Synthesis, crystal structure and photophysical properties of bis­[2,6-di­fluoro-3-(pyridin-2-yl)pyridine-κN](tri­fluoro­methane­sulfonato-κO)silver(I)

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

doi:10.1107/S2056989021011282

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ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1224-1228

https://doi.org/10.1107/S2056989021011282

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Synthesis, crystal structure and photophysical properties of bis[2,6-difluoro-3-(pyridin-2-yl)pyridine-κN](trifluoromethanesulfonato-κO)silver(I)

Suk-Hee Moon,^a Sanghyun Paek ^b and Youngjin Kang ^c ^*

^aDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea, ^bDepartment of Chemistry & Energy Engineering, Sangmyung University, Seoul 03016, Republic of Korea, and ^cDivision 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, Scotland (Received 1 October 2021; accepted 26 October 2021; online 4 November 2021)

In the title compound, [Ag(CF₃SO₃)(C₁₀H₆F₂N₂)₂], the Ag^I centre adopts a highly distorted trigonal–planar coordination environment resulting from its coordination by one O atom of the trifluoromethanesulfonate anion and the pyridine N atoms of two crystallographically independent 2′,6′-difluoro-2,3′-bipyridine ligands, which display very similar conformations to one another. Pairwise Ag⋯O–SO₂CF₃⁻ [Ag⋯O = 2.8314 (14) Å] interactions and intermolecular C—H⋯O interactions between inversion-related units lead to the formation of an eight-membered cyclic dimer in which the silver atoms are separated by 6.2152 (3) Å. In the crystal, the dimers are linked through C—H⋯O hydrogen bonds, halogen⋯π and weak π–π stacking interactions, resulting in the formation of a three-dimensional supramolecular network. The title compound exhibits a strong and broad emission band from 400 nm to 550 nm in solution and its photoluminescence quantum efficiency is estimated to be ca 0.2, indicating that the title compound could have applications as an emitting material in organic light-emitting diodes (OLEDs).

Keywords: crystal structure; 2,3′-bipyridine; silver complex; luminescence; OLED.

CCDC reference: 2118061

1. Chemical context

Recently, great attention has been paid to 2,3′-bipyridine-based Ir^III and Pt^II complexes by many researchers because of their applicability to OLEDs and solid-state lighting (Kang et al., 2021 ; Reddy & Bejoymohandas, 2016 ). In particular, 2′,6′-difluoro-2,3′-bipyridine complexes of iridium(III) are considered to be strong candidates as both blue triplet emitters in phosphorescent organic light-emitting diodes (PHOLEDs) and single dopants in white organic light-emitting diodes (WOLEDs) (Zaen et al., 2019 ; Kang et al., 2020 ; Lee et al., 2018 ). Despite these investigations, reports regarding the structures and photoluminescence properties of 2,3′-bipyridine-based group-11 metal complexes are scarce, and related research is limited (Li et al., 2019 ). Among the group-11 elements, coordination polymers of Ag^I have been demonstrated to exhibit structural diversity as a result of the d¹⁰ configuration of the metal ion (Lee et al., 2020 ). Moreover, the various coordination environments around the Ag^I centre are generally constructed by the ligands, solvent molecules, and counter-anions (Lee et al., 2016 ). Until now, there has been no report with respect to an Ag^I complex bearing a 2′,6′-difluoro-2,3′-bipyridine ligand as compared to 2,2-bipyridine-based Ag^I complexes (Pal et al., 2020 ). This fact prompted us to investigate the structures and luminescent properties of 2,3′-bipyridine-based Ag^I complexes: in this study, we report the preparation, structural characterization and luminescent properties of an Ag^I complex of 2′,6′-difluoro-2,3′-bipyridine.

