Synthesis and crystal structure of (1,10-phenanthroline-κ2N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ2N2,C1]iridium(III) hexa­fluorido­phosphate with an unknown number of solvent mol­ecules

Zeng, J.; Tang, G.; Qian, J.

doi:10.1107/S2056989020005861

research communications

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ISSN: 2056-9890

Volume 76| Part 6| June 2020| Pages 803-806

https://doi.org/10.1107/S2056989020005861

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Synthesis and crystal structure of (1,10-phenanthroline-κ²N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ²N²,C¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Juxiang Zeng,^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, People's Republic of China
^*Correspondence e-mail: junqian8203@ujs.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 February 2020; accepted 28 April 2020; online 5 May 2020)

The cationic complex in the title compound, [Ir(C₉H₇N₂)₂(C₁₂H₈N₂)]PF₆, comprises two phenylpyrazole (ppz) cyclometallating ligands and one 1,10-phenanthroline (phen) ancillary ligand. The asymmetric unit consists of one [Ir(ppz)₂(phen)]⁺ cation and one [PF₆]⁻ counter-ion. The central Ir^III ion is six-coordinated by two N atoms and two C atoms from the two ppz ligands as well as by two N atoms from the phen ligand within a distorted octahedral C₂N₄ coordination set. In the crystal structure, the [Ir(ppz)₂(phen)]⁺ cations and PF₆⁻ counter-ions are connected with each other through weak intermolecular C—H⋯F hydrogen bonds. Additional C—H⋯π interactions between the rings of neighbouring cations consolidate the three-dimensional network. Electron density associated with additional disordered solvent molecules inside cavities of the structure was removed with the SQUEEZE procedure in PLATON [Spek (2015 ). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown solvent molecule(s). The title compound has a different space-group symmetry (C2/c) from its solvatomorph (P2₁/c) comprising 1.5CH₂Cl₂ solvent molecules per ion pair.

Keywords: crystal structure; cyclometallated iridium complex; 1,10-phenanthroline; 1-phenylpyrazole; intermolecular hydrogen bonding.

CCDC reference: 1856996

1. Chemical context

Cyclometallated iridium(III) complexes have found applications in electroluminescent instruments such as sensors and light-emitting devices and in photocatalysis because of their high emission efficiencies, photo/thermal stabilities and easy tunability of the emission wavelength (Zhao et al., 2010 ; Shan et al., 2012 ). In this regard, a variety of cyclometallated iridium complexes have been reported and most of them have potential for the aforementioned applications (Flamigni et al., 2008 ; Li et al., 2011 ). The properties of iridium complexes can be tuned by rational design of either the cyclometallating or ancillary ligands (Chen et al., 2010 ; Goswami et al., 2014 ; Radwan et al., 2015 ; Congrave et al., 2017 ). Among numerous organic conjugate ligands, the cyclometallating ligand 1-phenylpyrazole (ppz) is known for its high triplet energy (Schlegel & Skancke, 1993 ). Consequently, some bis-cyclometallated Ir^III complexes with ppz ligands have been synthesized that exhibit high energy phosphorescence (Sajoto et al., 2005 ).

On the other hand, ancillary ligands with strong conjugated system such as 1,10-phenanthroline (phen) can also enhance the degree of delocalized π-electrons of cyclometallated iridium(III) complex systems through the interaction between the d orbitals of the transition metal and the π-electron orbitals of the organic conjugated system (Liu et al., 2018 ). This way, the high degree of delocalized π-electrons can increase the luminescent properties of Ir^III complexes (Choy et al., 2014 ). In this context, we report herein the synthesis and crystal structure of the cyclometallated iridium(III) complex, [Ir(ppz)₂(phen)][PF₆], which contains an unknown number of solvent molecules.

2. Structural commentary

The asymmetric unit of the title complex consists of one [Ir(ppz)₂(phen)]⁺ cation and one PF₆⁻ counter-ion (Fig. 1). The iridium(III) atom is six-coordinated by four nitrogen atoms and two carbon atoms within an octahedral [N₄C₂] coordination set. The axial positions are occupied by two nitrogen atoms (N3, N5) from two ppz ligands, while the equatorial plane is composed of two N atoms from the phen ligand (N1, N2) and two C atoms from two ppz ligands (C21, C30).

Figure 1
The structures of the molecular entities in the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms are represented by spheres of arbitrary radius.

