Bis(di-2-pyridyl­amine-κ²N²,N^2′)silver(I) trifluoro­methane­sulfonate: polar arrangement of trifluoro­methane­sulfonate anions in a pseudo-centrosymmetric framework of coordination cations

The asymmetric unit of the title compound, [Ag(C₁₀H₉N₂)₂]CF₃SO₃ or [Ag(dpa)₂]OTf (dpa is di-2-pyridyl­amine and OTf is the trifluoro­methane­sulfonate anion), contains two [Ag(dpa)₂]⁺ coordination cations and two OTf anions. The coordination geometry of the Ag^I atom is inter­mediate between square-planar and tetra­hedral, with similar deformations at the two symmetry-independent metal centres. The dpa ligands coordinate in a bidentate chelating mode. The OTf anions are in the outer coordination sphere and bridge the coordination cations via N—H...O inter­actions to form two symmetry-independent hydrogen-bonded chains. The [Ag(dpa)₂]⁺ cations are arranged via inter­actions involving the aromatic groups into a pseudo-centrosymmetric three-dimensional framework with two types of channels, each confining congeners of one of the symmetry-independent anions. The most inter­esting feature of this structure is its bulk polarity resulting from an approximately parallel alignment of the anions in the channels.

S1. Comment

The interest of coordination and supramolecular chemists in Ag^I is mainly related to the coordination flexibility of this d¹⁰ ion and its tendency to form strong complexes with nitrogen-donor ligands. It has been shown that di-2-pyridylamine (dpa) can coordinate to Ag^I both in its deprotonated and neutral forms. In the former case, a charge-neutral one-dimensional coordination polymer is formed with all three N donors involved in the coordination to Ag centres (Liao et al., 2001). In turn, neutral dpa can act as a bidentate ligand, in chelating or bridging mode, with a secondary amine group available as a donor for hydrogen bonding. It has been shown by Burgos et al. (2003) that in the reaction of silver(I) trifluoromethanesulfonate [Ag(OTf)] with neutral dpa, depending on the synthetic conditions employed, a discrete molecular complex [Ag(dpa)₂]OTf, (I), and a coordination polymer [Ag(OTf)(dpa)]_n, (II), can be formed. No crystal data were reported in the original paper, but the structure of (II) was published later on (Jones et al., 2006), revealing a one-dimensional polymeric structure with a bridging dpa ligand and a four-coordinate silver centre. An interesting feature of this structure was that one of the coordination bonds was formed to a pyridine C atom. Recently, in the course of our work on silver complexes with N-donor ligands, the synthesis of (I) was repeated using acetonitrile as a solvent; and good-quality single crystals were obtained. In this paper we report the crystal structure of (I), where the coordination cations form a virtually centrosymmetric pattern; however, the OTf^- anions show polar packing, resulting in an overall non-centrosymmetric structure.

The asymmetric unit of (I) consists of two [Ag(dpa)₂]⁺ coordination cations and two OTf^- anions (Fig. 1). In accord with spectroscopic studies (Burgos et al., 2003), the dpa units act as bidentate chelating ligands, coordinating to Ag through both pyridyl N atoms to form six-membered rings. The coordination geometry at Ag1 and Ag2 is intermediate between square-planar and tetrahedral, with similar deformations at the two metal centres (Table 1). The dpa ligands form one shorter and one longer Ag—N bond, with the former ranging from 2.269 (3) to 2.305 (3) Å [mean 2.283 (16) Å] and the longer bonds in the range 2.337 (3)–2.373 (3) Å [mean 2.357 (15) Å]. The structure of the two coordination cations is similar, as shown by their superposition in Fig. 2. They interact via two types of contacts involving the aromatic groups: (a) offset π–π stacking interactions between the pyridine rings N12/C62 and N14/C64 of the two symmetry-independent cations [centroid-to-centroid distance 3.662 (7) Å; dihedral angle between the best planes 1.72 (13)°; distance between the N12—C62 ring centroid and the plane of the N14—C64 ring 3.389 (1) Å]; (b) through edge-to-face contacts (C—H···π and C–H···C) between the pyridine rings belonging to the cations of the same type (Table 2). These interactions assemble the [Ag(dpa)₂]⁺ units into a virtually centrosymmetric three-dimensional framework, not deviating much from P2₁/c symmetry, with the pseudo-inversion centre at 1/2,1/4,1/2 relating the two symmetry-independent [Ag(dpa)₂]⁺ units (Fig. 3a).

There are two symmetry-independent channels formed in the cationic framework that extend along the c axis and are related by a pseudo-inversion centre. These channels, confining OTf^- anions, have their long axes situated on glide planes at y = (0, 1/2). One can see from Fig. 3(b), showing the arrangement of the anions in the two channels, that all polar OTf anions have their C—S axes oriented in nearly the same direction, viz. in the crystal studied, in the positive direction of the c axis, and that this packing of the anions renders the crystal structure non-centrosymmetric. This is an unusual behaviour for the OTf^- anion, which generally does not induce bulk polarity in the absence of chiral molecules. The OTf^- anions confined in the channels bridge the coordination cations via two N—H···O hydrogen bonds involving the N—H groups of dpa ligands from two cations. Two symmetry-independent hydrogen-bonded chains extended in the [2 0 1] direction which is inclined to the c axis by 72.5°.

