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Acta Crystallogr E Crystallogr Commun. 2021 Feb 1; 77(Pt 2): 107–110.
Published online 2021 Jan 8. doi: 10.1107/S2056989021000128
PMCID: PMC7869555
PMID: 33614135

Synthesis, crystal structure and photophysical properties of chlorido­[2-(2′,6′-di­fluoro-2,3′-bipyri­din-6-yl-κN 1)-6-(pyridin-2-yl­oxy-κN)phenyl-κC 1]platinum(II)

Ki-Min Park,a Cheol Joo Moon,a Sanghyun Paek,b and Youngjin Kangc,*
Author information Article notes Copyright and License information PMC Disclaimer

Associated Data

Supplementary Materials

In the crystal of the title compound, which shows blue–green emission, the mol­ecules are connected via C—H⋯Cl/F, halogen⋯π and weak π–π stacking inter­actions.

Keywords: crystal structure, 2,3′-bi­pyridine, platinum compound, luminescence, OLED

Abstract

The title compound, [Pt(C21H12F2N3O)Cl], crystallizes with two crystallographically independent mol­ecules (A and B) in the asymmetric unit, which adopt similar conformations. The PtII atoms in both mol­ecules adopt distorted square-planar geometries, coordinated by one C and two N atoms from the tridentate 2′,6′-di­fluoro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine ligand and a chloride anion: the C and Cl atoms are trans. In the crystal, C—H⋯Cl/F hydrogen bonds, F⋯π and weak π–π stacking inter­actions between adjacent A and B mol­ecules and between pairs of inversion-related B mol­ecules lead to the formation of a two-dimensional supra­molecular network lying parallel to the ab plane. The sheets are stacked along the c-axis direction and linked by F⋯π and weak π–π stacking inter­actions between pairs of inversion-related A mol­ecules, forming a three-dimensional supra­molecular network. The photoluminescence quantum efficiency of the title compound in the blue–green region of the visible region (λmax = 517 and 544 nm) is estimated to be ∼0.2–0.3, indicating that the title compound could be a suitable candidate as the emitting material in organic light-emitting diode (OLED) applications.

Keywords: crystal structure, 2,3′-bi­pyridine, platinum compound, luminescence, OLED

Chemical context  

The C,N-chelating 2,3′-bi­pyridine-based transition-metal compounds have attracted much inter­est because of their wide applications as biological labels, photosensitizers in water reduction, sensors and organic light-emitting diodes (OLEDs) (Zaen et al., 2019a ▸,b ▸). Especially, highly efficient phospho­rescent metal complexes containing IrIII and PtII can be synthesized by using 2,3′-bi­pyridine as ligand, which feature a high triplet-state energy (Lee et al., 2018 ▸). In terms of the efficiency and stability of OLEDs, tetra­dentate ligand-based PtII complexes are known to be very good candidates as triplet emitters (Wang & Wang, 2019 ▸). The design of tetra­dentate ligands is focused on making appropriate coordination modes in order to form five or six- membered metallacycles. To achieve blue emission in Pt-based triplet emitters, two strategies have been employed as follows: (i) incorporation of a high-triplet-energy moiety into the ligand framework; (ii) the breakage of π-conjugation in the ligand to increase the energy gap (Fleetham et al., 2016 ▸; Kang et al., 2020 ▸). With these in mind, we have recently synthesized 2′,6′-di­fluoro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine as a ligand with high triplet energy (Park et al., 2020 ▸). By using this ligand, we have synthesized its coordination metal complex containing PtII and determined its crystal structure: herein, we report the structural and photophysical characteristics of chlorido­[2′,6′-di­flu­o­ro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine-κ 3 N,C,N′]platinum(II).

An external file that holds a picture, illustration, etc. Object name is e-77-00107-scheme1.jpg

Structural commentary  

The asymmetric unit of the title compound, Pt(C21H12F2N3O)Cl, contains two crystallographically independent mol­ecules (A and B denote the Pt1- and Pt2-containing mol­ecules, respectively), which adopt similar conformations (Fig. 1 ▸ and Table 1 ▸). The coordination sphere of the PtII atoms in both mol­ecules is a distorted square-planar geometry, with the respective coordination sites occupied by one C and two N atoms from the 2′,6′-di­fluoro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine ligand together with a chloride anion. The average length [1.949 (4) Å] of the Pt—C bonds is slightly shorter than that [2.042 (3) Å] of the Pt—N bonds because of back bonding between the metal and the anionic C atom of the ligand. The Cl1 and Cl2 atoms deviate from the mean plane consisting of the Pt and coordinated N/C atoms [r.m.s. deviations = 0.013 (1) (A) and 0.017 (1) Å (B)] with deviations of 0.700 (6) Å for A and 0.720 (6) Å for B.

An external file that holds a picture, illustration, etc. Object name is e-77-00107-fig1.jpg

The mol­ecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level. Black and green dashed lines represent intra­molecular C—H⋯Cl/F and Cl⋯π inter­actions, respectively, and yellow dashed line represents inter­molecular C—H⋯Cl inter­action. H atoms not involved in intra- and inter­molecular inter­actions are not shown for clarity.