The bond lengths and angles related to the coordinating carbon and nitrogen atoms are normal and correspond to literature values. The average Ir—C bond length is 2.018 (5) Å, a typical value for the distance between an Ir^III and a C atom originating from a ppz ligand (Adamovich et al., 2019 ). There are two different Ir—N bond types in the cation of the title compound: the average Ir—N_C^N (C^N refers to the ppz ligand) bond length is 2.023 (2) Å, whereas the value for the Ir—N_N^N (N^N refers to the phen ligand) bond is much longer at 2.141 (8) Å. The bond angles around the Ir^III atom involving cis-arranged ligand atoms deviate clearly from 90° and range from 78.06 (15)° (the bite angle of the phen ligand) to 99.24 (17)°, except for C21—Ir1—C30 with a value of 89.44 (19)°, which correspond to a relatively low distortion from an ideal octahedral coordination polyhedron. The bond angles along the axes of the pseudo-octahedral coordination figure are 171.64 (16), 173.09 (18) and 173.97 (17)° for N3—Ir—N5, C30—Ir—N2 and C21—Ir—N1, respectively.

3. Supramolecular features

In the crystal structure, the complex cations are linked to the PF₆⁻ counter-ions by six C—H⋯F interactions (Table 1, Fig. 2), leading to the formation of a three-dimensional supramolecular network. In addition, there are also C—H⋯π interactions between the [Ir(ppz)₂(phen)]⁺ cations, involving the centroids of one of the pyrazole rings and of a phenyl ring (Table 1, Fig. 3). As can be seen in Fig. 4, the packing of the components leads to voids that are large enough to host solvent molecules of an unknown nature.

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 and Cg9 are the centroids of rings N3/N4/C15–C13 and C16–C21, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯F6ⁱ	0.93	2.57	3.184 (7)	124
C9—H9A⋯F3ⁱⁱ	0.93	2.49	3.024 (7)	117
C17—H17A⋯F4ⁱⁱⁱ	0.93	2.36	2.977 (8)	124
C23—H23A⋯F2^iv	0.93	2.53	3.383 (8)	152
C24—H24A⋯F1^v	0.93	2.48	3.368 (8)	161
C26—H26A⋯F5^v	0.93	2.47	3.348 (9)	158
C6—H6A⋯Cg9^vi	0.93	2.58	3.501 (6)	173
C29—H29A⋯Cg4	0.93	2.98	3.688 (7)	134
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (vi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
C—H⋯F hydrogen bonding interactions between complex cations and counter-ions (shown as dashed lines).

Figure 3
C—H⋯π interactions in the title structure (shown as dashed lines).

Figure 4
A packing diagram of the title compound viewed along the c axis, showing the porous structure with different cavities for the unknown solvent molecules.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.39, update November 2017; Groom et al., 2016 ) for complexes containing the iridium(III) ion with ppz ligand fragments yielded 36 hits. Among the 36 structures, only four contain auxiliary phen ligands or derivatives thereof. From these, one compound (JUPTIZ; Howarth et al., 2015 ) matches the title compound, but crystallizes in the space group P2₁/c and contains two molecular ion pairs in the asymmetric unit in contrast to the title compound, which crystallizes in space group C2/c with one ion pair in the asymmetric unit. Bond lengths and angles in the corresponding [Ir(ppz)₂(phen)]⁺ cations are very similar. In both structure refinements, the contributions of solvent molecules were not considered; for JUPTIZ, 1.5 CH₂Cl₂ solvent molecules were estimated per ion pair, but in the title structure the number and nature of solvent molecule(s) remains unknown. Hence JUPTIZ is a solvatomorph of the title compound. The three other structures comprise derivatives of the phen ligand, viz. JUPTEV/JUPTAR (Howarth et al., 2015) and DUCWOZ (Shan et al., 2012).

5. Synthesis and crystallization

The organometallated iridium(III) dimer, [Ir(μ-Cl)(ppz)₂]₂ (ppz = 1-phenylpyrazole), was prepared according to a literature protocol (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.

The title compound was synthesized from the reaction of [Ir(μ-Cl)(ppz)₂]₂ and 1,10-phenanthroline in a mixed solution of dichloromethane (CH₂Cl₂) and methanol (MeOH) (v/v = 2:1) at 358 K with KPF₆ as a source for the PF₆⁻ counter-ion. The mixture was dried under vacuum and separated by column chromatography on silica gel with CH₂Cl₂/petroleum ether (v/v = 4:1) as eluent. A pure product of the cyclometalated iridium(III) complex was obtained as a dark-yellow solid. Elemental analysis for C₃₀H₂₂F₆IrN₆P (calculated; found): C (44.83; 45.26); H (2.76, 2.73); N (10.46, 10.39)%.

