Bis{μ-3-[3-(2-pyrid­yl)pyrazol-1-yl­meth­yl]pyridine}disilver(I) bis­(tri­fluoro­methane­sulfonate): effect of counter-anions on the self-assembly of coordination complexes

As part of a study on the effect of different counter-anions on the self-assembly of coordination complexes, a new dinuclear Ag^I complex, [Ag₂(C₁₄H₁₂N₄)₂](CF₃SO₃)₂, with the 3-[3-(2-pyrid­yl)pyrazol-1-ylmeth­yl]pyridine (L) ligand was obtained through the reaction of L with AgCF₃SO₃. In this complex, each Ag^I center in the centrosymmetric dinuclear complex cation is coordinated by two pyridine and one pyrazole N-atom donor of two inversion-related L ligands in a trigonal planar geometry. This forms a unique box-like cyclic dimer with an intra­molecular nonbonding Ag...Ag separation of 6.379 (7) Å. Weak Ag...CF₃SO₃ and C—H...X (X = O and F) hydrogen-bonding inter­actions, together with π–π stacking inter­actions, link the complex cations along the [001] and [10] directions, respectively, generating two different one-dimensional chains and then an overall two-dimensional network of the complex running parallel to the (110) plane. Comparison of the structural differences with previous findings suggests that the presence of different counter-anions plays an important role in the construction of such supra­molecular frameworks.

S1. Comment

The rational design and synthesis of functional coordination architectures has attracted much attention in recent years owing to their interesting structures and their potential uses as functional materials (Chen et al., 2006; Janiak, 2003; Robin & Fromm, 2006; Steel, 2005; Wang et al., 2008). Although the principles for controlling the solid structures of the target products still need to be classified and established, many rational synthetic strategies have been brought forward and have proved significant in the design of metal-based coordination complexes. The selection of suitable ligands as building blocks is undoubtedly a key point in manipulating the final structures of the complexes (Robin & Fromm, 2006; Steel, 2005). Other factors, such as the coordination geometry or radius of the metal ions (Du et al., 2007; Liu, Wang et al., 2007), the size or coordination ability of the counter-anions (Campos-Fernández et al., 2005; Hirsch et al., 1997; Huang et al., 2004; Xie et al., 2004; Zou et al., 2004), the presence of auxiliary ligands (Liu, Shi et al., 2006; Liu, Wang et al., 2007) or solvents (Kasai et al., 2000; Raehm et al., 2003), metal/ligand ratio (Saalfrank et al., 2001), and even pH value (Du et al., 2002), have also been found to influence significantly the structural topologies of such coordination frameworks.

Numerous related bis-heterocyclic chelating or bridging ligands have been synthesized and used extensively to construct functional coordination complexes that contain different hetero-aromatic ring systems, for example, pyridine, pyrazine, quinoline, quinoxaline, pyrazole, imidazole, thiazoles and their benzo-analogues (Steel, 2005). Ward and co-workers have reported many coordination architectures involving 3-(2-pyridyl)-1H-pyrazole and its derivative ligands (Bell et al., 2003; Paul et al., 2004; Singh et al., 2003; Ward et al., 2001). In our previous work, a series of 3-(2-pyridyl)pyrazole-based ligands have also been used to construct complexes with various structures, including multi-nuclear discrete molecules as well as one- and two-dimensional coordination polymers, which also exhibit interesting properties (Liu, Chen et al., 2006, Liu, Li et al., 2007; Liu, Shi et al., 2006; Liu, Zhang et al., 2007; Zhang et al., 2005; Zou et al., 2006). Recently, we have reported the preparation of a nonplanar flexible ligand based on a pyrazolyl–pyridine chelating unit and a pendant pyridyl group, 3-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine (L) (Liu, Li et al., 2007). Its reaction with AgClO₄ produced a one-dimensional helical chain coordination polymer, {[Ag(L)](ClO₄)}_∞, (II). To further investigate the influence of different counter-anions on the self-assembly process of coordination complexes, we chose to use L to construct new functional Ag^I complexes through its reaction with AgCF₃SO₃. We report here the crystal structure of complex (I), {[Ag(L)](CF₃SO₃)}₂, and discuss the effect of different the counter-anions, ClO₄^- for (II) and CF₃SO₃^- for (I), on the final structures of the relevant coordination complexes.

