Supra­molecular framework in catena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfin­yl)pyrimidine-κ³N,O:N′]

In the title complex, [Ag(NO₃)(C₉H₇N₃OS)]_n, η¹:η¹:η¹:μ₂-bridging 2-(pyridin-4-ylsulfin­yl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the Ag^I cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [01] direction. An FT–IR spectroscopic study shows a decreased stretching frequency for the η¹-O-bonded S=O group compared with that of the free ligand. The parallel chains are arranged and inter­connected via O(S=O)...π(pyridine/pyrimidine) and C—H(pyridine)...O(NO₃⁻) inter­actions to furnish a layer almost parallel to the ac plane. Along the b axis, the layers are stacked and stabilized through anion(NO₃⁻)...π(pyrimidine) inter­actions to form a three-dimensional supra­molecular framework. The ligand behaviour of the new diheterocyclic sulfoxide and the unconventional O(S=O)...π(pyridine/pyrimidine) and anion(NO₃⁻)...π(pyrimidine) inter­actions in the supra­molecular assembly of the title complex are presented.

S1. Comment

Sulfoxides with an asymmetric chiral centre have attracted enormous attention. The interest in these compounds stems from their important synthetic applications in asymmetric synthesis (Posner, 1988; Carreno, 1995) and potential applications in medicinal chemistry (Hogan et al., 2002; Pitchen et al.,1994). The coordination chemistry of sulfoxides with a symmetric or an asymmetric centre has also undergone phenomenal development. Much effort has been devoted to the investigation of the variable S═O dimensions of dialkyl sulfoxides upon metal coordination and their related properties (Cotton & Francis, 1960; Alessio, 2004). The C—S(O)—C fragment with C_s local symmetry endows the dialkyl sulfoxide with flexible coordination sites at the S and/or O atoms, exhibiting η¹-O-bonded, η¹-S-bonded and µ-S,O-bonded modes with diverse S═ O bond lengths (Calligaris, 2004; Kato et al., 2009). Grafting pyridine groups onto a definite organic fragment is a method generally used by supramolecular chemists to construct various coordination architectures with interesting properties. However, the use of a pyridine-based sulfoxide as a ligand to construct coordination supramolecular architectures remains almost unexplored, except for several well characterized complexes of diphenyl sulfoxide (L), such as HgCl₂(L) (Biscarini et al., 1973), (Et₄N)[PtCl₃(L)] (Kukushkin et al., 1992), K[PtCl₃(L)]₃.Me₂CO (de Almeida et al., 1992) and the metal complexes with dipyrazinyl sulfoxide reported by our group recently (Wan et al., 2010).

To enrich the coordination chemistry of sulfoxides based on pyridine, we report herein the synthesis and characterization of a new ligand, 2-(pyridin-4-ylsulfinyl)pyrimidine (pypmSO, pyridin-4-yl pyrimidin-2-yl sulfoxide), and its silver(I) complex, [Ag(NO₃)(pypmSO)]_n, (I). The pypmSO ligand, with one pyridine and one pyrimidine ring attached to the the S═O group, is to the best of our knowledge the first asymmetric diheterocyclic sulfoxide.

As shown in Fig. 1 and Table 1, the silver(I) centre of (I) (Ag1) is coordinated by a pyridine N1 atom of the pypmSO ligand at (x, y, z) with R chirality, a pyrimidine N2ⁱ atom and a sulfinyl O1ⁱ atom from a second ligand with S chirality [symmetry code: (i) x - 1, -y + 1/2, z + 1/2], and one nitrate O3 atom. The large O3—Ag1—O1ⁱ angle of 141.73 (17)° indicates the presence of a distorted pyramidal N₂O₂ coordination geometry. The pyrimidine N2 and sulfinyl O1 atoms of the pypmSO ligand are in a cis relationship, with an N2═ C6—S1═O1 torsion angle of -3.1 (4)°, and chelate to the Ag1 centre. The planes of the two heterocyclic wings attached to the sulfinyl group exhibit a dihedral angle of 84.14 (1)°. The η¹-O-bonded S1═ O1 distance is 1.494 (4) Å, which is slightly longer than the mean for η¹-S-bonded S═O [1.474 (7) Å], but shorter than the mean for η¹-O-bonded S═O [1.528 (1) Å] in metal complexes of dialkyl sulfoxides surveyed by Calligaris (2004). The latter difference can be ascribed to the diheterocyclic feature of pypmSO, which resembles that of η¹-O-bonded S═O [1.496 (3) Å] in {[Cd(pyz₂SO)₂(H₂O)](ClO₄)₂.H₂O}_n (pyz2SO is dipyrazinyl sulfoxide [dipyrazin-2-yl?]), another diheterocyclic sulfoxide complex reported by us (Wan et al., 2010). An IR spectroscopic study indicated that the ν(S═O) stretching frequency is smaller for the η¹-O-bonded pypmSO (1041 cm^-1) than for the free ligand (1060 cm^-1).

