A one-dimensional silver(I) coordination polymer based on an asymmetric flexible N-donor carboxyl­ate ligand: catena-poly[(μ₃-4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]­methyl}­benzo­ato-κ³O:O′:N⁴)silver(I)]

The title compound, [Ag(C₁₅H₁₁N₄O₂S)]_n, was synthesized by the reaction of 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]­methyl}­ben­zoic acid (Hptmba) with silver nitrate and tri­ethyl­amine at room temperature. The asymmetric unit contains one crystallographically independent Ag^I cation and one ptmba⁻ ligand. Each Ag^I cation is tricoordinated by two carboxyl­ate O atoms and one tetra­zole N atom from three different ptmba⁻ ligands, displaying a distorted T-shaped geometry. Three Ag^I cations are linked by tris-monodentate bridging ptmba⁻ ligands to form a one-dimensional double chain along the c axis, which is further consolidated by an intra­chain π–π contact with an offset face-to-face distance of 4.176 (3) Å between the centroids of two adjacent aromatic rings in neighbouring benzo­ate groups. The one-dimensional chains are linked into a three-dimensional supra­molecular framework by additional π–π inter­chain inter­actions, viz. of 3.753 (3) Å between two phenyl substituents of the tetra­zole rings and of 4.326 (2) Å between a benzoate ring and a tetra­zole ring. Thermogravimetric analysis and the fluorescence spectrum of the title compound reveal its good thermal stability and a strong green luminescence at room temperature.

S1. Introduction

In recent years, coordination polymers (CPs) have been widely investigated in coordination chemistry and materials science due to their intriguing structural diversities and potential applications, for example in adsorption/separation (Li et al., 2011), magnetism (Kurmoo, 2009), catalysis (Lee et al., 2009) and luminescence (Cui et al., 2012). In particular, CPs based on silver are of current inter­est because the Ag^I cation principally exhibits various coordination numbers and a high affinity even for hard donor atoms such as nitro­gen or oxygen, and because it possesses a d¹⁰ electronic configuration with the possibility for direct Ag···Ag inter­actions and potential applications in luminescence (Cheng et al., 2011; Liu et al., 2012). From the viewpoint of crystal engineering, the rational selection of organic ligands assembling with Ag^I cations plays a very important role in the construction of the target silver CPs with desired structures and properties. Several silver(I) CPs with rigid organic ligands have been synthesized successfully; for example, Sun and co-workers have reported two silver(I) CPs constructed from rigid benzoguanamine and pyrazine-2-carb­oxy­lic acid or pyrazine-2,3-di­carb­oxy­lic acid as ligands (Sun, Hao et al., 2012). Huang et al. (2013) reported a silver(I) CP with the ligands benzene-1,3,5-tri­carb­oxy­lic acid and pyrazine. In addition, Guo's group successfully obtained a three-dimensional silver(I) CP based on 2-phenyl­quinoline-4-carboxyl­ate and 4,4'-bi­pyridine (Guo et al., 2013). However, less attention has hitherto been focused on flexible ligands, especially on asymmetric flexible bridges (Wei et al., 2009). In this work, we selected the asymmetric flexible N-donor ligand 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoate (ptmba; Zhang et al., 2012), which has at least three expected advantages: (i) strong coordination ability from the combination of carboxyl­ate and tetra­zole groups; (ii) a flexible conformation (due to the –SCH₂– group) and asymmetric character; (iii) potentially rich supra­molecular inter­actions, such as hydrogen bonds, π–π stacking and/or C—H···π inter­actions etc. Herein, we report the synthesis and crystal structure of the resulting one-dimensional silver(I) coordination polymer, (I), and discuss its thermal stability and luminescence properties.

