catena-Poly[[silver(I)-[mu]-1,3-bis­(4-pyrid­yl)propane] hemi(naphthalene-1,5-disulfonate) dihydrate]: a three-dimensional metallo-supra­molecular sandwich lamellar network

The title compound, {[Ag(C₁₃H₁₄N₂)](C₁₀H₆O₆S₂)_0.5·2H₂O}_n, (I), features a three-dimensional supra­molecular sandwich architecture that consists of two-dimensional cationic layers composed of polymeric chains of silver(I) ions and 1,3-bis­(4-pyrid­yl)propane (bpp) ligands, linked by Ag...Ag and [pi]-[pi] inter­actions, alternating with anionic layers in which uncoordinated naphthalene-1,5-disulfonate (nds^2-) anions and solvent water mol­ecules form a hydrogen-bonded network. The asymmetric unit consists of one Ag^I cation linearly coordinated by N atoms from two bpp ligands, one bpp ligand, one half of an nds^2- anion lying on a centre of inversion and two solvent water mol­ecules. The two-dimensional {[Ag(bpp)]⁺}_n cationic and {[(nds)·2H₂O]^2-}_n anionic layers are assembled into a three-dimensional supra­molecular framework through long secondary coordination Ag...O inter­actions between the sulfonate O atoms and Ag^I centres and through nonclassical C-H...O hydrogen bonds.

S1. Comment

The construction of coordination polymers and supramolecular compounds based on multitopic ligands and metal centres represents one of the most rapidly developing fields in current coordination chemistry, owing to their potential as functional materials (Blake et al., 1999, 2000; Kitagawa et al., 2004). In the past few years, supramolecular self-assembly chemistry has developed to allow the rational design and preparation of supramolecular architectures through non-covalent interactions, in which it is crucial to meet both geometric and energetic prerequisties (Pedireddi et al., 1996). The hydrogen bond is undoubtedly the most familiar secondary force in supramolecular assemblies, due to its moderately directional intermolecular interaction which may control molecular packing (Zartilas et al., 2007), and many studies have focused on it (Lough et al., 2000; Massoud & Langer, 2009). Compared with hydrogen bonds, π–π and metal–metal interactions have been somewhat less studied and only limited examples generated by a combination of multi-supramolecular interactions have been reported (Goodgame et al., 2002). The naphthalene-1,5-disulfonate anion (nds^2-), which possesses six O atoms, has been employed either as a ligand, with multiple binding sites available to construct coordination polymers with varying dimensionalities (Cai, 2004; Lian et al., 2007), or as a counterion, forming extensive hydrogen-bonding interactions with other species (Sakwa & Wheeler, 2003; Voogt & Blanch, 2005). Recently, we have pursued systematic investigations into the assembly of Ag^I cations with different angular and linear bipodal N-donor ligands, such as rigid aminopyrimidine (Luo, Huang, Zhang et al., 2008; Luo, Huang, Chen et al., 2008; Luo et al., 2009, 2010) and flexible 1,3-bis(4-pyridyl)propane (bpp) or 1,2-bis(4-pyridyl)ethane (bpe) (Luo, Xiong, Dai et al., 2011; Luo, Xiong, Sun et al., 2011; Xiong et al., 2011), with the principal aim of obtaining supramolecular frameworks or multifunctional coordination polymers. In an attempt to exploit the Ag–disulfonate–bpp system, we successfully obtained the title compound, (I), by the solution-phase ultrasonic synthesis technique, and we report its crystal structure here.

Compound (I) crystallizes in the monoclinic space group P2₁/n with an asymmetric unit comprising an Ag^I cation, one half of an nds^2- anion situated on a centre of inversion, a bpp ligand and two solvent water molecules (Fig. 1). The Ag^I centre is linearly coordinated by two symmetry-independent N atoms from two bpp ligands [Ag1—N1 = 2.125 (2), Ag1—N2ⁱ = 2.135 (2) Å and N1—Ag1—N2ⁱ = 171.16 (7)°; symmetry code: (i) x - 1/2, -y + 3/2, z + 1/2]. The average Ag—N distance is comparable with those in previously reported Ag-based compounds (Hao et al., 2009), where the Ag^I cations have similar coordination geometries.