Related literature

For related literature, see: Burgos et al. (2003); Jones et al. (2006); Liao et al. (2001).

S2. Experimental

AgOTf and dpa were purchased from Aldrich and used as received. AgOTf (0.030 g, 0.117 mmol) was added to an acetonitrile solution (5 ml) of dpa (0.040 g, 0.234 mmol). The solution was stirred for 10 min and left for slow evaporation. Colourless needle-shaped crystals formed within 2 weeks.

S3. Refinement

The absolute structure of (I) was determined from anomalous dispersion effects. H atoms of the N—H groups were located in difference electron-density maps and N—H bond lengths standardized to 0.90 Å. U_iso(H) was constrained to 1.2U_eq(N). All other H atoms were identified in difference maps but they were placed at calculated positions, with C—H = 0.95 Å, and were refined as riding on their carrier atoms with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I) with displacement ellipsoids shown at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. Superposition of the two symmetry-independent coordination cations. The coordination cation with Ag1 is shown with larger spheres and full lines. All atoms, excluding H atoms, were fitted; r.m.s. deviation of the fitted atoms is 0.097 Å.
	Fig. 3. (a) Pseudo-centrosymmetric three-dimensional framework of the coordination cations with anions removed from the channels, viewed along the c axis, and (b) polar arrangement of the anions in the two symmetry-independent channels, viewed along the b axis, [001] vertical.

Bis(di-2-pyridylamine-κ²N²,N^2')silver(I) trifluoromethanesulfonate

Crystal data

[Ag(C10H9N2)2]CF3SO3	F(000) = 1200
Mr = 599.34	Dx = 1.753 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 12067 reflections
a = 15.1215 (4) Å	θ = 1.9–27.8°
b = 13.2206 (3) Å	µ = 1.04 mm^−1
c = 11.9113 (3) Å	T = 130 K
β = 107.527 (3)°	Plate, colourless
V = 2270.70 (10) Å^3	0.30 × 0.10 × 0.10 mm
Z = 4

Data collection

Kuma KM-4-CCD (κ geometry) diffractometer	8833 independent reflections
Radiation source: fine-focus sealed tube	7362 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 8.1929 pixels mm^-1	θmax = 27.8°, θmin = 4.1°
ω scans	h = −19→18
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −16→16
Tmin = 0.735, Tmax = 0.913	l = −15→14
18407 measured reflections