The structure of (I) consists of a centrosymmetric dinuclear [Ag(L)]₂²⁺ unit and two uncoordinated CF₃SO₃^- ions. The dinuclear [Ag(L)]₂²⁺ cation (Fig. 1) comprises two L ligands and two Ag^I centers. Each Ag^I center adopts a distorted trigonal–planar geometry formed by three N-atom donors, two from the pyridyl–pyrazole ring system of one L ligand, and one from the pendant pyridine ring of another L ligand. All the Ag—N bond distances (Table 1) are in the normal range found in such complexes (Liu, Chen et al., 2006; Liu, Li et al., 2007). Meanwhile, each uncoordinated CF₃SO₃^- anion exhibits a weak interaction with the Ag^I center [Ag1···O2 = 2.660 (5) Å]. In addition, adjacent discrete dinuclear [Ag(L)]₂²⁺ units are assembled into different one-dimensional chains, along the [001] and [110] directions, by the combined effects of intermolecular face-to-face π–π stacking [the centroid–centroid separation being 3.804 (5) Å between the pyridyl–pyrazole ring systems; symmetry code: -x + 1, -y + 1, -z + 3] (Janiak, 2000), C—H···X hydrogen-bonding interactions (X = O and F) (Desiraju & Steiner, 1999) and the weak Ag···O interactions mentioned above (Fig. 2). The net result is a two-dimensional network running parallel to the (110) plane (Fig. 3).

In general, the effect of counter-anions on the self-assembly process of coordination complexes can be explained as being due to differences in sizes, shapes and coordination ability (Campos-Fernández et al., 2005; Hirsch et al., 1997; Huang et al., 2004; Xie et al., 2004; Zou et al., 2004).

The structural differences of complexes (I) and (II) serve to exemplify the eventual influence of counter-anions on the construction of supramolecular frameworks. Even if neither the ClO₄^- anion in (II) nor the CF₃SO₃^- anion in (I) coordinates to the Ag^I cation, owing to their size difference they fulfill quite different template roles, strongly affecting the building of the corresponding final frameworks through weak Ag···O interactions with the different cationic subunits [a dinuclear motif in complex (I) and a one-dimensional motif in complex (II); see the scheme below]. This analysis shows that changes in counter-anions could adjust the framework formation of such complexes, and this fact may provide an effective method for controlling the coordination architectures of compounds with potentially useful properties.

Related literature

For related literature, see: Bell et al. (2003); Campos-Fernández, Schottel, Chifotides, Bera, Bacsa, Koomen, Russell & Dunbar (2005); Chen et al. (2006); Desiraju & Steiner (1999); Du et al. (2002, 2007); Hirsch et al. (1997); Huang et al. (2004); Janiak (2000, 2003); Kasai et al. (2000); Liu, Chen, Yang, Tian, Bu, Li, Sun & Lin (2006); Liu, Li, Zou, Zhou, Shi, Wang & Bu (2007); Liu, Shi, Li, Wang & Bu (2006); Liu, Wang, Yan, Chang, Bu, Sañudo & Ribas (2007); Liu, Zhang, Chen, Shi, Bu & Yang (2007); Paul et al. (2004); Raehm et al. (2003); Robin & Fromm (2006); Saalfrank et al. (2001); Singh et al. (2003); Steel (2005); Wang et al. (2008); Ward et al. (2001); Xie et al. (2004); Zhang et al. (2005); Zou et al. (2004, 2006).

S2. Experimental

The ligand L was synthesized according to the method reported by Liu, Li et al. (2007). To AgCF₃SO₃ (0.1 mmol) in a mixed solution of methanol (15 ml) and acetonitrile (5 ml) was added L (0.1 mmol). A yellow solid formed, which was filtered off, and the resulting solution was kept at room temperature. Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent after several days (yield ~30%). Elemental analysis calculated for C₁₅H₁₂AgF₃N₄O₃S: C 36.53, H 2.45, N 11.36%; found: C 36.41, H 2.56, N 11.42%.