Generally, the flexible pyridyl-containing bpp ligand can assume four different conformations (TT, 9.1–10.1 Å; TG, 8.6–9.2 Å; GG, 6.7–8.6 Å; and GG, 3.9 Å, where T = trans, G = gauche, and the expected ranges in N···N separations are shown) with respect to the relative orientations of the methylene groups (Carlucci et al., 2002). In (I), each bpp ligand adopts a TG conformation with an N···N separation of 8.678 (2) Å and bridges two different metal centres, yielding one-dimensional sinusoidal cationic chains with Ag(bpp) repeating units [period 23.439 (6) Å]. Adjacent one-dimensional cationic chains interact with each other through Ag···Ag interactions to generate a two-dimensional cationic undulating brick-wall layer of composition {[Ag(bpp)]⁺}_n approximately in the bc plane (Fig. 2). The Ag···Ag separation of 3.0718 (6) Å in (I) is notably shorter than the sum of the van der Waals radii of two Ag⁺ ions (3.44 Å; Bondi, 1964), indicating the presence of argentophilic interactions (Pyykkö, 1997).

Among the known structures containing the flexible bpp ligand, similar undulating chains have been found in [Ag(bpp)](CFSO₃).EtOH and [Ag(bpp)]NO₃ (Carlucci et al., 1997; Bateen et al., 1999), but no metal–metal interactions were found in these compounds, in which the shortest Ag···Ag separations are 4.664 (1) Å in the former and 5.287 (2) Å in the latter. The structure of [Ag(bpp)]PF₆ is similar to (I) in that the Ag···Ag contact is 3.0852 (9) Å, but the bpp in [Ag(bpp)]PF₆ assumes a TT conformation with an N···N separation of 9.699 (7) Å (Pan et al., 2001). Besides argentophilic interactions, aromatic π–π stacking interactions, with centroid-to-centroid distances ranging from 3.6099 (6) to 3.8345 (6) Å between the pyridyl rings of neighbouring bpp ligands, also exist between the chains in (I), helping to consolidate the resulting two-dimensional layer. Topologically, if we define the bpp ligands as single spacers connecting the silver(I) centres, this type of layer can be classified as an example of a (6,3) net.

The H₂nds molecule is completely deprotonated to generate the nds^2- anion during the synthesis reaction. Each nds^2- anion is positioned on an inversion centre and serves as a counteranion to balance the polymeric host charge, while not participating in primary coordination to any Ag^I centres, reflecting the fact that the coordination ability of bpp is stronger than that of the nds^2- anion in this case. Water dimers composed of molecules O1W and O2W are crosslinked with the nds^2- sulfonate groups via strong intermolecular O—H···O hydrogen bonds (Table 1), giving rise to anionic double chains that are interconnected by O2W–H2WA···O1^vi [symmetry code: (vi) -x + 1/2, y + 1/2, -z + 1/2] hydrogen bonds to form an ordered two-dimensional water–nds anionic layer, {[(nds).2H₂O]^2-}_n (Fig. 3), parallel to the cationic {[Ag(bpp)]⁺}_n sheet. The hydrogen-bond motif R₅⁴(12) (Bernstein et al., 1995), constructed through water molecules and nds^2- sulfonate groups, can be found between the double chains.

The two-dimensional cationic and anionic layers in (I) are stacked following an alternating –ABAB– sequence, resulting in a three-dimensional metallo-supramolecular sandwich lamellar network, in which the water–anion layered species occupy the interlayer spacings between the metallo-organic networks (Fig. 4). Weak interactions between the sulfonate O atom and the Ag^I centre are present in the three-dimensional supramolecular framework. Compared with normal Ag—O coordination bonds in silver sulfonates spanning the range 2.377 (3)-2.574 (4) Å (Gao et al., 2005; Lian et al., 2007), the present Ag···O interactions of 2.7923 (6) Å are a little longer but still fall in the secondary-bonding range (the sum of the van der Waals radii of Ag and O is 3.24 Å; Bondi, 1964). Previously reported Ag(bpp) salts with simple inorganic anions (such as PF₆^-, ClO₄^-, NO₃^- etc.) do not exhibit these alternating cation–anion layers. Other Ag(bpp) salts containing non-coordinated organic carboxylates as counteranions (such as succinate) display similar –ABAB– stacking of cationic and anionic sheets (Luo, Xiong, Sun et al., 2011), but the main difference is that the layers are primarily linked by O—H···O hydrogen bonds between water molecules coordinated to the Ag^I cations and the carboxylate groups, instead of by long interlayer Ag···O interactions such as those found in (I).