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)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0283P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
8833 reflections	Δρmax = 0.57 e Å^−3
631 parameters	Δρmin = −0.64 e Å^−3
2 restraints	Absolute structure: Flack (1983), Friedel pairs 3456
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.009 (12)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Ag1	0.258551 (14)	0.119011 (17)	0.254218 (16)	0.02624 (7)
N11	0.16471 (18)	−0.0114 (2)	0.1418 (2)	0.0223 (6)
C21	0.0791 (2)	−0.0008 (3)	0.0659 (3)	0.0200 (8)
C31	0.0394 (2)	−0.0735 (3)	−0.0203 (3)	0.0265 (8)
H31	−0.0206	−0.0634	−0.0742	0.032*
C41	0.0891 (3)	−0.1599 (3)	−0.0256 (3)	0.0312 (9)
H41	0.0636	−0.2101	−0.0833	0.037*
C51	0.1764 (2)	−0.1729 (3)	0.0543 (4)	0.0316 (9)
H51	0.2117	−0.2322	0.0534	0.038*
C61	0.2101 (3)	−0.0980 (2)	0.1341 (4)	0.0302 (9)
H61	0.2700	−0.1073	0.1885	0.036*
N71	0.02371 (19)	0.0811 (2)	0.0719 (2)	0.0197 (6)
H71	−0.0355	0.0761	0.0260	0.024*
C81	0.0359 (2)	0.1721 (2)	0.1331 (3)	0.0170 (7)
N91	0.1214 (2)	0.2051 (2)	0.1934 (2)	0.0189 (6)
C101	0.1276 (2)	0.2974 (3)	0.2439 (3)	0.0244 (8)
H101	0.1874	0.3233	0.2838	0.029*
C111	0.0516 (3)	0.3558 (3)	0.2405 (3)	0.0259 (9)
H111	0.0590	0.4198	0.2785	0.031*
C121	−0.0356 (2)	0.3200 (3)	0.1808 (3)	0.0261 (8)
H121	−0.0893	0.3584	0.1779	0.031*
C131	−0.0432 (2)	0.2280 (2)	0.1259 (3)	0.0235 (8)
H131	−0.1025	0.2026	0.0831	0.028*
N12	0.3978 (2)	0.2045 (2)	0.3078 (2)	0.0218 (7)
C22	0.4793 (2)	0.1638 (2)	0.3610 (3)	0.0204 (8)
C32	0.5630 (2)	0.2184 (3)	0.3852 (3)	0.0235 (8)
H32	0.6209	0.1866	0.4215	0.028*
C42	0.5586 (2)	0.3200 (3)	0.3544 (3)	0.0275 (8)
H42	0.6136	0.3592	0.3697	0.033*
C52	0.4723 (3)	0.3636 (3)	0.3008 (3)	0.0296 (9)
H52	0.4673	0.4331	0.2795	0.035*
C62	0.3953 (2)	0.3042 (3)	0.2796 (3)	0.0253 (8)
H62	0.3366	0.3343	0.2430	0.030*
N72	0.4884 (2)	0.0616 (2)	0.3913 (3)	0.0256 (7)
H72	0.5482	0.0422	0.4148	0.031*
C82	0.4334 (2)	−0.0028 (2)	0.4329 (3)	0.0199 (8)
N92	0.34291 (19)	0.0156 (2)	0.4112 (3)	0.0253 (7)
C102	0.2932 (2)	−0.0509 (3)	0.4538 (3)	0.0288 (8)
H102	0.2290	−0.0374	0.4392	0.035*
C112	0.3283 (3)	−0.1363 (3)	0.5163 (3)	0.0338 (9)
H112	0.2900	−0.1815	0.5428	0.041*
C122	0.4234 (3)	−0.1539 (3)	0.5393 (3)	0.0343 (9)
H122	0.4519	−0.2117	0.5827	0.041*
C132	0.4743 (3)	−0.0863 (3)	0.4983 (3)	0.0331 (9)
H132	0.5392	−0.0967	0.5148	0.040*
Ag2	0.761250 (14)	0.388508 (17)	0.726177 (17)	0.02918 (8)
N13	0.86617 (19)	0.5019 (2)	0.8471 (2)	0.0214 (6)
C23	0.9508 (2)	0.4820 (3)	0.9184 (3)	0.0187 (7)
C33	0.9997 (2)	0.5486 (2)	1.0078 (3)	0.0257 (8)
H33	1.0601	0.5322	1.0570	0.031*
C43	0.9576 (3)	0.6382 (3)	1.0222 (3)	0.0273 (9)
