Crystal structure of catena-poly[[silver(I)-μ-N-(pyridin-2-ylmeth-yl)pyridine-3-amine-κ(2) N:N'] tri-fluoro-methane-sulfonate].

In the asymmetric unit of the title compound, {[Ag(C11H11N3)]CF3SO3} n , there are two Ag(I) atoms, two N-(pyridine-2-ylmeth-yl)pyridine-3-amine ligands (A and B) and two CF3SO3 (-) anions. Both Ag(I) atoms are bridged by two pyridine N atoms from two symmetry-related A or B ligands, forming right- or left-handed helical chains, respectively. The Ag(I) atom of the right-handed helical chain adopts a slightly distorted linear coordination geometry [N-Ag-N = 170.69 (14)°], while that of the left-handed helical chain adopts a bent geometry [N-Ag-N = 149.42 (14)°]. Both helical chains have the same pitch length [10.8437 (5) Å], propagate along the b-axial direction and are alternately arranged via Ag⋯Ag [3.0814 (5) Å] and π-π stacking inter-actions [centroid-centroid distances = 3.514 (3) and 3.487 (3) Å], resulting in the formation of a two-dimensional supra-molecular network extending parallel to the ab plane. Weak Ag⋯O [2.861 (4), 2.617 (3), and 2.624 (4) Å] and Ag⋯F [3.017 (3) Å] inter-actions as well as N-H⋯O and C-H⋯O, C-H⋯N and C-H⋯F hydrogen-bonding inter-actions occur between the helical chains and the anions.

Chemical context

A few silver coordination polymers based on unsymmetrical dipyridyl ligands composed of two terminal pyridines with different substituted-nitro­gen positions have been reported (Moon & Park, 2013 ▶, 2014 ▶; Zhang et al., 2013 ▶). In an extension of investigations on AgI coordination polymers with unsymmetrical dipyridyl ligands, the title compound was prepared by the reaction of silver tri­fluoro­metane­sulfonate with N-(pyridine-2-ylmeth­yl)pyridine-3-amine. The structure of title compound is related to that of the perchlorate salt (Moon & Park, 2014 ▶; Zhang et al., 2013 ▶).

Structural commentary

The molecular components of the title structure are shown in Fig. 1 ▶. The asymmetric unit contains two AgI atoms (Ag1 and Ag2), two N-(pyridine-2-ylmeth­yl)pyridine-3-amine (Lee et al., 2013 ▶) ligands (A and B) and two tri­fluoro­methane­sulfonate anions. The Ag1 atom is coordinated by two pyridine N atoms from two symmetry-related A ligands giving a geometry which is slightly distorted from linear [N1—Ag1—N2 = 170.69 (14)°], forming a right-handed helical chain, while the Ag2 atom is coordinated by two pyridine N atoms from two symmetry-related B ligands in a bent arrangement [N4—Ag2—N5 = 149.42 (14)°], forming a left-handed helical chain. Two pyridine rings coordinating to the Ag1 and Ag2 atoms are tilted by 14.1 (3) and 28.9 (2)°, respectively, with respect to each other.

Figure 1

A view of the mol­ecular structure of the title compound, with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level and dashed lines represent Ag⋯Ag and Ag⋯O inter­actions [symmetry codes: (i) −x + 1, y + , −z + ; (ii) −x, y + , −z + ; (iii) −x + 1, y − , −z + ; (iv) −x, y − , −z + ].

Supra­molecular features

Both helical chains in the structure have the same pitch length [10.8437 (5) Å], propagate along the b-axial direction and are alternately arranged via Ag1⋯Ag2 inter­actions [3.0814 (5) Å], resulting in the formation of a two-dimensional supra­molecular network extending parallel to the ab plane (Fig. 2 ▶). Furthermore, π–π stacking inter­actions [centroid–centroid distances = 3.514 (3) and 3.487 (3) Å] between pyridine rings of both helical chains contribute to the stabilization of the two-dimensional network. In the crystal structure, the two-dimensional networks are further stabilized by Ag⋯O and Ag⋯F inter­actions [Ag1⋯O1 2.861 (4), Ag1⋯O4 2.624 (4), Ag2⋯O2 2.617 (3), Ag2⋯F3iv 3.017 (3) Å; symmetry code: (iv) −x, y − , −z + ] (Figs. 1 ▶ and 2 ▶) as well as N—H⋯O and N—H⋯O and C—H⋯O and C—H⋯F hydrogen-bonds (Table 1 ▶) between the helical chains and CF3SO3 − anions.