S3. Refinement

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H distances of 0.93 (aromatic) or 0.97 Å (methylene), and with U_iso(H) equal to 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the title complex, showing the Ag···O weak interaction (dashed line). Displacement ellipsoids are drawn at the 30% probability level. The symmetry-related parts in the dinuclear unit are generated by the symmetry operation (-x + 1, -y + 1, -z + 2).
	Fig. 2. A view of (a) the one-dimensional chain, running along the [001] direction, formed by π–π stacking (double dashed lines), C—H···O hydrogen-bonding (fine dashed lines) and Ag···O (thick dashed lines) interactions, and (b) another one-dimensional chain, running along the [110] direction, formed by C—H···F hydrogen-bonding (fine dashed lines) and Ag···O (thick dashed lines) interactions. For clarity, only H atoms involved in the interactions are shown.
	Fig. 3. The two-dimensional network, parallel to the (110) plane, formed by the intermolecular interactions shown in Fig. 2 (with the same bond coding). For clarity, only H atoms involved in the interactions are shown.

Bis{µ₂-3-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine- κ³N¹:N²,N³}disilver(I) bis(trifluoromethanesulfonate)

Crystal data

[Ag2(C14H12N4)2](CF3SO3)2	Z = 1
Mr = 986.44	F(000) = 488
Triclinic, P1	Dx = 1.848 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9430 (16) Å	Cell parameters from 3009 reflections
b = 8.5368 (17) Å	θ = 2.5–26.3°
c = 13.739 (3) Å	µ = 1.31 mm^−1
α = 75.64 (3)°	T = 293 K
β = 86.57 (3)°	Block, yellow
γ = 79.16 (3)°	0.30 × 0.28 × 0.25 mm
V = 886.3 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3099 independent reflections
Radiation source: fine-focus sealed tube	2678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ϕ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→7
Tmin = 0.68, Tmax = 0.72	k = −10→10
4510 measured reflections	l = −16→15

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0386P)^2 + 1.1251P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3099 reflections	Δρmax = 0.59 e Å^−3
245 parameters	Δρmin = −0.53 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: 0.050 (2)