H43	0.9881	0.6836	1.0834	0.033*
C53	0.8706 (3)	0.6616 (3)	0.9472 (3)	0.0322 (9)
H53	0.8417	0.7241	0.9539	0.039*
C63	0.8270 (3)	0.5919 (3)	0.8622 (3)	0.0265 (8)
H63	0.7667	0.6073	0.8119	0.032*
N73	0.9981 (2)	0.39408 (19)	0.9060 (3)	0.0202 (7)
H73	1.0572	0.3951	0.9529	0.024*
C83	0.9754 (2)	0.3064 (2)	0.8416 (3)	0.0169 (7)
N93	0.8899 (2)	0.2894 (2)	0.7699 (2)	0.0195 (6)
C103	0.8755 (2)	0.2001 (2)	0.7095 (3)	0.0195 (7)
H103	0.8147	0.1868	0.6593	0.023*
C113	0.9420 (2)	0.1286 (2)	0.7158 (3)	0.0230 (8)
H113	0.9284	0.0681	0.6707	0.028*
C123	1.0301 (2)	0.1478 (2)	0.7905 (3)	0.0235 (8)
H123	1.0780	0.0995	0.7980	0.028*
C133	1.0487 (2)	0.2351 (2)	0.8533 (3)	0.0211 (8)
H133	1.1092	0.2485	0.9041	0.025*
N14	0.61745 (19)	0.3191 (2)	0.6773 (2)	0.0234 (7)
C24	0.5367 (2)	0.3671 (3)	0.6221 (3)	0.0200 (8)
C34	0.4512 (2)	0.3183 (3)	0.5988 (3)	0.0275 (8)
H34	0.3951	0.3538	0.5632	0.033*
C44	0.4499 (2)	0.2184 (3)	0.6282 (3)	0.0302 (9)
H44	0.3922	0.1838	0.6104	0.036*
C54	0.5318 (2)	0.1666 (3)	0.6839 (3)	0.0283 (8)
H54	0.5316	0.0975	0.7058	0.034*
C64	0.6130 (2)	0.2212 (3)	0.7054 (3)	0.0269 (8)
H64	0.6696	0.1872	0.7426	0.032*
N74	0.5352 (2)	0.4683 (2)	0.5909 (3)	0.0243 (7)
H74	0.4773	0.4939	0.5673	0.029*
C84	0.5980 (2)	0.5290 (2)	0.5574 (3)	0.0219 (7)
N94	0.68384 (18)	0.4979 (2)	0.5710 (2)	0.0211 (6)
C104	0.7409 (3)	0.5611 (3)	0.5343 (3)	0.0265 (8)
H104	0.8023	0.5393	0.5426	0.032*
C114	0.7141 (3)	0.6544 (3)	0.4862 (3)	0.0345 (9)
H114	0.7562	0.6964	0.4624	0.041*
C124	0.6250 (3)	0.6859 (3)	0.4733 (3)	0.0385 (10)
H124	0.6052	0.7508	0.4412	0.046*
C134	0.5640 (3)	0.6233 (3)	0.5069 (4)	0.0348 (10)
H134	0.5017	0.6430	0.4963	0.042*
S15	0.75611 (5)	0.01349 (6)	0.39994 (6)	0.01981 (16)
C15	0.7433 (2)	0.0582 (2)	0.2512 (3)	0.0255 (7)
O15	0.78134 (16)	0.10401 (16)	0.46901 (19)	0.0311 (5)
O25	0.66493 (13)	−0.02614 (16)	0.39086 (17)	0.0245 (5)
O35	0.82802 (14)	−0.06302 (17)	0.42036 (19)	0.0297 (5)
F15	0.82461 (16)	0.09384 (18)	0.24306 (19)	0.0461 (6)
F25	0.71515 (15)	−0.01391 (15)	0.17099 (15)	0.0414 (5)
F35	0.68361 (14)	0.13431 (15)	0.22196 (16)	0.0406 (5)
S16	0.26209 (5)	0.54551 (6)	0.47816 (7)	0.02433 (17)
C16	0.2496 (2)	0.5901 (2)	0.3289 (3)	0.0296 (8)
O16	0.23579 (17)	0.44104 (18)	0.4629 (2)	0.0387 (6)
O26	0.35897 (14)	0.56368 (17)	0.53840 (19)	0.0315 (5)
O36	0.19998 (14)	0.61062 (15)	0.51715 (19)	0.0277 (5)
F16	0.16206 (15)	0.58282 (17)	0.26083 (17)	0.0456 (6)
F26	0.27499 (15)	0.68592 (15)	0.32833 (18)	0.0481 (6)
F36	0.30125 (17)	0.53449 (18)	0.2797 (2)	0.0563 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.01513 (12)	0.02689 (13)	0.03138 (17)	−0.00027 (12)	−0.00103 (12)	−0.00142 (12)