Figure 2

The two-dimensional supra­molecular network formed through Ag⋯Ag and Ag⋯O inter­actions (yellow dashed lines) and π–π stacking inter­actions (black dashed lines).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3O6i	0.88	2.51	3.206(6)	136
N6H6O3ii	0.88	2.43	3.217(6)	149
C1H1O5iii	0.95	2.55	3.339(6)	141
C4H4O3ii	0.95	2.54	3.383(6)	147
C6H6AO5i	0.99	2.57	3.471(6)	151
C11H11F3iii	0.95	2.49	3.311(6)	145
C11H11O1iii	0.95	2.54	3.350(7)	143
C15H15O6ii	0.95	2.53	3.450(6)	164
C16H16O6iv	0.95	2.58	3.316(6)	135
C17H17BO3	0.99	2.58	3.422(6)	143

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Synthesis and crystallization

The ligand (N-(pyridin-2-ylmeth­yl)pyridine-3-amine) was prepared according to a procedure described by Lee et al. (2013 ▶). Crystals of the title compound suitable for X-ray analysis were obtained by vapour diffusion of diethyl ether into a DMSO solution of the white precipitate afforded by the reaction of the ligand with silver(I) hexa­fluorido­phosphate in the molar ratio 1:1 in methanol.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▶. All H atoms were positioned geometrically and refined using a riding model, with d(C—H) = 0.95 Å for Csp 2—H, 0.88 Å for amine N—H and 0.99 Å for methyl­ene C—H. For all H atoms U iso(H) = 1.2U eq(C,N).

Table 2

Experimental details

Crystal data
Chemical formula	[Ag(C11H11N3)]CF3SO3
M r	442.17
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	173
a, b, c ()	13.7529(6), 10.8437(5), 19.5795(9)
()	99.826(1)
V (3)	2877.1(2)
Z	8
Radiation type	Mo K
(mm1)	1.60
Crystal size (mm)	0.31 0.22 0.10
Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000 ▶)
T min, T max	0.637, 0.857
No. of measured, independent and observed [I > 2(I)] reflections	15852, 5629, 4286
R int	0.038
(sin /)max (1)	0.617
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.039, 0.093, 1.06
No. of reflections	5629
No. of parameters	415
H-atom treatment	H-atom parameters constrained
max, min (e 3)	1.04, 0.67

Computer programs: SMART and SAINT-Plus (Bruker, 2000 ▶), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2005 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022922/zs2318sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814022922/zs2318Isup2.hkl

CCDC reference: 1029928

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

[Ag(C11H11N3)]·CF3SO3	F(000) = 1744
Mr = 442.17	Dx = 2.042 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5639 reflections
a = 13.7529 (6) Å	θ = 2.4–28.2°
b = 10.8437 (5) Å	µ = 1.60 mm−1
c = 19.5795 (9) Å	T = 173 K
β = 99.826 (1)°	Plate, colorless
V = 2877.1 (2) Å3	0.31 × 0.22 × 0.10 mm
Z = 8

Bruker SMART CCD area detector diffractometer	5629 independent reflections
Radiation source: fine-focus sealed tube	4286 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
φ and ω scans	θmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→16
Tmin = 0.637, Tmax = 0.857	k = −13→9
15852 measured reflections	l = −23→24