Table 1

Selected geometric parameters (Å, °)
Pt1—C111.949 (4)Pt2—C321.948 (4)
Pt1—N12.035 (3)Pt2—N42.042 (3)
Pt1—N22.040 (3)Pt2—N52.049 (3)
Pt1—Cl12.4193 (8)Pt2—Cl22.4154 (8)
    
C11—Pt1—N190.92 (14)C32—Pt2—N490.87 (14)
C11—Pt1—N280.86 (14)C32—Pt2—N580.98 (13)
N1—Pt1—N2171.61 (12)N4—Pt2—N5171.56 (11)
C11—Pt1—Cl1163.28 (11)C32—Pt2—Cl2163.13 (11)
N1—Pt1—Cl194.81 (9)N4—Pt2—Cl294.78 (9)
N2—Pt1—Cl193.56 (9)N5—Pt2—Cl293.65 (8)

In each mol­ecule, there are intra­molecular C—H⋯Cl/F inter­actions, contributing to the stabilization of the mol­ecular structure (Table 2 ▸ and black dashed lines in Fig. 1 ▸). Moreover, an intra­molecular Cl⋯π inter­action [Cl1⋯Cg4 = 3.4537 (19) Å, Cl2⋯Cg8 = 3.455 (2) Å; green dashed lines in Fig. 1 ▸; Cg4 and Cg8 are the centroids of the N3/C17–C21 and N6/C38–C42 rings, respectively] between the coordinated chloride ion and the pyridine ring with fluorine substituents are also observed. Mol­ecules A and B are inter­linked by a C—H⋯Cl inter­action (Table 2 ▸ and yellow dashed line in Fig. 1 ▸). In the 6-phenyl-2,3′-bi­pyridine system in both mol­ecules, the phenyl­pyridine moieties are approximately coplanar with the dihedral angles between the pyridine ring and the attached phenyl rings being 10.01 (11) for A and 9.64 (11)° for B. However, the terminal di­fluoro-pyridine ring is tilted by 46.08 (9) for A and 46.96 (8)° for B with respect to phenyl­pyridine ring plane. This distortion may be caused by the intra­molecular Cl⋯π inter­action described above. The pyridine ring of the pyridine-2-yl­oxy group is slightly tilted by 22.09 (13) for A and 19.70 (13)° for B relative to the phenyl­pyridine ring plane.

Table 2

Hydrogen-bond geometry (Å, °)
D—H⋯A D—HH⋯A D⋯A D—H⋯A
C1—H1⋯Cl10.952.463.175 (4)132
C3—H3⋯F1i 0.952.533.474 (5)172
C15—H15⋯F10.952.562.989 (5)108
C22—H22⋯Cl20.952.453.170 (4)132
C23—H23⋯Cl2ii 0.952.823.540 (5)133
C24—H24⋯F3iii 0.952.503.443 (5)172
C36—H36⋯F30.952.552.975 (5)108
C41—H41⋯Cl10.952.793.684 (4)158

Symmetry codes: (i) An external file that holds a picture, illustration, etc. Object name is e-77-00107-efi1.jpg; (ii) An external file that holds a picture, illustration, etc. Object name is e-77-00107-efi2.jpg; (iii) An external file that holds a picture, illustration, etc. Object name is e-77-00107-efi3.jpg.

Supra­molecular features  

In the crystal structure, inter­molecular C–H⋯Cl/F hydrogen bonds (Table 2 ▸, yellow dashed lines in Figs. 1 ▸ and 2 ▸) between adjacent A and B mol­ecules and between pairs of inversion-related B mol­ecules lead to the formation of a two-dimensional supra­molecular network lying parallel to the ab plane. In addition, this network is consolidated by halogen⋯π and weak π–π stacking inter­actions [red and black dashed lines in Fig. 2 ▸, respectively; F2⋯Cg5i = 3.819 (3); Cg6⋯Cg7ii = 4.022 (2) Å; Cg5, Cg6 and Cg7 are the centroids of the N4/C22–C26, C27–C32 and N5/C33–C37 rings, respectively; symmetry codes: (i) −x + 2, −y + 1, −z; (ii) −x + 2, −y + 2, −z] between pairs of inversion-related B mol­ecules. These sheets are stacked along the c-axis direction and connected by F⋯π and weak π–π stacking inter­actions [sky-blue and green dashed lines in Fig. 3 ▸, respectively; F4⋯Cg1iii = 3.834 (3) Å; Cg2⋯Cg3iv = 4.073 (2) Å; Cg1, Cg2 and Cg3 are the centroids of the N1/C1–C5, C6–C11 and N2/C12–C16 rings, respectively; symmetry code: (iii) −x + 2, −y + 1, −z + 1; (iv) −x + 1, −y + 1, −z + 1] between pairs of inversion-related A mol­ecules, resulting in the formation of a three-dimensional supra­molecular network.

An external file that holds a picture, illustration, etc. Object name is e-77-00107-fig2.jpg

The two-dimensional supra­molecular network formed through inter­molecular C—H⋯Cl/F hydrogen bonds (yellow dashed lines), F⋯π (red dashed lines) and π–π stacking (black dashed lines) inter­actions between aromatic rings of inversion-related B mol­ecules. For clarity, H atoms not involved in the inter­molecular inter­actions have been omitted. Colour codes: violet = platinum, plum = chloride, green = fluorine, red = oxygen, blue = nitro­gen, grey = carbon and white = hydrogen.

An external file that holds a picture, illustration, etc. Object name is e-77-00107-fig3.jpg

The three-dimensional supra­molecular network formed through F⋯π and π–π stacking inter­actions (sky-blue and green dashed lines) between the two-dimensional networks stacked along the c-axis direction. H atoms not involved in the inter­molecular inter­actions have been omitted for clarity. Colour codes: violet = platinum, plum = chloride, green = fluorine, red = oxygen, blue = nitro­gen, grey = carbon and white = hydrogen.