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 > σ(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	0.63897 (4)	0.54485 (4)	0.77390 (2)	0.06530 (19)
C1	0.1667 (5)	0.4937 (5)	0.6284 (3)	0.0550 (9)
H1	0.0624	0.4606	0.6257	0.066*
C2	0.2346 (5)	0.6060 (5)	0.5562 (3)	0.0545 (9)
H2	0.1866	0.6655	0.4949	0.065*
C3	0.3926 (5)	0.6128 (4)	0.5939 (3)	0.0437 (8)
C4	0.5237 (5)	0.7115 (4)	0.5493 (3)	0.0427 (8)
C5	0.5137 (6)	0.8050 (5)	0.4513 (3)	0.0529 (9)
H5	0.4229	0.8067	0.4112	0.063*
C6	0.6396 (6)	0.8956 (5)	0.4138 (3)	0.0618 (11)
H6	0.6342	0.9598	0.3482	0.074*
C7	0.7720 (6)	0.8901 (5)	0.4737 (3)	0.0623 (11)
H7	0.8593	0.9490	0.4493	0.075*
C8	0.7744 (5)	0.7956 (5)	0.5712 (3)	0.0581 (10)
H8	0.8645	0.7934	0.6120	0.070*
C9	0.4209 (6)	0.2801 (5)	1.0526 (3)	0.0583 (10)
H9	0.4943	0.2064	1.1000	0.070*
C10	0.2303 (5)	0.5182 (5)	1.0065 (3)	0.0549 (9)
H10	0.1699	0.6147	1.0205	0.066*
C11	0.4087 (5)	0.2443 (5)	0.9613 (3)	0.0551 (9)
H11	0.4742	0.1497	0.9475	0.066*
C12	0.2094 (5)	0.4888 (5)	0.9143 (3)	0.0562 (10)
H12	0.1345	0.5636	0.8682	0.067*
C13	0.2989 (4)	0.3494 (4)	0.8906 (3)	0.0426 (8)
C14	0.2734 (5)	0.3048 (5)	0.7935 (3)	0.0510 (9)
H141	0.3619	0.2127	0.7868	0.061*
H142	0.1636	0.2695	0.7966	0.061*
C15	0.9695 (6)	−0.0467 (6)	0.8342 (4)	0.0765 (14)
N1	0.2785 (4)	0.4397 (4)	0.7044 (2)	0.0459 (7)
N2	0.4187 (4)	0.5090 (4)	0.6841 (2)	0.0443 (7)
N3	0.6536 (4)	0.7071 (4)	0.6097 (2)	0.0481 (7)
N4	0.3330 (4)	0.4149 (4)	1.0766 (2)	0.0472 (7)
O1	0.8952 (5)	0.1722 (6)	0.6747 (3)	0.1055 (14)
O2	0.8441 (5)	0.2540 (5)	0.8276 (4)	0.0998 (13)
O3	0.6633 (4)	0.0865 (5)	0.7823 (3)	0.0782 (9)
S1	0.82589 (12)	0.13590 (12)	0.77311 (7)	0.0504 (3)
F1	0.9638 (7)	−0.1678 (5)	0.7907 (5)	0.170 (2)
F2	0.9291 (5)	−0.1092 (6)	0.9244 (3)	0.155 (2)
F3	1.1288 (4)	−0.0274 (4)	0.8340 (4)	0.1178 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0686 (3)	0.0816 (3)	0.0446 (2)	−0.00971 (17)	−0.01809 (15)	−0.01210 (16)
C1	0.045 (2)	0.066 (3)	0.056 (2)	−0.0060 (18)	−0.0102 (17)	−0.019 (2)
C2	0.053 (2)	0.063 (2)	0.044 (2)	−0.0036 (19)	−0.0133 (17)	−0.0090 (18)
C3	0.0465 (19)	0.0465 (19)	0.0376 (18)	0.0009 (15)	−0.0071 (14)	−0.0147 (15)
C4	0.0467 (19)	0.0437 (19)	0.0365 (17)	0.0014 (15)	−0.0017 (14)	−0.0143 (15)
C5	0.068 (3)	0.052 (2)	0.0375 (19)	−0.0023 (19)	−0.0033 (17)	−0.0141 (16)
C6	0.083 (3)	0.055 (2)	0.042 (2)	−0.006 (2)	0.014 (2)	−0.0099 (18)
C7	0.065 (3)	0.059 (2)	0.063 (3)	−0.015 (2)	0.018 (2)	−0.016 (2)
C8	0.052 (2)	0.060 (2)	0.062 (3)	−0.0098 (19)	−0.0010 (19)	−0.014 (2)
C9	0.067 (3)	0.052 (2)	0.049 (2)	−0.0013 (19)	−0.0144 (19)	−0.0015 (18)
C10	0.057 (2)	0.054 (2)	0.050 (2)	0.0035 (18)	−0.0060 (18)	−0.0160 (18)
C11	0.065 (2)	0.045 (2)	0.051 (2)	−0.0018 (18)	−0.0070 (18)	−0.0088 (17)
C12	0.057 (2)	0.058 (2)	0.047 (2)	0.0077 (19)	−0.0155 (18)	−0.0115 (18)
C13	0.0413 (18)	0.0429 (18)	0.0431 (18)	−0.0134 (15)	0.0022 (14)	−0.0055 (15)
C14	0.057 (2)	0.049 (2)	0.050 (2)	−0.0177 (17)	−0.0016 (17)	−0.0123 (17)
C15	0.067 (3)	0.056 (3)	0.098 (4)	−0.013 (2)	−0.028 (3)	0.007 (3)
N1	0.0459 (17)	0.0519 (17)	0.0416 (16)	−0.0107 (14)	−0.0053 (13)	−0.0121 (13)
N2	0.0463 (16)	0.0481 (17)	0.0394 (15)	−0.0098 (13)	−0.0063 (13)	−0.0100 (13)
N3	0.0495 (17)	0.0497 (17)	0.0437 (16)	−0.0062 (14)	−0.0033 (13)	−0.0100 (13)
N4	0.0494 (17)	0.0544 (18)	0.0373 (15)	−0.0160 (14)	−0.0026 (13)	−0.0050 (13)
O1	0.094 (3)	0.140 (4)	0.053 (2)	−0.002 (2)	0.0086 (18)	0.014 (2)
O2	0.087 (3)	0.082 (2)	0.141 (4)	0.010 (2)	−0.033 (2)	−0.059 (3)
O3	0.0494 (17)	0.099 (2)	0.082 (2)	−0.0110 (16)	−0.0123 (15)	−0.0121 (19)
S1	0.0454 (5)	0.0531 (5)	0.0468 (5)	−0.0013 (4)	−0.0057 (4)	−0.0057 (4)
F1	0.180 (5)	0.069 (2)	0.264 (7)	0.024 (3)	−0.110 (4)	−0.057 (3)
F2	0.115 (3)	0.180 (4)	0.116 (3)	−0.046 (3)	−0.040 (2)	0.086 (3)
F3	0.0548 (17)	0.079 (2)	0.195 (4)	−0.0034 (15)	−0.033 (2)	0.015 (2)

