Synthesis, crystal structure and DFT calculations of (2′,6′-di­fluoro-2,3′-bi­pyridine-κN2)[2,6-di­fluoro-3-(pyridin-2-yl)phenyl-κ2C1,N3]methyl­platinum(II)

Moon, S.-H.; Choi, S.; Kang, Y.

doi:10.1107/S2056989022010519

research communications

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ISSN: 2056-9890

Volume 78| Part 12| December 2022| Pages 1169-1172

https://doi.org/10.1107/S2056989022010519

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Synthesis, crystal structure and DFT calculations of (2′,6′-difluoro-2,3′-bipyridine-κN²)[2,6-difluoro-3-(pyridin-2-yl)phenyl-κ²C¹,N³]methylplatinum(II)

Suk-Hee Moon,^a Seohyeon Choi ^b and Youngjin Kang ^b ^*

^aDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea, and ^bDivision of Science Education, Kangwon National University, Chuncheon 24341, Republic of Korea
^*Correspondence e-mail: kangy@kangwon.ac.kr

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 27 October 2022; accepted 1 November 2022; online 4 November 2022)

The title compound, [Pt(CH₃)(C₁₀H₅F₂N₂)(C₁₀H₆F₂N₂)], displays a distorted cis-PtN₂C₂ square-planar geometry around the Pt^II ion consisting of the bidentate C,N chelating anion, a monodentate N-bonded neutral ligand and a methyl group. In the crystal, the molecules are linked by C—H⋯F, C—H⋯N and C—H⋯π interactions. Time-dependent density functional theory (TD-DFT) at the B3LYP level with the 6–311++G(d,p) basis set was applied to optimize the ground-state geometry. The electronic properties, such as excitation energies and the HOMO–LUMO gap energies, were calculated and compared to related structures.

Keywords: crystal structure; biipyridine ligand; photophysical properties; DFT calculation.

CCDC reference: 2216704

1. Chemical context

Over the past two decades, there has been considerable interest in the design of phosphorescent Ir^III and Pt^II complexes based on C,N-chelating ligands, especially 2′,6′-difluoro-2,3′-bipyridine (dfpypy) (Kang et al., 2022b ,c ; Zaen et al., 2019 ). Among them, heteroleptic Pt^II compounds show high thermal stability and photoluminescence quantum efficiency (PLQY). Both characteristics make them suitable for applications as organic light-emitting diodes (OLEDs) and organic lighting (Kang et al., 2021 ; Lee et al., 2018 ). Despite the many advantages of Pt^II complexes based on bipyridine ligands, there are some problems that need to be addressed. For example, a gradient efficiency roll-off often occurs at high current densities owing to intrinsic triplet–triplet exciton annihilation (Zhang et al., 2020 ). To overcome this limitation, it is necessary to develop heavy transition-metal compounds with octahedral geometry. Therefore, Pt^IV complexes are highly desirable in OLED applications compared with those of their Pt^II analogues. However, reports on Pt^IV compounds based on C,N chelates are scarce, despite the compounds having similar geometries and electronic configurations to Ir^III complexes. To make C,N-based Pt^IV octahedral complexes, the syntheses of Pt^II complexes are needed as intermediates at the first step (Juliá et al., 2016 ). However, the structures and photophysical properties of these Pt^II precursors are still scarce, which prompted us to determine the structure of a Pt^II complex bearing a C,N chelating dfpypy ligand and investigate its photophysical properties (Juliá & González-Herrero, 2016 ). Herein, we describe the results of our investigation regarding the structural characterization, photophysical properties, and TD–DFT calculations of the title dfpypy-based Pt^II compound.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. Of the two 2,3′-bipyridyl units, the N1-containing pyridine ring is slightly tilted by 3.08 (7)° to the N2-containing one, while the N3-containing pyridine ring is almost perpendicular to N4-containing one with a dihedral angle of 80.95 (9)°. As expected, the title compound has a distorted PtN₂C₂ square-planar geometry around the platinum center with an N,N-cis structure (Table 1). The Pt—C and Pt—N bond lengths for the title compound are within the range reported for those of related compounds, namely [Pt(dfpypy)₂(Me)Cl] and [Pt(ppy)₂(Me)Cl] (ppy = 2-phenylpyridine) (Kang et al., 2022a ; Juliá et al., 2016). The Pt1—N1 bond length in the title compound [2.0943 (3) Å] is similar to that of Pt1—N3 [2.120 (3) Å]. However, the Pt1—C21 bond length [2.036 (4) Å] is significantly longer than that of Pt1—C1 [1.966 (3) Å]; this is attributed to the greater trans influence exerted by the N atom of the C,N ligand located at the trans position and the lack of π-back bonding between the Pt atom and the C atom of the methyl ligand.