Single crystals of the title compound were grown by inter-diffusion reaction between n-hexane and a dichloromethane solution of the pure solid with CH₂Cl₂/hexane (v/v = 1/1) as buffer solution at room temperature for 7 d (Nie et al., 2019 ). In should be noted that the dichloromethane sesquisolvate of [Ir(ppz)₂(phen)](PF₆) (JUPTIZ) was obtained by reacting [Ir(μ-Cl)(ppz)₂]₂ with 1,10-phenanthroline under microwave irradiation for 30 min. at 373 K (Howarth et al., 2015).

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) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C). The contribution of the missing solvent molecules to the diffraction pattern was subtracted from the reflection data by the SQUEEZE method (Spek, 2015) as implemented in PLATON (Spek, 2020 ). The solvent-accessible volume in the structure of the title compound as calculated by PLATON is 1136.1 Å³ (17.7%).

Table 2
Experimental details

Crystal data
Chemical formula	[Ir(C₉H₇N₂)₂(C₁₂H₈N₂)]PF₆
M_r	803.70
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.976 (3), 22.818 (5), 18.850 (4)
β (°)	95.98 (3)
V (Å³)	6406 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	4.28
Crystal size (mm)	0.25 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
No. of measured, independent and observed [I > 2σ(I)] reflections	29484, 6280, 5077
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.094, 1.11
No. of reflections	6280
No. of parameters	397
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.25, −0.96
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), PLATON (Spek, 2020) and DIAMOND (Brandenburg & Putz, 2016 ), publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1856996

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020005861/wm5544sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020005861/wm5544Isup2.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, 2020) and DIAMOND (Brandenburg & Putz, 2016); software used to prepare material for publication: publCIF (Westrip, 2010).

(1,10-Phenanthroline-κ²N,N')[2-(1H-pyrazol-1-yl)phenyl-κ²N²,C¹]iridium(III) hexafluoridophosphate top

Crystal data top

[Ir(C₉H₇N₂)₂(C₁₂H₈N₂)]PF₆	F(000) = 3120
M_r = 803.70	D_x = 1.667 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.976 (3) Å	Cell parameters from 10866 reflections
b = 22.818 (5) Å	θ = 3.0–26.0°
c = 18.850 (4) Å	µ = 4.28 mm⁻¹
β = 95.98 (3)°	T = 293 K
V = 6406 (2) Å³	Block, red
Z = 8	0.25 × 0.22 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	5077 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.039
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.0°, θ_min = 3.0°
	h = −15→18
29484 measured reflections	k = −28→25
6280 independent reflections	l = −23→23