N11	0.0171 (14)	0.0235 (15)	0.0274 (16)	−0.0002 (12)	0.0084 (12)	−0.0037 (13)
C21	0.0214 (18)	0.025 (2)	0.0170 (16)	−0.0063 (15)	0.0114 (14)	−0.0005 (13)
C31	0.0201 (18)	0.031 (2)	0.0263 (18)	−0.0050 (16)	0.0035 (14)	−0.0031 (16)
C41	0.038 (2)	0.024 (2)	0.037 (2)	−0.0149 (18)	0.0192 (18)	−0.0139 (17)
C51	0.029 (2)	0.0210 (19)	0.049 (2)	−0.0011 (15)	0.0182 (18)	−0.0069 (16)
C61	0.0267 (19)	0.027 (2)	0.038 (2)	0.0038 (15)	0.0110 (16)	−0.0006 (16)
N71	0.0109 (14)	0.0194 (15)	0.0230 (15)	−0.0015 (12)	−0.0035 (12)	−0.0042 (12)
C81	0.0144 (16)	0.0173 (18)	0.0187 (16)	−0.0039 (14)	0.0039 (13)	0.0015 (13)
N91	0.0178 (15)	0.0161 (15)	0.0235 (15)	0.0014 (12)	0.0071 (12)	−0.0017 (12)
C101	0.0237 (18)	0.0256 (19)	0.0228 (17)	−0.0019 (15)	0.0056 (14)	−0.0004 (14)
C111	0.035 (2)	0.0208 (18)	0.0271 (19)	0.0019 (16)	0.0170 (17)	−0.0040 (15)
C121	0.0284 (19)	0.025 (2)	0.0280 (18)	0.0069 (15)	0.0137 (15)	0.0037 (15)
C131	0.0182 (17)	0.026 (2)	0.0255 (17)	0.0027 (15)	0.0055 (14)	0.0018 (14)
N12	0.0152 (14)	0.0255 (16)	0.0222 (15)	0.0001 (13)	0.0019 (12)	0.0027 (12)
C22	0.0237 (19)	0.0188 (19)	0.0213 (17)	−0.0070 (15)	0.0107 (14)	−0.0020 (14)
C32	0.0137 (16)	0.032 (2)	0.0258 (18)	0.0002 (15)	0.0069 (13)	−0.0022 (15)
C42	0.0257 (18)	0.028 (2)	0.0318 (19)	−0.0142 (16)	0.0136 (15)	−0.0081 (15)
C52	0.032 (2)	0.030 (2)	0.0273 (19)	−0.0024 (16)	0.0108 (15)	−0.0013 (15)
C62	0.0242 (18)	0.0246 (19)	0.0266 (18)	0.0017 (15)	0.0069 (14)	0.0073 (14)
N72	0.0141 (14)	0.0248 (17)	0.0383 (17)	0.0032 (13)	0.0085 (12)	−0.0005 (13)
C82	0.0170 (17)	0.0183 (18)	0.0231 (16)	0.0016 (14)	0.0043 (13)	−0.0055 (14)
N92	0.0200 (15)	0.0261 (16)	0.0283 (16)	−0.0017 (12)	0.0048 (13)	0.0013 (13)
C102	0.0229 (19)	0.034 (2)	0.0294 (19)	−0.0043 (16)	0.0073 (15)	−0.0003 (16)
C112	0.050 (3)	0.028 (2)	0.0275 (19)	−0.0105 (17)	0.0184 (18)	−0.0044 (15)
C122	0.044 (2)	0.029 (2)	0.031 (2)	0.0080 (18)	0.0133 (18)	0.0043 (16)
C132	0.034 (2)	0.035 (2)	0.032 (2)	0.0148 (19)	0.0123 (17)	0.0039 (17)
Ag2	0.01447 (13)	0.02766 (14)	0.03755 (19)	0.00203 (13)	−0.00404 (13)	−0.00287 (12)
N13	0.0210 (15)	0.0207 (15)	0.0229 (15)	0.0002 (12)	0.0069 (12)	−0.0029 (12)
C23	0.0181 (17)	0.0200 (18)	0.0196 (16)	−0.0037 (14)	0.0080 (13)	−0.0028 (13)
C33	0.0290 (19)	0.0263 (19)	0.0205 (16)	−0.0086 (15)	0.0055 (14)	−0.0021 (14)
C43	0.036 (2)	0.0234 (19)	0.0238 (18)	−0.0067 (16)	0.0108 (16)	−0.0062 (15)
C53	0.045 (2)	0.0225 (19)	0.034 (2)	0.0037 (17)	0.0209 (19)	−0.0027 (16)
C63	0.0245 (19)	0.0269 (19)	0.031 (2)	0.0048 (15)	0.0124 (16)	0.0009 (15)
N73	0.0147 (15)	0.0200 (15)	0.0241 (15)	−0.0012 (11)	0.0033 (12)	−0.0052 (12)