2. Structural commentary

The asymmetric unit in the title compound consists of an Ag^I cation, a CF₃SO₃⁻ trifluoromethanesulfonate anion and two crystallographically independent C₁₀H₆F₂N₂ 2′,6′-difluoro-2,3′-bipyridine ligands, which adopt very similar conformations, such that the dihedral angles between the pyridyl rings in the N1- and N3-containing molecules are 53.11 (5) and 53.10 (7)°, respectively. As shown in Fig. 1, the Ag^I ion is coordinated by two pyridine N atoms (N2 and N4) from two 2′,6′-difluoro-2,3′-bipyridine ligands and one O atom from the trifluoromethanesulfonate anion, forming a highly distorted trigonal–planar geometry. Selected bond lengths and angles around the Ag1 atom are given in Table 1: the N—Ag—N and N—Ag—O angles fall in the range 86.55 (5)–148.65 (5)°, deviating significantly from an ideal trigonal–planar geometry. This may reflect the influence of an additional Ag⋯O–SO₂CF₃⁻ interaction between the metal ion and an O atom of an adjacent trifluoromethanesulfonate anion [Ag1⋯O2ⁱ = 2.8314 (14) Å; black dashed lines in Fig. 2; symmetry code: (i) −x + 1, −y, −z + 1]. The Ag^I atom is displaced out of the trigonal N2, N4, O1 coordination plane by 0.1057 (9) Å. The C6–C10/N2 and C16–C20/N4 pyridine rings coordinated to the Ag^I centre are tilted by 25.75 (10)° with respect to each other. The pairwise Ag⋯O links lead to the formation of an eight-membered [Ag—O—S—O—]₂ cyclic dimer, in which the silver atoms are separated by 6.2152 (3) Å. The cyclic dimer is consolidated by C—H⋯O interactions (Table 2; yellow dashed lines in Fig. 2).

Table 1
Selected geometric parameters (Å, °)

Ag1—N2	2.2305 (14)	Ag1—O1	2.4879 (13)
Ag1—N4	2.2496 (14)

N2—Ag1—N4	148.65 (5)	N4—Ag1—O1	86.55 (5)
N2—Ag1—O1	124.02 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O2ⁱ	0.95	2.60	3.239 (2)	125
C13—H13⋯O2ⁱ	0.95	2.60	3.173 (2)	119
C13—H13⋯O3ⁱ	0.95	2.50	3.400 (2)	159
C19—H19⋯O3ⁱⁱ	0.95	2.53	3.294 (2)	137
C20—H20⋯O1	0.95	2.55	3.197 (2)	126
Symmetry codes: (i) ; (ii) .

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level. The orange dashed line represents an intramolecular C—H⋯O interaction.

Figure 2
Dimeric structure formed by Ag⋯O (black dashed lines) and C—H⋯O (yellow dashed lines) interactions [symmetry code: (i) −x + 1, −y, −z + 1]. Atom colours: violet = silver, yellow = sulfur, green = fluorine, red = oxygen, blue = nitrogen, grey = carbon and white = hydrogen.

3. Supramolecular features

In the extended structure, the dimers are linked through C19—H19⋯O3 hydrogen bonds (Table 2) and weak π–π stacking interactions [yellow and sky-blue dashed lines in Fig. 3, respectively; Cg4⋯Cg4ⁱⁱ = 3.9737 (11) Å; Cg4 is the centroid of the C16–C20/N4 ring; symmetry code: (ii) −x, −y, −z + 1] between the pyridine rings, forming a chain structure propagating along the a-axis direction. Neighbouring chains are connected by halogen⋯π interactions [red dashed lines in Fig. 3; F6⋯Cg3ⁱⁱⁱ = 3.06 (2) Å; Cg3 is the centroid of the C11–C15/N3 ring; symmetry code: (iii) x + 1, y − 1, z], thereby generating a two-dimensional supramolecular network lying parallel to the ab plane. Finally, these networks are stacked along the c-axis direction and connected by halogen⋯π and weak π–π stacking interactions [red and sky-blue dashed lines in Fig. 4, respectively; F1⋯Cg2^iv = 3.974 (2) Å; F2⋯Cg1^iv = 3.1424 (19) Å; Cg1⋯Cg1^iv = 4.2435 (13) Å; Cg1 and Cg2 are the centroids of the C1–C5/N1 and C6–C10/N2 rings, respectively; symmetry code: (iv) −x + 1, −y, −z], resulting in the formation of a three-dimensional supramolecular network.

