A novel one-dimensional silver cylinder stabilized by mixed 2-mercaptobenzoic acid and ethylene­diamine ligands

A novel infinite one-dimensional silver cylinder, namely poly[[mu]-ethyl­enedi­am­ine-[mu]₅-(2-sulfanidylbenzoato)-[mu]₄-(2-sul­fanidylbenzoato)-tetra­silver(I)], [Ag₄(C₇H₄O₂S)₂(C₂H₈N₂)]_n, has been synthesized by one-pot reaction of equivalent molar silver nitrate and 2-mercaptobenzoic acid (H₂mba) in the presence of ethyl­enediamine (eda). One Ag atom is located in an AgS₂NO four-coordinated tetra­hedral geometry, two other Ag atoms are in an AgS₂O three-coordinated T-shaped geometry and the fourth Ag atom is in an AgSNO coordination environment. The two mba ligands show two different binding modes. The [mu]₂-N:N'-eda ligand, acting as a bridge, combines with mba ligands to extend the Ag^I ions into a one-dimensional silver cylinder incorporating abundant Ag...Ag inter­actions ranging from 2.9298 (11) to 3.2165 (13) Å. Inter­chain N-H...O hydrogen bonds extend the one-dimensional cylinder into an undulating two-dimensional sheet, which is further packed into a three-dimensional supra­molecular framework by van der Waals inter­actions; no [pi]-[pi] inter­actions were observed in the crystal structure.

S1. Comment

During recent decades, the crystal engineering of Ag^I coordination architectures has become a thriving and prosperous field that has attracted more and more interest because of the intriguing structural topologies and functional properties such as conduction and luminescence (Munakata et al., 1997; Jia & Wang, 2009; Wu et al., 2010; Kang et al., 2010; Anson et al., 2008). Ag^I-based coordination compounds, classified as discrete silver clusters and infinite coordination polymers, have been well [much?] studied (Mak et al., 2007; Xie et al., 2011; Jin et al., 2009; Zhang et al., 2007). The selection of chelating or bridging organic linkers favoring a structure-specific assembly is important for the construction of coordination architectures with expected structures and properties (Sun et al., 2006, 2011; Dai et al., 2008). However, the factors that govern the formation of such compounds are complicated and include not only the nature of the Ag^I ion and ligand structure but also anion-directed interactions as well as reaction conditions. In addition to covalent bonds, noncovalent interactions such as π–π, hydrogen bond, cation···π, anion···π and Ag···Ag interactions also play important roles in controlling molecular packing (Domasevitch et al., 2007; Yin et al., 2012; Chen et al., 2010; Li et al., 2010, 2011). Thus, in reality, it is hard to predict the structure of a Ag^I coordination compound with given ligand(s) until it has been characterized by the X-ray single-crystal diffraction technique. On the other hand, the bifunctional mba [2-mercaptobenzoic acid?] ligand has `soft' S and `hard' O donors, which could bind more than one Ag^I centers by S and O donors with diverse binding modes such as µ₃-S³:O¹, µ₃-S³, µ₂-S²:O¹, and so on. Meanwhile, the eda [ethylenediamine?] could act as a bridging or chelating ligand to anchor on the unsaturated Ag^I centers. Although Ag^I–mba (Sun, Wang et al., 2011) and Ag^I–eda (Ren et al., 2001; Yilmaz et al., 2006) coordination compounds were [have been?] widely investigated, the Ag^I–mba–eda system has not yet been documented. Based on the above consideration and our previous work (Sun, Luo et al., 2011; Sun, Wang, Han et al., 2011; Sun et al., 2010), herein we show [describe] a novel infinite one-dimensional silver cylinder, namely poly[[µ₅-2-sulfanidylbenzoate][µ₄-(2-carboxylatophenyl)sulfanido](µ-ethylenediamine)tetrasilver(I)], [Ag₄(mba)₂(eda)]_n, (I), which was obtained by one-pot reaction of equivalent molar silver nitrate and 2-mercaptobenzoic acid (H₂mba) in the presence of ethylenediamine (eda).