Related literature

For related literature, see: Bateen et al. (1999); Bernstein et al. (1995); Blake et al. (1999, 2000); Bondi (1964); Cai (2004); Carlucci et al. (1997, 2002); Gao et al. (2005); Goodgame et al. (2002); Hao et al. (2009); Kitagawa et al. (2004); Lian et al. (2007); Lough et al. (2000); Luo et al. (2009, 2010); Luo, Huang, Chen, Lin & Zheng (2008); Luo, Huang, Zhang, Lin & Zheng (2008); Luo, Xiong & Dai (2011); Luo, Xiong, Sun, Wu, Huang & Dai (2011); Massoud & Langer (2009); Pan et al. (2001); Pedireddi et al. (1996); Pyykkö (1997); Sakwa & Wheeler (2003); Voogt & Blanch (2005); Xiong et al. (2011); Zartilas (2007).

S2. Experimental

A mixture of Ag₂O (115 mg, 0.5 mmol), 1,3-bis(4-pyridyl)propane (205 mg, 1 mmol) and 1,5-naphthalenedisulfonic acid (280 mg, 1 mmol) in CH₃OH–H₂O (10 ml, 1:4 v/v) was subjected to ultrasonic treatment at ambient temperature for 10 min. Aqueous NH₃ (25%) was then added dropwise to the mixture to give a clear solution. The resulting solution was protected from light and allowed to evaporate slowly at room temperature. Colourless crystals of (I) were isolated after 6 d (yield 45% based on Ag₂O). Analysis, calculated for C₁₈H₂₁AgN₂O₅S: C 44.55, H 4.36, N 5.77%; found: C 44.36, H 4.41, N 5.81%.

S3. Refinement

All water H atoms were positioned from difference Fourier maps and included as riding atoms, with O—H = 0.85 Å and U_iso(H) = 1.2U_eq(O). C-bound H atoms were placed in calculated riding positions, with C—H = 0.95 (aromatic) or 0.99 Å (methyl) and U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure and atom-labelling scheme of (I), showing the coordination environment of the Ag^I centre. Displacement ellipsoids are drawn at the ??% probability level. [Please complete] [Symmetry codes: (i) x - 1/2, -y + 3/2, z + 1/2; (iv) -x, -y + 1, -z + 1.]
	Fig. 2. A view of the two-dimensional undulating cationic {[Ag(bpp)]^+}n layer, with the interchain Ag···Ag [A = 3.0718 (6) Å] and π–π interactions [B = 3.6099 (6) Å and C = 3.8345 (6) Å] shown as dadshed lines. [Symmetry code: (ii) -x + 1, -y + 1, -z + 1.]
	Fig. 3. A view of the two-dimensional water–nds anionic sheet, {[(nds).2H2O]^2-}n, constructed by double anion chains linked by hydrogen bonds (dotted lines). [Symmetry code: (vi) -x + 1/2, y + 1/2, -z + 1/2.]
	Fig. 4. The three-dimensional metallo-supramolecular sandwich-like network of (I) constructed from two-dimensional {[Ag(bpp)]^+}n and {[(nds).2H2O]^2-}n layers through Ag···O interactions (thick dashed lines).

catena-Poly[[silver(I)-µ-1,3-bis(4-pyridyl)propane] hemi(naphthalene-1,5-disulfonate) dihydrate]

Crystal data

[Ag(C13H14N2)](C10H6O6S2)0.5·2H2O	F(000) = 984
Mr = 485.30	Dx = 1.726 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 15345 reflections
a = 10.640 (2) Å	θ = 5.5–56.8°
b = 9.2720 (19) Å	µ = 1.22 mm^−1
c = 19.194 (4) Å	T = 173 K
β = 99.55 (3)°	Plate, colourless
V = 1867.4 (6) Å^3	0.19 × 0.16 × 0.09 mm
Z = 4

Data collection

Oxford Gemini S Ultra diffractometer	3666 independent reflections
Radiation source: fine-focus sealed tube	3398 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 26.0°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	h = −13→12
Tmin = 0.801, Tmax = 0.898	k = −10→11
13094 measured reflections	l = −23→23

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)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0273P)^2 + 1.4469P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
3666 reflections	Δρmax = 0.55 e Å^−3
245 parameters	Δρmin = −0.94 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: 0.0091 (5)