Luminescent property  

The bright blueish-green emission of the title compound in solution is dominated by phospho­rescence as supported by an excited-state lifetime of more than 1 ms. Emission maxima appear at 517 and 544 nm at room temperature, as shown in Fig. 4 ▸. The emission observed in the title compound is attributable to an intra-ligand charge transfer (ILCT) transition mixed with a metal-to-ligand charge-transfer (MLCT) transition based on previous reports (Wang & Wang, 2019 ▸). Contrary to our expectations, the title compound shows green emission. It may be that the chloride ion bound directly to the platinum ion causes this effect because 2′,6′-di­fluoro-2,3′-bi­pyridine (dfpypy)-based platinum complexes without chloride ions often exhibit blue emission at room temperature. The photoluminescence quantum efficiency of the title compound was estimated to be ∼0.2–0.3 (Fig. 4 ▸, inset). Such efficiency is enough to use the title compound as the emitting material in organic light-emitting diode (OLED) applications.

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Emission spectrum of the title compound in solution at room temperature (Inset: Emission photo).

Database survey  

A survey of SciFinder (SciFinder, 2020 ▸) for 6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine (i.e., the title ligand without specifying the fluorine substituents), gave two hits. These are the reports of the crystal structures and photophysical properties of the free ligands for 2′,6′-di­fluoro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine and 2′,6′-dimeth­oxy-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine (Park et al., 2020 ▸). The survey revealed no exact matches for the reported structure of the title ligand: to the best of our knowledge, this is the first crystal structure reported for a platinum complex with the title ligand.

Synthesis and crystallization  

All experiments were performed under a dry N2 atmosphere using standard Schlenk techniques. All solvents used in this study were freshly distilled over appropriate drying reagents prior to use. All starting materials were commercially purchased and used without further purification. The 1H NMR spectrum was recorded on a JEOL 400 MHz spectrometer. The ligand, 2′,3′-di­fluoro-6-[3-(pyridin-2-yl­oxy)phen­yl]-2,3′-bi­pyridine (Park et al., 2018 ▸, 2020 ▸) and starting material, PtCl2(PhCN)2, (Uchiyama et al., 1980 ▸) were synthesized according to previous reports.

The title compound was synthesized as follows: A mixture of the ligand (0.36 g, 1.0 mmol), PtCl2(PhCN)2 (0.47 g, 1.0 mmol) and xylene (10 ml) was refluxed (433 K) for 48 h under an N2 flow. The xylene was removed by distillation and the crude product was purified by silica gel column chromatography (CH2Cl2:hexane = 1:1, v/v) to give the title compound as a yellow solid in 40% yield. Orange–red crystals suitable for X-ray crystallography analysis were obtained from a CH2Cl2/hexane solution by slow evaporation. 1H NMR (400 MHz, CDCl3) δ 9.91 (dd, J = 6.0, 2.0 Hz, 1H), 8.20(m, 1H), 7.97 (t, J = 8.0 Hz, 1H), 7.90–7.84 (m, 2H), 7.50–7.42 (m, 2H), 7.30–7.22 (m, 2H), 7.06 (d, J = 7.6 Hz, 1H), 6.97-6.91 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 206.5, 167.3, 156.4, 155.9, 151.0, 148.1, 146.6, 146.5, 140.1, 139.0, 125.7, 125.0, 121.0, 118.4, 118.3, 117.6, 115.9, 106.0, 105.9, 105.7, 105.6. Analysis calculated for C21H12ClF2N3OPt: C 42.69; H 2.05; N 7.11%; found: C 42.70, H 2.06, N 7.09%.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were positioned geometrically and refined using a riding model: C—H = 0.95 Å with U iso(H) = 1.2U eq(C).

Table 3

Experimental details
Crystal data
Chemical formula[Pt(C21H12F2N3O)Cl]
M r 590.88
Crystal system, space groupTriclinic, P An external file that holds a picture, illustration, etc. Object name is e-77-00107-efi4.jpg
Temperature (K)173
a, b, c (Å)12.4924 (9), 12.5008 (9), 14.1163 (11)
α, β, γ (°)74.498 (3), 73.401 (3), 61.954 (3)
V (Å3)1841.3 (2)
Z 4
Radiation typeMo Kα
μ (mm−1)7.80
Crystal size (mm)0.46 × 0.32 × 0.24
 
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan (SADABS; Bruker, 2014 ▸)
T min, T max 0.233, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections34679, 9126, 7667
R int 0.045
(sin θ/λ)max (Å−1)0.667
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.028, 0.067, 1.03
No. of reflections9126
No. of parameters523
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.64, −1.21

Computer programs: APEX2 (Bruker, 2014 ▸), SAINT (Bruker, 2014 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014/7 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 2010 ▸), SHELXTL (Sheldrick, 2008 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989021000128/hb7960sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989021000128/hb7960Isup2.hkl

CCDC reference: 2053861

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

supplementary crystallographic information

Crystal data

[Pt(C21H12F2N3O)Cl]Z = 4
Mr = 590.88F(000) = 1120
Triclinic, P1Dx = 2.131 Mg m−3
a = 12.4924 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.5008 (9) ÅCell parameters from 9258 reflections
c = 14.1163 (11) Åθ = 2.6–28.3°
α = 74.498 (3)°µ = 7.80 mm−1
β = 73.401 (3)°T = 173 K
γ = 61.954 (3)°Block, yellow
V = 1841.3 (2) Å30.46 × 0.32 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer7667 reflections with I > 2σ(I)
φ and ω scansRint = 0.045
Absorption correction: multi-scan (SADABS; Bruker, 2014)θmax = 28.3°, θmin = 1.5°
Tmin = 0.233, Tmax = 0.746h = −16→16
34679 measured reflectionsk = −15→16
9126 independent reflectionsl = −18→18