S2. Experimental

S2.1. Synthesis and crystallization

All chemicals were purchased from commercial sources (Alfa–Aesar) and used without further purification. 4-{[(1-Phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoic acid (Hptmba) was synthesized according to our previously reported method (Zhang et al., 2012). For the preparation of (I), a solution of silver nitrate (0.085 g, 0.5 mmol) in aceto­nitrile (5 ml) was carefully layered onto an aqueous solution (5 ml) of Hptmba (0.156 g, 0.5 mmol) and tri­ethyl­amine (0.051 g, 0.5 mmol). The system was left in a dark room for about 5 d at ambient temperature, and colourless block-shaped crystals of (I) suitable for X-ray analysis were obtained (yield 0.164 g, 78%, based on silver). Elemental analysis, calculated for C₁₅H₁₁AgN₄O₂S: C 42.98, H 2.64, N 13.36, S 7.65%; found: C 42.90, H 2.72, N 13.32, S 7.70%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 2984 (w), 1590 (s), 1498 (s), 1438 (m), 1387 (s), 1303 (m), 1178 (m), 850 (m), 806 (m), 734 (m), 711 (m), 693 (m), 630 (w).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically, with C—H = 0.93 or 0.97 Å for aromatic or methyl­ene H atoms, respectively, and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The title compound, (I), crystallizes in the monoclinic space group P2₁/c, and the asymmetric unit consists of one crystallographically independent Ag^I cation and one 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoate (ptmba^-) ligand (Fig. 1). Each Ag^I cation is tricoordinated by two carboxyl­ate O atoms and one tetra­zole N atom from three different ptmba^- ligands, displaying a distorted T-shaped geometry. The Ag—O and Ag—N bond lengths (Table 2) are comparable with those reported in other Ag^I compounds (Yin et al., 2009; Sun et al., 2011; Sun, Liu et al., 2012). In (I), the ptmba^- ligand adopts a µ₃-O:O':N⁴ tris-monodentate bridging mode. The two carboxyl­ate C—O distances (Table 2) do not differ significantly, thus indicating substantial delocalization of the –CO₂^- π-electron density. The dihedral angle between the plane of the central tetra­zole ring and that of the carboxyl­ato­benzyl group is 82.92 (12)°, while the dihedral angle between the planes of the central tetra­zole ring and the attached phenyl ring is 41.16 (16)°, which is smaller than that found in free Hptmba [61.66 (11)°; Zhang et al., 2012], indicating that inter­annular conjugation is insignificant or absent.

As shown in Fig. 2, each ptmba^- ligand in (I) bridges three different Ag^I cations, and likewise each Ag^I cation connects to three different µ₃-ptmba^- ligands, thus generating an inter­esting one-dimensional [Ag(ptmba)]_n double-chain structure along the c axis, which is similar to that found in the silver compound [Ag(HL)].H₂O (L is the 4-hy­droxy-3-nitroso­naphthalene-1-sulfonate anion; Wu et al., 2009). Alternatively, the coordination polymer [Ag(ptmba)]_n can be understood as constructed from dimeric [Ag₂(CO₂)₂] units linked by bridging µ₃-ptmba^- ligands. The distance between the Ag^I cations in the [Ag₂(CO₂)₂] unit [Ag1···Ag1ⁱ = 2.9183 (7) Å; symmetry code: (i) -x + 2, -y + 1, -z + 2] is slightly longer than the Ag···Ag separation of 2.88 Å in the metal [Reference?], but significantly shorter than the van der Waals contact distance for Ag···Ag of 3.44 Å (Bondi, 1964). When compared with the related silver(I) coordination polymers [Ag(bpy)_0.5].Hdpa (H₂dpa = 1,1'-bi­phenyl-2,2'-di­carb­oxy­lic acid and bpy = 4,4'-bi­pyridine; Yin et al., 2009) and [Ag(abn)(4-cba)]₂ (abn = 2-amino­benzo­nitrile and 4-cbaH = 4-chloro­benzoic acid; Sun, Liu et al., 2012), the Ag···Ag distance in the [Ag₂(CO₂)₂] unit of (I) is longer than that in [Ag(abn)(4-cba)]₂ [2.8950 (9) Å] but shorter than that in [Ag(bpy)_0.5].Hdpa [2.9591 (2) Å], indicating the existence of ligand-supported argentophilic inter­actions (Wang & Mak, 2002).

