A stair-like two-dimensional silver(I) coordination polymer of N′-(3-cyano­benzyl­idene)nicotinohydrazide

The structure of the title compound, poly[[[μ₃-N′-(3-cyano­benzyl­idene)nicotinohydrazide]silver(I)] hexa­fluoro­arsenate], {[Ag(C₁₄H₁₀N₄O)](AsF₆)}_n, at 173 K exhibits a novel stair-like two-dimensional layer and a three-dimensional supra­molecular framework through C—H...Ag hydrogen bonds. The Ag^I cation is coordinated by three N atoms and one O atom from N′-(3-cyano­benzyl­idene)­nico­tino­hydrazide (L) ligands, resulting in a distorted tetra­hedral coordination geometry. The organic ligand acts as a μ₃-bridging ligand through the pyridyl and carbonitrile N atoms and deviates from planarity in order to adapt to the coordination geometry. Two ligands bridge two Ag^I cations to construct a small 2+2 Ag₂L₂ ring. Four ligands bridge one Ag^I cation from each of four of these small rings to form a large grid. An inter­esting stair-like two-dimensional (3,6)-net is formed through Ag^I metal centres acting as three-connection nodes and through L mol­ecules as tri-linkage spacers.

S1. Comment

The design and construction of novel coordination polymers are very important parts of crystal engineering, not only for functional materials purposes but also for the favorable architectures and topologies of these polymers (Murray & Dinca et al., 2009; Eddaoudi et al., 2001). Metal centers as connecting nodes and organic bridging ligands as spacers should be cogitatively selected before studies. For metal centers, silver ions are widely used because silver coordinating polymers possess strong luminescent emissions and antibiotic characters. In addition, the coordination number and metal stereochemistry for silver(I) is quite variable (Catalano et al., 1999; Dong et al., 2004; Zheng et al., 2003; Schottel et al., 2005). Furthermore, there are many significant inter- and intra-molecular interactions between silver centers (Ag···Ag metal interactions), and between silver and other elements, such as organic aromatic π systems (Ag···π interactions; Jung et al., 2004), O atoms (Ag···O interactions; Wang & Mak, 2002), S atoms (Ag···S interactions; Wang et al., 2006), halogen (X) atoms [X = F, Cl, Br and I; Ag···X interactions; Blake et al., 2000), and rare H, C, CH₂ and CH₃ (C—H···Ag weak hydrogen bonds, Ag···H—C agostic interactions and Ag···C organometallic interactions; Clarke et al., 2004; McMorran & Steel, 2002; Liu et al., 2006; Zhao & Mak, 2007). For organic ligands, pyridyl–carbonitrile ligands with labile coordinating properties and different coordinating groups with different coordinating abilities towards Ag atoms were used in some of our studies (Niu et al., 2007, 2008). For the series of Schiff base ligands synthesized from cyanobenzaldehyde and pyridylhydrazone, we noticed that, if we changed the position of the N atom on the pyridyl ring, the molecular or supramolecular structures of the silver coordination compounds were different. Thus, it should be reasonable to assume that, if the position of the carbonitrile group on the benzene ring is changed, a new silver coordinating compound with an unexpected structure might be obtained.

We report here the structure of a novel silver coordination polymer of the new bridging ligand N'-(3-cyanobenzylidene)nicotinohydrazide (L), namely {[Ag(C₁₄H₁₀N₄O)](AsF₆)}_n, (I). Its crystal structure determined by X-ray diffraction shows that (I) possesses a novel stair-like two-dimensional layer structure. More interestingly, weak C—H···Ag hydrogen bonds were found connecting these two-dimensional layers, forming a three-dimensional framework.