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0369P)2 + 6.3774P] where P = (Fo2 + 2Fc2)/3
5629 reflections	(Δ/σ)max = 0.001
415 parameters	Δρmax = 1.04 e Å−3
0 restraints	Δρmin = −0.67 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

	x	y	z	Uiso*/Ueq
Ag1	0.30869 (3)	0.63691 (3)	0.192614 (19)	0.02491 (11)
Ag2	0.17632 (3)	0.43820 (3)	0.24204 (2)	0.02787 (11)
N1	0.3183 (3)	0.4818 (4)	0.1251 (2)	0.0220 (9)
N2	0.7006 (3)	0.2705 (3)	0.2265 (2)	0.0223 (9)
N3	0.4684 (3)	0.2087 (4)	0.1066 (2)	0.0284 (10)
H3	0.4727	0.1538	0.0742	0.034*
C1	0.3913 (3)	0.3969 (4)	0.1368 (2)	0.0231 (11)
H1	0.4428	0.4078	0.1753	0.028*
C2	0.3940 (3)	0.2938 (4)	0.0943 (2)	0.0228 (10)
C3	0.3168 (3)	0.2794 (5)	0.0383 (2)	0.0252 (11)
H3A	0.3152	0.2103	0.0083	0.030*
C4	0.2434 (4)	0.3662 (5)	0.0272 (3)	0.0275 (11)
H4	0.1904	0.3569	−0.0104	0.033*
C5	0.2462 (4)	0.4662 (5)	0.0701 (2)	0.0237 (11)
H5	0.1956	0.5265	0.0607	0.028*
C6	0.5398 (4)	0.2033 (5)	0.1695 (3)	0.0288 (12)
H6A	0.5618	0.1167	0.1774	0.035*
H6B	0.5071	0.2279	0.2087	0.035*
C7	0.6299 (4)	0.2836 (4)	0.1702 (3)	0.0234 (11)
C8	0.6403 (4)	0.3658 (5)	0.1181 (3)	0.0327 (12)
H8	0.5897	0.3735	0.0787	0.039*
C9	0.7247 (4)	0.4367 (5)	0.1237 (3)	0.0346 (13)
H9	0.7330	0.4928	0.0879	0.042*
C10	0.7964 (4)	0.4258 (5)	0.1812 (3)	0.0324 (12)
H10	0.8543	0.4751	0.1868	0.039*
C11	0.7815 (4)	0.3405 (5)	0.2307 (3)	0.0314 (12)
H11	0.8318	0.3310	0.2701	0.038*
N4	−0.1913 (3)	0.0415 (3)	0.1616 (2)	0.0218 (9)
N5	0.1834 (3)	0.2634 (4)	0.1887 (2)	0.0224 (9)
N6	−0.0542 (3)	0.2536 (4)	0.0675 (2)	0.0295 (10)
H6	−0.0559	0.2757	0.0241	0.035*
C12	−0.1212 (3)	0.1180 (4)	0.1464 (2)	0.0211 (10)
H12	−0.0651	0.1334	0.1810	0.025*
C13	−0.1267 (3)	0.1755 (4)	0.0824 (2)	0.0221 (10)
C14	−0.2106 (4)	0.1521 (4)	0.0325 (2)	0.0273 (11)
H14	−0.2181	0.1902	−0.0118	0.033*
C15	−0.2815 (4)	0.0739 (5)	0.0483 (3)	0.0306 (12)
H15	−0.3385	0.0570	0.0148	0.037*
C16	−0.2702 (4)	0.0194 (4)	0.1130 (3)	0.0261 (11)
H16	−0.3197	−0.0352	0.1233	0.031*
C17	0.0244 (3)	0.3012 (5)	0.1190 (3)	0.0271 (11)
H17A	−0.0031	0.3203	0.1614	0.033*
H17B	0.0475	0.3798	0.1016	0.033*
C18	0.1121 (4)	0.2185 (4)	0.1389 (2)	0.0227 (10)
C19	0.1216 (4)	0.1044 (5)	0.1089 (3)	0.0313 (12)
H19	0.0706	0.0738	0.0742	0.038*
C20	0.2063 (4)	0.0352 (5)	0.1301 (3)	0.0351 (13)
H20	0.2139	−0.0430	0.1098	0.042*
C21	0.2788 (4)	0.0807 (5)	0.1806 (3)	0.0340 (13)
H21	0.3372	0.0348	0.1961	0.041*
C22	0.2647 (4)	0.1953 (5)	0.2082 (3)	0.0281 (11)
H22	0.3152	0.2273	0.2428	0.034*
S1	0.03658 (9)	0.65963 (11)	0.12069 (6)	0.0230 (3)
O1	0.1266 (3)	0.7218 (3)	0.1137 (2)	0.0390 (9)
O2	0.0406 (3)	0.5931 (3)	0.18476 (18)	0.0343 (9)
O3	−0.0106 (3)	0.5974 (3)	0.05959 (18)	0.0369 (9)
C23	−0.0469 (4)	0.7861 (5)	0.1303 (3)	0.0289 (12)
F1	−0.0609 (3)	0.8570 (3)	0.07437 (17)	0.0480 (9)
F2	−0.1350 (2)	0.7440 (3)	0.13945 (17)	0.0439 (8)
F3	−0.0113 (2)	0.8558 (3)	0.18486 (16)	0.0381 (8)
S2	0.47697 (9)	0.84803 (12)	0.12529 (6)	0.0269 (3)
O4	0.3758 (3)	0.8093 (3)	0.1188 (2)	0.0380 (9)
O5	0.5228 (3)	0.8873 (3)	0.19320 (19)	0.0403 (10)
O6	0.4983 (3)	0.9245 (4)	0.07004 (19)	0.0410 (10)
C24	0.5413 (4)	0.7040 (5)	0.1142 (3)	0.0311 (12)
F4	0.5337 (2)	0.6255 (3)	0.16634 (16)	0.0347 (7)
F5	0.6375 (2)	0.7235 (3)	0.11623 (17)	0.0428 (8)
F6	0.5059 (3)	0.6481 (3)	0.05552 (17)	0.0539 (10)