Figure 3
The two-dimensional supramolecular network formed through C—H⋯O hydrogen bonds (yellow dashed lines), F⋯π (red dashed lines) and π–π stacking (sky-blue dashed lines) interactions. For clarity, H atoms not involved in the intermolecular interactions have been omitted. Atom colours as in Fig. 2

Figure 4
The three-dimensional supramolecular network formed through F⋯π (red dashed lines) and π–π stacking (sky-blue dashed lines) interactions. For clarity, H atoms not involved in the intermolecular interactions have been omitted. Atom colours as in Fig. 2

4. Luminescent properties

In CH₂Cl₂ solution, the title compound exhibits a strong and broad emission band with λ_max = 400 nm, as shown in Fig. 5. This emission band may arise from π–π* transitions of the bipyridine ligand because the absorption of the title compound is very similar to that of the free ligand. Interestingly, upon the complexation of ligand with the Ag(CF₃SO₃) unit, significant blue-shifted emissions (> 50 nm) are observed as compared with bipyridine based Ir^III complexes (Lee et al., 2009 ). Moreover, a broad emission from 400 nm to 500 nm in the title compound may be due to the predominantly fluorescent emission from the 2′,6′-difluoro-2,3′-bipyridine ligand because the emission maximum of the free ligand, i.e. phosphorescent emission, occurs at approximately 450 nm (triplet energy, T₁ = 2.82 eV). The observed emission of the title compound is therefore attributed to ligand-centered π–π* transitions with a minor contribution of an Ag-based metal-to-ligand charge-transfer transition. Similar dual-emission behaviour has been noted for some Ag^I complexes with 2-methylthiothiazole (Rogovoy et al., 2019 ) and pyridylphosphine ligands (Baranov et al., 2019 ). The emission intensity of the title compound was also higher than that of free ligand, as shown in Fig. 5. The photoluminescence quantum efficiency of the title compound was estimated to be ca 0.2 (Fig. 5, inset). Such an efficiency is large enough to potentially use the title compound as the emitting material in an organic light-emitting diode (OLED) application.

Figure 5
Absorption and emission spectra of the free ligand and the title compound in solution [concentrations = 1.0 × 10⁻⁵ M] at room temperature (inset: emission photo); ɛ ≃ 100,000 M⁻¹ cm⁻¹.

5. Database survey

A survey of SciFinder (SciFinder, 2021 ) for transition-metal complexes bearing the 2′,6′-difluoro-2,3′-bipyridine moiety as a ligand gave 25 hits. They include reports about the crystal structures and photophysical properties of Ir^III and Pt^II complexes based on this ligand (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 silver complex with the title ligand.

6. 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 purchased commercially and used without further purification. The ¹H NMR spectrum was recorded on a JEOL 400 MHz spectrometer. The ligand, 2′,6′-difluoro-2,3′-bipyridine (Park et al., 2015) was synthesized according to the previous report. The title compound was synthesized as follows: the ligand (0.075 g, 0.39 mmol) in THF (2 ml) was added to Ag(CF₃SO₃) (0.47 g, 1.0 mmol) in MeOH (2 ml) in the dark at room temperature and the mixture was stirred for 10 min. After that, the mixture was slowly evaporated in the air and a dark environment to obtain crystals suitable for X-ray crystallographic analysis. ¹H NMR (400 MHz, CD₃CN) δ 8.67 (d, J = 4.4 Hz, 1H), 8.62 (td, J = 8.8, 1.2 Hz, 1H), 7.88–7.80 (m, 2H), 7.37–7.34 (m, 1H), 7.0.8 (dd, J = 9.2, 3.6 Hz, 1H). ¹⁹F NMR (376 MHz, CD₃CN) δ −69.7, −71.8, 79.1. Analysis calculated for C₂₁H₁₂F₇N₄O₃SAg: C 39.33; H 1.89; N 8.74%; found: C 39.44, H 1.86, N 8.70%.

