A dinuclear silver(I) com­plex of 6-phenyl-2,2′:6′,2′′-terpyridine

Nakaie, Y.; Abe, T.; Hosoya, Y.; Sugawa, K.; Otsuki, J.

doi:10.1107/S2414314626010436

metal-organic compounds

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ISSN: 2414-3146

Volume 11| Part 10| October 2026| x261043

https://doi.org/10.1107/S2414314626010436

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A dinuclear silver(I) complex of 6-phenyl-2,2′:6′,2′′-terpyridine

Yuto Nakaie,^a Tomoya Abe,^a Yosuke Hosoya,^a Kosuke Sugawa ^a and Joe Otsuki ^a ^*

^aDepartment of Applied and Materials Chemistry, College of Science and Technology, Nihon University, 1-8-14 Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan
^*Correspondence e-mail: [email protected]

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 7 October 2026; accepted 9 October 2026; online 15 October 2026)

A dinuclear silver(I) complex of 6-phenyl-2,2′:6′,2′′-terpyridine, bis(μ-6-phenyl-2,2′:6′,2′′-terpyridine)bis[(trifluoromethanesulfonato)silver(I)], [Ag₂(C₂₁H₁₅N₃)(CF₃SO₃)₂], was obtained by crystallization with silver trifluoromethanesulfonate and characterized by single-crystal X-ray diffraction. Two symmetry-related terpyridine ligands bridge two Ag^I ions. The Ag^I ion has a highly distorted four-coordinate N₃O environment comprising three pyridyl N atoms and one trifluoromethanesulfonate O atom. The intramolecular Ag⋯Ag separation of 2.8501 (8) Å is consistent with an argentophilic interaction. An intramolecular phenyl–pyridyl π–π contact is also present. The structure demonstrates that a single phenyl substituent at the 6-position is compatible with ligand bridging and the formation of a short Ag⋯Ag contact.

Keywords: argentophilic interaction; crystal structure; dinuclear complex; π–π stacking; silver(I); terpyridine.

CCDC reference: 2594042

Structure description

Ag^I complexes of 2,2′:6′,2′′-terpyridine (tpy) exhibit diverse coordination modes and solvent-dependent nuclearity. Crystallization from acetonitrile (MeCN) affords approximately square-planar [Ag(tpy)(MeCN)]⁺ units, which associate into dimers through an Ag⋯Ag contact of 3.170 Å (Constable et al., 1998a ,b ). Chiral tpy derivatives form mononuclear acetonitrile complexes but favour dinuclear double helicates in less coordinating solvents. These helicates contain intramolecular Ag⋯Ag contacts of 2.914–2.940 Å and associate into tetranuclear aggregates through additional Ag⋯Ag interactions (Baum et al., 1998 ). Similarly, 6,6′′-dimethyl-tpy forms dinuclear double helicates with Ag⋯Ag distances of 2.930–2.970 Å. Their structures depend on the counter-ion: nitrate and trifluoromethanesulfonate produce asymmetric helicates with one bridging central pyridine N atom, whereas BF₄⁻ and ClO₄⁻ give more symmetrical structures with both central N atoms bridging the Ag pair (Fik et al., 2014 ). Dinuclear Ag–tpy units can also form extended chains with gold complexes through Ag⋯Au and Au⋯Au interactions (Gil-Moles et al., 2017 ). Solution studies support mononuclear [Ag(tpy)₂]⁺ species. Thermodynamic measurements in dimethyl sulfoxide (DMSO) suggest five-coordinate bonds with one unbound pyridine ring (Del Piero et al., 2007 ), while selective formation of an [Ag(tpy)₂]⁺ unit was demonstrated in an Ag^I capture–release system (Paul et al., 2019 ).