Single-crystal X-ray diffraction study reveals that the asymmetric unit of (I) contains four crystallographic independent Ag^I ions, two dianionic mba ligands and one neutral eda ligand. As shown in Fig. 1, Ag1 is located in a distorted AgS₂NO four-coordinated tetrahedral geometry with a distortion parameter τ₄ of 0.82. The τ₄ index could easily be obtained by the sum of angles α and β – the two largest angles in the four-coordinated metal center subtracted from 360°, all divided by 141°. The values of τ₄ will range from 1.00 for a perfect tetrahedral geometry to 0 for a perfect square-planar geometry (Yang et al., 2007). Ag2 and Ag3 are in the AgS₂O three-coordinated T-shaped geometry with the largest angles of 152.41 (11) and 162.44 (12)°, respectively. The Ag4 also locates in a three-coordinated geometry but in an AgSNO coordination environment. The Ag—S [2.458 (3)-2.718 (3) Å, Ag—N [2.253 (9) and 2.310 (8) Å and Ag—O [2.308 (8)-2.532 (7) Å] bond lengths (Table 1) are comparable with those of reported values (Schottel et al., 2006; Tsyba et al., 2003). Two mba ligands show different binding modes, viz. µ₄-κ⁶S,O:S,O':S:S and µ₅-κ⁶S,O:S:S:S:O [please check]. The µ₂-N¹:N¹ eda acts as a bridge to anchor on the Ag^I ions. Notably, the torsion angle of N1—C1—C2—N2 of eda is 70.9 (13)° which fits well with a gauche conformation of eda according to the stereochemistry terminology (Moss, 1996). The Ag···Ag interactions vary from 2.9298 (11) to 3.2165 (13) Å with an average distance of 3.1123 (12) Å, which is 0.3 Å shorter than twice the van der Waals radius of Ag^I (3.44 Å; Bondi, 1964), indicating argentophilic interaction between them. This weak bonding interaction between two closed-shell d¹⁰ cations is possible via the participation of 5s and 5p orbitals which have similar energy to that of the 4d orbital. The similar argentophilic interaction was also found in the cluster compounds {[Ag₆₂S₁₃(SBu^t)₃₂](BF₄)₄} (Li, Lei, et al., 2010) and {(NH₄)₁₇[(µ₆-S)Ag₁₇(mba)₁₆].22H₂O} (Sun, Liu, et al., 2011), as well as the coordination polymer [Ag₄(mba)₂(H₂O)₂]_n (Sun, Luo, et al., 2010).

The crystal structure of (I) features a one-dimensional Ag^I cylinder (Fig. 2) running along the b axis which is reinforced by intrachain N1—H1C···O3 and N2—H2C···O1 hydrogen bonds (Table 2) with an average distance of 2.981 (12) Å, a C—H···π interaction [C1—H1A···Cg1 = 138°, H1A···Cg1 = 2.96 Å and C1···Cg1 = 3.738 (11) Å; Cg1 is the centroid of the C21–C26 ring], a nonclassical C22—H22A···O4 hydrogen bond of 3.449 (13) Å and argentophilic interactions. Moreover, interchain N1—H1D···O1^v and N2—H2D···O1^vi hydrogen bonds extend the one-dimensional cylinders into an undulating two-dimensional sheet (Fig. 3), which is further packed into a three-dimensional supramolecular framework by van der Waals interactions; no π–π interactions were observed in the crystal structure. To the best of our knowledge, most of the reported Ag^I–mba compounds are discrete clusters, such as mononuclear [Ag(Hmba)(triphenylphosphane)₃] (Nomiya et al., 1998), tetranuclear [Ag₄(Hmbonwaya)₄(triphenylphosphane)₄] (Noguchi et al., 2005) and octanuclear K₁₂[Ag₈(mba)₁₀] (Nomiya et al., 2000); however, infinite coordination polymers are still rare, which may be due to the strong coordinative ability of the Sdonor to the Ag^I ion, as a result, the metastable polynuclear Ag^I aggregation is protected by them.

Related literature

For related literature, see: Anson et al. (2008); Bondi (1964); Chen et al. (2010); Dai et al. (2008); Domasevitch et al. (2007); Jia & Wang (2009); Jin et al. (2009); Kang et al. (2010); Li et al. (2011); Li, Lei & Wang (2010); Li, Wei, Tao, Huang, Zheng & Zheng (2010); Mak et al. (2007); Moss (1996); Munakata et al. (1997); Noguchi et al. (2005); Nomiya et al. (1998, 2000); Ren et al. (2001); Schottel et al. (2006); Sun et al. (2006); Sun, Dai, Yuan, Bi, Zhao, Sun & Sun (2011); Sun, Liu, Huang & Zheng (2011); Sun, Luo, Zhang, Huang & Zheng (2011); Sun, Luo, Zhang, Xu, Jin, Wei, Yang, Lin, Huang & Zheng (2010); Sun, Wang, Han, Zhang, Huang & Zheng (2011); Sun, Wang, Liu, Hao, Zhang, Huang & Zheng (2011); Sun, Yang, Xu, Zhao, Wei, Zhang, Yu, Huang & Zheng (2010); Tsyba et al. (2003); Wu et al. (2010); Xie & Mak (2011); Yang et al. (2007); Yilmaz et al. (2006); Yin et al. (2012); Zhang et al. (2007).