7. 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	[Ag(CF₃O₃S)(C₁₀H₆F₂N₂)₂]
M_r	641.28
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	193
a, b, c (Å)	9.0627 (2), 10.9637 (3), 12.5727 (3)
α, β, γ (°)	82.4508 (11), 73.7215 (11), 71.5490 (11)
V (Å³)	1136.26 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.07
Crystal size (mm)	0.38 × 0.33 × 0.32

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.610, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	19973, 5623, 5262
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.067, 1.12
No. of reflections	5623
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.76
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: 2118061

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989021011282/hb7990sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011282/hb7990Isup2.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).

Bis[2,6-difluoro-3-(pyridin-2-yl)pyridine-κN](trifluoromethanesulfonato-κO)silver(I) top

Crystal data top

[Ag(CF₃O₃S)(C₁₀H₆F₂N₂)₂]	Z = 2
M_r = 641.28	F(000) = 632
Triclinic, P1	D_x = 1.874 Mg m⁻³
a = 9.0627 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9637 (3) Å	Cell parameters from 9858 reflections
c = 12.5727 (3) Å	θ = 2.5–28.3°
α = 82.4508 (11)°	µ = 1.07 mm⁻¹
β = 73.7215 (11)°	T = 193 K
γ = 71.5490 (11)°	Block, colourless
V = 1136.26 (5) Å³	0.38 × 0.33 × 0.32 mm

Data collection top

Bruker APEXII CCD diffractometer	5262 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.610, T_max = 0.746	h = −12→11
19973 measured reflections	k = −14→14
5623 independent reflections	l = −16→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0356P)² + 0.2813P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
5623 reflections	Δρ_max = 0.33 e Å⁻³
334 parameters	Δρ_min = −0.76 e Å⁻³
0 restraints