	U11	U22	U33	U12	U13	U23
Ag1	0.0246 (2)	0.0220 (2)	0.0286 (2)	−0.00393 (16)	0.00586 (15)	−0.00514 (16)
Ag2	0.0321 (2)	0.0252 (2)	0.0282 (2)	−0.00139 (17)	0.01060 (17)	−0.00680 (17)
N1	0.020 (2)	0.021 (2)	0.025 (2)	−0.0021 (17)	0.0048 (17)	0.0009 (17)
N2	0.022 (2)	0.016 (2)	0.029 (2)	0.0018 (16)	0.0050 (17)	−0.0032 (17)
N3	0.033 (2)	0.020 (2)	0.031 (2)	0.0039 (18)	0.0014 (19)	−0.0082 (18)
C1	0.022 (3)	0.027 (3)	0.021 (2)	−0.005 (2)	0.002 (2)	−0.001 (2)
C2	0.027 (3)	0.019 (2)	0.023 (3)	−0.002 (2)	0.006 (2)	0.001 (2)
C3	0.029 (3)	0.025 (3)	0.022 (3)	−0.005 (2)	0.005 (2)	−0.004 (2)
C4	0.025 (3)	0.032 (3)	0.024 (3)	−0.004 (2)	−0.001 (2)	0.002 (2)
C5	0.022 (3)	0.027 (3)	0.022 (3)	0.000 (2)	0.004 (2)	0.003 (2)
C6	0.024 (3)	0.024 (3)	0.038 (3)	0.004 (2)	0.007 (2)	0.002 (2)
C7	0.027 (3)	0.015 (2)	0.029 (3)	0.003 (2)	0.006 (2)	−0.004 (2)
C8	0.040 (3)	0.030 (3)	0.029 (3)	0.003 (2)	0.005 (2)	0.001 (2)
C9	0.046 (3)	0.023 (3)	0.038 (3)	0.004 (2)	0.018 (3)	0.009 (2)
C10	0.032 (3)	0.021 (3)	0.049 (3)	−0.002 (2)	0.018 (3)	−0.001 (2)
C11	0.024 (3)	0.029 (3)	0.040 (3)	0.001 (2)	0.002 (2)	−0.004 (2)
N4	0.025 (2)	0.016 (2)	0.025 (2)	0.0020 (16)	0.0047 (17)	−0.0005 (17)
N5	0.029 (2)	0.019 (2)	0.021 (2)	0.0012 (17)	0.0104 (17)	0.0035 (17)
N6	0.035 (2)	0.033 (2)	0.020 (2)	−0.006 (2)	0.0030 (18)	0.0102 (19)
C12	0.021 (2)	0.020 (2)	0.021 (2)	−0.0001 (19)	0.001 (2)	−0.0012 (19)
C13	0.026 (3)	0.016 (2)	0.025 (3)	0.0041 (19)	0.004 (2)	0.000 (2)
C14	0.038 (3)	0.023 (3)	0.017 (2)	0.005 (2)	−0.003 (2)	0.000 (2)
C15	0.027 (3)	0.028 (3)	0.033 (3)	0.000 (2)	−0.007 (2)	−0.009 (2)