Regarding the ligation mode of pypmSO, each ligand links to two symmetry-related Ag^I ions through its pyridine N atom, one pyrimidine N atom and the sulfinyl O atom, thereby exhibiting an η¹:η¹:η¹:µ₂-bridging mode. The pyrimidine N and sulfinyl O atoms exhibit a κ²N,O-chelating mode. The S atom is not involved in any coordination bonding. The preferred O-bonded mode could derive from steric entropic contributions of the κ²N,O-chelating effect (Calligaris & Carugo, 1996). The different chiralities of the ligands in this centrosymmetric structure exhibit no influence on their ligation mode. Thus, pypmSO ligands with opposite chiralities are alternately arranged to link the Ag^I cations into an infinite zigzag coordination chain structure which extends parallel to the [201] direction, as shown in Fig. 2.

It is noteworthy that the parallel infinite chains thus formed are interconnected through two S═O···π(pyridine/pyrimidine) contacts between each S═O group of one chain and the pyridine and pyrimidine rings of an adjacent chain, as well as a C5—H5(pyridine)···O2ⁱⁱ(NO₃^-) interaction [symmetry code: (ii) x, -y + 1/2, z + 1/2; Table 2]. As shown in Fig. 3, each S═O group is embraced by two wings of one pypmSO ligand from an adjacent chain, with O1ⁱⁱⁱ···Cg1 and Oⁱⁱⁱ···Cg2 distances of 3.117 (3) and 3.217 (4) Å, respectively, and S1ⁱⁱⁱ—O1ⁱⁱⁱ···Cg1 = 101.97 (3)° and S1ⁱⁱⁱ—O1ⁱⁱⁱ···Cg2 = 99.07 (4)° [Cg1 is the centroid of the pyridine ring defined by atoms N1/C1/C2/C3/C4/C5 and Cg2 is the centroid of the pyrimidine ring defined by atoms C6/N2/C7/C8/C9/N3; symmetry code: (iii) x - 1, y, z]. These distances are shorter than the sum of the van der Waals radii (3.25 Å) of the contacting atoms [taking the half thickness of a phenyl ring as 1.85 Å (Malone et al., 1997) and the van der Waals radius of oxygen as 1.40 Å (Pauling, 1960)]. The O···centroid distances of the S═O···π contacts also lie well within the 2.8–3.5 Å range surveyed by us (Wan et al., 2009) through a thorough search of the Cambridge Structural Database (CSD, Version 5.22, January 2009 update [Most recent update?]; Allen, 2002). The corresponding O(S═ O)···C/N(closest ring atom) distances are 3.317 (4) (O1ⁱⁱⁱ···N3) and 3.313 (4) Å (O1ⁱⁱⁱ···C3). Such S═O···π contacts represent one type of lone-pair aromatic affinity (Egli & Sarkhel, 2007; Mooibroek, Gamez & Reedijk, 2008), an analogue of anion–π interactions with a bonding energy (20–50 kJ kcal mol^-1; 1 kcal mol^-1 = 4.184 kJ mol^-1) comparable with that of hydrogen bonding. A number of density functional theory (DFT) calculations (Alkorta et al., 2002; Quiñonero et al., 2002) and CSD database searches have indicated that such interactions play an important role in the inducement of supramolecuar assembly (Schottel et al., 2006; Zhou et al., 2007) and in molecular recognition (de Hoog et al., 2004; Fairchild & Holman, 2005). The present S═O···π contacts can be explained in terms of the electrostatic potentials of the sulfinyl O atom and local dipoles of the coordinated heterocyclic rings, as indicated by Gung et al. (2008) through a quantitative study of lone-pair aromatic interactions. Herein, due to the S═O···π affinity, two adjacent chains are stacked together, so the coordinated nitrate anion is pushed away, leading to the flattened pyramidal geometry of the Ag^I centre (Figs. 1 and 3).