An additional intra­chain feature is the offset face-to-face π–π stacking between two adjacent benzene rings of -SCH₂C₆H₄CO₂^- groups (Cg1···Cg1ⁱⁱ; Table 3). This π–π contact further consolidates the double-chain structure. Inter­chain contacts are present due to face-to-face π–π stacking between the two neighbouring phenyl rings of [C₆H₅N₄C–] groups (Cg2···Cg2ⁱⁱⁱ; Table 2), thus yielding a two-dimensional (4,4)-connected supra­molecular network in the ac plane with re­cta­ngular windows (Fig. 3). The resulting layers are packed along the b axis, via additional π–π inter­actions between a benzene ring in the [–(SCH₂C₆H₄CO₂)^-] group and a tetra­zole ring (Cg1···Cg3^iv; see Table 3 for details) to form a three-dimensional supra­molecular framework (Fig. 4).

To determine the thermal stability of (I), thermogravimetric analysis (TGA) was carried out under a nitro­gen atmosphere in the temperature range 308–973 K at a heating rate of 10 K min^-1. The TG curve in Fig. 5(a) shows no obvious weight loss from 308 to 483 K; a rapid weight loss is observed upon further heating, indicating decomposition of the framework. This result confirms the absence of cocrystallized solvent molecules in (I), consistent with the single-crystal X-ray diffraction analysis. The powder X-ray diffraction (PXRD) pattern of an as-synthesized sample matches the simulation based on the single-crystal diffraction data and hence indicates phase purity of the product (Fig. 5b).

The photoluminescent properties of (I) were investigated at room temperature in the solid state. As shown in Fig. 6, (I) exhibits strong green luminescence, with a maximum at ca 546 nm upon excitation at 325 nm. Compared with the emission of the free Hptmba molecule (λ_em = 441 nm, λ_ex = 325 nm), the emission band of (I) is red-shifted by ca 105 nm, and this may be due to the electronic transition between occupied p orbitals of coordinated N or O atoms and the empty 5s orbital of the Ag^I cation, i.e. ligand-to-metal charge transfer (LMCT), mixed with metal-centred (d–s/d–p) transitions. Similar observations have been made for other photoluminescent silver(I) compounds (Liu et al., 2005; Luo et al., 2009).

In summary, a new one-dimensional silver(I) coordination polymer has been successfully synthesized based on the asymmetric flexible N-donor 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoate ligand. The observed π–π inter­actions not only consolidate the intra­chain one-dimensional structure but also help to link individual chains into a three-dimensional supra­molecular framework. Thermogravimetry and fluorescence spectroscopy revealed that the new coordination polymer shows good thermal stability and strong green luminescence at room temperature.

Related literature

For related literature, see: Bondi (1964); Cheng et al. (2011); Cui et al. (2012); Guo et al. (2013); Huang et al. (2013); Kurmoo (2009); Lee et al. (2009); Li et al. (2011); Liu et al. (2005, 2012); Luo et al. (2009); Sun et al. (2011); Sun, Hao, Liu, Su, Huang & Zheng (2012); Sun, Liu, Hao, Li, Huang & Zheng (2012); Wang & Mak (2002); Wei et al. (2009); Wu et al. (2009); Yin et al. (2009); Zhang et al. (2012).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the asymmetric unit of (I) and the local coordination of the Ag^I cation, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 2, -y + 1, -z + 2; (ii) -x + 2, -y + 1, -z + 1.]
	Fig. 2. The one-dimensional double-chain structure of (I) along the c axis, incorporating Ag^I···Ag^I interactions (turquoise dashed lines) and consolidated by face-to-face π–π interactions (red dashed lines). H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 2, -y + 1, -z + 2; (ii) -x + 2, -y + 1, -z + 1.]
	Fig. 3. Views of the two-dimensional network of (I) along the b axis, shown in (a) ball-and-stick and (b) space-filling modes. [Symmetry code: (iii) -x + 1, -y, -z.]
	Fig. 4. A packing diagram of the three-dimensional supramolecular framework of (I), extended via π–π interactions (dashed lines). H atoms have been omitted for clarity.
	Fig. 5. (a) The TGA curve for (I) under a nitrogen atmosphere. (b) The powder X-ray diffraction (PXRD) patterns for (I), both simulated and as-synthesized.
	Fig. 6. The solid-state emission spectra of (I) and the free Hptmba molecule at room temperature.