Table 1
Selected geometric parameters (Å, °)

Pt1—C1	1.966 (3)	Pt1—N1	2.094 (3)
Pt1—C21	2.036 (4)	Pt1—N3	2.120 (3)

C1—Pt1—C21	92.94 (14)	C1—Pt1—N3	177.73 (12)
C1—Pt1—N1	81.10 (12)	C21—Pt1—N3	89.33 (13)
C21—Pt1—N1	174.00 (12)	N1—Pt1—N3	96.63 (10)

Figure 1
The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

3. Supramolecular features

In the extended structure, C—H⋯F/N hydrogen bonds (Table 2, yellow dashed lines in Fig. 2) between adjacent molecules lead to the formation of a di-periodic supramolecular network. The network is consolidated by weak aromatic π–π stacking, C—H⋯π and C—F⋯π interactions [red, sky-blue, and black dashed lines in Fig. 2, respectively; Cg2⋯Cg3ⁱ = 3.865 (2) Å; C21—H21A⋯Cg4ⁱⁱ = 3.507 (4) Å; C3—F1⋯Cg1ⁱⁱⁱ = 3.968 (3) Å; C13—F3⋯Cg3^iv = 3.472 (3) Å; Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C6–C10, N2/C1–C5, N3/C16–C20 and N4/C11–C15 rings, respectively; symmetry codes: (i) x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ; (ii) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) −x + 2, −y + 1, −z + 1; (iv) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. These varied interactions presumably assist in the stabilization of the network structure.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯F2	0.95	2.24	2.858 (4)	122
C12—H12⋯F1ⁱ	0.95	2.44	3.259 (5)	144
C20—H20⋯N2ⁱⁱ	0.95	2.45	3.385 (5)	167
Symmetry codes: (i) ; (ii) .

Figure 2
The di-periodic supramolecular network formed through C—H⋯F/N hydrogen bonds (yellow dashed lines), F⋯π (black dashed lines) C—H⋯π (sky-blue dashed line) and π–π (red dashed lines) stacking interactions. For clarity, H atoms not involved in the intermolecular interactions have been omitted.

4. Photophysical properties

The absorption and emission spectra of title compound in solution are shown in Fig. 3. The title compound exhibits a similar absorption pattern in the 230–350 nm range, as compared to its analog [Pt(ppy)(ppyH)(Me)] (Juliá & González-Herrero, 2016). The most intense absorption band at 235 nm is assigned to a π–π* ligand-centered (¹LC) transition, and the next weak absorption band at longer wavelengths (380–440 nm) is assigned to a metal-to-ligand charge-transfer (MLCT) transition. The title compound shows weak blue and non-structured emission in CH₂Cl₂ solution at ambient temperature at approximately 455 nm, which is much shorter than that of the parent molecule, [Pt(ppy)(ppyH)(Me)] (λ_max = 468). Therefore, the blue-shifted absorption and emission could be due to the greater triplet energy of dfpypy relative to that of ppy.

Figure 3
Absorption and emission of title compound at ambient temperature. Inset: extended absorption in the region of 350–450 nm.