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
Ag1	0.39687 (2)	0.11579 (2)	0.28356 (2)	0.02967 (5)
S1	0.58088 (5)	−0.20353 (4)	0.43046 (4)	0.02529 (9)
O1	0.47418 (19)	−0.09076 (14)	0.39174 (14)	0.0444 (4)
O2	0.54144 (16)	−0.22732 (14)	0.54886 (11)	0.0356 (3)
O3	0.74849 (17)	−0.22309 (15)	0.37857 (12)	0.0400 (3)
C21	0.5358 (3)	−0.3333 (2)	0.38115 (18)	0.0392 (4)
F5	0.5511 (2)	−0.31983 (18)	0.27233 (12)	0.0745 (5)
F6	0.6317 (2)	−0.44672 (13)	0.40282 (16)	0.0701 (5)
F7	0.38549 (17)	−0.33477 (14)	0.42807 (13)	0.0562 (4)
F1	0.7648 (2)	−0.33112 (13)	−0.01970 (14)	0.0698 (5)
F2	0.63399 (17)	0.08741 (13)	−0.11751 (10)	0.0460 (3)
N1	0.7033 (2)	−0.12143 (18)	−0.06736 (14)	0.0414 (4)
N2	0.57260 (17)	0.21084 (14)	0.17341 (12)	0.0249 (3)
C1	0.7501 (3)	−0.21237 (19)	0.00565 (19)	0.0430 (5)
C2	0.7813 (3)	−0.1947 (2)	0.10241 (18)	0.0414 (5)
H2	0.8198	−0.2652	0.1500	0.050*
C3	0.7538 (2)	−0.06916 (18)	0.12668 (16)	0.0334 (4)
H3	0.7695	−0.0515	0.1940	0.040*
C4	0.7031 (2)	0.03212 (17)	0.05317 (14)	0.0277 (3)
C5	0.6836 (2)	−0.00397 (19)	−0.04231 (15)	0.0324 (4)
C6	0.6718 (2)	0.16833 (17)	0.07537 (14)	0.0274 (3)
C7	0.7452 (3)	0.2481 (2)	−0.00157 (18)	0.0443 (5)
H7	0.8157	0.2158	−0.0700	0.053*
C8	0.7154 (3)	0.3738 (2)	0.0216 (2)	0.0518 (6)
H8	0.7646	0.4294	−0.0304	0.062*
C9	0.6128 (3)	0.4179 (2)	0.12161 (18)	0.0408 (5)
H9	0.5885	0.5049	0.1393	0.049*
C10	0.5462 (2)	0.33348 (18)	0.19542 (16)	0.0313 (4)
H10	0.4783	0.3635	0.2652	0.038*
F3	0.13496 (19)	0.67539 (12)	0.27171 (13)	0.0583 (4)
F4	−0.07604 (18)	0.40180 (14)	0.17706 (12)	0.0545 (4)
N3	0.0298 (2)	0.53662 (16)	0.22662 (15)	0.0401 (4)
N4	0.14448 (16)	0.10066 (14)	0.33810 (12)	0.0244 (3)
C11	0.1051 (2)	0.56069 (17)	0.29307 (18)	0.0381 (4)
C12	0.1546 (2)	0.48149 (18)	0.37758 (17)	0.0348 (4)
H12	0.2070	0.5058	0.4234	0.042*
C13	0.1239 (2)	0.36367 (17)	0.39263 (15)	0.0280 (3)
H13	0.1566	0.3044	0.4499	0.034*
C14	0.04554 (19)	0.33106 (16)	0.32476 (14)	0.0259 (3)
C15	0.0017 (2)	0.42467 (19)	0.24485 (16)	0.0337 (4)
C16	0.0162 (2)	0.20399 (16)	0.33730 (14)	0.0252 (3)
C17	−0.1363 (2)	0.19243 (19)	0.35044 (16)	0.0327 (4)
H17	−0.2251	0.2670	0.3494	0.039*
C18	−0.1577 (2)	0.0716 (2)	0.36507 (17)	0.0356 (4)
H18	−0.2613	0.0619	0.3747	0.043*
C19	−0.0260 (2)	−0.03498 (18)	0.36549 (16)	0.0333 (4)
H19	−0.0369	−0.1194	0.3747	0.040*
C20	0.1222 (2)	−0.01603 (17)	0.35223 (15)	0.0289 (3)
H20	0.2124	−0.0894	0.3532	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.02256 (8)	0.02807 (8)	0.03687 (9)	−0.01100 (5)	−0.00184 (5)	0.00012 (5)
S1	0.0262 (2)	0.02496 (19)	0.0277 (2)	−0.00994 (16)	−0.01063 (16)	0.00272 (15)