Against this background, we report the crystal structure of the trifluoromethanesulfonate salt of a dinuclear Ag^I complex containing 6-phenyl-2,2′:6′,2′′-terpyridine (6-Phtpy). The asymmetric unit contains one 6-Phtpy ligand, one Ag^I ion and one trifluoromethanesulfonate anion. Two symmetry-related 6-Phtpy ligands bridge two central Ag^I ions in a helical arrangement, forming a chiral dinuclear complex (Fig. 1). A crystallographic twofold rotation axis passes through the midpoint of, and perpendicular to, the Ag⋯Ag vector. Each Ag^I centre has a highly distorted four-coordinate N₃O environment containing one pyridyl N atom from one ligand, two pyridyl N atoms from the other ligand and one trifluoromethanesulfonate O atom. The Ag1—N1, Ag1—N2ⁱ and Ag1—N3ⁱ distances are 2.240 (3), 2.412 (3) and 2.330 (2) Å, respectively, and Ag1—O1 is 2.578 (4) Å [symmetry code: (i) −x + 1, y, −z + $[{3\over 2}]$ ]. The intramolecular Ag1⋯Ag1ⁱ distance of 2.8500 (6) Å is consistent with an argentophilic interaction (Schmidbaur & Schier, 2015 ). The ligand adopts a nonplanar conformation. The dihedral angles between the N1- and N2-containing pyridine rings and between the N2- and N3-containing rings are 43.85 (16) and 16.62 (13)°, respectively. The phenyl substituent is inclined by 38.65 (16)° to the adjacent N3-containing pyridine ring. Within the dinuclear complex, the phenyl ring and a symmetry-related N2ⁱ-containing pyridine ring form a π–π contact, with a centroid–centroid distance of 3.750 (3) Å and an interplanar angle of 10.58 (15)°.

Figure 1
The molecular structure of the dinuclear Ag^I complex of 6-Phtpy. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) −x + 1, y, −z + $[{3\over 2}]$ .]

The dinuclear framework resembles that of Ag₂(tpy)₂, which contains bridging unsubstituted tpy ligands and weak Ag—O interactions with trifluoromethanesulfonate anions (Gil-Moles et al., 2017). The reported Ag₂(tpy)₂ complex has an Ag⋯Ag contact of 3.1698 (12) Å. The related [Ag(dptpy)(MeCN)]⁺ complex, with dptpy = 6,6′′-diphenyl-tpy, is mononuclear and has no short Ag⋯Ag contact; the shortest separation is 5.656 Å (Constable et al., 1998). Thus, a single phenyl substituent at the 6-position is compatible with ligand bridging and a short intramolecular Ag⋯Ag contact.

The crystal packing features offset π–π stacking between the central pyridine rings of neighbouring complexes, together with weak C—H⋯O contacts involving the trifluoromethanesulfonate anions (Fig. 2). The central pyridine rings of neighbouring complexes of opposite handedness, related by inversion (symmetry operation: −x, −y + 1, −z + 2), are parallel, with a centroid–centroid distance of 3.879 (3) Å. The C3—H3⋯O2 contact has a C⋯O distance of 3.273 (6) Å and a C—H⋯O angle of 150°. The H9 atom forms a bifurcated contact with O2 and O1, with C9⋯O distances of 3.278 (5) and 3.315 (5) Å, and angles of 132 and 130°, respectively. Details of the weak C—H⋯O contacts are given in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.93	2.43	3.273 (6)	150
C9—H9⋯O2ⁱⁱ	0.93	2.58	3.278 (5)	132
C9—H9⋯O1ⁱⁱ	0.93	2.65	3.315 (5)	130
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the dinuclear complex, showing phenyl–pyridyl–pyridyl–phenyl π–π stacking and C—H⋯O contacts (labelled distances are C⋯O separations).

Synthesis and crystallization

The synthetic route to 6-Phtpy is shown in Fig. 3.