5. TD-DFT calculations

To gain deeper insight into the geometrical configuration and nature of the luminescence properties, we performed TD–DFT calculations in the gas phase. Molecular orbital calculations were performed using the Gaussian 03 (Frisch et al., 2004 ) program. Fig. 4 shows the HOMO and LUMO energy levels of the optimized structures obtained from the single-crystal structure. The TDDFT results show that the triplet vertical excitation at the ground-state geometry corresponds to a π(dfpypy)/d(Pt) → π*(dfpypy) electronic promotion (³LC/MLCT). The HOMO level has significant contributions from the d orbital (64%) of Pt^II, with small contributions from the C-coordinating dfpypy. Notably, there is little contribution from N-coordinating dfpypy at the HOMO level. By contrast, the contribution from the π*orbitals of the dfpypy chelate is very significant at the LUMO level, whereas the contribution from the Pt^II atom is negligible. Thus, the electronic transition might arise from ligand-centered charge transfer [LCCT, π(dfpypy)–π*(dfpypy)] mixed with metal-to-ligand charge transfer [MLCT, (Pt(d)–π*(dfpypy)]. The HOMO energy level is −5.72 eV, which is much lower than that of its analogues, such as [Pt(ppy)(ppyH)(Me)] (E_HOMO = −5.27 eV). This lower HOMO energy level may be attributed to the replacement of the fluorine-substituted pyridine at the C,N chelate. The calculated LUMO energy is −1.95 eV and the energy gap (E_g) between HOMO and LUMO is 3.77 eV, which is comparable than that of [Pt(ppy)(ppyH)(Me)] (E_g = 3.80 eV).

Figure 4
Isodensity surfaces and energy levels of the MOs mainly involved in the S₀ → S₁ and S₀ → T₁ transitions. (Isocontour value = 0.03.)

6. Database survey

A survey of SciFinder (2021 ) for transition-metal complexes bearing the 2′,6′-difluoro-2,3′-bipyridine moiety as a ligand gave 25 hits. They include reports on the crystal structures and photophysical properties of Ir^III and Pt^II complexes based on this ligand (CSD refcode HOVHAC, Lee et al., 2009 ; OHUMUB01, Lee et al., 2015 ; JUDZAL, Park et al., 2015 ). The survey revealed no exact matches for the reported structure of the title complex. To the best of our knowledge, this is the first crystal structure reported for a platinum complex with the title ligand.

7. Synthesis and crystallization

All experiments were performed under a dry N₂ atmosphere using standard Schlenk techniques. All solvents were freshly distilled over appropriate drying reagents prior to use. All starting materials were purchased commercially and used without further purification. The ¹H NMR spectrum was recorded on a JEOL 400 MHz spectrometer. The starting material, 2′,6′-difluoro-2,3′-bipyridine was synthesized by a slight modification of the previous synthetic methodology reported by our group. (Kim et al., 2018 ; Oh et al., 2013 ). The title complex was also synthesized according to a previous report (Kang et al., 2022b). Slow evaporation from a dichloromethane/hexane solution afforded yellow crystals suitable for X-ray crystallography analysis. Yield 75%. ¹H NMR (400 MHz, CD₂Cl₂): δ 8.97 (dd, J = 5.6, 2.0 Hz, 1H), 8.58 (dd, J = 8.0, 1.6 Hz, 1H), 8.05 (m, 2H), 7.88 (t, J = 8.0 Hz, 1H), 7.74 (m, 2H), 7.05 (m, 2H), 7.57 (td, J = 6.8, 1.2 Hz, 1H), 6.77 (dd, J = 8.0, 2.4 Hz, 1H), 0.72 (s, J_HPt = 83.6 Hz, 3H). Analysis calculated for C₁₅H₁₄F₄N₄Pt; C 42.50; H 2.38; N 9.44; found: C 42.48, H 2.36, N 9.47%.

8. Refinement

Crystal data, data collection and crystal structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for Csp²—H, 0.98 Å for methyl C—H with U_iso(H) = 1.2–1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Pt(CH₃)(C₁₀H₅F₂N₂)(C₁₀H₆F₂N₂)]
M_r	593.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.1590 (4), 11.4767 (4), 16.1918 (5)
β (°)	109.1050 (12)
V (Å³)	1959.44 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.21
Crystal size (mm)	0.51 × 0.31 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.258, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	35428, 4873, 4088
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.066, 1.06
No. of reflections	4873
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.91, −1.66
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2216704

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010519/hb8042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010519/hb8042Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

(2',6'-Difluoro-2,3'-bipyridine-κN²)[2,6-difluoro-3-(pyridin-2-yl)phenyl-κ²C¹,N³]methylplatinum(II) top