Refinement

Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.067w = 1/[σ2(Fo2) + (0.0327P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
9126 reflectionsΔρmax = 1.64 e Å−3
523 parametersΔρmin = −1.21 e Å−3

Special details

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)

xyzUiso*/Ueq
Pt10.69646 (2)0.61157 (2)0.39509 (2)0.03247 (5)
Pt20.88563 (2)0.80611 (2)0.10492 (2)0.03240 (5)
Cl10.86494 (8)0.44909 (8)0.47237 (7)0.0410 (2)
Cl21.05014 (8)0.63393 (8)0.02853 (7)0.0413 (2)
F10.8999 (2)0.1430 (2)0.4219 (2)0.0689 (7)
F21.2132 (2)0.1920 (3)0.1978 (2)0.0730 (8)
F31.3562 (2)0.6034 (2)0.0774 (2)0.0685 (7)
F41.3006 (3)0.2977 (2)0.3009 (2)0.0711 (7)
O10.5471 (3)0.9163 (2)0.3614 (3)0.0668 (9)
O20.5792 (2)0.9597 (3)0.1333 (3)0.0674 (9)
N10.7262 (3)0.7497 (3)0.4159 (2)0.0358 (7)
N20.6446 (3)0.4930 (3)0.3661 (2)0.0340 (7)
N31.0540 (3)0.1720 (3)0.3099 (3)0.0504 (9)
N40.7472 (3)0.7748 (3)0.0861 (2)0.0358 (7)
N51.0042 (3)0.8593 (3)0.1331 (2)0.0340 (7)
N61.3250 (3)0.4527 (3)0.1888 (3)0.0479 (8)
C10.8297 (4)0.7229 (4)0.4491 (3)0.0421 (9)
H10.88090.63890.46880.050*
C20.8652 (5)0.8078 (4)0.4562 (4)0.0550 (11)
H20.93870.78330.47970.066*
C30.7916 (5)0.9306 (4)0.4283 (4)0.0661 (13)
H30.81380.99210.43220.079*
C40.6870 (5)0.9618 (4)0.3953 (4)0.0657 (13)
H40.63581.04550.37480.079*
C50.6559 (4)0.8701 (4)0.3920 (3)0.0511 (11)
C60.4800 (4)0.8536 (4)0.3637 (3)0.0505 (10)
C70.3573 (4)0.9249 (4)0.3571 (3)0.0586 (12)
H70.32441.01170.34990.070*
C80.2835 (4)0.8706 (4)0.3610 (3)0.0587 (12)
H80.19850.91990.35850.070*
C90.3308 (4)0.7440 (4)0.3685 (3)0.0490 (10)
H90.27910.70590.37200.059*
C100.4556 (4)0.6748 (4)0.3706 (3)0.0416 (9)
C110.5324 (4)0.7272 (3)0.3681 (3)0.0393 (8)
C120.5184 (3)0.5402 (3)0.3718 (3)0.0375 (8)
C130.4631 (4)0.4677 (4)0.3732 (3)0.0459 (10)
H130.37620.50210.37850.055*
C140.5330 (4)0.3454 (4)0.3668 (3)0.0498 (10)
H140.49490.29330.37190.060*
C150.6593 (4)0.2998 (4)0.3530 (3)0.0463 (9)
H150.70910.21610.34570.056*
C160.7148 (4)0.3742 (3)0.3495 (3)0.0370 (8)
C170.8482 (3)0.3332 (3)0.3148 (3)0.0365 (8)
C180.9353 (4)0.2176 (3)0.3469 (3)0.0461 (10)
C191.0912 (4)0.2433 (4)0.2383 (3)0.0492 (10)
C201.0203 (4)0.3602 (4)0.1990 (3)0.0475 (9)
H201.05440.40820.14730.057*
C210.8959 (4)0.4040 (3)0.2393 (3)0.0426 (9)
H210.84180.48470.21460.051*
C220.7757 (3)0.6672 (4)0.0570 (3)0.0408 (9)
H220.86060.61360.04030.049*
C230.6911 (4)0.6315 (5)0.0502 (4)0.0566 (12)
H230.71620.55560.02940.068*
C240.5660 (4)0.7100 (5)0.0748 (4)0.0658 (14)
H240.50420.68800.07150.079*
C250.5344 (4)0.8173 (5)0.1032 (4)0.0655 (13)
H250.44990.87180.12020.079*
C260.6258 (4)0.8477 (4)0.1076 (3)0.0500 (10)
C270.6426 (4)1.0252 (4)0.1338 (3)0.0480 (10)
C280.5712 (4)1.1484 (4)0.1399 (3)0.0576 (12)
H280.48411.18230.14630.069*
C290.6266 (4)1.2206 (4)0.1368 (3)0.0589 (12)
H290.57751.30560.13940.071*
C300.7530 (4)1.1732 (4)0.1298 (3)0.0507 (10)
H300.79101.22490.12610.061*
C310.8231 (4)1.0476 (4)0.1284 (3)0.0398 (9)
C320.7694 (3)0.9716 (3)0.1304 (3)0.0380 (8)
C330.9573 (4)0.9852 (4)0.1276 (3)0.0398 (9)
C341.0291 (4)1.0404 (4)0.1256 (3)0.0439 (9)
H340.99491.12720.11930.053*
C351.1513 (4)0.9709 (4)0.1327 (3)0.0499 (10)
H351.20351.00870.12810.060*
C361.1962 (4)0.8450 (4)0.1465 (3)0.0466 (9)
H361.27970.79550.15410.056*
C371.1221 (3)0.7895 (4)0.1496 (3)0.0370 (8)
C381.1627 (3)0.6569 (3)0.1841 (3)0.0349 (8)
C391.2793 (3)0.5693 (4)0.1529 (3)0.0452 (10)
C401.2510 (4)0.4174 (4)0.2611 (3)0.0494 (10)
C411.1313 (4)0.4895 (4)0.2994 (3)0.0463 (9)
H411.08100.45700.35020.056*
C421.0885 (3)0.6118 (4)0.2596 (3)0.0414 (9)
H421.00660.66650.28430.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pt10.03777 (9)0.02938 (8)0.03200 (8)−0.01344 (6)−0.01039 (6)−0.00506 (6)
Pt20.02768 (8)0.03840 (9)0.03250 (8)−0.01276 (6)−0.00509 (6)−0.01087 (6)