Figure 3
Synthetic route to 6-Phtpy. Reagents and conditions: (a) i) hexamethylditin, Pd(PPh₃)₄, DME, reflux, 18 h; ii) 2,6-dibromopyridine, Pd(PPh₃)₄, toluene, reflux, 24 h, 45%; (b) phenylboronic acid pinacol ester, Pd(PPh₃)₄, Na₂CO₃, H₂O, toluene, EtOH, reflux, 24 h, 85%.

6-Bromo-2,2′:6′,2′′-terpyridine (2). The known compound 2 was prepared according to literature procedures (Derrick et al., 2020 ; Stefankiewicz et al., 2013 ) using solvents without prior drying and with the purification procedure modified as follows. The product was purified by column chromatography (SiO₂, CHCl₃), followed by gel permeation chromatography (GPC), to afford compound 2 in 45% yield.

6-Phenyl-2,2′:6′,2′′-terpyridine (6-Phtpy). 6-Phtpy is a known compound (Constable et al., 1999 ), but its synthesis from compound 2 has not been reported previously. Compound 2 (168 mg, 0.537 mmol), phenylboronic acid pinacol ester (115 mg, 0.563 mmol), Pd(PPh₃)₄ (65 mg, 0.056 mmol) and Na₂CO₃ (286 mg, 2.69 mmol) were added to a mixture of H₂O (1.3 ml), toluene (5.0 ml) and EtOH (2.5 ml). The mixture was degassed by three freeze–pump–thaw cycles and refluxed under N₂ for 24 h. The solvents were removed under reduced pressure, and the residue was dissolved in CH₂Cl₂. The solution was washed with water three times, and the organic layer was concentrated under reduced pressure. The crude product was washed with MeOH and collected by filtration. The resulting solid was dissolved in CHCl₃, and the solution was filtered. The filtrate was concentrated under reduced pressure to afford 6-Phtpy as a white solid (yield: 142 mg, 0.458 mmol, 85%).

Crystallization. 6-Phtpy and silver(I) trifluoromethanesulfonate (AgOTf) were dissolved in acetone (10 ml) in a 10 ml vial, giving a concentration of 2.5 mM for each component. Slow evaporation at room temperature under ambient conditions afforded colourless needle-shaped crystals after 44 d. A block-shaped specimen was cut from a needle for single-crystal X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Reflections 200 and 110 were omitted because they were considered to be affected by the beamstop. The trifluoromethanesulfonate CF₃ group exhibits large anisotropic displacement parameters. Inspection of the difference electron-density map revealed no significant residual features near this group.

Table 2
Experimental details

Crystal data
Chemical formula	[Ag₂(C₂₁H₁₅N₃)(CF₃O₃S)₂]
M_r	1132.60
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	21.3041 (10), 11.7253 (4), 17.3544 (8)
V (Å³)	4335.1 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.08
Crystal size (mm)	0.35 × 0.1 × 0.06

Data collection
Diffractometer	Rigaku XtaLAB Mini II
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 )
T_min, T_max	0.700, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	26970, 6431, 3745
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.718

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.159, 0.92
No. of reflections	6431
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.79
Computer programs: CrysAlis PRO (Rigaku OD, 2022), SHELXT2018 (Sheldrick, 2015a ), SHELXL2025 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2594042

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314626010436/vm4086sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314626010436/vm4086Isup2.hkl

checkCIF report

Computing details top

Bis(µ-6-phenyl-2,2':6',2''-terpyridine)bis[(trifluoromethanesulfonato)silver(I)] top

Crystal data top

[Ag₂(C₂₁H₁₅N₃)(CF₃O₃S)₂]	D_x = 1.735 Mg m⁻³
M_r = 1132.60	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 5625 reflections
a = 21.3041 (10) Å	θ = 2.1–24.4°
b = 11.7253 (4) Å	µ = 1.08 mm⁻¹
c = 17.3544 (8) Å	T = 293 K
V = 4335.1 (3) Å³	Block, colourless
Z = 4	0.35 × 0.1 × 0.06 mm
F(000) = 2256

Data collection top

Rigaku XtaLAB Mini II diffractometer	6431 independent reflections
Radiation source: fine-focus sealed X-ray tube, Rigaku (Mo) X-ray Source	3745 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 10.0000 pixels mm^-1	θ_max = 30.7°, θ_min = 2.3°
ω scans	h = −30→26
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	k = −16→16
T_min = 0.700, T_max = 1.000	l = −24→19
26970 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.159	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.001
6431 reflections	Δρ_max = 0.57 e Å⁻³
298 parameters	Δρ_min = −0.79 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.