A layer almost parallel to the ac plane is formed through the cooperative S═O···π and C—H···O(NO₃^-) interactions between successive chains (Fig. 4). The layers stack along the b axis and are further connected through anion(NO₃^-)···π(pyrimidine) interactions to form a three-dimensional supramolecular framework (Fig. 5). The O4^v(NO₃^-)···Cg2 distance in the anion···π interaction is 3.180 (3) Å [Fig. 6; N4^v—O4^v···Cg2 = 103.40 (3)°; symmetry code: (v) -x + 1, y - 1/2, -z + 1/2], which is comparable with the mean value of 3.190 Å found for O(NO₃^-)···centroid(pyrimidine) distances from a CSD statistical study conducted recently by Mooibroek, Black et al. (2008), but slightly longer than the mean value of 3.084 Å in O(NO₃^-)···centroid(1,2,4-triazine) systems, due to the less π-acidic nature of pyrazine than 1,2,4-triazine.

The solid-state structural analysis presented here thus provides further experimental evidence for unconventional lone pair–aromatic and anion···π interactions involving heterocycles.

Related literature

For related literature, see: Alessio (2004); Alkorta et al. (2002); Allen (2002); Almeida et al. (1992); Biscarini et al. (1973); Calligaris (2004); Calligaris & Carugo (1996); Carreno (1995); Cotton & Francis (1960); Egli & Sarkhel (2007); Fairchild & Holman (2005); Gung et al. (2008); Hogan et al. (2002); Hoog et al. (2004); Kato et al. (2009); Kukushkin et al. (1992); Malone et al. (1997); Mooibroek, Black, Gamez & Reedijk (2008); Mooibroek, Gamez & Reedijk (2008); Pauling (1960); Pitchen et al. (1994); Posner (1988); Quiñonero et al. (2002); Schottel et al. (2006); Wan et al. (2009, 2010); Zhou et al. (2007).

S2. Experimental

2-Bromopyrimidine (500 mg, 3.1 mmol) was added to a solution of sodium pyridine-4-thiolate (3 mmol) in ethanol (50 ml) at room temperature. The mixture was stirred for 10 h. After removal of the solvent [In vacuo? By Heating?], the resulting solid mixtures were separated and purified by column chromatography on silica gel (eluent dichloromethane/methanol = 95:5 v/v). 2-(Pyridin-4-ylsulfanyl)pyrimidine was obtained as a white powder (yield: 215.01 mg, 35%). Spectroscopic analysis: ¹H NMR (600M Hz, CDCl₃, δ, p.p.m.): 8.634 (s, 2H), 8.559–8.567 (d, J = 5 Hz, 2H), 7.609–7.617 (d, J = 5 Hz, 2H), 7.085–7.101 (t, J = 10 Hz, 1H). 2-(Pyridin-4-ylsulfinyl)pyrimidine was prepared following the procedure developed previously for dipyrazinyl sulfoxide (Wan et al., 2010), with 2-(pyridin-4-ylsulfanyl)pyrimidine as the starting material. Racemic 2-(pyridin-4-ylsulfinyl)pyrimidine was obtained as a yellow powder (yield 35%; m.p. 383–389 K). IR (KBr, ν, cm^-1): 1060 (vs) (S═O). 2-(Pyridin-4-ylsulfinyl)pyrimidine (20 mg, 0.1 mmol) and AgNO₃ (17 mg, 0.1 mmol) were added to acetonitrile (5 ml) and stirred at room temperature for 3 h. After filtration, slow evaporation of the filtrate yielded block-like yellow crystals of the title complex, (I), suitable for X-ray diffraction (yield 16.85 mg, 45%). Analysis, calculated (found) for C₉H₇AgN₄O₄S (%): C 28.82 (29.05), H 1.88 (1.85), N 14.94 (14.90). IR (KBr, ν, cm^-1): 1041 (vs) (S═O).