S2. Experimental

All reagents and solvents were used as obtained commercially without further purification. A mixture of AgNO₃ (85 mg, 0.5 mmol), H₂mba (78 mg, 0.5 mmol) and eda (1 ml) was added in CH₃OH–H₂O mixed solvent (12 ml, 1:2 v/v) under ultrasonic conditions which helped to dissolve the white precipitate. An aqueous NH₃ solution (25%) was then dropped into the mixture to give a clear solution. The resultant solution was allowed to evaporate slowly in darkness at room temperature for 2 weeks to give colorless block-shaped crystals of (I). The crystals were washed with deionized water and dried in air (yield: ca 52%, based on Ag). Elemental analysis calculated for C₁₆H₁₆AgN₂O₄S₂: C 40.69, H 3.41, N 5.93%; found: C 40.18, H. 3.09, N 5.29%.

S3. Refinement

All H atoms were generated geometrically and were allowed to ride on their parent atoms in the riding-model approximation, with C—H = 0.93 (aromatic) or 0.97 Å (CH₂) or N—H = 0.90 Å and with U_iso(H) = 1.2U_eq(C,N).

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) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2010).

Figures

	Fig. 1. The structure of (I), showing the coordination environments around the Ag^I centers. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) x, y+1, z; (ii) -x+3/2, y+1/2, z; (iii) -x+3/2, y-1/2, z; (iv) x, y-1, z.]
	Fig. 2. A ball-and-stick perspective view of the one-dimensional cylinder viewed (a) along c and (b) along b. The argentophilic interaction and hydrogen bond are highlighted by dashed lines (purple and green, respectively, in the electronic version of the paper).
	Fig. 3. A perspective view of the two-dimensional undulating sheet viewed (a) along c and (b) along b. The argentophilic interaction and hydrogen bond are highlighted by dashed lines (purple and green, respectively, in the electronic version of the paper).

(I)

Crystal data

[Ag4(C7H4O2S)2(C2H8N2)]	Dx = 2.740 Mg m^−3
Mr = 795.91	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 15021 reflections
a = 22.1562 (2) Å	θ = 6.1–54.9°
b = 6.9556 (7) Å	µ = 4.24 mm^−1
c = 25.0366 (5) Å	T = 298 K
V = 3858.4 (4) Å^3	Block, colorless
Z = 8	0.15 × 0.08 × 0.05 mm
F(000) = 3024

Data collection

Oxford Diffraction Gemini S Ultra CCD diffractometer	3392 independent reflections
Radiation source: fine-focus sealed tube	2660 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
ω scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	h = −25→26
Tmin = 0.569, Tmax = 0.816	k = −8→8
22503 measured reflections	l = −29→29

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.P)^2 + 78.8999P] where P = (Fo^2 + 2Fc^2)/3
S = 1.20	(Δ/σ)max = 0.001
3392 reflections	Δρmax = 1.74 e Å^−3
254 parameters	Δρmin = −1.47 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00033 (4)

