1—C10	1.999 (4)	C11—H11A	0.9300
Ir1—N3	2.010 (3)	C12—C13	1.373 (7)
Ir1—N1	2.015 (3)	C12—H12A	0.9300
Ir1—C1	2.016 (4)	C13—C14	1.374 (7)
Ir1—N6	2.183 (3)	C13—H13A	0.9300
Ir1—N5	2.232 (3)	C14—C15	1.384 (6)
N1—C9	1.333 (5)	C14—H14A	0.9300
N1—N2	1.361 (4)	C16—C17	1.372 (7)
N2—C7	1.344 (5)	C16—H16A	0.9300
N2—C6	1.424 (5)	C17—C18	1.385 (6)
N3—C18	1.333 (5)	C17—H17A	0.9300
N3—N4	1.364 (4)	C18—H18A	0.9300
N4—C16	1.336 (6)	C19—C20	1.404 (6)
N4—C15	1.428 (5)	C19—H19A	0.9300
N5—C25	1.317 (5)	C20—C21	1.363 (6)
N5—C26	1.366 (4)	C20—H20A	0.9300
N6—C19	1.319 (5)	C21—C22	1.418 (5)
N6—C26	1.355 (4)	C21—H21A	0.9300
C1—C2	1.394 (6)	C22—C26	1.390 (5)
C1—C6	1.397 (6)	C22—C23	1.411 (5)
C2—C3	1.396 (7)	C23—C24	1.363 (6)
C2—H2A	0.9300	C23—H23A	0.9300
C3—C4	1.372 (8)	C24—C25	1.407 (5)
C3—H3A	0.9300	C24—H24A	0.9300
C4—C5	1.378 (7)	C25—H25A	0.9300
C4—H4A	0.9300	P1—F4	1.595 (2)
C5—C6	1.396 (6)	P1—F3	1.595 (3)
C5—H5A	0.9300	P1—F2	1.597 (3)
C7—C8	1.366 (7)	P1—F1	1.600 (2)
C7—H7A	0.9300	P1—F6	1.604 (2)
C8—C9	1.394 (6)	P1—F5	1.609 (2)
C8—H8A	0.9300	Cl1—C27	1.567 (14)
C9—H9A	0.9300	Cl2—C27	1.882 (19)
C10—C11	1.388 (5)	C27—H27A	0.9700
C10—C15	1.398 (6)	C27—H27B	0.9700
C11—C12	1.391 (5)
C10—Ir1—N3	80.52 (14)	C13—C12—C11	120.2 (4)
C10—Ir1—N1	96.21 (14)	C13—C12—H12A	119.9
N3—Ir1—N1	173.28 (13)	C11—C12—H12A	119.9
C10—Ir1—C1	87.88 (14)	C12—C13—C14	120.4 (4)
N3—Ir1—C1	93.67 (15)	C12—C13—H13A	119.8
N1—Ir1—C1	80.29 (14)	C14—C13—H13A	119.8
C10—Ir1—N6	101.05 (13)	C13—C14—C15	118.5 (5)
N3—Ir1—N6	92.10 (13)	C13—C14—H14A	120.7
N1—Ir1—N6	94.29 (11)	C15—C14—H14A	120.7
C1—Ir1—N6	170.06 (13)	C14—C15—C10	123.3 (4)
C10—Ir1—N5	161.07 (13)	C14—C15—N4	122.4 (4)
N3—Ir1—N5	94.28 (12)	C10—C15—N4	114.2 (3)
N1—Ir1—N5	90.63 (11)	N4—C16—C17	107.7 (4)
C1—Ir1—N5	110.71 (12)	N4—C16—H16A	126.1
N6—Ir1—N5	60.74 (10)	C17—C16—H16A	126.1
C9—N1—N2	106.6 (3)	C16—C17—C18	105.7 (4)
C9—N1—Ir1	138.3 (3)	C16—C17—H17A	127.1
N2—N1—Ir1	115.0 (2)	C18—C17—H17A	127.1
C7—N2—N1	109.7 (3)	N3—C18—C17	110.1 (4)