S3. Refinement

All H atoms were discernible in difference electron-density maps. They were subsequently added in idealized positions and allowed to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The largest peak and deepest hole of the residual electron density are within 0.8 Å of the Ag1 atom.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2009).

Figures

	Fig. 1. The Ag^I coordination environment of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) x - 1, -y + 1/2, z + 1/2.]
	Fig. 2. The extended zigzag chain structure of (I).
	Fig. 3. The S═O···π interactions in (I). Cg1 and Cg2 are the centroids of the pyridine and pyrimidine rings, respectively. [Symmetry codes: (iii) x - 1, y, z; (iv) x, -y + 1/2, z - 1/2.]
	Fig. 4. The layer almost parallel to the ac plane, constructed by the S═O···π (red dashed lines in the electronic version of the paper) and C—H···O (blue dashed lines) interactions between the chain motifs. The nitrate ligands are shown using thick bonds and all H atoms except that involved in hydrogen bonding have been omitted for clarity.
	Fig. 5. The anion(NO3^-)···π interactions (dashed lines) linking the layers stacked along the b axis.
	Fig. 6. A detailed view of the anion(NO3^-)···π(pyrimidine) interaction. Cg2 represents the centroid of the pyrimidine ring. [Symmetry code: (v) -x + 1, y - 1/2, -z + 1/2.]

catena-poly[[(nitrato-κO)silver(I)]-µ-(R,S)- 2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N']

Crystal data

[Ag(NO3)(C9H7N3OS)]	F(000) = 736
Mr = 375.12	Dx = 2.169 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 216 reflections
a = 4.9972 (1) Å	θ = 2.2–27.9°
b = 21.8972 (6) Å	µ = 1.95 mm^−1
c = 10.4994 (3) Å	T = 296 K
β = 90.668 (1)°	Block, yellow
V = 1148.82 (5) Å^3	0.36 × 0.20 × 0.12 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2737 independent reflections
Radiation source: fine-focus sealed tube	2513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→6
Tmin = 0.652, Tmax = 0.791	k = −28→27
20256 measured reflections	l = −13→13

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0637P)^2 + 2.9205P] where P = (Fo^2 + 2Fc^2)/3
2737 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 1.81 e Å^−3
0 restraints	Δρmin = −1.56 e Å^−3

