Synthesis and crystal structure of (1,8-naphth­yridine-κ2N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ2N2,C1]iridium(III) hexa­fluorido­phosphate di­chloro­methane monosolvate

Ye, Y.; Tang, G.; Qian, J.

doi:10.1107/S2056989019016773

research communications

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ISSN: 2056-9890

Volume 76| Part 1| January 2020| Pages 82-85

https://doi.org/10.1107/S2056989019016773

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Synthesis and crystal structure of (1,8-naphthyridine-κ²N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ²N²,C¹]iridium(III) hexafluoridophosphate dichloromethane monosolvate

Yunfeng Ye,^a Guodong Tang ^b and Jun Qian ^c ^*

^aJiangsu Nursing Vocational College, Huaian 223300, Jiangsu Province, People's Republic of China, ^bJiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin, Normal University, Huaian 223300, Jiangsu Province, People's Republic of China, and ^cSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, Jiangsu Province, People's Republic of China
^*Correspondence e-mail: junqian8203@ujs.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 December 2019; accepted 15 December 2019; online 1 January 2020)

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-phenylpyrazole (ppz) ligand. The asymmetric unit comprises one [Ir(ppz)₂(NAP)]⁺ cation, one PF₆⁻ counter-ion and one CH₂Cl₂ solvent molecule. The central Ir^III atom of the [Ir(ppz)₂(NAP)]⁺ cation is distorted-octahedrally 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 intermolecular C—H⋯F hydrogen bonds. Together with an additional C—H⋯F interaction involving the solvent molecule, a three-dimensional network structure is formed.

Keywords: crystal structure; cyclometalated iridium complex; 1-phenylpyrazole; C—H⋯F hydrogen bonds.

CCDC reference: 1874317

1. 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, d⁶ 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 [(N $[^\wedge]$ N)Ir(C $[^\wedge]$ N)₂]⁺ in which N $[^\wedge]$ N refers to a diimine ligand and C $[^\wedge]$ N refers to a cyclometalated ligand, the combination and variation of N $[^\wedge]$ N and C $[^\wedge]$ N 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 Ir^III 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.

2. 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 Ir^III 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—N_CN (C $[^\wedge]$ N refers to the ppz ligand) and Ir—C bond lengths are 2.013 and 2.008 Å, respectively, while the average Ir—N_NN (N $[^\wedge]$ N refers to the NAP ligand) bond length is much longer at 2.208 Å. The bond angles around the Ir^III 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.

3. 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⋯F2^iv) 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⋯F2^iv	0.97	2.52	3.370 (13)	146
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

4. 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 ).

5. 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%.

6. 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[F² > 2σ(F²)], wR(F²), S	0.024, 0.062, 1.04
No. of reflections	6387
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 1874317

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019016773/wm5533sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019016773/wm5533Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(1,8-Naphthyridine-κ²N,N')[2-(1H-pyrazol-1-yl)phenyl-κ²N²,C¹]iridium(III) hexafluoridophosphate dichloromethane monosolvate top

Crystal data top

[Ir(C₉H₇N₂)₂(C₈H₆N₂)]PF₆·CH₂Cl₂	F(000) = 1624
M_r = 838.57	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0254P)² + 8.5285P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
6387 reflections	Δρ_max = 1.29 e Å⁻³
388 parameters	Δρ_min = −1.03 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	0.69497 (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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···F2^iv	0.97	2.52	3.370 (13)	146

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

Funding information

Funding for this research was provided by: National Natural Science Foundation of China ( grant No. 51602130).

References

Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Congrave, D. G., Hsu, Y., Batsanov, A. S., Beeby, A. & Bryce, M. R. (2017). Organometallics, 36, 981–993. Web of Science CSD CrossRef CAS Google Scholar
Davies, D. L., Lelj, F., Lowe, M. P., Ryder, K. S., Singh, K. & Singh, S. (2014). Dalton Trans. 43, 4026–4039. Web of Science CSD CrossRef CAS PubMed Google Scholar
Dixon, I. M., Collin, J. P., Sauvage, J. P., Flamigni, L., Encinas, S. & Barigelletti, F. (2000). Chem. Soc. Rev. 29, 385–391. CrossRef CAS Google Scholar
Fan, C., Zhu, L., Jiang, B., Li, Y., Zhao, F., Ma, D., Qin, J. & Yang, C. (2013). J. Phys. Chem. C, 117, 19134–19141. CrossRef CAS Google Scholar
Goswami, S., Sengupta, D., Paul, N. D., Mondal, T. K. & Goswami, S. (2014). Chem. Eur. J. 20, 6103–6111. Web of Science CSD CrossRef CAS PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Howarth, A. J., Majewski, M. B., Brown, C. M., Lelj, F., Wolf, M. O. & Patrick, B. O. (2015). Dalton Trans. 44, 16272–16279. Web of Science CSD CrossRef CAS PubMed Google Scholar
Jiang, W. L., Gao, Y., Sun, Y., Ding, F., Xu, Y., Bian, Z. Q., Li, F., Bian, J. & Huang, C. H. (2010). Inorg. Chem. 49, 3252–3260. CSD CrossRef CAS PubMed Google Scholar
Kwon, T. H., Cho, H. S., Kim, M. K., Kim, J. W., Kim, J. J., Lee, K. H., Park, S. J., Shin, I. S., Kim, H., Shin, D. M., Chung, Y. K. & Hong, J. I. (2005). Organometallics, 24, 1578–1585. Web of Science CSD CrossRef CAS Google Scholar
Lee, S., Kim, S. O., Shin, H., Yun, H. J., Yang, K., Kwon, S. K., Kim, J. J. & Kim, Y. H. (2013). J. Am. Chem. Soc. 135, 14321–14328. CrossRef CAS PubMed Google Scholar
Liu, B., Monro, S., Lystrom, L., Cameron, C. G., Colón, K., Yin, H., Kilina, S., McFarland, S. A. & Sun, W. (2018). Inorg. Chem. 57, 7122–7131. Google Scholar
Majewicz, T. G. & Caluwe, P. (1975). J. Org. Chem. 40, 3407–3410. CrossRef CAS Google Scholar
Nie, Q. Y., Qian, J. & Zhang, C. (2019). J. Mol. Struct. 1186, 434–439. Web of Science CSD CrossRef CAS Google Scholar
Radwan, Y. K., Maity, A. & Teets, T. S. (2015). Inorg. Chem. 54, 7122–7131. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sauvageot, E., Marion, R., Sguerra, F., Grimault, A., Daniellou, R., Hamel, M., Gaillard, S. & Renaud, J. (2014). Org. Chem. Front. 1, 639–644. CSD CrossRef CAS 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tamayo, A. B., Alleyne, B. D., Djurovich, P. I., Lamansky, S., Tsyba, I., Ho, N. N., Bau, R. & Thompson, M. E. (2003). J. Am. Chem. Soc. 125, 7377–7387. Web of Science CSD CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, X., Lystrom, L., Kilina, S. & Sun, W. (2016). Inorg. Chem. 55, 11908–11919. CrossRef CAS PubMed Google Scholar

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