In (I), the silver ion is four-coordinated by one O atom and one N atom (O1 and N3) from the hydrazide chain and by the pyridyl and carbonitrile N atoms (N1ⁱⁱ and N4ⁱ; for symmetry codes, see Table 1) from two other bridging ligands, giving a distorted tetrahedral coordination geometry (Fig. 1). Ligand donor atoms O1 and N3 are coordinated to the silver ion in a bidentate coordinating mode to form a planar five-membered chelate ring (Ag1/O1/C6/N2/N3). The Ag—O bond distance is 2.415 (2) Å, and the Ag–N bond distances range from 2.151 (3) Å to 2.462 (2) Å (Table 1). The Ag—N_carbonitrile bond distance is the shortest. The distortion of the tetrahedral coordination geometry is largely a result of the widely varying bond angles about the metal center [67.08 (7)–133.08 (10)°; Table 2]. The hydrazide ligand molecule is distorted from planarity in accommodating the metal coordination centres. The Ag1/O1/C6/N2/N3 ring is not coplanar with the benzene ring of the same ligand [the dihedral angle is 47.15 (2)°; Fig. 2]. The plane of the pyridyl ring is also twisted slightly from that of the above-mentioned chelate ring and makes a dihedral angle of 74.91 (2)° with the plane of the aromatic ring. Two L molecules bridge pairs of Ag coordination centers through the carbonitrile N atom and the primary bidentate chelate ligand interaction, to form a small centrosymmetric 2+2 Ag₂L₂ ring. The Ag···Ag separation in one ring is 6.5147 (6)Å. Four of these small rings are linked to each other by pyridyl atom N1, coordinating to Ag atoms in adjacent rings to produce a large nearly rectangular grid. Thus, two Ag atoms from different 2+2 rings are bridged by the entire length of L via the pyridyl and carbonitrile N atoms, and this bridging ligand is not planar. The Ag···Ag separation for atoms bridged in this way is 13.2985 (9)Å. The distance between two neighbouring Ag atoms bridged via the bidentate hydrazide O1 and N3 atoms and the monodentate pyridyl N1 atom is 8.5129 (5)Å. The spaces within this grid are not void but occupied by two parallel benzene rings, which are also parallel to two pyridyl rings of the large grid. Weak π–π interactions exist between two neighbouring parallel benzene rings, and between neighbouring parallel benzene and pyridyl rings, with centroid–centroid distances of about 3.9Å, and interplanar angles of 0° and about 14°, respectively. These weak interactions help the stability of the large grid constructed by the deformed L molecules. The AsF₆^- counter-anions are located on the outside of the grids and are associated with the hydrazide chains through N—H···F hydrogen bonds (Table 2).

It is noteworthy that a stair-like two-dimensional (3,6)-net is formed through Ag metal centers acting as three-connection nodes and L molecules as tri-linkage spacers using two bottom and one middle coordinating atoms. These nets are unlike most reported two-dimensional planar brick-wall (3,6)-nets but can be seen as deformed or even folded planar (3,6)-nets driven by the tetrahedral coordination environment of the metal centers, instead of the square-planar type, together with the deformation from planarity of the L ligand molecule. Two adjacent ladders bend in two different directions, one up and the other down, both by nearly 90° (Fig. 3). Deformed hydrazide chains and pyridyl rings coordinating to Ag atoms are located at the corners of the stairs, whereas carbonitrile chains link two edges, constructing the equatorial and right platforms of the stairs (Fig. 4).

Another striking feature of the structure of this compound is the occurence of the rare intermolecular C—H···Ag interactions between two neighbouring stair-like layers. The intermolecular distances indicate the presence of obvious close complementary C—H···M close interactions between the metal centers and the pyridyl ring H atoms [Ag···H = 2.8394 (3) Å, Ag···C = 3.576 (4) Å and C—H···Ag = 135.0 (2)°]. From the above-mentioned bond distances and angle, such C—H···Ag close interactions should be described as a weak intermolecular C—H···M hydrogen bonding, as previously described (Thakur & Desiraju, 2005). Furthermore, donors and acceptors involve two separate coordination centers, strengthening contacts between the two components (Fig. 5). Although neighbouring stair-like layers contacting each other via C—H···Ag produce grid-like one-dimensional tunnels with diameters from about 0.6 to 1 nm, AsF₆^- counter-anions occupy these tunnels, diminishing the gas absorption ability of the solid material. However, ion-exchange from AsF₆^- anions to other analogues such as PF₆^- is possible.

Finally, C—H···Ag inter- or intra-molecular interactions were found in only a few silver compounds and act as connectors to link some finite components (e.g. {[AgL²](ClO₄)}₂, L² = 9-[3-(2-pyridyl)pyrazol-1-yl]acridine; Ag···H = 2.657–2.706 Å, Ag···C = 3.198–3.231 Å and C—H···Ag = 116.60–117.73°; Clarke et al., 2004; McMorran & Steel, 2002; Liu et al., 2006; Zhao & Mak, 2007). However, to the best of our knowledge, these authors found no C—H···Ag interactions that connect infinite one-dimensional chains or two-dimensional layers of silver coordination polymers to construct higher-dimensional frameworks. This work may therefore provide a new method for the construction of supramolecular high-dimensional frameworks.