Geometric parameters (Å, º)

Ag1—N4^i	2.196 (3)	C9—H9	0.9300
Ag1—N2	2.307 (3)	C10—N4	1.331 (5)
Ag1—N3	2.346 (3)	C10—C12	1.376 (5)
C1—N1	1.345 (5)	C10—H10	0.9300
C1—C2	1.362 (6)	C11—C13	1.372 (5)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.402 (5)	C12—C13	1.370 (5)
C2—H2	0.9300	C12—H12	0.9300
C3—N2	1.334 (5)	C13—C14	1.509 (5)
C3—C4	1.472 (5)	C14—N1	1.463 (5)
C4—N3	1.352 (5)	C14—H141	0.9700
C4—C5	1.383 (5)	C14—H142	0.9700
C5—C6	1.376 (6)	C15—F2	1.270 (7)
C5—H5	0.9300	C15—F3	1.306 (6)
C6—C7	1.360 (7)	C15—F1	1.325 (7)
C6—H6	0.9300	C15—S1	1.798 (5)
C7—C8	1.381 (6)	N1—N2	1.341 (4)
C7—H7	0.9300	N4—Ag1^i	2.196 (3)
C8—N3	1.336 (5)	O1—S1	1.412 (4)
C8—H8	0.9300	O2—S1	1.429 (4)
C9—N4	1.334 (5)	O3—S1	1.421 (3)
C9—C11	1.376 (6)
N4^i—Ag1—N2	136.04 (11)	C13—C12—C10	120.0 (4)
N4^i—Ag1—N3	133.89 (11)	C13—C12—H12	120.0
N2—Ag1—N3	72.05 (11)	C10—C12—H12	120.0
N1—C1—C2	107.2 (3)	C12—C13—C11	117.4 (3)
N1—C1—H1	126.4	C12—C13—C14	122.5 (3)
C2—C1—H1	126.4	C11—C13—C14	120.0 (3)
C1—C2—C3	105.2 (3)	N1—C14—C13	113.7 (3)
C1—C2—H2	127.4	N1—C14—H141	108.8
C3—C2—H2	127.4	C13—C14—H141	108.8
N2—C3—C2	110.3 (3)	N1—C14—H142	108.8
N2—C3—C4	119.5 (3)	C13—C14—H142	108.8
C2—C3—C4	130.2 (3)	H141—C14—H142	107.7
N3—C4—C5	121.7 (4)	F2—C15—F3	107.2 (5)
N3—C4—C3	116.4 (3)	F2—C15—F1	101.6 (5)
C5—C4—C3	121.9 (3)	F3—C15—F1	108.2 (5)
C6—C5—C4	119.3 (4)	F2—C15—S1	115.0 (4)
C6—C5—H5	120.3	F3—C15—S1	113.8 (3)
C4—C5—H5	120.3	F1—C15—S1	110.2 (4)
C7—C6—C5	119.3 (4)	N2—N1—C1	111.8 (3)
C7—C6—H6	120.4	N2—N1—C14	119.7 (3)
C5—C6—H6	120.4	C1—N1—C14	127.9 (3)
C6—C7—C8	118.8 (4)	C3—N2—N1	105.5 (3)
C6—C7—H7	120.6	C3—N2—Ag1	115.2 (2)
C8—C7—H7	120.6	N1—N2—Ag1	136.9 (2)
N3—C8—C7	123.1 (4)	C8—N3—C4	117.7 (3)
N3—C8—H8	118.4	C8—N3—Ag1	126.8 (3)
C7—C8—H8	118.4	C4—N3—Ag1	115.4 (2)
N4—C9—C11	123.4 (4)	C10—N4—C9	116.6 (3)