Cl10.0438 (5)0.0350 (4)0.0486 (5)−0.0142 (4)−0.0198 (4)−0.0065 (4)
Cl20.0340 (5)0.0435 (5)0.0498 (5)−0.0123 (4)−0.0076 (4)−0.0212 (4)
F10.0752 (18)0.0410 (13)0.0822 (19)−0.0289 (13)−0.0188 (15)0.0153 (13)
F20.0478 (15)0.0675 (18)0.093 (2)−0.0155 (14)−0.0027 (14)−0.0253 (15)
F30.0387 (13)0.0711 (17)0.0841 (19)−0.0261 (13)0.0130 (12)−0.0154 (14)
F40.0702 (18)0.0477 (15)0.0856 (19)−0.0189 (14)−0.0214 (15)−0.0003 (14)
O10.071 (2)0.0312 (15)0.105 (3)−0.0161 (15)−0.047 (2)0.0014 (16)
O20.0295 (15)0.071 (2)0.104 (3)−0.0123 (15)−0.0051 (15)−0.0447 (19)
N10.0453 (18)0.0280 (15)0.0366 (16)−0.0167 (14)−0.0065 (13)−0.0082 (12)
N20.0411 (17)0.0318 (16)0.0313 (16)−0.0158 (14)−0.0099 (13)−0.0047 (12)
N30.050 (2)0.0360 (18)0.067 (2)−0.0129 (17)−0.0152 (18)−0.0159 (17)
N40.0288 (15)0.0432 (18)0.0364 (16)−0.0142 (14)−0.0073 (12)−0.0088 (14)
N50.0321 (16)0.0387 (17)0.0330 (16)−0.0136 (14)−0.0054 (12)−0.0122 (13)
N60.0372 (18)0.045 (2)0.061 (2)−0.0130 (16)−0.0155 (17)−0.0106 (17)
C10.048 (2)0.042 (2)0.045 (2)−0.0228 (19)−0.0103 (18)−0.0106 (17)
C20.064 (3)0.051 (3)0.062 (3)−0.030 (2)−0.014 (2)−0.015 (2)
C30.090 (4)0.049 (3)0.079 (3)−0.040 (3)−0.024 (3)−0.012 (2)
C40.084 (3)0.031 (2)0.092 (4)−0.022 (2)−0.039 (3)−0.006 (2)
C50.062 (3)0.037 (2)0.052 (3)−0.015 (2)−0.018 (2)−0.0069 (19)
C60.056 (3)0.037 (2)0.053 (3)−0.011 (2)−0.021 (2)−0.0040 (19)
C70.063 (3)0.041 (2)0.066 (3)−0.006 (2)−0.031 (2)−0.008 (2)
C80.046 (2)0.061 (3)0.057 (3)−0.008 (2)−0.022 (2)−0.006 (2)
C90.041 (2)0.056 (3)0.047 (2)−0.011 (2)−0.0166 (18)−0.011 (2)
C100.045 (2)0.045 (2)0.034 (2)−0.0149 (19)−0.0134 (17)−0.0064 (17)
C110.044 (2)0.038 (2)0.0312 (19)−0.0135 (18)−0.0126 (16)−0.0006 (16)
C120.041 (2)0.042 (2)0.0297 (19)−0.0163 (18)−0.0118 (16)−0.0026 (16)
C130.045 (2)0.061 (3)0.041 (2)−0.025 (2)−0.0128 (18)−0.0124 (19)
C140.063 (3)0.054 (3)0.052 (2)−0.038 (2)−0.018 (2)−0.007 (2)
C150.058 (3)0.042 (2)0.046 (2)−0.025 (2)−0.0131 (19)−0.0092 (18)
C160.049 (2)0.0316 (18)0.0343 (19)−0.0173 (17)−0.0125 (16)−0.0048 (15)
C170.045 (2)0.0310 (18)0.037 (2)−0.0149 (17)−0.0091 (16)−0.0110 (16)
C180.055 (3)0.034 (2)0.053 (3)−0.020 (2)−0.012 (2)−0.0076 (18)
C190.043 (2)0.047 (2)0.058 (3)−0.013 (2)−0.010 (2)−0.022 (2)
C200.052 (2)0.052 (2)0.041 (2)−0.026 (2)−0.0040 (18)−0.0090 (19)
C210.054 (2)0.036 (2)0.035 (2)−0.0141 (18)−0.0130 (17)−0.0053 (16)
C220.0339 (19)0.048 (2)0.047 (2)−0.0187 (18)−0.0086 (16)−0.0132 (18)
C230.051 (3)0.067 (3)0.065 (3)−0.033 (2)−0.011 (2)−0.016 (2)
C240.042 (3)0.094 (4)0.081 (3)−0.039 (3)−0.010 (2)−0.027 (3)
C250.032 (2)0.081 (3)0.091 (4)−0.020 (2)−0.008 (2)−0.038 (3)
C260.036 (2)0.064 (3)0.052 (3)−0.017 (2)−0.0089 (18)−0.020 (2)
C270.036 (2)0.055 (3)0.048 (2)−0.011 (2)−0.0038 (18)−0.021 (2)
C280.039 (2)0.063 (3)0.064 (3)−0.004 (2)−0.011 (2)−0.032 (2)
C290.055 (3)0.045 (2)0.060 (3)−0.001 (2)−0.010 (2)−0.024 (2)
C300.058 (3)0.044 (2)0.045 (2)−0.013 (2)−0.008 (2)−0.0184 (19)
C310.040 (2)0.040 (2)0.037 (2)−0.0118 (18)−0.0059 (16)−0.0147 (17)
C320.035 (2)0.042 (2)0.0330 (19)−0.0118 (17)−0.0047 (15)−0.0111 (16)
C330.042 (2)0.043 (2)0.033 (2)−0.0153 (18)0.0004 (16)−0.0188 (17)
C340.052 (2)0.042 (2)0.040 (2)−0.019 (2)−0.0089 (18)−0.0125 (17)
C350.053 (3)0.060 (3)0.055 (3)−0.035 (2)−0.0053 (19)−0.019 (2)
C360.036 (2)0.058 (3)0.052 (2)−0.021 (2)−0.0093 (17)−0.015 (2)
C370.036 (2)0.047 (2)0.0302 (19)−0.0164 (18)−0.0043 (15)−0.0132 (16)
C380.0292 (18)0.044 (2)0.0349 (19)−0.0143 (16)−0.0083 (15)−0.0107 (16)
C390.032 (2)0.062 (3)0.047 (2)−0.025 (2)−0.0054 (17)−0.011 (2)
C400.050 (2)0.045 (2)0.058 (3)−0.017 (2)−0.022 (2)−0.008 (2)
C410.050 (2)0.055 (3)0.035 (2)−0.025 (2)−0.0102 (18)−0.0031 (18)
C420.035 (2)0.053 (2)0.034 (2)−0.0157 (18)−0.0054 (15)−0.0114 (17)