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	0.455371 (19)	0.624463 (19)	0.542728 (9)	0.03071 (9)
N1	0.50747 (19)	0.7807 (2)	0.47167 (10)	0.0242 (4)
N2	0.89809 (19)	1.0048 (2)	0.12405 (10)	0.0241 (4)
C6	0.4456 (2)	0.7965 (2)	0.40516 (12)	0.0244 (5)
H6A	0.3739	0.7369	0.3893	0.029*
C7	0.4822 (2)	0.8963 (2)	0.35890 (12)	0.0239 (5)
H7A	0.4354	0.9046	0.3124	0.029*
C8	0.5874 (2)	0.9846 (2)	0.38001 (11)	0.0219 (5)
C9	0.6500 (2)	0.9683 (2)	0.44929 (12)	0.0255 (5)
H9A	0.7215	1.0270	0.4667	0.031*
C10	0.6077 (2)	0.8666 (2)	0.49267 (12)	0.0266 (5)
H10A	0.6519	0.8573	0.5397	0.032*
C11	0.6282 (2)	1.0906 (3)	0.32836 (12)	0.0259 (5)
H11A	0.5618	1.1660	0.3183	0.031*
H11B	0.6317	1.0392	0.2835	0.031*
C12	0.7561 (2)	1.1643 (2)	0.35204 (12)	0.0249 (5)
H12A	0.8221	1.0898	0.3660	0.030*
H12B	0.7507	1.2245	0.3940	0.030*
C13	0.7961 (2)	1.2594 (2)	0.29392 (12)	0.0261 (5)
H13A	0.7252	1.3255	0.2755	0.031*
H13B	0.8703	1.3188	0.3145	0.031*
C14	0.8303 (2)	1.1719 (2)	0.23389 (11)	0.0215 (4)
C15	0.9413 (2)	1.0900 (3)	0.24266 (12)	0.0254 (5)
H15A	0.9964	1.0899	0.2870	0.031*
C16	0.9719 (2)	1.0094 (2)	0.18824 (12)	0.0262 (5)
H16A	1.0484	0.9545	0.1960	0.031*
C17	0.7913 (2)	1.0835 (3)	0.11507 (12)	0.0270 (5)
H17A	0.7382	1.0821	0.0701	0.032*
C18	0.7541 (2)	1.1667 (2)	0.16777 (12)	0.0260 (5)
H18A	0.6768	1.2200	0.1589	0.031*
O1	0.21665 (17)	0.25635 (17)	0.35755 (8)	0.0296 (4)
O2	0.29815 (15)	0.47979 (17)	0.41289 (9)	0.0282 (4)
O3	0.11503 (16)	0.48200 (17)	0.31876 (8)	0.0273 (4)
C1	0.0845 (2)	0.3843 (2)	0.44168 (10)	0.0171 (4)
C2	0.0555 (2)	0.2488 (2)	0.46246 (11)	0.0206 (4)
H2A	0.0869	0.1666	0.4412	0.025*
C3	0.0212 (2)	0.7694 (2)	0.48456 (11)	0.0218 (5)
H3A	0.0411	0.8639	0.4706	0.026*
C4	0.0668 (2)	0.6530 (2)	0.45328 (11)	0.0201 (4)
H4A	0.1180	0.6671	0.4178	0.024*
C5	0.03842 (19)	0.5103 (2)	0.47328 (10)	0.0161 (4)
S1	0.18676 (5)	0.40246 (5)	0.37745 (3)	0.01914 (13)
O1W	0.16149 (18)	−0.04413 (18)	0.37627 (9)	0.0354 (4)
H1WA	0.1796	0.0418	0.3661	0.042*
H1WB	0.1704	−0.0986	0.3418	0.042*
O2W	0.1826 (2)	0.75097 (18)	0.27239 (10)	0.0417 (5)
H2WA	0.2119	0.7462	0.2339	0.050*