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0321P)² + 39.6215P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
6280 reflections	Δρ_max = 1.25 e Å⁻³
397 parameters	Δρ_min = −0.96 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	0.25544 (2)	−0.00046 (2)	0.00566 (2)	0.02570 (9)
N1	0.3343 (3)	0.06189 (18)	0.0705 (2)	0.0289 (10)
N2	0.1946 (3)	−0.00380 (17)	0.1030 (2)	0.0254 (9)
N3	0.3270 (3)	−0.07374 (19)	0.0323 (2)	0.0289 (10)
N4	0.2938 (3)	−0.12375 (18)	−0.0004 (2)	0.0317 (10)
N5	0.1815 (3)	0.06810 (19)	−0.0356 (2)	0.0323 (10)
N6	0.2036 (3)	0.08734 (19)	−0.1000 (2)	0.0362 (11)
C1	0.4018 (4)	0.0938 (2)	0.0528 (3)	0.0362 (13)
H1A	0.4237	0.0871	0.0091	0.043*
C2	0.4418 (4)	0.1377 (3)	0.0976 (3)	0.0416 (14)
H2A	0.4888	0.1598	0.0831	0.050*
C3	0.4118 (4)	0.1478 (2)	0.1623 (3)	0.0397 (14)
H3A	0.4386	0.1764	0.1926	0.048*
C4	0.3391 (4)	0.1142 (2)	0.1827 (3)	0.0348 (12)
C5	0.3015 (4)	0.1213 (3)	0.2491 (3)	0.0408 (14)
H5A	0.3250	0.1498	0.2811	0.049*
C6	0.2328 (4)	0.0877 (2)	0.2662 (3)	0.0378 (13)
H6A	0.2101	0.0930	0.3099	0.045*
C7	0.1946 (3)	0.0440 (2)	0.2182 (3)	0.0296 (11)
C8	0.1236 (4)	0.0068 (2)	0.2333 (3)	0.0334 (12)
H8A	0.0989	0.0101	0.2764	0.040*
C9	0.0914 (4)	−0.0341 (2)	0.1843 (3)	0.0326 (12)
H9A	0.0450	−0.0589	0.1940	0.039*
C10	0.1287 (3)	−0.0384 (2)	0.1192 (3)	0.0300 (11)
H10A	0.1063	−0.0665	0.0863	0.036*
C11	0.2288 (3)	0.0364 (2)	0.1529 (2)	0.0264 (11)
C12	0.3025 (3)	0.0718 (2)	0.1349 (3)	0.0277 (11)
C13	0.4046 (4)	−0.0891 (3)	0.0694 (3)	0.0367 (13)
H13A	0.4422	−0.0638	0.0973	0.044*
C14	0.4207 (4)	−0.1483 (3)	0.0602 (3)	0.0445 (15)
H14A	0.4698	−0.1697	0.0805	0.053*
C15	0.3503 (4)	−0.1691 (3)	0.0154 (3)	0.0417 (14)
H15A	0.3426	−0.2073	−0.0011	0.050*
C16	0.2090 (4)	−0.1185 (2)	−0.0414 (3)	0.0302 (12)
C17	0.1642 (4)	−0.1663 (3)	−0.0724 (3)	0.0422 (14)
H17A	0.1892	−0.2036	−0.0679	0.051*
C18	0.0812 (4)	−0.1576 (3)	−0.1106 (3)	0.0465 (16)
H18A	0.0498	−0.1892	−0.1320	0.056*
C19	0.0454 (4)	−0.1023 (3)	−0.1166 (3)	0.0426 (14)
H19A	−0.0103	−0.0966	−0.1424	0.051*
C20	0.0912 (4)	−0.0547 (2)	−0.0845 (3)	0.0332 (12)
H20A	0.0653	−0.0176	−0.0887	0.040*
C21	0.1757 (3)	−0.0614 (2)	−0.0458 (3)	0.0287 (11)
C22	0.1125 (4)	0.0995 (3)	−0.0200 (3)	0.0428 (14)
H22A	0.0840	0.0954	0.0213	0.051*
C23	0.0886 (4)	0.1395 (3)	−0.0738 (4)	0.0528 (17)
H23A	0.0421	0.1666	−0.0757	0.063*
C24	0.1476 (5)	0.1307 (3)	−0.1235 (3)	0.0515 (17)
H24A	0.1487	0.1511	−0.1661	0.062*
C25	0.2783 (4)	0.0599 (2)	−0.1271 (3)	0.0358 (13)
C26	0.3100 (4)	0.0767 (3)	−0.1898 (3)	0.0478 (16)
H26A	0.2833	0.1077	−0.2163	0.057*
C27	0.3814 (5)	0.0474 (3)	−0.2130 (3)	0.0514 (17)
H27A	0.4039	0.0586	−0.2551	0.062*
C28	0.4198 (5)	0.0012 (3)	−0.1737 (3)	0.0514 (17)
H28A	0.4680	−0.0188	−0.1896	0.062*
C29	0.3863 (4)	−0.0159 (3)	−0.1097 (3)	0.0371 (13)
H29A	0.4128	−0.0472	−0.0839	0.045*
C30	0.3144 (4)	0.0132 (2)	−0.0845 (3)	0.0308 (12)
P1	0.35528 (11)	0.28676 (7)	0.33205 (8)	0.0404 (4)
F1	0.3359 (4)	0.2677 (2)	0.2511 (2)	0.105 (2)
F2	0.3773 (4)	0.3061 (2)	0.4122 (2)	0.0877 (15)
F3	0.4239 (4)	0.3339 (2)	0.3101 (3)	0.0978 (17)
F4	0.2835 (5)	0.2436 (3)	0.3520 (4)	0.152 (3)