O1	0.0493 (9)	0.0297 (7)	0.0602 (10)	−0.0111 (6)	−0.0309 (8)	0.0128 (7)
O2	0.0324 (7)	0.0467 (8)	0.0274 (7)	−0.0118 (6)	−0.0074 (5)	−0.0002 (6)
O3	0.0313 (7)	0.0560 (9)	0.0356 (7)	−0.0211 (6)	−0.0045 (6)	−0.0003 (6)
C21	0.0471 (11)	0.0352 (10)	0.0392 (11)	−0.0220 (9)	−0.0053 (9)	−0.0027 (8)
F5	0.1206 (15)	0.0919 (12)	0.0389 (8)	−0.0719 (12)	−0.0136 (9)	−0.0112 (8)
F6	0.0722 (10)	0.0270 (6)	0.1019 (14)	−0.0094 (7)	−0.0113 (9)	−0.0083 (7)
F7	0.0522 (8)	0.0609 (9)	0.0689 (10)	−0.0393 (7)	−0.0093 (7)	−0.0056 (7)
F1	0.0974 (13)	0.0359 (7)	0.0692 (10)	−0.0239 (8)	0.0022 (9)	−0.0199 (7)
F2	0.0640 (8)	0.0479 (7)	0.0289 (6)	−0.0161 (6)	−0.0189 (6)	0.0037 (5)
N1	0.0518 (11)	0.0434 (10)	0.0307 (9)	−0.0190 (8)	−0.0027 (7)	−0.0116 (7)
N2	0.0255 (7)	0.0279 (7)	0.0233 (7)	−0.0113 (6)	−0.0053 (5)	−0.0013 (5)
C1	0.0499 (12)	0.0298 (10)	0.0431 (12)	−0.0127 (9)	0.0041 (9)	−0.0126 (8)
C2	0.0435 (11)	0.0324 (10)	0.0394 (11)	−0.0061 (8)	−0.0046 (9)	0.0026 (8)
C3	0.0355 (10)	0.0351 (9)	0.0281 (9)	−0.0097 (8)	−0.0075 (7)	0.0003 (7)
C4	0.0286 (8)	0.0309 (8)	0.0229 (8)	−0.0108 (7)	−0.0028 (6)	−0.0022 (7)
C5	0.0373 (10)	0.0373 (10)	0.0228 (8)	−0.0135 (8)	−0.0047 (7)	−0.0017 (7)
C6	0.0299 (8)	0.0311 (8)	0.0232 (8)	−0.0128 (7)	−0.0061 (7)	−0.0003 (6)
C7	0.0578 (13)	0.0455 (11)	0.0290 (10)	−0.0285 (10)	0.0060 (9)	−0.0039 (8)
C8	0.0740 (16)	0.0464 (12)	0.0401 (12)	−0.0392 (12)	0.0005 (11)	0.0017 (10)
C9	0.0546 (13)	0.0319 (9)	0.0409 (11)	−0.0217 (9)	−0.0095 (9)	−0.0024 (8)
C10	0.0337 (9)	0.0309 (9)	0.0317 (9)	−0.0126 (7)	−0.0072 (7)	−0.0046 (7)
F3	0.0732 (10)	0.0287 (6)	0.0657 (9)	−0.0207 (6)	−0.0007 (7)	0.0006 (6)
F4	0.0618 (9)	0.0655 (9)	0.0485 (8)	−0.0220 (7)	−0.0370 (7)	0.0138 (7)
N3	0.0418 (9)	0.0312 (8)	0.0376 (9)	−0.0032 (7)	−0.0069 (7)	0.0060 (7)
N4	0.0206 (6)	0.0277 (7)	0.0248 (7)	−0.0079 (5)	−0.0052 (5)	−0.0006 (5)
C11	0.0393 (10)	0.0217 (8)	0.0430 (11)	−0.0070 (7)	0.0041 (8)	−0.0032 (8)
C12	0.0344 (10)	0.0314 (9)	0.0384 (10)	−0.0093 (7)	−0.0060 (8)	−0.0089 (8)
C13	0.0257 (8)	0.0286 (8)	0.0284 (9)	−0.0055 (6)	−0.0071 (7)	−0.0019 (7)
C14	0.0205 (7)	0.0268 (8)	0.0275 (8)	−0.0030 (6)	−0.0057 (6)	−0.0016 (6)
C15	0.0308 (9)	0.0368 (10)	0.0306 (9)	−0.0044 (7)	−0.0108 (7)	0.0010 (8)
C16	0.0226 (8)	0.0303 (8)	0.0228 (8)	−0.0074 (6)	−0.0063 (6)	−0.0015 (6)
C17	0.0219 (8)	0.0396 (10)	0.0364 (10)	−0.0064 (7)	−0.0077 (7)	−0.0069 (8)
C18	0.0241 (8)	0.0488 (11)	0.0380 (10)	−0.0162 (8)	−0.0032 (7)	−0.0121 (8)
C19	0.0326 (9)	0.0345 (9)	0.0365 (10)	−0.0173 (8)	−0.0034 (8)	−0.0074 (8)
C20	0.0271 (8)	0.0274 (8)	0.0307 (9)	−0.0085 (7)	−0.0048 (7)	−0.0006 (7)