C83	0.0169 (16)	0.0200 (17)	0.0143 (15)	−0.0023 (14)	0.0053 (13)	0.0019 (13)
N93	0.0159 (14)	0.0221 (16)	0.0218 (14)	−0.0004 (12)	0.0076 (12)	−0.0014 (12)
C103	0.0165 (15)	0.0230 (17)	0.0197 (16)	0.0001 (14)	0.0061 (13)	−0.0044 (13)
C113	0.033 (2)	0.0162 (16)	0.0222 (17)	−0.0051 (14)	0.0114 (15)	−0.0017 (13)
C123	0.0241 (19)	0.0231 (18)	0.0256 (17)	0.0063 (15)	0.0110 (15)	0.0043 (14)
C133	0.0169 (16)	0.0267 (19)	0.0183 (16)	0.0016 (14)	0.0033 (12)	0.0014 (14)
N14	0.0140 (14)	0.0313 (18)	0.0232 (15)	0.0007 (12)	0.0030 (12)	−0.0025 (12)
C24	0.0166 (17)	0.0205 (19)	0.0212 (17)	0.0065 (14)	0.0031 (13)	0.0021 (13)
C34	0.0161 (16)	0.036 (2)	0.0290 (18)	0.0021 (15)	0.0043 (14)	0.0030 (15)
C44	0.0216 (18)	0.037 (2)	0.0292 (19)	−0.0053 (17)	0.0029 (15)	−0.0019 (16)
C54	0.027 (2)	0.029 (2)	0.0267 (18)	−0.0043 (16)	0.0051 (15)	0.0027 (15)
C64	0.0232 (18)	0.028 (2)	0.0249 (18)	0.0022 (15)	0.0006 (14)	−0.0011 (15)
N74	0.0176 (15)	0.0204 (16)	0.0313 (15)	0.0079 (12)	0.0021 (12)	0.0021 (12)
C84	0.0221 (17)	0.0233 (18)	0.0200 (16)	0.0013 (14)	0.0061 (13)	0.0002 (13)
N94	0.0168 (14)	0.0242 (15)	0.0205 (14)	0.0001 (12)	0.0032 (11)	−0.0038 (12)
C104	0.0276 (19)	0.032 (2)	0.0219 (17)	−0.0034 (16)	0.0102 (15)	−0.0058 (15)
C114	0.041 (2)	0.034 (2)	0.033 (2)	−0.0010 (18)	0.0168 (17)	0.0023 (17)
C124	0.052 (3)	0.029 (2)	0.040 (2)	0.0055 (19)	0.022 (2)	0.0061 (17)
C134	0.042 (2)	0.030 (2)	0.039 (2)	0.0149 (17)	0.0208 (19)	0.0096 (17)
S15	0.0161 (3)	0.0232 (4)	0.0182 (3)	−0.0009 (3)	0.0023 (3)	−0.0001 (3)
C15	0.0249 (19)	0.0275 (18)	0.0261 (17)	0.0045 (15)	0.0111 (14)	0.0031 (15)
O15	0.0359 (13)	0.0294 (13)	0.0243 (12)	−0.0095 (10)	0.0033 (10)	−0.0061 (10)
O25	0.0164 (11)	0.0293 (13)	0.0265 (12)	−0.0017 (9)	0.0046 (9)	−0.0039 (9)
O35	0.0183 (11)	0.0364 (14)	0.0327 (13)	0.0063 (10)	0.0052 (10)	0.0091 (10)
F15	0.0425 (13)	0.0575 (15)	0.0422 (13)	−0.0039 (11)	0.0186 (11)	0.0170 (10)
F25	0.0590 (14)	0.0416 (13)	0.0214 (10)	0.0038 (10)	0.0086 (9)	−0.0041 (9)
F35	0.0461 (13)	0.0411 (13)	0.0312 (10)	0.0166 (10)	0.0065 (9)	0.0110 (9)
S16	0.0178 (4)	0.0243 (4)	0.0257 (4)	0.0035 (3)	−0.0013 (3)	−0.0040 (3)
C16	0.0335 (19)	0.0246 (19)	0.0303 (17)	−0.0028 (15)	0.0089 (15)	−0.0073 (14)
O16	0.0447 (15)	0.0247 (14)	0.0375 (14)	−0.0035 (11)	−0.0012 (11)	−0.0038 (11)
O26	0.0144 (11)	0.0387 (14)	0.0356 (13)	0.0064 (10)	−0.0010 (10)	−0.0098 (11)
O36	0.0166 (11)	0.0353 (14)	0.0290 (12)	0.0086 (10)	0.0034 (9)	−0.0016 (10)
F16	0.0437 (14)	0.0497 (13)	0.0286 (11)	−0.0051 (11)	−0.0113 (10)	0.0001 (10)
F26	0.0609 (15)	0.0357 (12)	0.0468 (13)	−0.0132 (11)	0.0148 (11)	0.0008 (10)
F36	0.0687 (18)	0.0618 (16)	0.0459 (14)	0.0191 (13)	0.0286 (13)	−0.0089 (12)