C16	0.022 (3)	0.020 (3)	0.036 (3)	0.001 (2)	0.006 (2)	−0.001 (2)
C17	0.026 (3)	0.024 (3)	0.031 (3)	−0.003 (2)	0.005 (2)	0.003 (2)
C18	0.029 (3)	0.018 (2)	0.025 (3)	−0.003 (2)	0.013 (2)	0.001 (2)
C19	0.039 (3)	0.024 (3)	0.032 (3)	−0.006 (2)	0.011 (2)	−0.001 (2)
C20	0.051 (4)	0.023 (3)	0.035 (3)	0.002 (3)	0.019 (3)	−0.004 (2)
C21	0.035 (3)	0.031 (3)	0.038 (3)	0.004 (2)	0.011 (3)	0.004 (3)
C22	0.030 (3)	0.027 (3)	0.029 (3)	0.000 (2)	0.011 (2)	0.004 (2)
S1	0.0249 (6)	0.0222 (6)	0.0208 (6)	0.0063 (5)	0.0006 (5)	−0.0015 (5)
O1	0.029 (2)	0.037 (2)	0.054 (2)	0.0034 (17)	0.0158 (18)	−0.0033 (19)
O2	0.046 (2)	0.031 (2)	0.0251 (19)	0.0098 (17)	0.0012 (17)	0.0060 (16)
O3	0.044 (2)	0.033 (2)	0.030 (2)	0.0092 (17)	−0.0026 (17)	−0.0112 (17)
C23	0.029 (3)	0.028 (3)	0.028 (3)	0.004 (2)	−0.001 (2)	−0.006 (2)
F1	0.062 (2)	0.0397 (19)	0.0404 (19)	0.0274 (17)	0.0022 (16)	0.0099 (16)
F2	0.0218 (16)	0.052 (2)	0.058 (2)	0.0028 (15)	0.0059 (15)	−0.0139 (17)
F3	0.0315 (16)	0.0381 (18)	0.0420 (18)	0.0053 (14)	−0.0013 (14)	−0.0205 (15)
S2	0.0274 (7)	0.0256 (7)	0.0266 (7)	−0.0033 (5)	0.0018 (5)	0.0070 (5)
O4	0.030 (2)	0.031 (2)	0.055 (3)	0.0000 (16)	0.0120 (18)	0.0148 (19)
O5	0.061 (3)	0.028 (2)	0.030 (2)	−0.0019 (19)	0.0017 (19)	−0.0031 (17)
O6	0.035 (2)	0.048 (2)	0.036 (2)	−0.0173 (18)	−0.0061 (17)	0.0191 (19)
C24	0.031 (3)	0.038 (3)	0.027 (3)	−0.005 (2)	0.011 (2)	−0.005 (2)
F4	0.0365 (17)	0.0227 (15)	0.0456 (18)	0.0006 (13)	0.0087 (14)	0.0061 (14)
F5	0.0282 (17)	0.049 (2)	0.055 (2)	−0.0043 (15)	0.0179 (15)	−0.0013 (17)
F6	0.061 (2)	0.061 (2)	0.0378 (19)	−0.0073 (19)	0.0040 (17)	−0.0228 (18)