S2. Experimental

A solution of AgAsF₆ (0.1 mmol) in methanol (10 ml) was carefully layered on a solution of (3-cyanobenzylidene)nicotinohydrazide (L) (0.1 mmol) in chloroform (10 ml) in a straight glass tube. After about two weeks, single crystals suitable for X-ray analysis appeared at the boundary between the two layers (yield ca 40%). Analysis calculated for C₁₄H₁₀AgAsF₆N₄O: C 30.74, H 1.84, N 10.24%; found: C 30.89, H 1.77, N 10.27%. IR (KBr, ν, cm^-1): 3339 (m), 3068 (w), 2267 (m), 1663 (s), 1598 (w), 1534 (m), 1476 (w), 1429 (w), 1362 (w), 1290 (m), 1164 (w), 1145 (w), 955 (w), 810 (w), 705 (vs), 583 (w), 530 (w).

S3. Refinement

H atoms were placed in calculated positions and refined using a riding model [C—H = 0.95 Å, N—H = 0.88 Å and U_iso(H) = 1.2U_eq(C,N)]. The highest peak in the final difference Fourier map was 1.02 Å from atom F1 and the deepest hole was 0.66 Å from atom Ag1, but the map was otherwise featureless.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The local coordination around the Ag^I centre in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For symmetry codes, see Table 1.
	Fig. 2. A ball-and-stick diagram showing the large ring and the intermolecular π–π interactions (dashed lines).
	Fig. 3. The transition from the usual brick-wall (3,6)-net (left) to a stair-like framework (right).
	Fig. 4. Ball-and-stick (left) and spacefilling (right) diagrams, showing the stair-like framework of (I).
	Fig. 5. A ball-and-stick diagram showing the rare intermolecular C—H···Ag hydrogen bonds (dashed lines) in (I).

Poly[[[µ₃-N'-(3-cyanobenzylidene)nicotinohydrazide]silver(I)] hexafluoroarsenate]

Crystal data

[Ag(C14H10N4O)](AsF6)	F(000) = 1056
Mr = 547.05	Dx = 2.084 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4687 reflections
a = 12.7022 (10) Å	θ = 2.5–27.5°
b = 10.6710 (8) Å	µ = 3.11 mm^−1
c = 13.5477 (11) Å	T = 173 K
β = 108.316 (1)°	Block, colourless
V = 1743.3 (2) Å^3	0.29 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	3988 independent reflections
Radiation source: fine-focus sealed tube	3330 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→16
Tmin = 0.466, Tmax = 0.575	k = −13→12
11028 measured reflections	l = −17→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0441P)^2 + 1.0766P] where P = (Fo^2 + 2Fc^2)/3
3988 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