Geometric parameters (Å, º) top

Ag1—N2	2.2305 (14)	C8—C9	1.378 (3)
Ag1—N4	2.2496 (14)	C8—H8	0.9500
Ag1—O1	2.4879 (13)	C9—C10	1.377 (3)
S1—O1	1.4317 (14)	C9—H9	0.9500
S1—O3	1.4331 (14)	C10—H10	0.9500
S1—O2	1.4389 (14)	F3—C11	1.346 (2)
S1—C21	1.821 (2)	F4—C15	1.338 (2)
C21—F6	1.317 (3)	N3—C15	1.310 (3)
C21—F7	1.329 (2)	N3—C11	1.314 (3)
C21—F5	1.329 (3)	N4—C20	1.339 (2)
F1—C1	1.338 (2)	N4—C16	1.344 (2)
F2—C5	1.343 (2)	C11—C12	1.364 (3)
N1—C5	1.311 (3)	C12—C13	1.384 (3)
N1—C1	1.314 (3)	C12—H12	0.9500
N2—C10	1.341 (2)	C13—C14	1.393 (2)
N2—C6	1.345 (2)	C13—H13	0.9500
C1—C2	1.374 (3)	C14—C15	1.384 (2)
C2—C3	1.379 (3)	C14—C16	1.480 (2)
C2—H2	0.9500	C16—C17	1.390 (2)
C3—C4	1.394 (3)	C17—C18	1.380 (3)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.385 (2)	C18—C19	1.382 (3)
C4—C6	1.478 (2)	C18—H18	0.9500
C6—C7	1.389 (3)	C19—C20	1.384 (2)
C7—C8	1.372 (3)	C19—H19	0.9500
C7—H7	0.9500	C20—H20	0.9500

N2—Ag1—N4	148.65 (5)	C7—C8—H8	120.6
N2—Ag1—O1	124.02 (5)	C9—C8—H8	120.6
N4—Ag1—O1	86.55 (5)	C10—C9—C8	118.71 (19)
O1—S1—O3	115.37 (9)	C10—C9—H9	120.6
O1—S1—O2	114.61 (9)	C8—C9—H9	120.6
O3—S1—O2	115.25 (8)	N2—C10—C9	123.12 (18)
O1—S1—C21	102.70 (10)	N2—C10—H10	118.4
O3—S1—C21	103.67 (10)	C9—C10—H10	118.4
O2—S1—C21	102.70 (9)	C15—N3—C11	115.31 (16)
S1—O1—Ag1	156.68 (10)	C20—N4—C16	118.07 (14)
F6—C21—F7	107.60 (17)	C20—N4—Ag1	119.02 (11)
F6—C21—F5	108.1 (2)	C16—N4—Ag1	121.76 (11)
F7—C21—F5	106.53 (18)	N3—C11—F3	114.28 (18)
F6—C21—S1	111.59 (15)	N3—C11—C12	126.40 (18)
F7—C21—S1	111.55 (15)	F3—C11—C12	119.3 (2)
F5—C21—S1	111.22 (14)	C11—C12—C13	116.10 (18)
C5—N1—C1	115.27 (18)	C11—C12—H12	121.9
C10—N2—C6	118.01 (15)	C13—C12—H12	121.9
C10—N2—Ag1	114.60 (12)	C12—C13—C14	120.70 (17)
C6—N2—Ag1	125.25 (11)	C12—C13—H13	119.7
N1—C1—F1	114.4 (2)	C14—C13—H13	119.7
N1—C1—C2	126.05 (19)	C15—C14—C13	114.98 (16)
F1—C1—C2	119.5 (2)	C15—C14—C16	123.52 (16)
C1—C2—C3	116.39 (19)	C13—C14—C16	121.49 (15)
C1—C2—H2	121.8	N3—C15—F4	114.67 (16)
C3—C2—H2	121.8	N3—C15—C14	126.49 (18)
C2—C3—C4	120.53 (18)	F4—C15—C14	118.84 (17)
C2—C3—H3	119.7	N4—C16—C17	121.95 (16)
C4—C3—H3	119.7	N4—C16—C14	116.22 (14)
C5—C4—C3	115.13 (17)	C17—C16—C14	121.82 (15)
C5—C4—C6	122.25 (16)	C18—C17—C16	119.40 (17)
C3—C4—C6	122.62 (16)	C18—C17—H17	120.3
N1—C5—F2	114.19 (16)	C16—C17—H17	120.3
N1—C5—C4	126.55 (18)	C17—C18—C19	118.87 (16)
F2—C5—C4	119.21 (17)	C17—C18—H18	120.6
N2—C6—C7	121.54 (17)	C19—C18—H18	120.6
N2—C6—C4	117.53 (15)	C18—C19—C20	118.52 (17)
C7—C6—C4	120.92 (17)	C18—C19—H19	120.7
C8—C7—C6	119.7 (2)	C20—C19—H19	120.7
C8—C7—H7	120.1	N4—C20—C19	123.19 (16)
C6—C7—H7	120.1	N4—C20—H20	118.4
C7—C8—C9	118.86 (19)	C19—C20—H20	118.4