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	0.61643 (4)	0.57842 (13)	0.65672 (3)	0.0333 (2)
Ag2	0.73427 (4)	0.59199 (12)	0.59542 (3)	0.0309 (2)
Ag3	0.74726 (4)	0.55368 (13)	0.71139 (3)	0.0341 (3)
Ag4	0.61174 (4)	0.14528 (14)	0.70152 (4)	0.0389 (3)
S1	0.67214 (12)	0.8166 (4)	0.72588 (11)	0.0292 (6)
S2	0.67417 (12)	0.2968 (4)	0.60997 (11)	0.0282 (6)
C1	0.4973 (5)	0.2825 (17)	0.6291 (4)	0.034 (3)
H1A	0.5276	0.3405	0.6062	0.041*
H1B	0.4647	0.2383	0.6064	0.041*
C2	0.4734 (5)	0.4330 (17)	0.6657 (5)	0.036 (3)
H2A	0.4492	0.5228	0.6452	0.044*
H2B	0.4473	0.3729	0.6919	0.044*
C11	0.6730 (5)	0.7783 (16)	0.7973 (4)	0.026 (2)
C12	0.6525 (5)	0.6025 (16)	0.8191 (4)	0.029 (2)
C13	0.6540 (5)	0.5820 (17)	0.8754 (4)	0.034 (3)
H13A	0.6402	0.4685	0.8908	0.041*
C14	0.6753 (5)	0.726 (2)	0.9077 (5)	0.045 (3)
H14A	0.6773	0.7085	0.9445	0.053*
C15	0.6939 (5)	0.8983 (18)	0.8852 (5)	0.038 (3)
H15A	0.7070	0.9977	0.9072	0.046*
C16	0.6931 (5)	0.9240 (17)	0.8303 (4)	0.033 (3)
H16A	0.7061	1.0396	0.8157	0.039*
C17	0.6293 (5)	0.4385 (16)	0.7879 (4)	0.030 (2)
C21	0.6315 (5)	0.2696 (17)	0.5497 (4)	0.029 (3)
C22	0.6116 (5)	0.4255 (15)	0.5207 (4)	0.030 (2)
H22A	0.6244	0.5481	0.5303	0.036*
C23	0.5732 (6)	0.4036 (18)	0.4779 (5)	0.042 (3)
H23A	0.5607	0.5110	0.4588	0.050*
C24	0.5533 (5)	0.2230 (18)	0.4633 (4)	0.036 (3)
H24A	0.5270	0.2093	0.4346	0.044*
C25	0.5725 (5)	0.0613 (17)	0.4915 (4)	0.032 (3)
H25A	0.5593	−0.0612	0.4823	0.039*
C26	0.6125 (5)	0.0890 (15)	0.5343 (4)	0.028 (2)
C27	0.6339 (5)	−0.0938 (17)	0.5635 (5)	0.036 (3)
N1	0.5246 (4)	0.1131 (14)	0.6561 (3)	0.032 (2)
H1C	0.5305	0.0223	0.6310	0.038*
H1D	0.4969	0.0664	0.6790	0.038*
N2	0.5216 (4)	0.5400 (14)	0.6937 (4)	0.033 (2)
H2C	0.5268	0.4829	0.7256	0.040*
H2D	0.5072	0.6586	0.7002	0.040*
O1	0.5762 (3)	0.3827 (12)	0.7951 (3)	0.0371 (19)
O2	0.6647 (3)	0.3566 (11)	0.7549 (3)	0.0345 (18)
O3	0.5989 (4)	−0.1657 (11)	0.5971 (3)	0.0358 (19)