Refinement. H atoms were placed in calculated positions, with C–H = 0.93 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.55847 (2)	0.37117 (2)	0.71012 (2)	0.04187 (12)
S1	0.63201 (6)	0.16608 (9)	0.55585 (6)	0.0504 (3)
O2	0.63818 (18)	0.1843 (3)	0.47493 (17)	0.0703 (10)
N2	0.52874 (14)	0.4296 (2)	0.86920 (16)	0.0349 (7)
N3	0.43146 (14)	0.5640 (2)	0.81989 (18)	0.0366 (7)
N1	0.57184 (17)	0.2271 (3)	0.79332 (17)	0.0424 (8)
O1	0.6101 (2)	0.2597 (3)	0.59889 (19)	0.0825 (12)
C5	0.57356 (19)	0.2413 (3)	0.8704 (2)	0.0428 (9)
C15	0.3861 (2)	0.6287 (3)	0.7889 (2)	0.0439 (9)
C16	0.33765 (19)	0.5713 (3)	0.7428 (3)	0.0447 (9)
C10	0.52524 (18)	0.5368 (3)	0.8959 (2)	0.0378 (8)
O3	0.6053 (3)	0.0596 (3)	0.5772 (2)	0.1148 (17)
C11	0.47793 (19)	0.6128 (3)	0.8607 (2)	0.0390 (8)
C6	0.57040 (18)	0.3592 (3)	0.9001 (2)	0.0401 (9)
C4	0.5773 (3)	0.1487 (4)	0.9198 (3)	0.0651 (14)
H4	0.578236	0.160036	0.972827	0.078*
C1	0.5747 (2)	0.1201 (3)	0.7656 (3)	0.0531 (11)
H1	0.573638	0.108782	0.712619	0.064*
C9	0.56347 (19)	0.5729 (4)	0.9560 (2)	0.0501 (11)
H9	0.560162	0.647151	0.974331	0.060*
C14	0.3842 (3)	0.7457 (4)	0.8025 (3)	0.0607 (13)
H14	0.351214	0.789498	0.783776	0.073*
C7	0.6099 (2)	0.3925 (4)	0.9606 (2)	0.0524 (11)
H7	0.638705	0.341642	0.981709	0.063*
C12	0.4795 (2)	0.7297 (3)	0.8721 (2)	0.0551 (12)
H12	0.512633	0.763195	0.898656	0.066*
C17	0.3135 (2)	0.6216 (4)	0.6760 (3)	0.0582 (12)
H17	0.327801	0.693085	0.660634	0.070*
C21	0.3146 (2)	0.4648 (4)	0.7633 (3)	0.0523 (10)
H21	0.328688	0.430119	0.808279	0.063*
C3	0.5797 (3)	0.0418 (4)	0.8908 (3)	0.0798 (17)
H3	0.581669	−0.020786	0.923677	0.096*
C20	0.2711 (2)	0.4099 (5)	0.7176 (3)	0.0697 (14)
H20	0.256916	0.337755	0.731366	0.084*
C8	0.6052 (2)	0.5010 (4)	0.9877 (3)	0.0558 (11)
H8	0.630689	0.525308	1.028020	0.067*
C18	0.2689 (3)	0.5661 (6)	0.6329 (3)	0.0784 (16)
H18	0.252173	0.601509	0.589576	0.094*
C2	0.5792 (3)	0.0269 (4)	0.8136 (3)	0.0674 (14)
H2	0.581911	−0.046140	0.792846	0.081*
C19	0.2489 (2)	0.4599 (6)	0.6529 (3)	0.0799 (16)
H19	0.220032	0.421740	0.622141	0.096*
C13	0.4315 (3)	0.7954 (4)	0.8438 (3)	0.0652 (14)
H13	0.431054	0.873627	0.852724	0.078*
F1	0.7124 (3)	0.1423 (6)	0.6626 (3)	0.207 (3)
F3	0.7404 (3)	0.0703 (7)	0.5574 (3)	0.214 (3)
C22	0.7109 (5)	0.1506 (10)	0.5893 (5)	0.129 (3)