N4—C9—H9	118.3	C10—N4—Ag1^i	123.6 (3)
C11—C9—H9	118.3	C9—N4—Ag1^i	119.7 (2)
N4—C10—C12	123.0 (4)	O1—S1—O3	115.7 (3)
N4—C10—H10	118.5	O1—S1—O2	112.6 (3)
C12—C10—H10	118.5	O3—S1—O2	115.6 (2)
C13—C11—C9	119.5 (4)	O1—S1—C15	102.8 (3)
C13—C11—H11	120.3	O3—S1—C15	103.9 (2)
C9—C11—H11	120.3	O2—S1—C15	104.1 (2)
N1—C1—C2—C3	0.6 (4)	C1—N1—N2—Ag1	162.0 (3)
C1—C2—C3—N2	0.3 (4)	C14—N1—N2—Ag1	−26.5 (5)
C1—C2—C3—C4	179.7 (4)	N4^i—Ag1—N2—C3	125.3 (2)
N2—C3—C4—N3	−9.0 (5)	N3—Ag1—N2—C3	−10.3 (2)
C2—C3—C4—N3	171.7 (4)	N4^i—Ag1—N2—N1	−33.8 (4)
N2—C3—C4—C5	171.7 (3)	N3—Ag1—N2—N1	−169.3 (4)
C2—C3—C4—C5	−7.7 (6)	C7—C8—N3—C4	0.1 (6)
N3—C4—C5—C6	0.3 (5)	C7—C8—N3—Ag1	−179.0 (3)
C3—C4—C5—C6	179.6 (3)	C5—C4—N3—C8	−0.6 (5)
C4—C5—C6—C7	0.5 (6)	C3—C4—N3—C8	−180.0 (3)
C5—C6—C7—C8	−1.1 (6)	C5—C4—N3—Ag1	178.5 (3)
C6—C7—C8—N3	0.8 (6)	C3—C4—N3—Ag1	−0.8 (4)
N4—C9—C11—C13	−1.2 (7)	N4^i—Ag1—N3—C8	47.1 (4)
N4—C10—C12—C13	−1.2 (7)	N2—Ag1—N3—C8	−175.3 (3)
C10—C12—C13—C11	−0.6 (6)	N4^i—Ag1—N3—C4	−131.9 (2)
C10—C12—C13—C14	176.1 (4)	N2—Ag1—N3—C4	5.6 (2)
C9—C11—C13—C12	1.7 (6)	C12—C10—N4—C9	1.8 (6)
C9—C11—C13—C14	−175.0 (4)	C12—C10—N4—Ag1^i	−177.7 (3)
C12—C13—C14—N1	49.0 (5)	C11—C9—N4—C10	−0.5 (6)
C11—C13—C14—N1	−134.4 (4)	C11—C9—N4—Ag1^i	178.9 (3)
C2—C1—N1—N2	−1.4 (4)	F2—C15—S1—O1	−176.9 (5)
C2—C1—N1—C14	−172.0 (4)	F3—C15—S1—O1	59.0 (5)
C13—C14—N1—N2	58.6 (4)	F1—C15—S1—O1	−62.9 (5)
C13—C14—N1—C1	−131.5 (4)	F2—C15—S1—O3	−55.9 (5)
C2—C3—N2—N1	−1.1 (4)	F3—C15—S1—O3	179.9 (4)
C4—C3—N2—N1	179.4 (3)	F1—C15—S1—O3	58.1 (5)
C2—C3—N2—Ag1	−166.5 (2)	F2—C15—S1—O2	65.5 (5)
C4—C3—N2—Ag1	14.0 (4)	F3—C15—S1—O2	−58.7 (5)
C1—N1—N2—C3	1.6 (4)	F1—C15—S1—O2	179.5 (5)
C14—N1—N2—C3	173.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^ii	0.93	2.45	3.375 (6)	171
C12—H12···F1^iii	0.93	2.45	3.326 (7)	156

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