H2WB	0.1638	0.6662	0.2841	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.04047 (15)	0.02924 (13)	0.02606 (12)	0.00629 (7)	0.01622 (9)	0.00518 (7)
N1	0.0274 (11)	0.0269 (9)	0.0200 (9)	0.0060 (8)	0.0094 (8)	0.0009 (7)
N2	0.0257 (11)	0.0273 (10)	0.0206 (9)	−0.0041 (8)	0.0081 (8)	0.0002 (7)
C6	0.0213 (12)	0.0253 (11)	0.0271 (12)	0.0021 (8)	0.0057 (9)	−0.0006 (9)
C7	0.0220 (12)	0.0266 (11)	0.0228 (11)	0.0028 (9)	0.0027 (9)	−0.0006 (9)
C8	0.0203 (12)	0.0236 (10)	0.0227 (11)	0.0043 (8)	0.0059 (9)	−0.0013 (8)
C9	0.0223 (13)	0.0288 (11)	0.0252 (11)	0.0006 (9)	0.0032 (9)	−0.0038 (9)
C10	0.0300 (14)	0.0326 (12)	0.0171 (11)	0.0060 (10)	0.0037 (9)	−0.0012 (9)
C11	0.0244 (13)	0.0319 (12)	0.0216 (11)	−0.0015 (9)	0.0040 (9)	0.0025 (9)
C12	0.0260 (13)	0.0289 (11)	0.0213 (11)	−0.0006 (9)	0.0078 (9)	−0.0035 (9)
C13	0.0267 (13)	0.0246 (11)	0.0288 (12)	−0.0017 (9)	0.0094 (10)	−0.0033 (9)
C14	0.0206 (12)	0.0202 (10)	0.0252 (11)	−0.0036 (8)	0.0080 (9)	0.0023 (8)
C15	0.0205 (12)	0.0348 (12)	0.0203 (11)	0.0019 (9)	0.0009 (9)	0.0016 (9)
C16	0.0207 (13)	0.0320 (12)	0.0269 (12)	0.0047 (9)	0.0062 (9)	0.0025 (9)
C17	0.0250 (13)	0.0341 (12)	0.0208 (11)	−0.0033 (10)	0.0002 (9)	0.0019 (9)
C18	0.0171 (12)	0.0303 (11)	0.0299 (12)	0.0015 (9)	0.0016 (9)	0.0041 (9)
O1	0.0412 (11)	0.0234 (8)	0.0283 (8)	0.0031 (7)	0.0184 (8)	−0.0005 (6)
O2	0.0181 (9)	0.0326 (8)	0.0355 (9)	−0.0033 (7)	0.0089 (7)	−0.0012 (7)
O3	0.0359 (10)	0.0301 (8)	0.0168 (7)	0.0009 (7)	0.0068 (7)	0.0042 (6)
C1	0.0144 (11)	0.0236 (10)	0.0133 (9)	0.0001 (8)	0.0023 (8)	−0.0006 (7)
C2	0.0187 (12)	0.0203 (10)	0.0232 (11)	0.0001 (8)	0.0045 (9)	−0.0027 (8)
C3	0.0229 (12)	0.0185 (10)	0.0249 (11)	−0.0033 (8)	0.0063 (9)	0.0024 (8)
C4	0.0174 (11)	0.0223 (10)	0.0208 (10)	−0.0030 (8)	0.0043 (8)	0.0022 (8)
C5	0.0130 (11)	0.0201 (10)	0.0144 (9)	−0.0005 (8)	−0.0001 (8)	0.0005 (7)
S1	0.0206 (3)	0.0208 (3)	0.0179 (3)	0.00009 (19)	0.0087 (2)	0.00049 (19)
O1W	0.0444 (12)	0.0287 (9)	0.0362 (10)	0.0007 (8)	0.0156 (8)	0.0007 (7)
O2W	0.0702 (15)	0.0273 (9)	0.0334 (9)	−0.0045 (9)	0.0256 (9)	0.0001 (7)