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	0.14570 (8)	0.346987 (19)	0.59538 (4)	0.05956 (17)
S1	1.0697 (2)	0.13542 (5)	0.42376 (10)	0.0408 (2)
O1	1.2438 (6)	0.16867 (16)	0.3321 (3)	0.0509 (7)
C1	0.6279 (9)	0.2882 (2)	0.4531 (4)	0.0467 (9)
H1	0.6161	0.3251	0.4098	0.056*
C2	0.8164 (9)	0.2460 (2)	0.4145 (4)	0.0445 (9)
H2	0.9319	0.2547	0.3480	0.053*
C3	0.8279 (8)	0.19082 (18)	0.4773 (4)	0.0372 (8)
C4	0.6625 (9)	0.1796 (2)	0.5791 (4)	0.0431 (9)
H4	0.6709	0.1429	0.6238	0.052*
C5	0.4823 (9)	0.2255 (2)	0.6123 (4)	0.0468 (10)
H5	0.3709	0.2189	0.6813	0.056*
C6	0.8241 (8)	0.09190 (17)	0.3285 (4)	0.0361 (7)
C7	0.6465 (9)	0.0651 (2)	0.1390 (4)	0.0440 (9)
H7	0.6392	0.0679	0.0507	0.053*
C8	0.4710 (9)	0.0273 (2)	0.2002 (5)	0.0480 (10)
H8	0.3430	0.0050	0.1551	0.058*
N3	0.6707 (8)	0.05667 (17)	0.3973 (3)	0.0445 (8)
N1	0.4623 (7)	0.27834 (17)	0.5496 (3)	0.0450 (8)
C9	0.4911 (10)	0.0236 (2)	0.3305 (5)	0.0485 (10)
H9	0.3772	−0.0026	0.3738	0.058*
N2	0.8301 (7)	0.09850 (15)	0.2042 (3)	0.0384 (7)
N4	0.0953 (8)	0.40869 (18)	0.3220 (4)	0.0483 (8)
O2	0.183 (2)	0.3610 (4)	0.3070 (10)	0.182 (5)
O3	0.0806 (17)	0.4309 (3)	0.4289 (5)	0.127 (3)
O4	0.0188 (13)	0.4358 (3)	0.2239 (5)	0.0975 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0544 (3)	0.0627 (3)	0.0618 (3)	0.01872 (17)	0.00948 (18)	−0.01192 (17)
S1	0.0341 (5)	0.0468 (5)	0.0415 (5)	0.0059 (4)	−0.0020 (4)	−0.0078 (4)
O1	0.0374 (15)	0.0587 (18)	0.0566 (19)	−0.0063 (13)	0.0084 (13)	−0.0125 (15)
C1	0.051 (2)	0.044 (2)	0.045 (2)	0.0063 (18)	−0.0005 (18)	−0.0021 (17)
C2	0.042 (2)	0.049 (2)	0.043 (2)	0.0014 (17)	0.0045 (16)	−0.0002 (17)
C3	0.0342 (17)	0.0416 (19)	0.0357 (18)	0.0032 (15)	−0.0031 (14)	−0.0094 (15)
C4	0.049 (2)	0.047 (2)	0.0324 (18)	0.0081 (18)	−0.0011 (16)	−0.0024 (16)
C5	0.047 (2)	0.062 (3)	0.0313 (19)	0.009 (2)	0.0019 (16)	−0.0051 (18)
C6	0.0358 (18)	0.0359 (17)	0.0368 (18)	0.0033 (14)	0.0023 (14)	−0.0032 (14)
C7	0.048 (2)	0.048 (2)	0.0359 (19)	−0.0042 (18)	0.0012 (16)	−0.0054 (17)
C8	0.049 (2)	0.042 (2)	0.052 (2)	−0.0074 (18)	0.0005 (19)	−0.0100 (18)
N3	0.052 (2)	0.0419 (18)	0.0393 (18)	−0.0033 (15)	0.0078 (15)	0.0017 (14)
N1	0.0446 (19)	0.050 (2)	0.0400 (18)	0.0108 (15)	−0.0035 (14)	−0.0103 (15)
C9	0.053 (2)	0.041 (2)	0.052 (2)	−0.0080 (18)	0.0112 (19)	0.0018 (18)
N2	0.0403 (17)	0.0393 (16)	0.0357 (16)	−0.0038 (13)	0.0047 (13)	−0.0005 (13)
N4	0.053 (2)	0.0435 (19)	0.049 (2)	0.0016 (16)	0.0066 (16)	−0.0003 (16)
O2	0.250 (11)	0.122 (6)	0.173 (8)	0.119 (7)	−0.028 (8)	−0.012 (6)
O3	0.195 (8)	0.124 (5)	0.063 (3)	−0.007 (5)	0.035 (4)	−0.007 (3)
O4	0.120 (4)	0.103 (4)	0.070 (3)	0.010 (3)	−0.023 (3)	0.015 (3)

Geometric parameters (Å, º)