Geometric parameters (Å, º)

Ag1—N91	2.284 (3)	C23—C33	1.408 (4)
Ag1—N12	2.305 (3)	C33—C43	1.380 (5)
Ag1—N92	2.357 (3)	C33—H33	0.9500
Ag1—N11	2.373 (3)	C43—C53	1.384 (5)
N11—C21	1.344 (4)	C43—H43	0.9500
N11—C61	1.353 (4)	C53—C63	1.381 (5)
C21—N71	1.384 (4)	C53—H53	0.9500
C21—C31	1.403 (5)	C63—H63	0.9500
C31—C41	1.379 (5)	N73—C83	1.375 (4)
C31—H31	0.9500	N73—H73	0.8998
C41—C51	1.387 (5)	C83—N93	1.336 (4)
C41—H41	0.9500	C83—C133	1.429 (4)
C51—C61	1.361 (5)	N93—C103	1.365 (4)
C51—H51	0.9500	C103—C113	1.366 (5)
C61—H61	0.9500	C103—H103	0.9500
N71—C81	1.390 (4)	C113—C123	1.385 (4)
N71—H71	0.8997	C113—H113	0.9500
C81—N91	1.350 (4)	C123—C133	1.357 (4)
C81—C131	1.386 (5)	C123—H123	0.9500
N91—C101	1.351 (4)	C133—H133	0.9500
C101—C111	1.375 (5)	N14—C64	1.344 (4)
C101—H101	0.9500	N14—C24	1.357 (4)
C111—C121	1.379 (5)	C24—N74	1.387 (4)
C111—H111	0.9500	C24—C34	1.396 (5)
C121—C131	1.369 (5)	C34—C44	1.368 (5)
C121—H121	0.9500	C34—H34	0.9500
C131—H131	0.9500	C44—C54	1.396 (5)
N12—C22	1.319 (5)	C44—H44	0.9500
N12—C62	1.358 (4)	C54—C64	1.380 (5)
C22—N72	1.394 (4)	C54—H54	0.9500
C22—C32	1.410 (5)	C64—H64	0.9500
C32—C42	1.389 (5)	N74—C84	1.390 (4)
C32—H32	0.9500	N74—H74	0.9001
C42—C52	1.392 (5)	C84—N94	1.325 (4)
C42—H42	0.9500	C84—C134	1.412 (5)
C52—C62	1.364 (5)	N94—C104	1.364 (4)
C52—H52	0.9500	C104—C114	1.368 (5)
C62—H62	0.9500	C104—H104	0.9500
N72—C82	1.383 (4)	C114—C124	1.374 (5)
N72—H72	0.8999	C114—H114	0.9500
C82—N92	1.336 (4)	C124—C134	1.385 (5)
C82—C132	1.385 (5)	C124—H124	0.9500
N92—C102	1.351 (4)	C134—H134	0.9500
C102—C112	1.369 (5)	S15—O15	1.437 (2)
C102—H102	0.9500	S15—O25	1.448 (2)
C112—C122	1.400 (5)	S15—O35	1.451 (2)
C112—H112	0.9500	S15—C15	1.822 (3)
C122—C132	1.362 (5)	C15—F25	1.326 (4)
C122—H122	0.9500	C15—F35	1.326 (3)
C132—H132	0.9500	C15—F15	1.348 (4)
Ag2—N14	2.269 (3)	S16—O16	1.434 (2)
Ag2—N93	2.273 (3)	S16—O26	1.444 (2)
Ag2—N13	2.337 (3)	S16—O36	1.450 (2)
Ag2—N94	2.361 (3)	S16—C16	1.829 (3)
N13—C23	1.332 (4)	C16—F26	1.324 (4)
N13—C63	1.365 (4)	C16—F36	1.330 (4)
C23—N73	1.396 (4)	C16—F16	1.331 (4)
N91—Ag1—N12	120.66 (8)	C43—C33—C23	118.3 (3)
N91—Ag1—N92	139.76 (10)	C43—C33—H33	120.8
N12—Ag1—N92	80.44 (9)	C23—C33—H33	120.8
N91—Ag1—N11	81.47 (10)	C33—C43—C53	119.7 (3)
N12—Ag1—N11	148.62 (10)	C33—C43—H43	120.1
N92—Ag1—N11	96.61 (10)	C53—C43—H43	120.1
C21—N11—C61	116.6 (3)	C63—C53—C43	118.4 (3)
C21—N11—Ag1	126.5 (2)	C63—C53—H53	120.8
C61—N11—Ag1	115.1 (2)	C43—C53—H53	120.8
N11—C21—N71	121.4 (3)	N13—C63—C53	123.2 (3)
N11—C21—C31	122.3 (3)	N13—C63—H63	118.4
N71—C21—C31	116.2 (3)	C53—C63—H63	118.4
C41—C31—C21	118.8 (3)	C83—N73—C23	135.3 (3)
C41—C31—H31	120.6	C83—N73—H73	113.1
C21—C31—H31	120.6	C23—N73—H73	111.5
C31—C41—C51	119.4 (3)	N93—C83—N73	122.0 (3)
C31—C41—H41	120.3	N93—C83—C133	121.6 (3)
C51—C41—H41	120.3	N73—C83—C133	116.5 (3)
C61—C51—C41	117.9 (3)	C83—N93—C103	116.9 (3)
C61—C51—H51	121.1	C83—N93—Ag2	130.3 (2)
C41—C51—H51	121.1	C103—N93—Ag2	112.8 (2)
N11—C61—C51	125.0 (4)	N93—C103—C113	124.8 (3)
N11—C61—H61	117.5	N93—C103—H103	117.6
C51—C61—H61	117.5	C113—C103—H103	117.6
C21—N71—C81	135.9 (3)	C103—C113—C123	117.2 (3)
C21—N71—H71	114.8	C103—C113—H113	121.4
C81—N71—H71	109.4	C123—C113—H113	121.4
N91—C81—C131	122.1 (3)	C133—C123—C113	120.7 (3)
N91—C81—N71	120.9 (3)	C133—C123—H123	119.7
C131—C81—N71	117.0 (3)	C113—C123—H123	119.7