Geometric parameters (Å, º)

Pt1—C111.949 (4)C12—C131.368 (5)
Pt1—N12.035 (3)C13—C141.370 (6)
Pt1—N22.040 (3)C13—H130.9500
Pt1—Cl12.4193 (8)C14—C151.375 (6)
Pt2—C321.948 (4)C14—H140.9500
Pt2—N42.042 (3)C15—C161.381 (5)
Pt2—N52.049 (3)C15—H150.9500
Pt2—Cl22.4154 (8)C16—C171.465 (5)
F1—C181.334 (5)C17—C211.380 (5)
F2—C191.356 (5)C17—C181.389 (5)
F3—C391.341 (4)C19—C201.363 (6)
F4—C401.347 (5)C20—C211.379 (5)
O1—C51.354 (5)C20—H200.9500
O1—C61.380 (5)C21—H210.9500
O2—C261.347 (5)C22—C231.360 (6)
O2—C271.385 (5)C22—H220.9500
N1—C51.344 (5)C23—C241.398 (6)
N1—C11.364 (5)C23—H230.9500
N2—C161.369 (5)C24—C251.348 (7)
N2—C121.385 (5)C24—H240.9500
N3—C191.292 (6)C25—C261.382 (6)
N3—C181.311 (5)C25—H250.9500
N4—C261.344 (5)C27—C281.382 (6)
N4—C221.366 (5)C27—C321.391 (5)
N5—C371.365 (5)C28—C291.357 (7)
N5—C331.386 (5)C28—H280.9500
N6—C401.301 (6)C29—C301.384 (6)
N6—C391.302 (5)C29—H290.9500
C1—C21.364 (6)C30—C311.395 (5)
C1—H10.9500C30—H300.9500
C2—C31.383 (6)C31—C321.389 (5)
C2—H20.9500C31—C331.477 (5)
C3—C41.359 (7)C33—C341.355 (5)
C3—H30.9500C34—C351.374 (6)
C4—C51.388 (6)C34—H340.9500
C4—H40.9500C35—C361.378 (6)
C6—C71.380 (6)C35—H350.9500
C6—C111.388 (5)C36—C371.381 (5)
C7—C81.362 (7)C36—H360.9500
C7—H70.9500C37—C381.470 (5)
C8—C91.391 (6)C38—C391.380 (5)
C8—H80.9500C38—C421.386 (5)
C9—C101.387 (5)C40—C411.369 (6)
C9—H90.9500C41—C421.371 (5)
C10—C111.383 (6)C41—H410.9500
C10—C121.482 (5)C42—H420.9500
C11—Pt1—N190.92 (14)C21—C17—C16121.3 (3)
C11—Pt1—N280.86 (14)C18—C17—C16123.7 (4)
N1—Pt1—N2171.61 (12)N3—C18—F1114.5 (4)
C11—Pt1—Cl1163.28 (11)N3—C18—C17125.7 (4)
N1—Pt1—Cl194.81 (9)F1—C18—C17119.7 (4)
N2—Pt1—Cl193.56 (9)N3—C19—F2114.7 (4)
C32—Pt2—N490.87 (14)N3—C19—C20126.8 (4)
C32—Pt2—N580.98 (13)F2—C19—C20118.4 (4)
N4—Pt2—N5171.56 (11)C19—C20—C21115.4 (4)
C32—Pt2—Cl2163.13 (11)C19—C20—H20122.3
N4—Pt2—Cl294.78 (9)C21—C20—H20122.3
N5—Pt2—Cl293.65 (8)C20—C21—C17121.5 (4)
C5—O1—C6127.3 (3)C20—C21—H21119.3
C26—O2—C27128.0 (3)C17—C21—H21119.3
C5—N1—C1114.8 (3)C23—C22—N4124.6 (4)
C5—N1—Pt1125.2 (3)C23—C22—H22117.7
C1—N1—Pt1119.8 (2)N4—C22—H22117.7
C16—N2—C12117.5 (3)C22—C23—C24118.0 (4)
C16—N2—Pt1129.2 (3)C22—C23—H23121.0
C12—N2—Pt1113.1 (2)C24—C23—H23121.0
C19—N3—C18115.8 (4)C25—C24—C23119.1 (4)
C26—N4—C22115.1 (3)C25—C24—H24120.5
C26—N4—Pt2125.5 (3)C23—C24—H24120.5
C22—N4—Pt2119.2 (2)C24—C25—C26119.6 (4)
C37—N5—C33117.7 (3)C24—C25—H25120.2
C37—N5—Pt2129.0 (2)C26—C25—H25120.2
C33—N5—Pt2113.1 (2)N4—C26—O2124.0 (4)
C40—N6—C39115.3 (4)N4—C26—C25123.7 (4)
C2—C1—N1124.8 (4)O2—C26—C25112.2 (4)
C2—C1—H1117.6C28—C27—O2115.6 (4)
N1—C1—H1117.6C28—C27—C32121.5 (4)