catena-Poly[(µ₃-4-{[(1-phenyl-1H-tetrazol-5- yl)sulfanyl]methyl}benzoato-κ³O:O':N⁴)silver(I)]

Crystal data

[Ag(C15H11N4O2S)]	F(000) = 832
Mr = 419.21	Dx = 1.803 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3290 reflections
a = 15.1501 (13) Å	θ = 2.7–28.0°
b = 8.2900 (7) Å	µ = 1.45 mm^−1
c = 12.3879 (11) Å	T = 298 K
β = 96.936 (2)°	Block, colourless
V = 1544.5 (2) Å^3	0.40 × 0.38 × 0.19 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	3684 independent reflections
Radiation source: fine-focus sealed tube	2383 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
φ and ω scans	θmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −20→8
Tmin = 0.594, Tmax = 0.770	k = −10→10
9195 measured reflections	l = −15→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.050P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3684 reflections	Δρmax = 0.78 e Å^−3
209 parameters	Δρmin = −1.10 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0092 (9)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ag1	1.08271 (2)	0.42668 (4)	0.97501 (2)	0.05051 (17)
S1	0.76232 (8)	0.33620 (12)	0.27351 (7)	0.0438 (3)
O1	0.8883 (2)	0.5799 (3)	0.8464 (2)	0.0465 (7)
O2	0.9989 (2)	0.4112 (3)	0.81849 (19)	0.0467 (7)
N1	0.6551 (2)	0.3178 (4)	0.0795 (2)	0.0400 (8)
N2	0.6434 (3)	0.3882 (5)	−0.0212 (3)	0.0562 (10)
N3	0.7071 (3)	0.4924 (5)	−0.0222 (3)	0.0614 (11)
N4	0.7620 (2)	0.4911 (4)	0.0755 (2)	0.0452 (8)
C1	0.9312 (3)	0.4953 (4)	0.7860 (3)	0.0320 (8)
C2	0.9003 (3)	0.4942 (4)	0.6663 (2)	0.0308 (8)
C3	0.9312 (3)	0.3776 (5)	0.5982 (3)	0.0398 (9)
H3	0.9694	0.2969	0.6278	0.048*
C4	0.9052 (3)	0.3816 (5)	0.4862 (3)	0.0406 (10)
H4	0.9251	0.3021	0.4420	0.049*
C5	0.8498 (3)	0.5033 (4)	0.4402 (3)	0.0343 (8)
C6	0.8172 (3)	0.6176 (4)	0.5071 (3)	0.0346 (8)
H6	0.7788	0.6976	0.4769	0.041*
C7	0.8419 (3)	0.6130 (4)	0.6195 (3)	0.0343 (8)
H7	0.8193	0.6897	0.6636	0.041*
C8	0.8253 (3)	0.5159 (5)	0.3169 (3)	0.0446 (10)
H8A	0.8787	0.5223	0.2809	0.053*
H8B	0.7899	0.6117	0.2988	0.053*
C9	0.7280 (3)	0.3840 (4)	0.1379 (3)	0.0363 (9)
C10	0.5951 (3)	0.1960 (5)	0.1099 (3)	0.0429 (10)
C11	0.6302 (4)	0.0633 (5)	0.1684 (4)	0.0556 (12)