Crystal data top

[Pt(CH₃)(C₁₀H₅F₂N₂)(C₁₀H₆F₂N₂)]	F(000) = 1128
M_r = 593.45	D_x = 2.012 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.1590 (4) Å	Cell parameters from 9651 reflections
b = 11.4767 (4) Å	θ = 2.6–28.3°
c = 16.1918 (5) Å	µ = 7.21 mm⁻¹
β = 109.1050 (12)°	T = 173 K
V = 1959.44 (12) Å³	Block, yellow
Z = 4	0.51 × 0.31 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	4088 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.050
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 28.3°, θ_min = 1.9°
T_min = 0.258, T_max = 0.746	h = −14→13
35428 measured reflections	k = −15→14
4873 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)] = 0.026	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0339P)² + 1.3145P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
4873 reflections	Δρ_max = 1.91 e Å⁻³
271 parameters	Δρ_min = −1.66 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
Pt1	0.79889 (2)	0.62391 (2)	0.38446 (2)	0.02333 (6)
F1	0.8075 (3)	0.4105 (2)	0.68292 (16)	0.0611 (7)
F2	1.1104 (2)	0.6711 (2)	0.70353 (13)	0.0498 (6)
F3	0.4034 (2)	0.9425 (2)	0.43326 (16)	0.0567 (7)
F4	0.7227 (2)	0.9395 (2)	0.32471 (16)	0.0525 (6)
N1	0.9578 (3)	0.7325 (2)	0.42974 (17)	0.0273 (6)
N2	0.9587 (3)	0.5417 (3)	0.69091 (18)	0.0356 (7)
N3	0.7423 (3)	0.6787 (2)	0.25218 (17)	0.0259 (6)
N4	0.5636 (3)	0.9383 (3)	0.37943 (19)	0.0374 (7)
C1	0.8571 (3)	0.5774 (3)	0.5081 (2)	0.0254 (7)
C2	0.8049 (4)	0.4979 (3)	0.5511 (2)	0.0333 (8)
H2	0.7332	0.4526	0.5197	0.040*
C3	0.8589 (4)	0.4860 (3)	0.6398 (2)	0.0363 (8)
C4	1.0080 (4)	0.6150 (3)	0.6493 (2)	0.0319 (8)
C5	0.9668 (3)	0.6381 (3)	0.5607 (2)	0.0259 (7)
C6	1.0230 (3)	0.7225 (3)	0.5166 (2)	0.0274 (7)
C7	1.1322 (4)	0.7899 (4)	0.5540 (2)	0.0404 (9)
H7	1.1767	0.7851	0.6149	0.048*
C8	1.1747 (4)	0.8630 (4)	0.5023 (3)	0.0493 (11)
H8	1.2493	0.9079	0.5273	0.059*
C9	1.1092 (4)	0.8711 (3)	0.4146 (3)	0.0437 (10)
H9	1.1380	0.9207	0.3781	0.052*
C10	0.9997 (4)	0.8051 (3)	0.3804 (2)	0.0359 (8)
H10	0.9530	0.8117	0.3200	0.043*
C11	0.4600 (4)	0.7447 (3)	0.2797 (3)	0.0381 (9)
H11	0.4238	0.6785	0.2454	0.046*
C12	0.4010 (4)	0.7948 (4)	0.3344 (3)	0.0406 (9)
H12	0.3245	0.7640	0.3392	0.049*
C13	0.4575 (4)	0.8898 (4)	0.3807 (3)	0.0390 (9)
C14	0.6162 (4)	0.8884 (3)	0.3281 (3)	0.0356 (9)
C15	0.5722 (3)	0.7921 (3)	0.2758 (2)	0.0292 (7)
C16	0.6394 (3)	0.7474 (3)	0.2168 (2)	0.0284 (7)
C17	0.5998 (4)	0.7774 (3)	0.1295 (2)	0.0380 (9)
H17	0.5262	0.8241	0.1059	0.046*
C18	0.6668 (4)	0.7397 (3)	0.0763 (2)	0.0382 (9)
H18	0.6413	0.7617	0.0164	0.046*
C19	0.7699 (4)	0.6705 (3)	0.1114 (2)	0.0364 (8)