C1—C2—C3118.4 (4)O2—C27—C32122.9 (4)
C1—C2—H2120.8C29—C28—C27119.5 (4)
C3—C2—H2120.8C29—C28—H28120.3
C4—C3—C2118.9 (4)C27—C28—H28120.3
C4—C3—H3120.5C28—C29—C30121.5 (4)
C2—C3—H3120.5C28—C29—H29119.2
C3—C4—C5119.3 (4)C30—C29—H29119.2
C3—C4—H4120.4C29—C30—C31118.4 (4)
C5—C4—H4120.4C29—C30—H30120.8
N1—C5—O1124.2 (4)C31—C30—H30120.8
N1—C5—C4123.8 (4)C32—C31—C30121.4 (4)
O1—C5—C4112.0 (4)C32—C31—C33115.2 (3)
O1—C6—C7115.9 (4)C30—C31—C33123.3 (4)
O1—C6—C11122.8 (4)C31—C32—C27117.6 (4)
C7—C6—C11121.3 (4)C31—C32—Pt2114.9 (3)
C8—C7—C6119.9 (4)C27—C32—Pt2126.6 (3)
C8—C7—H7120.1C34—C33—N5122.0 (4)
C6—C7—H7120.1C34—C33—C31125.6 (4)
C7—C8—C9120.9 (4)N5—C33—C31112.4 (3)
C7—C8—H8119.5C33—C34—C35120.1 (4)
C9—C8—H8119.5C33—C34—H34120.0
C10—C9—C8118.0 (4)C35—C34—H34120.0
C10—C9—H9121.0C34—C35—C36118.3 (4)
C8—C9—H9121.0C34—C35—H35120.8
C11—C10—C9122.3 (4)C36—C35—H35120.8
C11—C10—C12114.5 (3)C35—C36—C37121.1 (4)
C9—C10—C12123.1 (4)C35—C36—H36119.4
C10—C11—C6117.4 (4)C37—C36—H36119.4
C10—C11—Pt1115.3 (3)N5—C37—C36120.1 (4)
C6—C11—Pt1126.4 (3)N5—C37—C38119.0 (3)
C13—C12—N2121.7 (4)C36—C37—C38120.3 (3)
C13—C12—C10125.7 (4)C39—C38—C42114.6 (3)
N2—C12—C10112.5 (3)C39—C38—C37124.0 (3)
C12—C13—C14120.2 (4)C42—C38—C37121.1 (3)
C12—C13—H13119.9N6—C39—F3114.3 (4)
C14—C13—H13119.9N6—C39—C38126.7 (4)
C13—C14—C15118.6 (4)F3—C39—C38118.9 (4)
C13—C14—H14120.7N6—C40—F4115.0 (4)
C15—C14—H14120.7N6—C40—C41126.4 (4)
C14—C15—C16120.9 (4)F4—C40—C41118.6 (4)
C14—C15—H15119.6C40—C41—C42115.7 (4)
C16—C15—H15119.6C40—C41—H41122.1
N2—C16—C15120.5 (4)C42—C41—H41122.1
N2—C16—C17118.4 (3)C41—C42—C38121.2 (4)
C15—C16—C17120.5 (3)C41—C42—H42119.4
C21—C17—C18114.7 (4)C38—C42—H42119.4
C5—N1—C1—C2−1.9 (6)C26—N4—C22—C23−0.8 (6)
Pt1—N1—C1—C2173.2 (3)Pt2—N4—C22—C23174.2 (3)
N1—C1—C2—C30.3 (7)N4—C22—C23—C24−0.1 (7)
C1—C2—C3—C40.2 (7)C22—C23—C24—C250.5 (8)
C2—C3—C4—C51.0 (8)C23—C24—C25—C260.0 (8)
C1—N1—C5—O1−177.3 (4)C22—N4—C26—O2−176.9 (4)
Pt1—N1—C5—O18.0 (6)Pt2—N4—C26—O28.5 (6)
C1—N1—C5—C43.2 (6)C22—N4—C26—C251.3 (6)
Pt1—N1—C5—C4−171.6 (4)Pt2—N4—C26—C25−173.3 (4)
C6—O1—C5—N110.8 (7)C27—O2—C26—N46.4 (7)
C6—O1—C5—C4−169.6 (4)C27—O2—C26—C25−172.0 (4)
C3—C4—C5—N1−2.9 (8)C24—C25—C26—N4−0.9 (8)
C3—C4—C5—O1177.5 (5)C24—C25—C26—O2177.5 (5)
C5—O1—C6—C7161.3 (4)C26—O2—C27—C28165.0 (4)
C5—O1—C6—C11−21.3 (7)C26—O2—C27—C32−16.3 (7)
O1—C6—C7—C8−178.6 (4)O2—C27—C28—C29−177.4 (4)
C11—C6—C7—C84.0 (7)C32—C27—C28—C293.9 (7)
C6—C7—C8—C9−2.0 (7)C27—C28—C29—C30−1.5 (7)
C7—C8—C9—C10−0.8 (7)C28—C29—C30—C31−1.5 (7)
C8—C9—C10—C111.7 (6)C29—C30—C31—C322.1 (6)
C8—C9—C10—C12−176.0 (4)C29—C30—C31—C33−176.0 (4)
C9—C10—C11—C60.2 (6)C30—C31—C32—C270.1 (6)