F5	0.2829 (4)	0.3381 (3)	0.3221 (4)	0.140 (2)
F6	0.4276 (5)	0.2399 (3)	0.3409 (3)	0.147 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.02768 (12)	0.02890 (14)	0.02103 (12)	−0.00258 (8)	0.00499 (8)	0.00069 (8)
N1	0.029 (2)	0.029 (2)	0.028 (2)	−0.0065 (19)	0.0014 (19)	−0.0035 (18)
N2	0.026 (2)	0.026 (2)	0.024 (2)	−0.0003 (17)	0.0036 (17)	0.0014 (17)
N3	0.033 (2)	0.034 (2)	0.022 (2)	−0.0015 (19)	0.0107 (19)	−0.0002 (18)
N4	0.042 (3)	0.029 (2)	0.025 (2)	−0.001 (2)	0.008 (2)	0.0023 (18)
N5	0.036 (3)	0.029 (2)	0.031 (2)	−0.005 (2)	0.002 (2)	−0.0001 (19)
N6	0.042 (3)	0.037 (3)	0.029 (2)	−0.006 (2)	0.000 (2)	0.010 (2)
C1	0.040 (3)	0.037 (3)	0.032 (3)	−0.010 (3)	0.004 (2)	−0.001 (2)
C2	0.037 (3)	0.046 (4)	0.042 (4)	−0.012 (3)	0.005 (3)	0.000 (3)
C3	0.040 (3)	0.042 (3)	0.035 (3)	−0.010 (3)	−0.005 (3)	−0.008 (3)
C4	0.039 (3)	0.037 (3)	0.028 (3)	−0.005 (2)	0.000 (2)	−0.003 (2)
C5	0.053 (4)	0.043 (3)	0.026 (3)	−0.005 (3)	0.002 (3)	−0.004 (2)
C6	0.043 (3)	0.046 (3)	0.026 (3)	−0.004 (3)	0.008 (2)	−0.003 (2)
C7	0.033 (3)	0.031 (3)	0.024 (3)	0.004 (2)	0.003 (2)	0.001 (2)
C8	0.037 (3)	0.041 (3)	0.023 (3)	0.002 (2)	0.013 (2)	0.007 (2)
C9	0.035 (3)	0.037 (3)	0.027 (3)	0.000 (2)	0.009 (2)	0.001 (2)
C10	0.031 (3)	0.030 (3)	0.029 (3)	−0.003 (2)	0.007 (2)	0.003 (2)
C11	0.031 (3)	0.029 (3)	0.019 (2)	0.000 (2)	0.000 (2)	−0.001 (2)
C12	0.027 (3)	0.034 (3)	0.022 (3)	0.001 (2)	0.001 (2)	−0.001 (2)
C13	0.029 (3)	0.052 (4)	0.029 (3)	0.000 (3)	0.001 (2)	0.007 (3)
C14	0.047 (4)	0.045 (4)	0.042 (4)	0.014 (3)	0.008 (3)	0.014 (3)
C15	0.055 (4)	0.034 (3)	0.038 (3)	0.007 (3)	0.014 (3)	0.008 (3)
C16	0.039 (3)	0.033 (3)	0.019 (3)	−0.005 (2)	0.006 (2)	−0.002 (2)
C17	0.065 (4)	0.035 (3)	0.027 (3)	−0.008 (3)	0.009 (3)	0.000 (2)
C18	0.059 (4)	0.046 (4)	0.033 (3)	−0.028 (3)	0.000 (3)	−0.005 (3)
C19	0.041 (3)	0.057 (4)	0.029 (3)	−0.014 (3)	0.000 (3)	0.002 (3)
C20	0.034 (3)	0.043 (3)	0.022 (3)	−0.008 (2)	0.005 (2)	0.001 (2)
C21	0.034 (3)	0.035 (3)	0.019 (2)	−0.009 (2)	0.010 (2)	0.000 (2)
C22	0.033 (3)	0.044 (3)	0.051 (4)	0.010 (3)	0.004 (3)	−0.001 (3)
C23	0.042 (4)	0.051 (4)	0.063 (5)	0.007 (3)	−0.009 (3)	0.011 (3)
C24	0.062 (4)	0.045 (4)	0.044 (4)	0.001 (3)	−0.011 (3)	0.018 (3)
C25	0.038 (3)	0.041 (3)	0.028 (3)	−0.007 (3)	0.001 (2)	0.002 (2)
C26	0.061 (4)	0.047 (4)	0.035 (3)	−0.019 (3)	0.004 (3)	0.011 (3)
C27	0.058 (4)	0.071 (5)	0.028 (3)	−0.026 (4)	0.016 (3)	−0.002 (3)
C28	0.051 (4)	0.072 (5)	0.033 (3)	−0.017 (3)	0.015 (3)	−0.009 (3)
C29	0.038 (3)	0.050 (3)	0.025 (3)	−0.008 (3)	0.012 (2)	−0.005 (2)
C30	0.032 (3)	0.044 (3)	0.017 (2)	−0.012 (2)	0.004 (2)	−0.004 (2)
P1	0.0506 (9)	0.0377 (8)	0.0325 (8)	−0.0028 (7)	0.0030 (7)	0.0021 (6)
F1	0.163 (5)	0.105 (4)	0.041 (3)	−0.067 (4)	−0.014 (3)	0.005 (2)
F2	0.127 (4)	0.095 (3)	0.041 (2)	−0.017 (3)	0.009 (2)	−0.019 (2)
F3	0.128 (4)	0.083 (3)	0.086 (3)	−0.054 (3)	0.027 (3)	−0.018 (3)
F4	0.198 (7)	0.158 (6)	0.116 (5)	−0.125 (5)	0.084 (5)	−0.035 (4)
F5	0.103 (4)	0.108 (4)	0.200 (7)	0.049 (4)	−0.023 (4)	0.011 (4)
F6	0.183 (7)	0.146 (5)	0.104 (5)	0.135 (5)	−0.024 (4)	−0.014 (4)