O4	0.6855 (3)	−0.1518 (11)	0.5508 (3)	0.0353 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0353 (5)	0.0319 (5)	0.0325 (5)	−0.0016 (4)	0.0007 (4)	0.0010 (4)
Ag2	0.0320 (5)	0.0289 (5)	0.0319 (4)	−0.0033 (4)	0.0004 (3)	0.0015 (4)
Ag3	0.0329 (5)	0.0376 (5)	0.0318 (4)	0.0046 (4)	0.0007 (4)	0.0019 (4)
Ag4	0.0391 (5)	0.0357 (5)	0.0421 (5)	0.0009 (4)	−0.0073 (4)	0.0002 (4)
S1	0.0302 (15)	0.0291 (15)	0.0284 (14)	−0.0004 (12)	−0.0042 (11)	−0.0009 (12)
S2	0.0279 (14)	0.0286 (15)	0.0281 (13)	−0.0026 (12)	−0.0025 (11)	0.0020 (12)
C1	0.031 (6)	0.042 (7)	0.029 (6)	−0.006 (6)	0.001 (5)	0.000 (5)
C2	0.031 (6)	0.032 (6)	0.046 (7)	−0.009 (5)	0.002 (5)	−0.001 (6)
C11	0.024 (5)	0.026 (6)	0.029 (6)	0.002 (5)	0.005 (4)	−0.003 (5)
C12	0.029 (6)	0.031 (6)	0.028 (6)	0.008 (5)	0.004 (5)	−0.007 (5)
C13	0.031 (6)	0.036 (7)	0.034 (6)	0.007 (5)	0.005 (5)	−0.008 (5)
C14	0.030 (7)	0.076 (10)	0.027 (6)	−0.012 (7)	0.007 (5)	0.006 (6)
C15	0.040 (7)	0.040 (7)	0.033 (6)	−0.008 (6)	0.007 (5)	−0.029 (6)
C16	0.028 (6)	0.031 (6)	0.040 (6)	−0.005 (5)	0.010 (5)	−0.015 (5)
C17	0.034 (6)	0.023 (6)	0.033 (6)	0.000 (5)	0.003 (5)	0.003 (5)
C21	0.023 (5)	0.046 (7)	0.019 (5)	−0.010 (5)	−0.001 (4)	−0.002 (5)
C22	0.045 (7)	0.016 (5)	0.028 (6)	−0.004 (5)	−0.002 (5)	0.003 (4)
C23	0.046 (8)	0.031 (7)	0.048 (7)	0.003 (6)	−0.010 (6)	0.003 (6)
C24	0.036 (6)	0.045 (7)	0.028 (6)	0.001 (6)	−0.015 (5)	−0.004 (5)
C25	0.029 (6)	0.030 (6)	0.038 (6)	−0.006 (5)	−0.013 (5)	0.000 (5)
C26	0.035 (6)	0.023 (6)	0.027 (5)	−0.003 (5)	0.008 (5)	0.007 (5)
C27	0.037 (7)	0.035 (7)	0.035 (6)	−0.015 (6)	−0.006 (5)	−0.002 (5)
N1	0.033 (5)	0.043 (6)	0.019 (4)	0.006 (5)	0.004 (4)	0.000 (4)
N2	0.027 (5)	0.032 (6)	0.040 (5)	0.008 (4)	0.009 (4)	−0.002 (4)
O1	0.033 (5)	0.039 (5)	0.039 (4)	−0.004 (4)	0.003 (4)	−0.001 (4)
O2	0.034 (4)	0.030 (4)	0.040 (4)	−0.006 (4)	0.008 (4)	0.001 (4)
O3	0.042 (5)	0.021 (4)	0.044 (5)	0.000 (4)	0.004 (4)	0.008 (4)
O4	0.025 (4)	0.035 (5)	0.046 (5)	0.007 (4)	0.001 (4)	0.006 (4)