F2	0.7406 (3)	0.2552 (8)	0.5666 (4)	0.250 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0483 (2)	0.03713 (17)	0.04016 (18)	0.00238 (13)	−0.00214 (13)	0.00872 (11)
S1	0.0657 (7)	0.0467 (5)	0.0389 (6)	0.0138 (5)	−0.0019 (5)	−0.0025 (4)
O2	0.115 (3)	0.0550 (18)	0.0406 (17)	0.019 (2)	0.0045 (18)	−0.0009 (14)
N2	0.0374 (17)	0.0374 (15)	0.0298 (15)	−0.0032 (14)	−0.0029 (13)	−0.0024 (12)
N3	0.0409 (19)	0.0332 (15)	0.0356 (16)	0.0001 (13)	0.0039 (14)	−0.0032 (12)
N1	0.053 (2)	0.0381 (16)	0.0358 (17)	0.0046 (15)	0.0000 (14)	0.0043 (13)
O1	0.131 (4)	0.062 (2)	0.054 (2)	0.034 (2)	0.011 (2)	−0.0065 (16)
C5	0.041 (2)	0.047 (2)	0.040 (2)	0.0065 (17)	−0.0031 (17)	0.0083 (17)
C15	0.048 (2)	0.0402 (19)	0.044 (2)	0.0071 (18)	0.0108 (18)	0.0025 (16)
C16	0.036 (2)	0.049 (2)	0.049 (2)	0.0111 (18)	0.0039 (18)	−0.0010 (19)
C10	0.040 (2)	0.0407 (19)	0.0327 (18)	−0.0107 (17)	0.0041 (16)	−0.0069 (15)
O3	0.186 (5)	0.077 (3)	0.081 (3)	−0.052 (3)	0.022 (3)	0.002 (2)
C11	0.046 (2)	0.0348 (18)	0.036 (2)	−0.0051 (16)	0.0078 (16)	−0.0026 (14)
C6	0.039 (2)	0.050 (2)	0.0320 (19)	−0.0040 (17)	−0.0026 (15)	0.0033 (15)
C4	0.086 (4)	0.062 (3)	0.047 (3)	0.015 (3)	−0.008 (2)	0.017 (2)
C1	0.070 (3)	0.040 (2)	0.050 (2)	0.010 (2)	0.002 (2)	0.0018 (18)
C9	0.049 (3)	0.056 (2)	0.046 (2)	−0.017 (2)	−0.0024 (19)	−0.0128 (19)
C14	0.066 (3)	0.040 (2)	0.077 (3)	0.011 (2)	0.003 (3)	−0.002 (2)
C7	0.046 (2)	0.071 (3)	0.041 (2)	−0.001 (2)	−0.0093 (18)	0.001 (2)
C12	0.070 (3)	0.035 (2)	0.060 (3)	−0.014 (2)	−0.003 (2)	−0.0083 (18)
C17	0.058 (3)	0.060 (3)	0.057 (3)	0.016 (2)	0.002 (2)	0.006 (2)
C21	0.039 (2)	0.057 (3)	0.061 (3)	0.000 (2)	0.002 (2)	0.004 (2)
C3	0.117 (5)	0.053 (3)	0.070 (4)	0.019 (3)	−0.009 (3)	0.027 (3)
C20	0.048 (3)	0.075 (3)	0.086 (4)	−0.010 (3)	0.000 (3)	−0.009 (3)
C8	0.048 (3)	0.079 (3)	0.041 (2)	−0.018 (2)	−0.010 (2)	−0.006 (2)
C18	0.061 (4)	0.113 (5)	0.061 (3)	0.023 (4)	−0.013 (3)	−0.001 (3)
C2	0.086 (4)	0.038 (2)	0.078 (3)	0.014 (2)	0.005 (3)	0.005 (2)
C19	0.044 (3)	0.123 (5)	0.073 (4)	−0.001 (3)	−0.015 (3)	−0.025 (4)
C13	0.090 (4)	0.0279 (19)	0.078 (3)	0.002 (2)	0.003 (3)	−0.006 (2)
F1	0.163 (5)	0.365 (9)	0.092 (4)	0.131 (5)	−0.056 (3)	−0.014 (4)
F3	0.167 (5)	0.332 (8)	0.144 (5)	0.182 (6)	0.015 (4)	−0.002 (5)
C22	0.102 (7)	0.201 (10)	0.084 (6)	0.045 (7)	−0.001 (5)	0.003 (6)
F2	0.129 (5)	0.393 (12)	0.228 (7)	−0.107 (7)	−0.015 (5)	0.004 (7)