C7—N2—C6	134.6 (4)	N3—C18—H18A	125.0
N1—N2—C6	115.7 (3)	C17—C18—H18A	125.0
C18—N3—N4	106.1 (3)	N6—C19—C20	121.4 (3)
C18—N3—Ir1	138.4 (3)	N6—C19—H19A	119.3
N4—N3—Ir1	114.9 (2)	C20—C19—H19A	119.3
C16—N4—N3	110.3 (4)	C21—C20—C19	120.7 (4)
C16—N4—C15	134.2 (4)	C21—C20—H20A	119.7
N3—N4—C15	115.5 (3)	C19—C20—H20A	119.7
C25—N5—C26	117.6 (3)	C20—C21—C22	119.2 (4)
C25—N5—Ir1	149.1 (3)	C20—C21—H21A	120.4
C26—N5—Ir1	93.3 (2)	C22—C21—H21A	120.4
C19—N6—C26	117.9 (3)	C26—C22—C23	116.2 (3)
C19—N6—Ir1	146.3 (3)	C26—C22—C21	115.6 (3)
C26—N6—Ir1	95.8 (2)	C23—C22—C21	128.1 (4)
C2—C1—C6	115.7 (4)	C24—C23—C22	119.1 (4)
C2—C1—Ir1	130.2 (3)	C24—C23—H23A	120.4
C6—C1—Ir1	114.1 (3)	C22—C23—H23A	120.4
C1—C2—C3	121.1 (5)	C23—C24—C25	120.6 (4)
C1—C2—H2A	119.5	C23—C24—H24A	119.7
C3—C2—H2A	119.5	C25—C24—H24A	119.7
C4—C3—C2	121.1 (5)	N5—C25—C24	121.8 (4)
C4—C3—H3A	119.5	N5—C25—H25A	119.1
C2—C3—H3A	119.5	C24—C25—H25A	119.1
C3—C4—C5	120.2 (4)	N6—C26—N5	110.2 (3)
C3—C4—H4A	119.9	N6—C26—C22	125.1 (3)
C5—C4—H4A	119.9	N5—C26—C22	124.6 (3)
C4—C5—C6	117.8 (5)	F4—P1—F3	90.16 (14)
C4—C5—H5A	121.1	F4—P1—F2	90.57 (15)
C6—C5—H5A	121.1	F3—P1—F2	179.07 (15)
C5—C6—C1	124.1 (4)	F4—P1—F1	90.17 (12)
C5—C6—N2	121.1 (4)	F3—P1—F1	89.89 (13)
C1—C6—N2	114.8 (3)	F2—P1—F1	89.53 (13)
N2—C7—C8	108.4 (4)	F4—P1—F6	90.47 (13)
N2—C7—H7A	125.8	F3—P1—F6	90.46 (14)
C8—C7—H7A	125.8	F2—P1—F6	90.11 (14)
C7—C8—C9	105.4 (4)	F1—P1—F6	179.27 (14)
C7—C8—H8A	127.3	F4—P1—F5	179.49 (15)
C9—C8—H8A	127.3	F3—P1—F5	89.43 (14)
N1—C9—C8	109.9 (4)	F2—P1—F5	89.85 (14)
N1—C9—H9A	125.1	F1—P1—F5	89.54 (12)
C8—C9—H9A	125.1	F6—P1—F5	89.83 (13)
C11—C10—C15	116.0 (3)	Cl1—C27—Cl2	110.9 (11)
C11—C10—Ir1	129.2 (3)	Cl1—C27—H27A	109.5
C15—C10—Ir1	114.7 (3)	Cl2—C27—H27A	109.5
C10—C11—C12	121.5 (4)	Cl1—C27—H27B	109.5
C10—C11—H11A	119.2	Cl2—C27—H27B	109.5
C12—C11—H11A	119.2	H27A—C27—H27B	108.1
C9—N1—N2—C7	−0.1 (4)	Ir1—C10—C15—C14	175.5 (4)
Ir1—N1—N2—C7	178.7 (2)	C11—C10—C15—N4	−178.0 (4)