Ag1—N1	2.238 (4)	C5—N1	1.335 (6)
Ag1—N2^i	2.293 (3)	C5—H5	0.9300
Ag1—O1^i	2.551 (3)	C6—N3	1.310 (5)
Ag1—O3	2.554 (7)	C6—N2	1.314 (5)
S1—O1	1.494 (4)	C7—N2	1.353 (5)
S1—C3	1.806 (4)	C7—C8	1.371 (6)
S1—C6	1.840 (4)	C7—H7	0.9300
O1—Ag1^ii	2.551 (3)	C8—C9	1.372 (7)
C1—N1	1.333 (6)	C8—H8	0.9300
C1—C2	1.383 (6)	N3—C9	1.345 (6)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.378 (6)	N2—Ag1^ii	2.293 (3)
C2—H2	0.9300	N4—O2	1.145 (7)
C3—C4	1.382 (6)	N4—O3	1.226 (7)
C4—C5	1.396 (6)	N4—O4	1.245 (6)
C4—H4	0.9300
N1—Ag1—N2^i	161.48 (13)	C4—C5—H5	118.5
N1—Ag1—O1^i	89.46 (12)	N3—C6—N2	129.2 (4)
N2^i—Ag1—O1^i	73.13 (11)	N3—C6—S1	113.3 (3)
N1—Ag1—O3	114.89 (19)	N2—C6—S1	117.4 (3)
N2^i—Ag1—O3	83.33 (18)	N2—C7—C8	121.5 (4)
O1^i—Ag1—O3	141.73 (17)	N2—C7—H7	119.2
O1—S1—C3	105.6 (2)	C8—C7—H7	119.2
O1—S1—C6	106.97 (18)	C7—C8—C9	117.6 (4)
C3—S1—C6	94.17 (17)	C7—C8—H8	121.2
S1—O1—Ag1^ii	117.09 (17)	C9—C8—H8	121.2
N1—C1—C2	123.1 (4)	C6—N3—C9	114.9 (4)
N1—C1—H1	118.4	C1—N1—C5	118.1 (4)
C2—C1—H1	118.4	C1—N1—Ag1	120.1 (3)
C3—C2—C1	118.0 (4)	C5—N1—Ag1	121.7 (3)
C3—C2—H2	121.0	N3—C9—C8	121.9 (4)
C1—C2—H2	121.0	N3—C9—H9	119.1
C2—C3—C4	120.3 (4)	C8—C9—H9	119.1
C2—C3—S1	117.7 (3)	C6—N2—C7	114.8 (3)
C4—C3—S1	122.0 (3)	C6—N2—Ag1^ii	125.2 (3)
C3—C4—C5	117.3 (4)	C7—N2—Ag1^ii	119.7 (3)
C3—C4—H4	121.4	O2—N4—O3	121.0 (7)
C5—C4—H4	121.4	O2—N4—O4	115.9 (7)
N1—C5—C4	123.1 (4)	O3—N4—O4	123.1 (6)
N1—C5—H5	118.5	N4—O3—Ag1	109.4 (5)
C3—S1—O1—Ag1^ii	−100.0 (2)	C4—C5—N1—C1	−1.9 (6)
C6—S1—O1—Ag1^ii	−0.5 (2)	C4—C5—N1—Ag1	174.4 (3)
N1—C1—C2—C3	1.6 (7)	N2^i—Ag1—N1—C1	−158.6 (4)
C1—C2—C3—C4	−2.7 (6)	O1^i—Ag1—N1—C1	−139.0 (3)
C1—C2—C3—S1	178.6 (3)	O3—Ag1—N1—C1	10.5 (4)
O1—S1—C3—C2	10.0 (4)	N2^i—Ag1—N1—C5	25.1 (6)
C6—S1—C3—C2	−98.9 (3)	O1^i—Ag1—N1—C5	44.7 (3)
O1—S1—C3—C4	−168.6 (3)	O3—Ag1—N1—C5	−165.8 (3)
C6—S1—C3—C4	82.4 (4)	C6—N3—C9—C8	−0.5 (7)
C2—C3—C4—C5	1.6 (6)	C7—C8—C9—N3	1.7 (7)
S1—C3—C4—C5	−179.8 (3)	N3—C6—N2—C7	1.8 (6)
C3—C4—C5—N1	0.8 (7)	S1—C6—N2—C7	179.6 (3)
O1—S1—C6—N3	175.0 (3)	N3—C6—N2—Ag1^ii	−171.9 (3)
C3—S1—C6—N3	−77.2 (3)	S1—C6—N2—Ag1^ii	5.9 (4)
O1—S1—C6—N2	−3.1 (4)	C8—C7—N2—C6	−0.4 (6)
C3—S1—C6—N2	104.7 (3)	C8—C7—N2—Ag1^ii	173.6 (3)
N2—C7—C8—C9	−1.2 (7)	O2—N4—O3—Ag1	−15.3 (10)
N2—C6—N3—C9	−1.4 (7)	O4—N4—O3—Ag1	165.0 (5)
S1—C6—N3—C9	−179.2 (3)	N1—Ag1—O3—N4	40.3 (6)
C2—C1—N1—C5	0.7 (7)	N2^i—Ag1—O3—N4	−143.2 (6)
C2—C1—N1—Ag1	−175.7 (3)	O1^i—Ag1—O3—N4	165.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^iii	0.93	2.39	3.173 (10)	142

Symmetry code: (iii) x, −y+1/2, z+1/2.