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	0.46567 (2)	0.42080 (2)	0.720067 (18)	0.04525 (9)
N1	0.7892 (2)	0.1581 (2)	1.17785 (19)	0.0395 (5)
N2	0.5757 (2)	0.1867 (2)	0.87079 (18)	0.0422 (6)
H14	0.6006	0.1125	0.8959	0.051*
N3	0.5292 (2)	0.2041 (2)	0.76497 (18)	0.0367 (5)
N4	0.4610 (2)	0.4308 (3)	0.3436 (2)	0.0505 (7)
O1	0.5429 (2)	0.3875 (2)	0.90517 (17)	0.0480 (5)
C1	0.7640 (3)	0.2276 (3)	1.2496 (2)	0.0503 (8)
H1	0.8045	0.2146	1.3208	0.060*
C2	0.6818 (3)	0.3172 (4)	1.2241 (3)	0.0627 (11)
H2	0.6665	0.3655	1.2770	0.075*
C3	0.6220 (3)	0.3361 (4)	1.1211 (3)	0.0525 (8)
H3	0.5661	0.3987	1.1018	0.063*
C4	0.6446 (2)	0.2623 (3)	1.0467 (2)	0.0361 (6)
C5	0.7289 (2)	0.1747 (3)	1.0786 (2)	0.0358 (6)
H5	0.7447	0.1241	1.0273	0.043*
C6	0.5827 (2)	0.2850 (3)	0.9353 (2)	0.0368 (6)
C7	0.5010 (3)	0.1073 (3)	0.7080 (2)	0.0412 (7)
H7	0.5134	0.0261	0.7383	0.049*
C8	0.4497 (2)	0.1209 (3)	0.5957 (2)	0.0352 (6)
C9	0.3725 (3)	0.0322 (3)	0.5413 (2)	0.0403 (6)
H9	0.3593	−0.0403	0.5764	0.048*
C10	0.3153 (3)	0.0483 (3)	0.4373 (2)	0.0421 (7)
H10	0.2619	−0.0120	0.4017	0.051*
C11	0.3354 (3)	0.1520 (3)	0.3844 (2)	0.0410 (7)
H11	0.2951	0.1642	0.3130	0.049*
C12	0.4159 (2)	0.2382 (3)	0.4378 (2)	0.0355 (6)
C13	0.4730 (2)	0.2234 (3)	0.5425 (2)	0.0351 (6)
H13	0.5276	0.2827	0.5778	0.042*
C14	0.4402 (3)	0.3460 (3)	0.3840 (2)	0.0418 (7)
As1	0.68466 (3)	0.82580 (3)	0.92847 (3)	0.04731 (11)
F1	0.6108 (3)	0.9114 (3)	0.9890 (3)	0.1103 (11)
F2	0.7995 (3)	0.8381 (5)	1.0311 (2)	0.1263 (14)
F3	0.6474 (3)	0.6924 (2)	0.9767 (2)	0.0920 (8)
F4	0.5701 (2)	0.8156 (3)	0.8211 (2)	0.0855 (8)
F5	0.7177 (2)	0.9631 (2)	0.8776 (2)	0.0816 (7)
F6	0.7572 (2)	0.7454 (2)	0.8622 (2)	0.0771 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.05425 (16)	0.03737 (14)	0.04115 (14)	−0.00764 (10)	0.01072 (11)	0.00614 (9)
N1	0.0386 (13)	0.0451 (14)	0.0305 (12)	0.0035 (11)	0.0045 (10)	−0.0025 (10)