Geometric parameters (Å, º)

Ag1—N1	2.1250 (19)	C14—C15	1.391 (3)
Ag1—N2^i	2.1353 (19)	C14—C18	1.389 (3)
Ag1—Ag1^ii	3.0718 (6)	C15—C16	1.367 (3)
N1—C10	1.339 (3)	C15—H15A	0.9500
N1—C6	1.344 (3)	C16—H16A	0.9500
N2—C17	1.338 (3)	C17—C18	1.381 (3)
N2—C16	1.348 (3)	C17—H17A	0.9500
N2—Ag1^iii	2.1353 (19)	C18—H18A	0.9500
C6—C7	1.382 (3)	O1—S1	1.4570 (16)
C6—H6A	0.9500	O2—S1	1.4540 (17)
C7—C8	1.391 (3)	O3—S1	1.4526 (16)
C7—H7A	0.9500	C1—C2	1.369 (3)
C8—C9	1.393 (3)	C1—C5	1.440 (3)
C8—C11	1.510 (3)	C1—S1	1.782 (2)
C9—C10	1.382 (3)	C2—C3^iv	1.415 (3)
C9—H9A	0.9500	C2—H2A	0.9500
C10—H10A	0.9500	C3—C4	1.364 (3)
C11—C12	1.523 (3)	C3—C2^iv	1.415 (3)
C11—H11A	0.9900	C3—H3A	0.9500
C11—H11B	0.9900	C4—C5	1.423 (3)
C12—C13	1.537 (3)	C4—H4A	0.9500
C12—H12A	0.9900	C5—C5^iv	1.427 (4)
C12—H12B	0.9900	O1W—H1WA	0.8499
C13—C14	1.502 (3)	O1W—H1WB	0.8499
C13—H13A	0.9900	O2W—H2WA	0.8503
C13—H13B	0.9900	O2W—H2WB	0.8501
N1—Ag1—N2^i	171.16 (7)	C12—C13—H13B	109.2
N1—Ag1—Ag1^ii	91.88 (5)	H13A—C13—H13B	107.9
N2^i—Ag1—Ag1^ii	96.87 (5)	C15—C14—C18	116.5 (2)
C10—N1—C6	117.5 (2)	C15—C14—C13	120.7 (2)
C10—N1—Ag1	119.48 (15)	C18—C14—C13	122.7 (2)
C6—N1—Ag1	123.05 (16)	C16—C15—C14	120.8 (2)
C17—N2—C16	117.0 (2)	C16—C15—H15A	119.6
C17—N2—Ag1^iii	123.46 (15)	C14—C15—H15A	119.6
C16—N2—Ag1^iii	119.49 (16)	N2—C16—C15	122.6 (2)
N1—C6—C7	122.5 (2)	N2—C16—H16A	118.7
N1—C6—H6A	118.7	C15—C16—H16A	118.7
C7—C6—H6A	118.7	N2—C17—C18	123.4 (2)
C6—C7—C8	120.4 (2)	N2—C17—H17A	118.3
C6—C7—H7A	119.8	C18—C17—H17A	118.3
C8—C7—H7A	119.8	C17—C18—C14	119.6 (2)
C7—C8—C9	116.6 (2)	C17—C18—H18A	120.2
C7—C8—C11	119.8 (2)	C14—C18—H18A	120.2
C9—C8—C11	123.6 (2)	C2—C1—C5	120.89 (19)
C10—C9—C8	119.8 (2)	C2—C1—S1	118.78 (16)
C10—C9—H9A	120.1	C5—C1—S1	120.26 (15)
C8—C9—H9A	120.1	C1—C2—C3^iv	120.23 (19)
N1—C10—C9	123.2 (2)	C1—C2—H2A	119.9
N1—C10—H10A	118.4	C3^iv—C2—H2A	119.9
C9—C10—H10A	118.4	C4—C3—C2^iv	120.8 (2)
C8—C11—C12	115.85 (19)	C4—C3—H3A	119.6
C8—C11—H11A	108.3	C2^iv—C3—H3A	119.6
C12—C11—H11A	108.3	C3—C4—C5	120.7 (2)
C8—C11—H11B	108.3	C3—C4—H4A	119.7
C12—C11—H11B	108.3	C5—C4—H4A	119.7
H11A—C11—H11B	107.4	C4—C5—C5^iv	119.4 (2)
C11—C12—C13	112.47 (19)	C4—C5—C1	122.58 (19)
C11—C12—H12A	109.1	C5^iv—C5—C1	118.0 (2)
C13—C12—H12A	109.1	O3—S1—O2	113.27 (10)
C11—C12—H12B	109.1	O3—S1—O1	112.23 (10)
C13—C12—H12B	109.1	O2—S1—O1	112.63 (10)
H12A—C12—H12B	107.8	O3—S1—C1	106.37 (10)
C14—C13—C12	112.25 (18)	O2—S1—C1	105.48 (10)
C14—C13—H13A	109.2	O1—S1—C1	106.14 (9)
C12—C13—H13A	109.2	H1WA—O1W—H1WB	108.6
C14—C13—H13B	109.2	H2WA—O2W—H2WB	108.5

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x+1/2, −y+3/2, z−1/2; (iv) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.85	2.04	2.882 (2)	171
O1W—H1WB···O2W^v	0.85	1.95	2.790 (2)	171
O2W—H2WA···O1^vi	0.85	2.03	2.874 (2)	174
O2W—H2WB···O3	0.85	1.94	2.782 (2)	174
C6—H6A···O2	0.95	2.58	3.344 (3)	138
C7—H7A···O3^vi	0.95	2.59	3.487 (3)	158

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