C9—N1—N2—C6	178.2 (3)	Ir1—C10—C15—N4	−2.2 (5)
Ir1—N1—N2—C6	−3.0 (4)	C16—N4—C15—C14	9.1 (9)
C18—N3—N4—C16	0.1 (6)	N3—N4—C15—C14	−172.8 (5)
Ir1—N3—N4—C16	173.1 (4)	C16—N4—C15—C10	−173.1 (6)
C18—N3—N4—C15	−178.5 (4)	N3—N4—C15—C10	5.0 (6)
Ir1—N3—N4—C15	−5.4 (5)	N3—N4—C16—C17	−0.2 (7)
C6—C1—C2—C3	0.2 (6)	C15—N4—C16—C17	177.9 (6)
Ir1—C1—C2—C3	177.0 (3)	N4—C16—C17—C18	0.3 (8)
C1—C2—C3—C4	−0.3 (7)	N4—N3—C18—C17	0.1 (6)
C2—C3—C4—C5	0.3 (7)	Ir1—N3—C18—C17	−170.4 (4)
C3—C4—C5—C6	−0.2 (6)	C16—C17—C18—N3	−0.3 (7)
C4—C5—C6—C1	0.1 (6)	C26—N6—C19—C20	−0.5 (6)
C4—C5—C6—N2	−179.4 (4)	Ir1—N6—C19—C20	−178.8 (3)
C2—C1—C6—C5	−0.1 (5)	N6—C19—C20—C21	0.0 (7)
Ir1—C1—C6—C5	−177.4 (3)	C19—C20—C21—C22	0.4 (7)
C2—C1—C6—N2	179.4 (3)	C20—C21—C22—C26	−0.2 (6)
Ir1—C1—C6—N2	2.2 (4)	C20—C21—C22—C23	−179.6 (5)
C7—N2—C6—C5	−2.1 (6)	C26—C22—C23—C24	0.1 (7)
N1—N2—C6—C5	−179.9 (3)	C21—C22—C23—C24	179.5 (5)
C7—N2—C6—C1	178.3 (4)	C22—C23—C24—C25	0.4 (7)
N1—N2—C6—C1	0.5 (4)	C26—N5—C25—C24	0.0 (6)
N1—N2—C7—C8	0.0 (4)	Ir1—N5—C25—C24	−179.4 (4)
C6—N2—C7—C8	−177.8 (4)	C23—C24—C25—N5	−0.5 (7)
N2—C7—C8—C9	0.0 (4)	C19—N6—C26—N5	−179.5 (3)
N2—N1—C9—C8	0.1 (4)	Ir1—N6—C26—N5	−0.5 (3)
Ir1—N1—C9—C8	−178.2 (3)	C19—N6—C26—C22	0.7 (6)
C7—C8—C9—N1	−0.1 (4)	Ir1—N6—C26—C22	179.7 (3)
C15—C10—C11—C12	1.4 (6)	C25—N5—C26—N6	−179.2 (3)
Ir1—C10—C11—C12	−173.6 (3)	Ir1—N5—C26—N6	0.5 (3)
C10—C11—C12—C13	−1.4 (6)	C25—N5—C26—C22	0.6 (6)
C11—C12—C13—C14	0.1 (8)	Ir1—N5—C26—C22	−179.7 (3)
C12—C13—C14—C15	1.1 (8)	C23—C22—C26—N6	179.1 (4)
C13—C14—C15—C10	−1.0 (8)	C21—C22—C26—N6	−0.3 (6)
C13—C14—C15—N4	176.6 (5)	C23—C22—C26—N5	−0.6 (6)
C11—C10—C15—C14	−0.3 (7)	C21—C22—C26—N5	179.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···F1	0.93	2.47	3.239 (4)	140
C9—H9A···F4	0.93	2.48	3.386 (5)	164
C16—H16A···F5i	0.93	2.46	3.018 (5)	118
C16—H16A···F6i	0.93	2.51	3.418 (6)	167
C7—H7A···F5ii	0.93	2.46	3.201 (5)	136
C25—H25A···F5iii	0.93	2.32	3.215 (4)	160
C27—H27A···F2iv	0.97	2.52	3.370 (13)	146