N2	0.0566 (15)	0.0335 (12)	0.0280 (11)	0.0033 (11)	0.0012 (11)	0.0030 (9)
N3	0.0420 (13)	0.0357 (12)	0.0278 (11)	0.0031 (10)	0.0044 (10)	0.0031 (9)
N4	0.0599 (17)	0.0460 (16)	0.0484 (16)	−0.0061 (13)	0.0210 (14)	0.0084 (12)
O1	0.0601 (14)	0.0417 (12)	0.0365 (11)	0.0114 (10)	0.0069 (10)	−0.0002 (9)
C1	0.0502 (18)	0.070 (2)	0.0281 (14)	0.0079 (16)	0.0086 (13)	−0.0029 (14)
C2	0.060 (2)	0.088 (3)	0.0375 (17)	0.028 (2)	0.0128 (16)	−0.0135 (17)
C3	0.0491 (18)	0.065 (2)	0.0397 (16)	0.0193 (16)	0.0092 (14)	−0.0049 (15)
C4	0.0342 (14)	0.0425 (15)	0.0300 (14)	−0.0008 (11)	0.0077 (11)	−0.0008 (11)
C5	0.0392 (14)	0.0366 (14)	0.0292 (13)	0.0001 (11)	0.0075 (11)	−0.0026 (10)
C6	0.0381 (14)	0.0393 (15)	0.0316 (14)	0.0010 (12)	0.0091 (11)	0.0024 (11)
C7	0.0532 (17)	0.0324 (15)	0.0337 (14)	0.0049 (13)	0.0075 (13)	0.0044 (11)
C8	0.0433 (15)	0.0296 (13)	0.0324 (14)	0.0049 (11)	0.0114 (12)	−0.0007 (11)
C9	0.0533 (17)	0.0297 (14)	0.0399 (15)	−0.0023 (12)	0.0177 (14)	−0.0012 (11)
C10	0.0506 (17)	0.0366 (15)	0.0383 (15)	−0.0102 (13)	0.0125 (13)	−0.0093 (12)
C11	0.0470 (16)	0.0468 (17)	0.0282 (13)	−0.0035 (13)	0.0103 (12)	−0.0023 (12)
C12	0.0437 (15)	0.0326 (14)	0.0334 (14)	−0.0003 (11)	0.0165 (12)	0.0021 (11)
C13	0.0372 (14)	0.0331 (14)	0.0339 (14)	−0.0031 (11)	0.0097 (12)	−0.0041 (11)
C14	0.0479 (17)	0.0410 (16)	0.0379 (15)	−0.0020 (13)	0.0157 (13)	−0.0011 (13)
As1	0.0536 (2)	0.0445 (2)	0.04202 (19)	0.00445 (14)	0.01238 (15)	−0.00200 (13)
F1	0.127 (3)	0.096 (2)	0.144 (3)	−0.0092 (18)	0.093 (2)	−0.0450 (19)
F2	0.0750 (18)	0.236 (4)	0.0504 (15)	−0.020 (2)	−0.0051 (13)	−0.003 (2)
F3	0.114 (2)	0.0740 (17)	0.093 (2)	0.0031 (15)	0.0399 (17)	0.0327 (15)
F4	0.0696 (15)	0.102 (2)	0.0684 (15)	−0.0089 (14)	−0.0025 (13)	0.0133 (14)
F5	0.0957 (18)	0.0479 (12)	0.113 (2)	−0.0072 (12)	0.0505 (16)	−0.0014 (13)
F6	0.1012 (18)	0.0667 (14)	0.0728 (15)	0.0294 (13)	0.0410 (14)	0.0064 (11)