H19	0.8172	0.6424	0.0763	0.044*
C20	0.8051 (4)	0.6414 (3)	0.1992 (2)	0.0342 (8)
H20	0.8771	0.5928	0.2231	0.041*
C21	0.6504 (4)	0.5106 (3)	0.3531 (2)	0.0383 (9)
H21A	0.6027	0.5169	0.2906	0.057*
H21B	0.6824	0.4309	0.3665	0.057*
H21C	0.5947	0.5294	0.3871	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.02173 (9)	0.02615 (9)	0.01832 (7)	−0.00107 (5)	0.00136 (5)	−0.00167 (4)
F1	0.086 (2)	0.0583 (15)	0.0389 (13)	−0.0253 (15)	0.0204 (13)	0.0103 (12)
F2	0.0438 (14)	0.0766 (16)	0.0194 (10)	−0.0193 (13)	−0.0028 (9)	−0.0036 (10)
F3	0.0405 (14)	0.0813 (19)	0.0549 (15)	0.0043 (13)	0.0243 (12)	−0.0113 (14)
F4	0.0407 (13)	0.0626 (16)	0.0616 (15)	−0.0250 (12)	0.0267 (12)	−0.0259 (13)
N1	0.0235 (14)	0.0344 (16)	0.0218 (13)	−0.0019 (12)	0.0044 (11)	−0.0006 (11)
N2	0.0425 (18)	0.0406 (18)	0.0239 (14)	0.0026 (15)	0.0110 (13)	0.0027 (12)
N3	0.0252 (14)	0.0243 (14)	0.0231 (13)	−0.0043 (12)	0.0008 (11)	−0.0029 (11)
N4	0.0296 (17)	0.048 (2)	0.0330 (16)	−0.0036 (15)	0.0080 (13)	−0.0094 (14)
C1	0.0286 (18)	0.0247 (17)	0.0218 (15)	0.0005 (14)	0.0066 (13)	−0.0037 (13)
C2	0.039 (2)	0.0299 (18)	0.0281 (17)	−0.0070 (16)	0.0071 (15)	−0.0012 (14)
C3	0.048 (2)	0.033 (2)	0.0296 (17)	−0.0009 (17)	0.0154 (16)	0.0039 (15)
C4	0.0282 (19)	0.042 (2)	0.0219 (16)	0.0013 (16)	0.0025 (14)	−0.0040 (14)
C5	0.0211 (16)	0.0328 (19)	0.0223 (15)	0.0010 (14)	0.0051 (13)	−0.0029 (13)
C6	0.0244 (17)	0.0363 (19)	0.0205 (15)	−0.0004 (15)	0.0062 (13)	−0.0027 (13)
C7	0.037 (2)	0.058 (3)	0.0226 (16)	−0.0141 (19)	0.0048 (15)	−0.0071 (16)
C8	0.042 (2)	0.065 (3)	0.038 (2)	−0.029 (2)	0.0086 (18)	−0.0128 (19)
C9	0.044 (3)	0.054 (3)	0.034 (2)	−0.016 (2)	0.0139 (18)	−0.0024 (17)
C10	0.035 (2)	0.045 (2)	0.0272 (17)	−0.0077 (17)	0.0085 (15)	0.0037 (15)
C11	0.029 (2)	0.033 (2)	0.046 (2)	−0.0004 (16)	0.0039 (16)	0.0021 (16)
C12	0.0227 (19)	0.044 (2)	0.053 (2)	−0.0001 (17)	0.0097 (17)	0.0070 (19)
C13	0.028 (2)	0.055 (3)	0.034 (2)	0.0036 (18)	0.0094 (16)	0.0003 (17)
C14	0.032 (2)	0.040 (2)	0.0322 (19)	−0.0058 (16)	0.0069 (16)	−0.0042 (15)
C15	0.0227 (17)	0.0321 (19)	0.0266 (16)	0.0024 (15)	−0.0004 (13)	0.0061 (14)
C16	0.0265 (17)	0.0286 (18)	0.0241 (15)	−0.0045 (14)	0.0002 (13)	−0.0017 (13)
C17	0.037 (2)	0.041 (2)	0.0276 (17)	0.0062 (17)	−0.0014 (15)	0.0065 (15)
C18	0.049 (2)	0.037 (2)	0.0223 (16)	−0.0066 (18)	0.0031 (16)	0.0015 (14)
C19	0.046 (2)	0.036 (2)	0.0278 (17)	−0.0094 (18)	0.0136 (16)	−0.0063 (15)
C20	0.037 (2)	0.034 (2)	0.0293 (18)	0.0016 (16)	0.0073 (16)	−0.0023 (14)
C21	0.033 (2)	0.040 (2)	0.0319 (18)	−0.0073 (17)	−0.0022 (15)	−0.0036 (16)