Geometric parameters (Å, º) top

Ir1—C21	2.016 (5)	C11—C12	1.437 (7)
Ir1—C30	2.019 (5)	C13—C14	1.388 (8)
Ir1—N3	2.021 (4)	C13—H13A	0.9300
Ir1—N5	2.025 (4)	C14—C15	1.365 (9)
Ir1—N2	2.133 (4)	C14—H14A	0.9300
Ir1—N1	2.148 (4)	C15—H15A	0.9300
N1—C1	1.317 (7)	C16—C17	1.378 (7)
N1—C12	1.367 (6)	C16—C21	1.394 (7)
N2—C10	1.324 (6)	C17—C18	1.383 (9)
N2—C11	1.374 (6)	C17—H17A	0.9300
N3—C13	1.339 (7)	C18—C19	1.370 (9)
N3—N4	1.366 (6)	C18—H18A	0.9300
N4—C15	1.349 (7)	C19—C20	1.390 (8)
N4—C16	1.420 (7)	C19—H19A	0.9300
N5—C22	1.315 (7)	C20—C21	1.401 (7)
N5—N6	1.364 (6)	C20—H20A	0.9300
N6—C24	1.341 (7)	C22—C23	1.383 (8)
N6—C25	1.422 (7)	C22—H22A	0.9300
C1—C2	1.402 (8)	C23—C24	1.369 (9)
C1—H1A	0.9300	C23—H23A	0.9300
C2—C3	1.364 (8)	C24—H24A	0.9300
C2—H2A	0.9300	C25—C26	1.374 (8)
C3—C4	1.418 (8)	C25—C30	1.408 (8)
C3—H3A	0.9300	C26—C27	1.372 (9)
C4—C12	1.395 (7)	C26—H26A	0.9300
C4—C5	1.434 (8)	C27—C28	1.378 (9)
C5—C6	1.350 (8)	C27—H27A	0.9300
C5—H5A	0.9300	C28—C29	1.409 (8)
C6—C7	1.425 (7)	C28—H28A	0.9300
C6—H6A	0.9300	C29—C30	1.391 (8)
C7—C11	1.393 (7)	C29—H29A	0.9300
C7—C8	1.413 (7)	P1—F6	1.520 (5)
C8—C9	1.364 (7)	P1—F4	1.534 (5)
C8—H8A	0.9300	P1—F3	1.572 (5)
C9—C10	1.404 (7)	P1—F2	1.575 (4)
C9—H9A	0.9300	P1—F1	1.584 (5)
C10—H10A	0.9300	P1—F5	1.593 (5)