Geometric parameters (Å, º)

Ag1—N4^i	2.151 (3)	C4—C6	1.486 (4)
Ag1—N1^ii	2.293 (2)	C5—H5	0.9500
Ag1—O1	2.415 (2)	C7—C8	1.462 (4)
Ag1—N3	2.462 (2)	C7—H7	0.9500
N1—C5	1.334 (4)	C8—C13	1.391 (4)
N1—C1	1.339 (4)	C8—C9	1.395 (4)
N1—Ag1^iii	2.293 (2)	C9—C10	1.378 (4)
N2—C6	1.350 (4)	C9—H9	0.9500
N2—N3	1.381 (3)	C10—C11	1.384 (4)
N2—H14	0.8800	C10—H10	0.9500
N3—C7	1.272 (4)	C11—C12	1.397 (4)
N4—C14	1.131 (4)	C11—H11	0.9500
N4—Ag1^i	2.151 (3)	C12—C13	1.384 (4)
O1—C6	1.220 (3)	C12—C14	1.446 (4)
C1—C2	1.378 (5)	C13—H13	0.9500
C1—H1	0.9500	As1—F2	1.674 (3)
C2—C3	1.378 (5)	As1—F3	1.694 (3)
C2—H2	0.9500	As1—F1	1.694 (3)
C3—C4	1.379 (4)	As1—F6	1.707 (2)
C3—H3	0.9500	As1—F4	1.708 (2)
C4—C5	1.384 (4)	As1—F5	1.726 (2)
N4^i—Ag1—N1^ii	133.08 (10)	N3—C7—H7	120.0
N4^i—Ag1—O1	116.06 (10)	C8—C7—H7	120.0
N1^ii—Ag1—O1	104.56 (9)	C13—C8—C9	119.2 (3)
N4^i—Ag1—N3	129.89 (10)	C13—C8—C7	121.3 (3)
N1^ii—Ag1—N3	86.31 (9)	C9—C8—C7	119.4 (3)
O1—Ag1—N3	67.08 (7)	C10—C9—C8	120.8 (3)
C5—N1—C1	117.8 (3)	C10—C9—H9	119.6
C5—N1—Ag1^iii	120.4 (2)	C8—C9—H9	119.6
C1—N1—Ag1^iii	117.4 (2)	C9—C10—C11	120.4 (3)
C6—N2—N3	119.2 (2)	C9—C10—H10	119.8
C6—N2—H14	120.4	C11—C10—H10	119.8
N3—N2—H14	120.4	C10—C11—C12	118.8 (3)
C7—N3—N2	117.9 (2)	C10—C11—H11	120.6
C7—N3—Ag1	127.25 (19)	C12—C11—H11	120.6
N2—N3—Ag1	112.50 (17)	C13—C12—C11	121.2 (3)
C14—N4—Ag1^i	168.5 (3)	C13—C12—C14	118.8 (3)
C6—O1—Ag1	118.00 (19)	C11—C12—C14	120.0 (3)
N1—C1—C2	122.5 (3)	C12—C13—C8	119.5 (3)
N1—C1—H1	118.7	C12—C13—H13	120.2
C2—C1—H1	118.7	C8—C13—H13	120.2
C3—C2—C1	119.2 (3)	N4—C14—C12	178.6 (4)
C3—C2—H2	120.4	F2—As1—F3	91.25 (19)
C1—C2—H2	120.4	F2—As1—F1	91.49 (19)
C2—C3—C4	118.8 (3)	F3—As1—F1	90.14 (16)
C2—C3—H3	120.6	F2—As1—F6	90.17 (17)
C4—C3—H3	120.6	F3—As1—F6	92.47 (14)
C3—C4—C5	118.4 (3)	F1—As1—F6	176.88 (15)
C3—C4—C6	119.0 (3)	F2—As1—F4	177.93 (17)
C5—C4—C6	122.5 (3)	F3—As1—F4	90.50 (14)
N1—C5—C4	123.2 (3)	F1—As1—F4	89.62 (17)
N1—C5—H5	118.4	F6—As1—F4	88.64 (15)
C4—C5—H5	118.4	F2—As1—F5	90.40 (19)
O1—C6—N2	123.0 (3)	F3—As1—F5	177.99 (14)
O1—C6—C4	121.1 (3)	F1—As1—F5	88.68 (14)
N2—C6—C4	115.9 (2)	F6—As1—F5	88.67 (12)
N3—C7—C8	119.9 (3)	F4—As1—F5	87.87 (14)
C6—N2—N3—C7	−164.8 (3)	Ag1—O1—C6—C4	172.0 (2)
C6—N2—N3—Ag1	−0.8 (3)	N3—N2—C6—O1	5.1 (5)
N4^i—Ag1—N3—C7	−93.8 (3)	N3—N2—C6—C4	−173.6 (3)
N1^ii—Ag1—N3—C7	53.1 (3)	C3—C4—C6—O1	25.3 (5)
O1—Ag1—N3—C7	160.6 (3)	C5—C4—C6—O1	−150.9 (3)
N4^i—Ag1—N3—N2	104.0 (2)	C3—C4—C6—N2	−155.9 (3)
N1^ii—Ag1—N3—N2	−109.0 (2)	C5—C4—C6—N2	27.9 (4)
O1—Ag1—N3—N2	−1.54 (18)	N2—N3—C7—C8	179.0 (3)
N4^i—Ag1—O1—C6	−120.4 (2)	Ag1—N3—C7—C8	17.7 (4)
N1^ii—Ag1—O1—C6	83.7 (2)	N3—C7—C8—C13	29.0 (5)
N3—Ag1—O1—C6	4.2 (2)	N3—C7—C8—C9	−148.5 (3)
C5—N1—C1—C2	−2.2 (5)	C13—C8—C9—C10	−3.4 (4)
Ag1^iii—N1—C1—C2	154.4 (3)	C7—C8—C9—C10	174.1 (3)
N1—C1—C2—C3	0.5 (6)	C8—C9—C10—C11	1.4 (5)
C1—C2—C3—C4	1.5 (6)	C9—C10—C11—C12	1.2 (5)
C2—C3—C4—C5	−1.8 (5)	C10—C11—C12—C13	−1.8 (5)
C2—C3—C4—C6	−178.1 (3)	C10—C11—C12—C14	178.7 (3)
C1—N1—C5—C4	1.9 (5)	C11—C12—C13—C8	−0.2 (4)
Ag1^iii—N1—C5—C4	−154.0 (2)	C14—C12—C13—C8	179.3 (3)
C3—C4—C5—N1	0.1 (5)	C9—C8—C13—C12	2.8 (4)
C6—C4—C5—N1	176.3 (3)	C7—C8—C13—C12	−174.7 (3)
Ag1—O1—C6—N2	−6.7 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H14···F5^iv	0.88	2.25	2.975 (4)	140
N2—H14···F1^iv	0.88	2.47	3.308 (4)	159

Symmetry code: (iv) x, y−1, z.