Geometric parameters (Å, º) top

Ag1—Ag1ⁱ	2.8501 (8)	C1—H1	0.9300
Ag1—N2ⁱ	2.412 (3)	C1—C2	1.377 (6)
Ag1—N3ⁱ	2.330 (3)	C9—H9	0.9300
Ag1—N1	2.240 (3)	C9—C8	1.343 (6)
Ag1—O1	2.578 (3)	C14—H14	0.9300
S1—O2	1.427 (3)	C14—C13	1.366 (7)
S1—O1	1.407 (3)	C7—H7	0.9300
S1—O3	1.421 (4)	C7—C8	1.361 (6)
S1—C22	1.786 (9)	C12—H12	0.9300
N2—C10	1.342 (4)	C12—C13	1.372 (6)
N2—C6	1.326 (5)	C17—H17	0.9300
N3—C15	1.342 (5)	C17—C18	1.373 (7)
N3—C11	1.345 (5)	C21—H21	0.9300
N1—C5	1.349 (5)	C21—C20	1.380 (7)
N1—C1	1.345 (5)	C3—H3	0.9300
C5—C6	1.476 (5)	C3—C2	1.353 (7)
C5—C4	1.386 (5)	C20—H20	0.9300
C15—C16	1.468 (6)	C20—C19	1.351 (7)
C15—C14	1.393 (5)	C8—H8	0.9300
C16—C17	1.399 (6)	C18—H18	0.9300
C16—C21	1.388 (6)	C18—C19	1.362 (8)
C10—C11	1.478 (5)	C2—H2	0.9300
C10—C9	1.389 (5)	C19—H19	0.9300
C11—C12	1.385 (5)	C13—H13	0.9300
C6—C7	1.402 (5)	F1—C22	1.277 (9)
C4—H4	0.9300	F3—C22	1.260 (9)
C4—C3	1.351 (7)	C22—F2	1.436 (11)