C21—Ir1—C30	89.44 (19)	N3—C13—C14	110.0 (5)
C21—Ir1—N3	79.7 (2)	N3—C13—H13A	125.0
C30—Ir1—N3	94.0 (2)	C14—C13—H13A	125.0
C21—Ir1—N5	94.3 (2)	C15—C14—C13	106.3 (5)
C30—Ir1—N5	80.0 (2)	C15—C14—H14A	126.8
N3—Ir1—N5	171.64 (16)	C13—C14—H14A	126.8
C21—Ir1—N2	96.00 (17)	N4—C15—C14	107.3 (5)
C30—Ir1—N2	173.09 (18)	N4—C15—H15A	126.3
N3—Ir1—N2	91.16 (15)	C14—C15—H15A	126.3
N5—Ir1—N2	95.29 (16)	C17—C16—C21	123.9 (5)
C21—Ir1—N1	173.97 (17)	C17—C16—N4	122.2 (5)
C30—Ir1—N1	96.56 (18)	C21—C16—N4	114.0 (4)
N3—Ir1—N1	99.24 (17)	C16—C17—C18	118.6 (6)
N5—Ir1—N1	87.33 (17)	C16—C17—H17A	120.7
N2—Ir1—N1	78.06 (15)	C18—C17—H17A	120.7
C1—N1—C12	118.8 (4)	C19—C18—C17	119.8 (5)
C1—N1—Ir1	127.8 (4)	C19—C18—H18A	120.1
C12—N1—Ir1	113.1 (3)	C17—C18—H18A	120.1
C10—N2—C11	118.2 (4)	C18—C19—C20	120.9 (6)
C10—N2—Ir1	128.0 (3)	C18—C19—H19A	119.6
C11—N2—Ir1	113.8 (3)	C20—C19—H19A	119.6
C13—N3—N4	105.8 (4)	C19—C20—C21	121.2 (5)
C13—N3—Ir1	139.0 (4)	C19—C20—H20A	119.4
N4—N3—Ir1	114.8 (3)	C21—C20—H20A	119.4
C15—N4—N3	110.5 (5)	C16—C21—C20	115.7 (5)
C15—N4—C16	133.6 (5)	C16—C21—Ir1	115.2 (4)
N3—N4—C16	116.0 (4)	C20—C21—Ir1	129.2 (4)
C22—N5—N6	107.0 (5)	N5—C22—C23	110.2 (6)
C22—N5—Ir1	138.2 (4)	N5—C22—H22A	124.9
N6—N5—Ir1	114.6 (3)	C23—C22—H22A	124.9
C24—N6—N5	109.3 (5)	C24—C23—C22	105.6 (6)
C24—N6—C25	133.9 (5)	C24—C23—H23A	127.2
N5—N6—C25	116.8 (4)	C22—C23—H23A	127.2
N1—C1—C2	122.2 (5)	N6—C24—C23	107.9 (5)
N1—C1—H1A	118.9	N6—C24—H24A	126.0
C2—C1—H1A	118.9	C23—C24—H24A	126.0
C3—C2—C1	120.0 (5)	C26—C25—C30	123.7 (6)
C3—C2—H2A	120.0	C26—C25—N6	122.8 (5)
C1—C2—H2A	120.0	C30—C25—N6	113.4 (5)
C2—C3—C4	119.0 (5)	C27—C26—C25	119.2 (6)
C2—C3—H3A	120.5	C27—C26—H26A	120.4
C4—C3—H3A	120.5	C25—C26—H26A	120.4
C12—C4—C3	117.5 (5)	C26—C27—C28	119.9 (6)
C12—C4—C5	118.6 (5)	C26—C27—H27A	120.1
C3—C4—C5	123.9 (5)	C28—C27—H27A	120.1
C6—C5—C4	121.5 (5)	C27—C28—C29	120.4 (6)
C6—C5—H5A	119.2	C27—C28—H28A	119.8
C4—C5—H5A	119.2	C29—C28—H28A	119.8
C5—C6—C7	120.7 (5)	C30—C29—C28	121.1 (6)
C5—C6—H6A	119.6	C30—C29—H29A	119.4
C7—C6—H6A	119.6	C28—C29—H29A	119.4
C11—C7—C8	117.1 (5)	C29—C30—C25	115.6 (5)
C11—C7—C6	119.3 (5)	C29—C30—Ir1	129.5 (4)
C8—C7—C6	123.6 (5)	C25—C30—Ir1	114.9 (4)
C9—C8—C7	119.7 (5)	F6—P1—F4	91.8 (5)
C9—C8—H8A	120.2	F6—P1—F3	91.8 (4)
C7—C8—H8A	120.2	F4—P1—F3	176.4 (4)
C8—C9—C10	119.6 (5)	F6—P1—F2	91.0 (3)
C8—C9—H9A	120.2	F4—P1—F2	91.5 (3)
C10—C9—H9A	120.2	F3—P1—F2	89.1 (3)
N2—C10—C9	122.3 (5)	F6—P1—F1	88.2 (3)
N2—C10—H10A	118.9	F4—P1—F1	89.8 (3)
C9—C10—H10A	118.9	F3—P1—F1	89.6 (3)
N2—C11—C7	122.9 (5)	F2—P1—F1	178.4 (3)
N2—C11—C12	117.0 (4)	F6—P1—F5	177.3 (4)
C7—C11—C12	120.0 (4)	F4—P1—F5	90.9 (4)
N1—C12—C4	122.5 (5)	F3—P1—F5	85.5 (3)
N1—C12—C11	117.7 (4)	F2—P1—F5	88.8 (3)
C4—C12—C11	119.8 (4)	F1—P1—F5	92.0 (4)