Geometric parameters (Å, º) top

Pt1—C1	1.966 (3)	C7—H7	0.9500
Pt1—C21	2.036 (4)	C8—C9	1.371 (6)
Pt1—N1	2.094 (3)	C8—H8	0.9500
Pt1—N3	2.120 (3)	C9—C10	1.389 (6)
F1—C3	1.352 (4)	C9—H9	0.9500
F2—C4	1.354 (4)	C10—H10	0.9500
F3—C13	1.339 (4)	C11—C15	1.386 (5)
F4—C14	1.342 (4)	C11—C12	1.390 (5)
N1—C10	1.340 (4)	C11—H11	0.9500
N1—C6	1.360 (4)	C12—C13	1.356 (6)
N2—C4	1.306 (5)	C12—H12	0.9500
N2—C3	1.316 (5)	C14—C15	1.382 (5)
N3—C20	1.343 (5)	C15—C16	1.484 (5)
N3—C16	1.356 (4)	C16—C17	1.379 (5)
N4—C14	1.297 (5)	C17—C18	1.383 (5)
N4—C13	1.314 (5)	C17—H17	0.9500
C1—C2	1.386 (5)	C18—C19	1.361 (6)
C1—C5	1.423 (5)	C18—H18	0.9500
C2—C3	1.371 (5)	C19—C20	1.386 (5)
C2—H2	0.9500	C19—H19	0.9500
C4—C5	1.382 (5)	C20—H20	0.9500
C5—C6	1.461 (5)	C21—H21A	0.9800
C6—C7	1.402 (5)	C21—H21B	0.9800
C7—C8	1.374 (6)	C21—H21C	0.9800

C1—Pt1—C21	92.94 (14)	C10—C9—H9	120.8
C1—Pt1—N1	81.10 (12)	N1—C10—C9	122.3 (3)
C21—Pt1—N1	174.00 (12)	N1—C10—H10	118.8
C1—Pt1—N3	177.73 (12)	C9—C10—H10	118.8
C21—Pt1—N3	89.33 (13)	C15—C11—C12	119.4 (4)
N1—Pt1—N3	96.63 (10)	C15—C11—H11	120.3
C10—N1—C6	119.7 (3)	C12—C11—H11	120.3
C10—N1—Pt1	125.6 (2)	C13—C12—C11	116.9 (4)
C6—N1—Pt1	114.7 (2)	C13—C12—H12	121.5
C4—N2—C3	113.7 (3)	C11—C12—H12	121.5
C20—N3—C16	117.6 (3)	N4—C13—F3	114.5 (3)
C20—N3—Pt1	120.3 (2)	N4—C13—C12	126.2 (4)
C16—N3—Pt1	122.0 (2)	F3—C13—C12	119.3 (4)
C14—N4—C13	114.9 (3)	N4—C14—F4	115.2 (3)
C2—C1—C5	116.3 (3)	N4—C14—C15	127.0 (4)
C2—C1—Pt1	129.6 (3)	F4—C14—C15	117.7 (3)
C5—C1—Pt1	114.1 (2)	C14—C15—C11	115.5 (3)
C3—C2—C1	118.6 (3)	C14—C15—C16	121.2 (3)
C3—C2—H2	120.7	C11—C15—C16	123.2 (3)
C1—C2—H2	120.7	N3—C16—C17	121.4 (3)
N2—C3—F1	113.7 (3)	N3—C16—C15	117.7 (3)
N2—C3—C2	127.0 (3)	C17—C16—C15	120.9 (3)
F1—C3—C2	119.3 (3)	C16—C17—C18	120.3 (4)
N2—C4—F2	112.4 (3)	C16—C17—H17	119.9
N2—C4—C5	127.3 (3)	C18—C17—H17	119.9
F2—C4—C5	120.4 (3)	C19—C18—C17	118.5 (3)
C4—C5—C1	117.1 (3)	C19—C18—H18	120.7
C4—C5—C6	125.7 (3)	C17—C18—H18	120.7
C1—C5—C6	117.1 (3)	C18—C19—C20	119.1 (4)
N1—C6—C7	119.7 (3)	C18—C19—H19	120.4
N1—C6—C5	113.0 (3)	C20—C19—H19	120.4
C7—C6—C5	127.4 (3)	N3—C20—C19	123.1 (4)
C8—C7—C6	119.9 (3)	N3—C20—H20	118.5
C8—C7—H7	120.0	C19—C20—H20	118.5
C6—C7—H7	120.0	Pt1—C21—H21A	109.5
C9—C8—C7	119.9 (4)	Pt1—C21—H21B	109.5
C9—C8—H8	120.1	H21A—C21—H21B	109.5
C7—C8—H8	120.1	Pt1—C21—H21C	109.5
C8—C9—C10	118.5 (4)	H21A—C21—H21C	109.5
C8—C9—H9	120.8	H21B—C21—H21C	109.5