O3—S1—O1—Ag1	−5.5 (3)	C4—C6—C7—C8	−179.3 (2)
O2—S1—O1—Ag1	131.9 (2)	C6—C7—C8—C9	0.1 (4)
C21—S1—O1—Ag1	−117.5 (3)	C7—C8—C9—C10	1.1 (4)
O1—S1—C21—F6	175.69 (16)	C6—N2—C10—C9	1.5 (3)
O3—S1—C21—F6	55.24 (17)	Ag1—N2—C10—C9	−162.77 (16)
O2—S1—C21—F6	−65.08 (17)	C8—C9—C10—N2	−2.0 (3)
O1—S1—C21—F7	−63.92 (17)	C15—N3—C11—F3	179.02 (17)
O3—S1—C21—F7	175.64 (15)	C15—N3—C11—C12	−0.4 (3)
O2—S1—C21—F7	55.32 (17)	N3—C11—C12—C13	1.2 (3)
O1—S1—C21—F5	54.86 (19)	F3—C11—C12—C13	−178.21 (17)
O3—S1—C21—F5	−65.58 (18)	C11—C12—C13—C14	−0.6 (3)
O2—S1—C21—F5	174.10 (16)	C12—C13—C14—C15	−0.6 (3)
C5—N1—C1—F1	178.08 (19)	C12—C13—C14—C16	178.07 (17)
C5—N1—C1—C2	−1.0 (3)	C11—N3—C15—F4	179.57 (17)
N1—C1—C2—C3	3.0 (4)	C11—N3—C15—C14	−1.1 (3)
F1—C1—C2—C3	−175.97 (19)	C13—C14—C15—N3	1.5 (3)
C1—C2—C3—C4	−2.4 (3)	C16—C14—C15—N3	−177.11 (18)
C2—C3—C4—C5	0.1 (3)	C13—C14—C15—F4	−179.13 (17)
C2—C3—C4—C6	179.92 (18)	C16—C14—C15—F4	2.2 (3)
C1—N1—C5—F2	−179.29 (18)	C20—N4—C16—C17	−0.1 (3)
C1—N1—C5—C4	−1.8 (3)	Ag1—N4—C16—C17	167.60 (13)
C3—C4—C5—N1	2.2 (3)	C20—N4—C16—C14	178.26 (15)
C6—C4—C5—N1	−177.59 (19)	Ag1—N4—C16—C14	−14.0 (2)
C3—C4—C5—F2	179.54 (17)	C15—C14—C16—N4	127.08 (18)
C6—C4—C5—F2	−0.2 (3)	C13—C14—C16—N4	−51.5 (2)
C10—N2—C6—C7	−0.1 (3)	C15—C14—C16—C17	−54.6 (3)
Ag1—N2—C6—C7	162.31 (15)	C13—C14—C16—C17	126.87 (19)
C10—N2—C6—C4	178.53 (15)	N4—C16—C17—C18	0.2 (3)
Ag1—N2—C6—C4	−19.0 (2)	C14—C16—C17—C18	−178.09 (17)
C5—C4—C6—N2	127.75 (19)	C16—C17—C18—C19	−0.4 (3)
C3—C4—C6—N2	−52.0 (2)	C17—C18—C19—C20	0.6 (3)
C5—C4—C6—C7	−53.6 (3)	C16—N4—C20—C19	0.3 (3)
C3—C4—C6—C7	126.7 (2)	Ag1—N4—C20—C19	−167.75 (14)
N2—C6—C7—C8	−0.7 (3)	C18—C19—C20—N4	−0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O2ⁱ	0.95	2.60	3.239 (2)	125
C13—H13···O2ⁱ	0.95	2.60	3.173 (2)	119
C13—H13···O3ⁱ	0.95	2.50	3.400 (2)	159
C19—H19···O3ⁱⁱ	0.95	2.53	3.294 (2)	137
C20—H20···O1	0.95	2.55	3.197 (2)	126

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

Funding information

Funding for this research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2016R1D1A1B01012630).

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