H11	0.6912	0.0526	0.1866	0.067*
C12	0.5722 (5)	−0.0535 (7)	0.1991 (5)	0.0818 (19)
H12	0.5941	−0.1417	0.2403	0.098*
C13	0.4812 (5)	−0.0378 (8)	0.1679 (5)	0.0816 (19)
H13	0.4423	−0.1170	0.1864	0.098*
C14	0.4501 (4)	0.0925 (8)	0.1110 (4)	0.0778 (18)
H14	0.3891	0.1017	0.0908	0.093*
C15	0.5052 (3)	0.2131 (6)	0.0813 (3)	0.0568 (12)
H15	0.4821	0.3033	0.0431	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0478 (3)	0.0737 (3)	0.02751 (19)	0.00522 (18)	−0.00578 (14)	−0.00075 (13)
S1	0.0517 (7)	0.0466 (6)	0.0298 (4)	−0.0125 (5)	−0.0088 (4)	0.0028 (4)
O1	0.056 (2)	0.0565 (17)	0.0265 (12)	0.0103 (16)	0.0054 (13)	−0.0024 (11)
O2	0.0449 (18)	0.0663 (18)	0.0251 (12)	0.0140 (16)	−0.0107 (12)	−0.0001 (11)
N1	0.0393 (19)	0.0488 (18)	0.0302 (14)	−0.0097 (17)	−0.0030 (13)	−0.0014 (13)
N2	0.053 (2)	0.076 (3)	0.0343 (17)	−0.016 (2)	−0.0160 (16)	0.0094 (16)
N3	0.066 (3)	0.081 (3)	0.0334 (18)	−0.022 (3)	−0.0120 (18)	0.0119 (17)
N4	0.045 (2)	0.059 (2)	0.0295 (15)	−0.009 (2)	−0.0022 (14)	0.0054 (14)
C1	0.035 (2)	0.0360 (18)	0.0241 (16)	−0.0085 (18)	0.0002 (15)	0.0005 (14)
C2	0.035 (2)	0.0339 (17)	0.0229 (15)	−0.0057 (18)	0.0024 (14)	−0.0022 (13)
C3	0.048 (3)	0.0356 (19)	0.0346 (18)	0.006 (2)	0.0004 (17)	−0.0009 (15)
C4	0.050 (3)	0.041 (2)	0.0287 (17)	0.006 (2)	−0.0004 (17)	−0.0079 (15)
C5	0.039 (2)	0.0376 (18)	0.0250 (16)	−0.0112 (19)	−0.0032 (15)	0.0007 (14)
C6	0.034 (2)	0.0354 (18)	0.0323 (17)	−0.0018 (18)	−0.0061 (15)	0.0040 (14)
C7	0.039 (2)	0.0348 (18)	0.0289 (17)	−0.0004 (18)	0.0038 (16)	−0.0061 (14)
C8	0.057 (3)	0.050 (2)	0.0240 (17)	−0.015 (2)	−0.0054 (17)	−0.0004 (15)
C9	0.039 (2)	0.0381 (19)	0.0288 (17)	−0.0013 (19)	−0.0063 (15)	−0.0048 (14)
C10	0.042 (2)	0.050 (2)	0.0356 (19)	−0.014 (2)	0.0034 (17)	−0.0129 (17)
C11	0.053 (3)	0.052 (3)	0.061 (3)	−0.013 (2)	0.002 (2)	−0.004 (2)
C12	0.097 (5)	0.075 (4)	0.073 (4)	−0.032 (4)	0.009 (4)	0.009 (3)
C13	0.085 (5)	0.102 (5)	0.059 (3)	−0.048 (4)	0.014 (3)	−0.008 (3)
C14	0.043 (3)	0.125 (5)	0.067 (3)	−0.028 (4)	0.012 (3)	−0.024 (3)
C15	0.037 (2)	0.081 (3)	0.050 (2)	−0.006 (3)	−0.0051 (19)	−0.012 (2)

Geometric parameters (Å, º)