C13—N3—N4—C15	−0.8 (5)	C7—C11—C12—C4	−0.5 (7)
Ir1—N3—N4—C15	174.3 (3)	N4—N3—C13—C14	0.2 (6)
C13—N3—N4—C16	177.8 (4)	Ir1—N3—C13—C14	−173.0 (4)
Ir1—N3—N4—C16	−7.1 (5)	N3—C13—C14—C15	0.4 (6)
C22—N5—N6—C24	0.0 (6)	N3—N4—C15—C14	1.0 (6)
Ir1—N5—N6—C24	177.0 (4)	C16—N4—C15—C14	−177.2 (5)
C22—N5—N6—C25	178.9 (5)	C13—C14—C15—N4	−0.9 (6)
Ir1—N5—N6—C25	−4.1 (6)	C15—N4—C16—C17	3.6 (9)
C12—N1—C1—C2	−0.2 (8)	N3—N4—C16—C17	−174.6 (5)
Ir1—N1—C1—C2	173.0 (4)	C15—N4—C16—C21	−177.5 (5)
N1—C1—C2—C3	0.9 (9)	N3—N4—C16—C21	4.3 (6)
C1—C2—C3—C4	−1.0 (9)	C21—C16—C17—C18	0.2 (8)
C2—C3—C4—C12	0.4 (8)	N4—C16—C17—C18	179.0 (5)
C2—C3—C4—C5	−179.5 (6)	C16—C17—C18—C19	−0.1 (8)
C12—C4—C5—C6	0.8 (9)	C17—C18—C19—C20	−0.3 (9)
C3—C4—C5—C6	−179.3 (6)	C18—C19—C20—C21	0.8 (8)
C4—C5—C6—C7	−0.6 (9)	C17—C16—C21—C20	0.3 (7)
C5—C6—C7—C11	−0.1 (8)	N4—C16—C21—C20	−178.6 (4)
C5—C6—C7—C8	179.0 (5)	C17—C16—C21—Ir1	179.4 (4)
C11—C7—C8—C9	−0.5 (8)	N4—C16—C21—Ir1	0.5 (5)
C6—C7—C8—C9	−179.6 (5)	C19—C20—C21—C16	−0.8 (7)
C7—C8—C9—C10	−0.5 (8)	C19—C20—C21—Ir1	−179.8 (4)
C11—N2—C10—C9	1.9 (7)	N6—N5—C22—C23	0.1 (7)
Ir1—N2—C10—C9	−176.7 (4)	Ir1—N5—C22—C23	−175.8 (4)
C8—C9—C10—N2	−0.2 (8)	N5—C22—C23—C24	−0.1 (7)
C10—N2—C11—C7	−3.0 (7)	N5—N6—C24—C23	−0.1 (7)
Ir1—N2—C11—C7	175.8 (4)	C25—N6—C24—C23	−178.8 (6)
C10—N2—C11—C12	177.8 (4)	C22—C23—C24—N6	0.1 (7)
Ir1—N2—C11—C12	−3.4 (5)	C24—N6—C25—C26	1.4 (10)
C8—C7—C11—N2	2.3 (7)	N5—N6—C25—C26	−177.2 (5)
C6—C7—C11—N2	−178.5 (5)	C24—N6—C25—C30	−176.9 (6)
C8—C7—C11—C12	−178.5 (5)	N5—N6—C25—C30	4.5 (7)
C6—C7—C11—C12	0.7 (8)	C30—C25—C26—C27	−0.7 (9)
C1—N1—C12—C4	−0.5 (8)	N6—C25—C26—C27	−178.9 (5)
Ir1—N1—C12—C4	−174.6 (4)	C25—C26—C27—C28	0.7 (9)
C1—N1—C12—C11	180.0 (5)	C26—C27—C28—C29	−0.3 (9)
Ir1—N1—C12—C11	5.9 (6)	C27—C28—C29—C30	−0.2 (9)
C3—C4—C12—N1	0.3 (8)	C28—C29—C30—C25	0.2 (8)
C5—C4—C12—N1	−179.8 (5)	C28—C29—C30—Ir1	−178.3 (4)
C3—C4—C12—C11	179.9 (5)	C26—C25—C30—C29	0.2 (8)
C5—C4—C12—C11	−0.2 (8)	N6—C25—C30—C29	178.5 (5)
N2—C11—C12—N1	−1.7 (7)	C26—C25—C30—Ir1	179.0 (4)
C7—C11—C12—N1	179.1 (5)	N6—C25—C30—Ir1	−2.7 (6)
N2—C11—C12—C4	178.7 (5)

Hydrogen-bond geometry (Å, º) top

Cg4 and Cg9 are the centroids of rings N3/N4/C15–C13 and C16–C21, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F6ⁱ	0.93	2.57	3.184 (7)	124
C9—H9A···F3ⁱⁱ	0.93	2.49	3.024 (7)	117
C17—H17A···F4ⁱⁱⁱ	0.93	2.36	2.977 (8)	124
C23—H23A···F2^iv	0.93	2.53	3.383 (8)	152
C24—H24A···F1^v	0.93	2.48	3.368 (8)	161
C26—H26A···F5^v	0.93	2.47	3.348 (9)	158
C6—H6A···Cg9^vi	0.93	2.58	3.501 (6)	173
C29—H29A···Cg4	0.93	2.98	3.688 (7)	134

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

Funding information

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

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