C5—C1—C2—C3	2.0 (5)	C8—C9—C10—N1	−1.4 (6)
Pt1—C1—C2—C3	−175.8 (3)	C15—C11—C12—C13	0.7 (6)
C4—N2—C3—F1	−179.7 (3)	C14—N4—C13—F3	−179.5 (3)
C4—N2—C3—C2	−0.2 (6)	C14—N4—C13—C12	0.2 (6)
C1—C2—C3—N2	−0.9 (6)	C11—C12—C13—N4	−0.7 (6)
C1—C2—C3—F1	178.6 (3)	C11—C12—C13—F3	178.9 (4)
C3—N2—C4—F2	180.0 (3)	C13—N4—C14—F4	178.2 (3)
C3—N2—C4—C5	0.0 (6)	C13—N4—C14—C15	0.4 (6)
N2—C4—C5—C1	1.2 (6)	N4—C14—C15—C11	−0.4 (6)
F2—C4—C5—C1	−178.8 (3)	F4—C14—C15—C11	−178.1 (3)
N2—C4—C5—C6	178.7 (3)	N4—C14—C15—C16	177.0 (4)
F2—C4—C5—C6	−1.2 (5)	F4—C14—C15—C16	−0.8 (5)
C2—C1—C5—C4	−2.1 (5)	C12—C11—C15—C14	−0.2 (5)
Pt1—C1—C5—C4	176.0 (2)	C12—C11—C15—C16	−177.5 (3)
C2—C1—C5—C6	−179.9 (3)	C20—N3—C16—C17	0.5 (5)
Pt1—C1—C5—C6	−1.8 (4)	Pt1—N3—C16—C17	−176.6 (3)
C10—N1—C6—C7	1.2 (5)	C20—N3—C16—C15	−178.0 (3)
Pt1—N1—C6—C7	179.1 (3)	Pt1—N3—C16—C15	5.0 (4)
C10—N1—C6—C5	−178.7 (3)	C14—C15—C16—N3	81.1 (4)
Pt1—N1—C6—C5	−0.7 (4)	C11—C15—C16—N3	−101.7 (4)
C4—C5—C6—N1	−175.9 (3)	C14—C15—C16—C17	−97.3 (4)
C1—C5—C6—N1	1.6 (4)	C11—C15—C16—C17	79.8 (5)
C4—C5—C6—C7	4.2 (6)	N3—C16—C17—C18	−1.5 (5)
C1—C5—C6—C7	−178.2 (4)	C15—C16—C17—C18	176.9 (3)
N1—C6—C7—C8	−1.9 (6)	C16—C17—C18—C19	1.6 (6)
C5—C6—C7—C8	178.0 (4)	C17—C18—C19—C20	−0.8 (6)
C6—C7—C8—C9	0.9 (7)	C16—N3—C20—C19	0.4 (5)
C7—C8—C9—C10	0.7 (7)	Pt1—N3—C20—C19	177.5 (3)
C6—N1—C10—C9	0.5 (6)	C18—C19—C20—N3	−0.2 (6)
Pt1—N1—C10—C9	−177.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F2	0.95	2.24	2.858 (4)	122
C12—H12···F1ⁱ	0.95	2.44	3.259 (5)	144
C20—H20···N2ⁱⁱ	0.95	2.45	3.385 (5)	167

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

Funding information

Funding for this research was provided by: National Research Foundation of Korea (grant No. 2022R1F1A1063758); Ministry of Trade, Industry and Energy, Korea Evaluation Institute of Industrial Technology (grant No. 20018956).

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