Ag1—N1	2.156 (4)	N6—C13	1.377 (6)
Ag1—N2i	2.167 (4)	N6—C17	1.443 (6)
Ag1—Ag2	3.0814 (5)	N6—H6	0.8800
Ag2—N4ii	2.174 (4)	C12—C13	1.390 (7)
Ag2—N5	2.175 (4)	C12—H12	0.9500
N1—C5	1.344 (6)	C13—C14	1.402 (7)
N1—C1	1.353 (6)	C14—C15	1.367 (7)
N2—C11	1.338 (6)	C14—H14	0.9500
N2—C7	1.347 (6)	C15—C16	1.383 (7)
N2—Ag1iii	2.167 (4)	C15—H15	0.9500
N3—C2	1.369 (6)	C16—H16	0.9500
N3—C6	1.439 (6)	C17—C18	1.500 (7)
N3—H3	0.8800	C17—H17A	0.9900
C1—C2	1.398 (7)	C17—H17B	0.9900
C1—H1	0.9500	C18—C19	1.385 (7)
C2—C3	1.398 (6)	C19—C20	1.389 (8)
C3—C4	1.369 (7)	C19—H19	0.9500
C3—H3A	0.9500	C20—C21	1.370 (8)
C4—C5	1.368 (7)	C20—H20	0.9500
C4—H4	0.9500	C21—C22	1.381 (7)
C5—H5	0.9500	C21—H21	0.9500
C6—C7	1.512 (7)	C22—H22	0.9500
C6—H6A	0.9900	S1—O3	1.429 (4)
C6—H6B	0.9900	S1—O1	1.436 (4)
C7—C8	1.380 (7)	S1—O2	1.440 (4)
C8—C9	1.382 (8)	S1—C23	1.819 (5)
C8—H8	0.9500	C23—F1	1.324 (6)
C9—C10	1.369 (8)	C23—F3	1.332 (5)
C9—H9	0.9500	C23—F2	1.336 (6)
C10—C11	1.379 (7)	S2—O6	1.433 (4)
C10—H10	0.9500	S2—O5	1.435 (4)
C11—H11	0.9500	S2—O4	1.438 (4)
N4—C16	1.336 (6)	S2—C24	1.826 (6)
N4—C12	1.343 (6)	C24—F6	1.317 (6)
N4—Ag2iv	2.174 (4)	C24—F5	1.334 (6)
N5—C22	1.341 (6)	C24—F4	1.347 (6)
N5—C18	1.349 (6)
N1—Ag1—N2i	170.69 (14)	N4—C12—C13	123.1 (4)
N1—Ag1—Ag2	75.41 (10)	N4—C12—H12	118.4
N2i—Ag1—Ag2	97.25 (10)	C13—C12—H12	118.4
N4ii—Ag2—N5	149.42 (14)	N6—C13—C12	122.5 (4)
N4ii—Ag2—Ag1	86.49 (10)	N6—C13—C14	120.2 (4)
N5—Ag2—Ag1	112.41 (10)	C12—C13—C14	117.3 (4)
C5—N1—C1	118.3 (4)	C15—C14—C13	119.3 (5)
C5—N1—Ag1	118.4 (3)	C15—C14—H14	120.4
C1—N1—Ag1	123.3 (3)	C13—C14—H14	120.4
C11—N2—C7	117.9 (4)	C14—C15—C16	120.0 (5)
C11—N2—Ag1iii	119.1 (3)	C14—C15—H15	120.0
C7—N2—Ag1iii	122.9 (3)	C16—C15—H15	120.0
C2—N3—C6	124.0 (4)	N4—C16—C15	121.7 (5)
C2—N3—H3	118.0	N4—C16—H16	119.1
C6—N3—H3	118.0	C15—C16—H16	119.1
N1—C1—C2	122.6 (4)	N6—C17—C18	116.2 (4)
N1—C1—H1	118.7	N6—C17—H17A	108.2
C2—C1—H1	118.7	C18—C17—H17A	108.2
N3—C2—C1	121.9 (4)	N6—C17—H17B	108.2
N3—C2—C3	120.5 (4)	C18—C17—H17B	108.2