N2ⁱ—Ag1—Ag1ⁱ	66.66 (7)	N1—C1—C2	121.9 (5)
N2ⁱ—Ag1—O1	92.60 (11)	C2—C1—H1	119.1
N3ⁱ—Ag1—Ag1ⁱ	100.90 (8)	C10—C9—H9	119.8
N3ⁱ—Ag1—N2ⁱ	70.59 (10)	C8—C9—C10	120.4 (4)
N3ⁱ—Ag1—O1	106.58 (11)	C8—C9—H9	119.8
N1—Ag1—Ag1ⁱ	78.35 (9)	C15—C14—H14	120.3
N1—Ag1—N2ⁱ	132.85 (12)	C13—C14—C15	119.3 (5)
N1—Ag1—N3ⁱ	149.76 (12)	C13—C14—H14	120.3
N1—Ag1—O1	92.64 (11)	C6—C7—H7	120.8
O1—Ag1—Ag1ⁱ	137.45 (10)	C8—C7—C6	118.4 (4)
O2—S1—C22	104.4 (3)	C8—C7—H7	120.8
O1—S1—O2	115.9 (2)	C11—C12—H12	120.4
O1—S1—O3	114.4 (3)	C13—C12—C11	119.1 (4)
O1—S1—C22	102.7 (4)	C13—C12—H12	120.4
O3—S1—O2	115.2 (2)	C16—C17—H17	119.8
O3—S1—C22	101.7 (4)	C18—C17—C16	120.3 (5)
C10—N2—Ag1ⁱ	114.9 (2)	C18—C17—H17	119.8
C6—N2—Ag1ⁱ	124.7 (2)	C16—C21—H21	119.7
C6—N2—C10	118.7 (3)	C20—C21—C16	120.6 (5)
C15—N3—Ag1ⁱ	121.7 (3)	C20—C21—H21	119.7
C15—N3—C11	120.1 (3)	C4—C3—H3	120.4
C11—N3—Ag1ⁱ	117.6 (2)	C4—C3—C2	119.3 (4)
C5—N1—Ag1	123.3 (3)	C2—C3—H3	120.4
C1—N1—Ag1	118.6 (3)	C21—C20—H20	119.7
C1—N1—C5	117.9 (4)	C19—C20—C21	120.7 (5)
S1—O1—Ag1	159.1 (2)	C19—C20—H20	119.7
N1—C5—C6	117.4 (3)	C9—C8—C7	119.6 (4)
N1—C5—C4	121.2 (4)	C9—C8—H8	120.2
C4—C5—C6	121.4 (4)	C7—C8—H8	120.2
N3—C15—C16	117.8 (3)	C17—C18—H18	119.6
N3—C15—C14	120.5 (4)	C19—C18—C17	120.7 (5)
C14—C15—C16	121.6 (4)	C19—C18—H18	119.6
C17—C16—C15	121.1 (4)	C1—C2—H2	120.1
C21—C16—C15	121.4 (4)	C3—C2—C1	119.8 (5)
C21—C16—C17	117.6 (4)	C3—C2—H2	120.1
N2—C10—C11	117.4 (3)	C20—C19—C18	120.0 (5)
N2—C10—C9	120.8 (4)	C20—C19—H19	120.0
C9—C10—C11	121.8 (4)	C18—C19—H19	120.0
N3—C11—C10	117.6 (3)	C14—C13—C12	119.8 (4)
N3—C11—C12	120.9 (4)	C14—C13—H13	120.1
C12—C11—C10	121.4 (4)	C12—C13—H13	120.1
N2—C6—C5	118.2 (3)	F1—C22—S1	110.9 (6)
N2—C6—C7	122.1 (4)	F1—C22—F2	109.0 (10)
C7—C6—C5	119.6 (4)	F3—C22—S1	113.8 (8)
C5—C4—H4	120.0	F3—C22—F1	111.6 (8)
C3—C4—C5	120.0 (5)	F3—C22—F2	107.2 (9)
C3—C4—H4	120.0	F2—C22—S1	103.9 (6)
N1—C1—H1	119.1