Ag1—O1^i	2.204 (2)	C4—C5	1.390 (6)
Ag1—O2	2.190 (3)	C4—H4	0.9300
Ag1—N4^ii	2.598 (4)	C5—C6	1.388 (5)
Ag1—Ag1^i	2.9183 (7)	C5—C8	1.532 (4)
S1—C9	1.743 (3)	C6—C7	1.398 (5)
S1—C8	1.815 (4)	C6—H6	0.9300
C1—O1	1.261 (4)	C7—H7	0.9300
O1—Ag1^i	2.204 (2)	C8—H8A	0.9700
C1—O2	1.265 (5)	C8—H8B	0.9700
N1—C9	1.360 (5)	C10—C15	1.373 (6)
N1—N2	1.370 (4)	C10—C11	1.387 (6)
N1—C10	1.439 (5)	C11—C12	1.391 (7)
N2—N3	1.295 (5)	C11—H11	0.9300
N3—N4	1.384 (4)	C12—C13	1.391 (10)
N4—C9	1.322 (5)	C12—H12	0.9300
N4—Ag1^ii	2.598 (4)	C13—C14	1.344 (8)
C1—C2	1.500 (4)	C13—H13	0.9300
C2—C3	1.401 (5)	C14—C15	1.381 (7)
C2—C7	1.402 (5)	C14—H14	0.9300
C3—C4	1.396 (5)	C15—H15	0.9300
C3—H3	0.9300
O2—Ag1—O1^i	155.70 (13)	C5—C6—H6	119.9
O2—Ag1—N4^ii	104.32 (11)	C7—C6—H6	119.9
O1^i—Ag1—N4^ii	99.92 (11)	C6—C7—C2	120.7 (3)
O2—Ag1—Ag1^i	77.95 (8)	C6—C7—H7	119.6
O1^i—Ag1—Ag1^i	82.48 (8)	C2—C7—H7	119.6
N4^ii—Ag1—Ag1^i	140.16 (9)	C5—C8—S1	107.2 (2)
C9—S1—C8	100.60 (17)	C5—C8—H8A	110.3
C1—O1—Ag1^i	121.8 (2)	S1—C8—H8A	110.3
C1—O2—Ag1	127.6 (2)	C5—C8—H8B	110.3
C9—N1—N2	108.6 (3)	S1—C8—H8B	110.3
C9—N1—C10	130.0 (3)	H8A—C8—H8B	108.5
N2—N1—C10	121.4 (3)	N4—C9—N1	108.0 (3)
N3—N2—N1	106.1 (3)	N4—C9—S1	128.6 (3)
N2—N3—N4	110.9 (3)	N1—C9—S1	123.3 (3)
C9—N4—N3	106.3 (3)	C15—C10—C11	121.5 (4)
C9—N4—Ag1^ii	138.2 (3)	C15—C10—N1	119.9 (4)
N3—N4—Ag1^ii	104.7 (2)	C11—C10—N1	118.6 (4)
O1—C1—O2	125.0 (3)	C10—C11—C12	118.7 (5)
O1—C1—C2	117.9 (3)	C10—C11—H11	120.7
O2—C1—C2	117.1 (3)	C12—C11—H11	120.7
C3—C2—C7	118.4 (3)	C13—C12—C11	119.7 (6)
C3—C2—C1	120.8 (3)	C13—C12—H12	120.1
C7—C2—C1	120.7 (3)	C11—C12—H12	120.1
C4—C3—C2	120.5 (4)	C14—C13—C12	119.6 (6)
C4—C3—H3	119.8	C14—C13—H13	120.2
C2—C3—H3	119.8	C12—C13—H13	120.2
C5—C4—C3	120.6 (3)	C13—C14—C15	122.4 (6)
C5—C4—H4	119.7	C13—C14—H14	118.8
C3—C4—H4	119.7	C15—C14—H14	118.8
C6—C5—C4	119.5 (3)	C10—C15—C14	118.0 (5)
C6—C5—C8	119.2 (3)	C10—C15—H15	121.0
C4—C5—C8	121.3 (3)	C14—C15—H15	121.0
C5—C6—C7	120.3 (3)

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