C1—C2—C3	117.5 (4)	H17A—C17—H17B	107.4
C4—C3—C2	119.2 (5)	N5—C18—C19	121.3 (5)
C4—C3—H3A	120.4	N5—C18—C17	115.1 (4)
C2—C3—H3A	120.4	C19—C18—C17	123.6 (5)
C5—C4—C3	120.3 (5)	C18—C19—C20	119.4 (5)
C5—C4—H4	119.8	C18—C19—H19	120.3
C3—C4—H4	119.8	C20—C19—H19	120.3
N1—C5—C4	122.1 (5)	C21—C20—C19	119.4 (5)
N1—C5—H5	119.0	C21—C20—H20	120.3
C4—C5—H5	119.0	C19—C20—H20	120.3
N3—C6—C7	115.1 (4)	C20—C21—C22	118.3 (5)
N3—C6—H6A	108.5	C20—C21—H21	120.9
C7—C6—H6A	108.5	C22—C21—H21	120.9
N3—C6—H6B	108.5	N5—C22—C21	123.3 (5)
C7—C6—H6B	108.5	N5—C22—H22	118.3
H6A—C6—H6B	107.5	C21—C22—H22	118.3
N2—C7—C8	121.4 (5)	O3—S1—O1	114.7 (2)
N2—C7—C6	115.0 (4)	O3—S1—O2	115.9 (2)
C8—C7—C6	123.6 (5)	O1—S1—O2	114.3 (2)
C7—C8—C9	119.5 (5)	O3—S1—C23	103.8 (2)
C7—C8—H8	120.3	O1—S1—C23	103.0 (2)
C9—C8—H8	120.3	O2—S1—C23	102.7 (2)
C10—C9—C8	119.7 (5)	F1—C23—F3	108.4 (4)
C10—C9—H9	120.2	F1—C23—F2	107.6 (4)
C8—C9—H9	120.2	F3—C23—F2	107.6 (4)
C9—C10—C11	117.6 (5)	F1—C23—S1	111.0 (4)
C9—C10—H10	121.2	F3—C23—S1	111.0 (3)
C11—C10—H10	121.2	F2—C23—S1	111.0 (4)
N2—C11—C10	123.9 (5)	O6—S2—O5	114.4 (2)
N2—C11—H11	118.0	O6—S2—O4	115.0 (2)
C10—C11—H11	118.0	O5—S2—O4	115.7 (2)
C16—N4—C12	118.7 (4)	O6—S2—C24	103.9 (2)
C16—N4—Ag2iv	118.0 (3)	O5—S2—C24	102.6 (2)
C12—N4—Ag2iv	123.0 (3)	O4—S2—C24	102.7 (2)
C22—N5—C18	118.4 (4)	F6—C24—F5	108.4 (4)
C22—N5—Ag2	116.5 (3)	F6—C24—F4	107.8 (4)
C18—N5—Ag2	125.1 (3)	F5—C24—F4	106.4 (4)
C13—N6—C17	123.7 (4)	F6—C24—S2	112.5 (4)
C13—N6—H6	118.2	F5—C24—S2	111.0 (4)
C17—N6—H6	118.2	F4—C24—S2	110.4 (3)
N1—Ag1—Ag2—N4ii	160.70 (15)	N4—C12—C13—N6	−179.9 (4)
N2i—Ag1—Ag2—N4ii	−13.47 (14)	N4—C12—C13—C14	0.6 (7)
N1—Ag1—Ag2—N5	5.50 (15)	N6—C13—C14—C15	179.7 (5)
N2i—Ag1—Ag2—N5	−168.67 (15)	C12—C13—C14—C15	−0.8 (7)
Ag2—Ag1—N1—C5	82.5 (3)	C13—C14—C15—C16	0.3 (7)
Ag2—Ag1—N1—C1	−95.0 (4)	C12—N4—C16—C15	−0.6 (7)
C5—N1—C1—C2	−0.6 (7)	Ag2iv—N4—C16—C15	−174.9 (4)
Ag1—N1—C1—C2	177.0 (3)	C14—C15—C16—N4	0.4 (8)
C6—N3—C2—C1	11.5 (7)	C13—N6—C17—C18	83.2 (6)