C81—N91—C101	117.1 (3)	C123—C133—C83	118.8 (3)
C81—N91—Ag1	129.8 (2)	C123—C133—H133	120.6
C101—N91—Ag1	112.0 (2)	C83—C133—H133	120.6
N91—C101—C111	123.3 (3)	C64—N14—C24	117.8 (3)
N91—C101—H101	118.4	C64—N14—Ag2	116.2 (2)
C111—C101—H101	118.4	C24—N14—Ag2	126.0 (2)
C101—C111—C121	118.9 (3)	N14—C24—N74	121.4 (3)
C101—C111—H111	120.6	N14—C24—C34	121.7 (3)
C121—C111—H111	120.6	N74—C24—C34	116.9 (3)
C131—C121—C111	118.8 (3)	C44—C34—C24	118.6 (3)
C131—C121—H121	120.6	C44—C34—H34	120.7
C111—C121—H121	120.6	C24—C34—H34	120.7
C121—C131—C81	119.8 (3)	C34—C44—C54	121.1 (3)
C121—C131—H131	120.1	C34—C44—H44	119.5
C81—C131—H131	120.1	C54—C44—H44	119.5
C22—N12—C62	117.9 (3)	C64—C54—C44	116.4 (3)
C22—N12—Ag1	125.2 (2)	C64—C54—H54	121.8
C62—N12—Ag1	116.9 (2)	C44—C54—H54	121.8
N12—C22—N72	121.7 (3)	N14—C64—C54	124.5 (3)
N12—C22—C32	122.7 (3)	N14—C64—H64	117.8
N72—C22—C32	115.5 (3)	C54—C64—H64	117.8
C42—C32—C22	118.2 (3)	C24—N74—C84	132.5 (3)
C42—C32—H32	120.9	C24—N74—H74	112.5
C22—C32—H32	120.9	C84—N74—H74	112.1
C32—C42—C52	119.1 (3)	N94—C84—N74	121.0 (3)
C32—C42—H42	120.5	N94—C84—C134	122.9 (3)
C52—C42—H42	120.5	N74—C84—C134	116.1 (3)
C62—C52—C42	118.4 (3)	C84—N94—C104	117.4 (3)
C62—C52—H52	120.8	C84—N94—Ag2	121.5 (2)
C42—C52—H52	120.8	C104—N94—Ag2	114.5 (2)
N12—C62—C52	123.7 (3)	N94—C104—C114	123.4 (3)
N12—C62—H62	118.2	N94—C104—H104	118.3
C52—C62—H62	118.2	C114—C104—H104	118.3
C82—N72—C22	131.8 (3)	C104—C114—C124	118.5 (4)
C82—N72—H72	111.7	C104—C114—H114	120.8
C22—N72—H72	111.6	C124—C114—H114	120.8
N92—C82—N72	120.7 (3)	C114—C124—C134	120.1 (4)
N92—C82—C132	120.9 (3)	C114—C124—H124	119.9
N72—C82—C132	118.5 (3)	C134—C124—H124	119.9
C82—N92—C102	117.5 (3)	C124—C134—C84	117.6 (4)
C82—N92—Ag1	122.5 (2)	C124—C134—H134	121.2
C102—N92—Ag1	116.5 (2)	C84—C134—H134	121.2
N92—C102—C112	124.9 (3)	O15—S15—O25	115.25 (13)
N92—C102—H102	117.5	O15—S15—O35	115.35 (13)
C112—C102—H102	117.5	O25—S15—O35	114.14 (13)
C102—C112—C122	116.8 (3)	O15—S15—C15	102.63 (14)
C102—C112—H112	121.6	O25—S15—C15	102.97 (13)
C122—C112—H112	121.6	O35—S15—C15	104.14 (14)
C132—C122—C112	118.6 (4)	F25—C15—F35	108.2 (3)
C132—C122—H122	120.7	F25—C15—F15	107.5 (3)
C112—C122—H122	120.7	F35—C15—F15	106.2 (3)
C122—C132—C82	121.3 (4)	F25—C15—S15	112.6 (2)
C122—C132—H132	119.4	F35—C15—S15	111.5 (2)
C82—C132—H132	119.4	F15—C15—S15	110.5 (2)
N14—Ag2—N93	120.92 (10)	O16—S16—O26	115.12 (14)
N14—Ag2—N13	146.92 (10)	O16—S16—O36	115.53 (15)
N93—Ag2—N13	81.55 (10)	O26—S16—O36	113.59 (13)
N14—Ag2—N94	80.54 (10)	O16—S16—C16	104.11 (15)
N93—Ag2—N94	136.16 (10)	O26—S16—C16	102.82 (15)
N13—Ag2—N94	100.03 (9)	O36—S16—C16	103.47 (14)
C23—N13—C63	117.4 (3)	F26—C16—F36	108.5 (3)
C23—N13—Ag2	127.6 (2)	F26—C16—F16	107.6 (3)
C63—N13—Ag2	113.5 (2)	F36—C16—F16	107.5 (3)
N13—C23—N73	121.5 (3)	F26—C16—S16	111.6 (2)
N13—C23—C33	122.9 (3)	F36—C16—S16	110.3 (2)
N73—C23—C33	115.6 (3)	F16—C16—S16	111.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N72—H72···O25	0.90	2.08	2.912 (4)	154
N74—H74···O26	0.90	1.95	2.842 (3)	171
N71—H71···O35^i	0.90	2.08	2.976 (3)	179
N73—H73···O36^ii	0.90	2.06	2.939 (4)	164
C122—H122···Cg1^iii	0.95	2.95	3.622 (6)	129
C41—H41···Cg2^iv	0.95	2.76	3.561 (6)	143
C43—H43···Cg3^v	0.95	2.82	3.603 (6)	140
C124—H124···C64^vi	0.95	2.87	3.373 (6)	114

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