C12—C10—C11—C6178.1 (3)C33—C31—C32—C27178.4 (3)
C9—C10—C11—Pt1169.8 (3)C30—C31—C32—Pt2169.9 (3)
C12—C10—C11—Pt1−12.4 (4)C33—C31—C32—Pt2−11.8 (4)
O1—C6—C11—C10179.7 (4)C28—C27—C32—C31−3.2 (6)
C7—C6—C11—C10−3.1 (6)O2—C27—C32—C31178.2 (4)
O1—C6—C11—Pt111.4 (6)C28—C27—C32—Pt2−171.7 (3)
C7—C6—C11—Pt1−171.3 (3)O2—C27—C32—Pt29.7 (6)
C16—N2—C12—C137.8 (5)C37—N5—C33—C348.4 (5)
Pt1—N2—C12—C13−167.8 (3)Pt2—N5—C33—C34−167.7 (3)
C16—N2—C12—C10−169.1 (3)C37—N5—C33—C31−169.4 (3)
Pt1—N2—C12—C1015.3 (4)Pt2—N5—C33—C3114.5 (4)
C11—C10—C12—C13−179.3 (4)C32—C31—C33—C34179.9 (4)
C9—C10—C12—C13−1.5 (6)C30—C31—C33—C34−1.8 (6)
C11—C10—C12—N2−2.5 (5)C32—C31—C33—N5−2.3 (5)
C9—C10—C12—N2175.3 (3)C30—C31—C33—N5175.9 (3)
N2—C12—C13—C14−1.3 (6)N5—C33—C34—C35−2.4 (6)
C10—C12—C13—C14175.2 (4)C31—C33—C34—C35175.1 (4)
C12—C13—C14—C15−4.0 (6)C33—C34—C35—C36−3.1 (6)
C13—C14—C15—C162.6 (6)C34—C35—C36—C372.4 (6)
C12—N2—C16—C15−9.2 (5)C33—N5—C37—C36−8.9 (5)
Pt1—N2—C16—C15165.6 (3)Pt2—N5—C37—C36166.4 (3)
C12—N2—C16—C17162.7 (3)C33—N5—C37—C38162.7 (3)
Pt1—N2—C16—C17−22.5 (5)Pt2—N5—C37—C38−21.9 (5)
C14—C15—C16—N24.2 (6)C35—C36—C37—N53.8 (6)
C14—C15—C16—C17−167.5 (4)C35—C36—C37—C38−167.8 (4)
N2—C16—C17—C21−45.1 (5)N5—C37—C38—C39142.1 (4)
C15—C16—C17—C21126.7 (4)C36—C37—C38—C39−46.3 (5)
N2—C16—C17—C18141.4 (4)N5—C37—C38—C42−44.8 (5)
C15—C16—C17—C18−46.8 (5)C36—C37—C38—C42126.8 (4)
C19—N3—C18—F1−178.8 (4)C40—N6—C39—F3−178.8 (3)
C19—N3—C18—C171.0 (6)C40—N6—C39—C380.3 (6)
C21—C17—C18—N3−2.0 (6)C42—C38—C39—N6−1.7 (6)
C16—C17—C18—N3171.9 (4)C37—C38—C39—N6171.7 (4)
C21—C17—C18—F1177.7 (3)C42—C38—C39—F3177.4 (3)
C16—C17—C18—F1−8.4 (6)C37—C38—C39—F3−9.2 (5)
C18—N3—C19—F2−176.8 (3)C39—N6—C40—F4−177.1 (3)
C18—N3—C19—C201.0 (6)C39—N6—C40—C412.3 (6)
N3—C19—C20—C21−1.7 (6)N6—C40—C41—C42−3.1 (6)
F2—C19—C20—C21176.1 (3)F4—C40—C41—C42176.4 (3)
C19—C20—C21—C170.4 (5)C40—C41—C42—C381.3 (5)
C18—C17—C21—C201.2 (5)C39—C38—C42—C410.8 (5)
C16—C17—C21—C20−172.8 (3)C37—C38—C42—C41−172.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
C1—H1···Cl10.952.463.175 (4)132
C3—H3···F1i0.952.533.474 (5)172
C15—H15···F10.952.562.989 (5)108
C22—H22···Cl20.952.453.170 (4)132
C23—H23···Cl2ii0.952.823.540 (5)133
C24—H24···F3iii0.952.503.443 (5)172
C36—H36···F30.952.552.975 (5)108
C41—H41···Cl10.952.793.684 (4)158

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

Funding Statement

This work was funded by National Research Foundation of Korea (NRF) grants NRF-2016R1D1A1B01012630; and NRF-2018R1D1A3A03000716. Kangwon National University grant .

References

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