Ag1ⁱ—N2—C10—C11	−13.4 (4)	C15—C16—C21—C20	−177.2 (4)
Ag1ⁱ—N2—C10—C9	164.6 (3)	C15—C14—C13—C12	−0.9 (8)
Ag1ⁱ—N2—C6—C5	15.1 (5)	C16—C15—C14—C13	−178.0 (4)
Ag1ⁱ—N2—C6—C7	−163.3 (3)	C16—C17—C18—C19	−2.2 (8)
Ag1ⁱ—N3—C15—C16	7.7 (5)	C16—C21—C20—C19	−1.6 (7)
Ag1ⁱ—N3—C15—C14	−174.5 (3)	C10—N2—C6—C5	179.7 (3)
Ag1ⁱ—N3—C11—C10	−11.5 (4)	C10—N2—C6—C7	1.3 (6)
Ag1ⁱ—N3—C11—C12	171.5 (3)	C10—C11—C12—C13	−174.3 (4)
Ag1—N1—C5—C6	−4.0 (5)	C10—C9—C8—C7	0.1 (7)
Ag1—N1—C5—C4	175.2 (3)	O3—S1—O1—Ag1	18.4 (9)
Ag1—N1—C1—C2	−176.2 (4)	O3—S1—C22—F1	−64.9 (9)
O2—S1—O1—Ag1	156.1 (7)	O3—S1—C22—F3	61.9 (9)
O2—S1—C22—F1	175.0 (7)	O3—S1—C22—F2	178.1 (6)
O2—S1—C22—F3	−58.2 (9)	C11—N3—C15—C16	178.0 (3)
O2—S1—C22—F2	58.0 (7)	C11—N3—C15—C14	−4.1 (6)
N2—C10—C11—N3	17.0 (5)	C11—C10—C9—C8	178.7 (4)
N2—C10—C11—C12	−166.0 (4)	C11—C12—C13—C14	−2.4 (7)
N2—C10—C9—C8	0.8 (6)	C6—N2—C10—C11	−179.5 (3)
N2—C6—C7—C8	−0.4 (6)	C6—N2—C10—C9	−1.4 (5)
N3—C15—C16—C17	−141.8 (4)	C6—C5—C4—C3	179.5 (5)
N3—C15—C16—C21	37.5 (6)	C6—C7—C8—C9	−0.3 (7)
N3—C15—C14—C13	4.2 (7)	C4—C5—C6—N2	−134.9 (4)
N3—C11—C12—C13	2.6 (6)	C4—C5—C6—C7	43.6 (6)
N1—C5—C6—N2	44.3 (5)	C4—C3—C2—C1	−1.6 (9)
N1—C5—C6—C7	−137.2 (4)	C1—N1—C5—C6	180.0 (4)
N1—C5—C4—C3	0.4 (8)	C1—N1—C5—C4	−0.8 (7)
N1—C1—C2—C3	1.2 (9)	C9—C10—C11—N3	−161.0 (3)
O1—S1—C22—F1	53.7 (9)	C9—C10—C11—C12	16.0 (6)
O1—S1—C22—F3	−179.5 (8)	C14—C15—C16—C17	40.4 (6)
O1—S1—C22—F2	−63.2 (6)	C14—C15—C16—C21	−140.3 (4)
C5—N1—C1—C2	0.1 (7)	C17—C16—C21—C20	2.1 (6)
C5—C6—C7—C8	−178.8 (4)	C17—C18—C19—C20	2.8 (9)
C5—C4—C3—C2	0.9 (9)	C21—C16—C17—C18	−0.2 (7)
C15—N3—C11—C10	177.7 (3)	C21—C20—C19—C18	−0.9 (8)
C15—N3—C11—C12	0.7 (6)	C22—S1—O1—Ag1	−90.8 (8)
C15—C16—C17—C18	179.1 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱⁱ	0.93	2.43	3.273 (6)	150
C9—H9···O2ⁱⁱⁱ	0.93	2.58	3.278 (5)	132
C9—H9···O1ⁱⁱⁱ	0.93	2.65	3.315 (5)	130

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

Acknowledgements

Author contributions: Yuto Nakaie: investigation, writing – original draft. Tomoya Abe: investigation. Yosuke Hosoya: supervision. Kosuke Sugawa: supervision. Joe Otsuki: conceptualization, supervision, writing – review and editing.

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (grant No. 24K08386).

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