C6—N3—C2—C3	−167.8 (5)	C22—N5—C18—C19	0.6 (7)
N1—C1—C2—N3	−180.0 (4)	Ag2—N5—C18—C19	−178.2 (3)
N1—C1—C2—C3	−0.6 (7)	C22—N5—C18—C17	−178.9 (4)
N3—C2—C3—C4	−180.0 (4)	Ag2—N5—C18—C17	2.3 (6)
C1—C2—C3—C4	0.6 (7)	N6—C17—C18—N5	−178.1 (4)
C2—C3—C4—C5	0.5 (7)	N6—C17—C18—C19	2.3 (7)
C1—N1—C5—C4	1.8 (7)	N5—C18—C19—C20	−0.4 (7)
Ag1—N1—C5—C4	−175.9 (4)	C17—C18—C19—C20	179.1 (5)
C3—C4—C5—N1	−1.8 (7)	C18—C19—C20—C21	0.3 (8)
C2—N3—C6—C7	−87.1 (6)	C19—C20—C21—C22	−0.4 (8)
C11—N2—C7—C8	0.5 (7)	C18—N5—C22—C21	−0.7 (7)
Ag1iii—N2—C7—C8	−177.0 (4)	Ag2—N5—C22—C21	178.1 (4)
C11—N2—C7—C6	−179.0 (4)	C20—C21—C22—N5	0.7 (8)
Ag1iii—N2—C7—C6	3.6 (6)	O3—S1—C23—F1	−57.7 (4)
N3—C6—C7—N2	−174.5 (4)	O1—S1—C23—F1	62.2 (4)
N3—C6—C7—C8	6.1 (7)	O2—S1—C23—F1	−178.8 (4)
N2—C7—C8—C9	−0.3 (8)	O3—S1—C23—F3	−178.4 (4)
C6—C7—C8—C9	179.1 (5)	O1—S1—C23—F3	−58.5 (4)
C7—C8—C9—C10	−0.8 (8)	O2—S1—C23—F3	60.5 (4)
C8—C9—C10—C11	1.7 (8)	O3—S1—C23—F2	61.9 (4)
C7—N2—C11—C10	0.5 (7)	O1—S1—C23—F2	−178.2 (3)
Ag1iii—N2—C11—C10	178.1 (4)	O2—S1—C23—F2	−59.2 (4)
C9—C10—C11—N2	−1.6 (8)	O6—S2—C24—F6	−64.1 (4)
N4ii—Ag2—N5—C22	−48.9 (5)	O5—S2—C24—F6	176.4 (4)
Ag1—Ag2—N5—C22	75.7 (3)	O4—S2—C24—F6	56.0 (4)
N4ii—Ag2—N5—C18	129.9 (4)	O6—S2—C24—F5	57.6 (4)
Ag1—Ag2—N5—C18	−105.5 (3)	O5—S2—C24—F5	−61.9 (4)
C16—N4—C12—C13	0.1 (7)	O4—S2—C24—F5	177.7 (3)
Ag2iv—N4—C12—C13	174.1 (3)	O6—S2—C24—F4	175.4 (3)
C17—N6—C13—C12	−11.8 (7)	O5—S2—C24—F4	56.0 (4)
C17—N6—C13—C14	167.7 (4)	O4—S2—C24—F4	−64.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O6v	0.88	2.51	3.206 (6)	136
N6—H6···O3vi	0.88	2.43	3.217 (6)	149
C1—H1···O5iii	0.95	2.55	3.339 (6)	141
C4—H4···O3vi	0.95	2.54	3.383 (6)	147
C6—H6A···O5v	0.99	2.57	3.471 (6)	151
C8—H8···N3	0.95	2.57	2.891 (7)	100
C11—H11···F3iii	0.95	2.49	3.311 (6)	145
C11—H11···O1iii	0.95	2.54	3.350 (7)	143
C15—H15···O6vi	0.95	2.53	3.450 (6)	164
C16—H16···O6vii	0.95	2.58	3.316 (6)	135
C17—H17B···O3	0.99	2.58	3.422 (6)	143
C19—H19···N6	0.95	2.59	2.906 (7)	100