Geometric parameters (Å, º)

Ag1—N2	2.310 (8)	C11—C16	1.381 (15)
Ag1—O3^i	2.356 (7)	C11—C12	1.415 (15)
Ag1—S2	2.616 (3)	C12—C13	1.418 (15)
Ag1—S1	2.696 (3)	C12—C17	1.476 (15)
Ag1—Ag2	3.0300 (12)	C13—C14	1.372 (17)
Ag1—Ag3	3.2102 (12)	C13—H13A	0.9300
Ag1—Ag4	3.2165 (13)	C14—C15	1.386 (18)
Ag2—O4^i	2.365 (8)	C14—H14A	0.9300
Ag2—S2	2.474 (3)	C15—C16	1.387 (16)
Ag2—S2^ii	2.506 (3)	C15—H15A	0.9300
Ag2—Ag3	2.9298 (11)	C16—H16A	0.9300
Ag3—S1^iii	2.458 (3)	C17—O1	1.253 (13)
Ag3—S1	2.499 (3)	C17—O2	1.273 (13)
Ag3—O2	2.532 (7)	C21—C22	1.376 (15)
Ag3—Ag4^ii	3.1980 (13)	C21—C26	1.380 (15)
Ag4—N1	2.253 (9)	C22—C23	1.376 (16)
Ag4—O2	2.308 (8)	C22—H22A	0.9300
Ag4—S1^iv	2.718 (3)	C23—C24	1.381 (16)
Ag4—S2	2.877 (3)	C23—H23A	0.9300
Ag4—Ag3^iii	3.1980 (13)	C24—C25	1.396 (16)
S1—C11	1.808 (11)	C24—H24A	0.9300
S1—Ag3^ii	2.458 (3)	C25—C26	1.404 (15)
S1—Ag4^i	2.718 (3)	C25—H25A	0.9300
S2—C21	1.791 (10)	C26—C27	1.541 (16)
S2—Ag2^iii	2.506 (3)	C27—O3	1.248 (13)
C1—C2	1.487 (16)	C27—O4	1.254 (14)
C1—N1	1.486 (14)	N1—H1C	0.9000
C1—H1A	0.9700	N1—H1D	0.9000
C1—H1B	0.9700	N2—H2C	0.9000
C2—N2	1.479 (14)	N2—H2D	0.9000
C2—H2A	0.9700	O3—Ag1^iv	2.356 (7)
C2—H2B	0.9700	O4—Ag2^iv	2.365 (8)
N2—Ag1—O3^i	101.0 (3)	Ag2^iii—S2—Ag1	152.47 (12)
N2—Ag1—S2	122.5 (2)	C21—S2—Ag4	112.3 (4)
O3^i—Ag1—S2	111.3 (2)	Ag2—S2—Ag4	132.85 (11)
N2—Ag1—S1	103.3 (2)	Ag2^iii—S2—Ag4	107.26 (10)
O3^i—Ag1—S1	91.1 (2)	Ag1—S2—Ag4	71.51 (7)
S2—Ag1—S1	121.58 (9)	C2—C1—N1	115.1 (9)
N2—Ag1—Ag2	171.8 (2)	C2—C1—H1A	108.5
O3^i—Ag1—Ag2	78.32 (19)	N1—C1—H1A	108.5
S2—Ag1—Ag2	51.34 (6)	C2—C1—H1B	108.5
S1—Ag1—Ag2	84.93 (7)	N1—C1—H1B	108.5
N2—Ag1—Ag3	130.1 (2)	H1A—C1—H1B	107.5
O3^i—Ag1—Ag3	117.4 (2)	N2—C2—C1	112.8 (9)
S2—Ag1—Ag3	73.08 (6)	N2—C2—H2A	109.0
S1—Ag1—Ag3	49.13 (6)	C1—C2—H2A	109.0
Ag2—Ag1—Ag3	55.91 (3)	N2—C2—H2B	109.0
N2—Ag1—Ag4	73.9 (2)	C1—C2—H2B	109.0
O3^i—Ag1—Ag4	157.4 (2)	H2A—C2—H2B	107.8
S2—Ag1—Ag4	58.03 (6)	C16—C11—C12	120.4 (10)
S1—Ag1—Ag4	111.50 (7)	C16—C11—S1	119.1 (9)
Ag2—Ag1—Ag4	103.51 (3)	C12—C11—S1	120.4 (8)
Ag3—Ag1—Ag4	80.23 (3)	C11—C12—C13	117.6 (10)
O4^i—Ag2—S2	116.7 (2)	C11—C12—C17	125.1 (9)
O4^i—Ag2—S2^ii	90.6 (2)	C13—C12—C17	117.3 (10)
S2—Ag2—S2^ii	152.41 (11)	C14—C13—C12	121.4 (12)
O4^i—Ag2—Ag3	125.55 (19)	C14—C13—H13A	119.3
S2—Ag2—Ag3	80.30 (7)	C12—C13—H13A	119.3
S2^ii—Ag2—Ag3	80.10 (7)	C13—C14—C15	119.6 (11)
O4^i—Ag2—Ag1	82.46 (18)	C13—C14—H14A	120.2
S2—Ag2—Ag1	55.65 (7)	C15—C14—H14A	120.2
S2^ii—Ag2—Ag1	129.92 (7)	C16—C15—C14	120.7 (11)
Ag3—Ag2—Ag1	65.16 (3)	C16—C15—H15A	119.7
S1^iii—Ag3—S1	162.44 (12)	C14—C15—H15A	119.7
S1^iii—Ag3—O2	95.62 (19)	C11—C16—C15	120.2 (11)
S1—Ag3—O2	81.54 (19)	C11—C16—H16A	119.9
S1^iii—Ag3—Ag2	106.18 (7)	C15—C16—H16A	119.9
S1—Ag3—Ag2	90.68 (7)	O1—C17—O2	122.3 (10)
O2—Ag3—Ag2	113.88 (18)	O1—C17—C12	119.3 (10)
S1^iii—Ag3—Ag4^ii	55.61 (7)	O2—C17—C12	118.4 (10)
S1—Ag3—Ag4^ii	121.06 (7)	C22—C21—C26	118.2 (9)
O2—Ag3—Ag4^ii	147.85 (18)	C22—C21—S2	122.0 (9)
Ag2—Ag3—Ag4^ii	90.07 (3)	C26—C21—S2	119.5 (9)
S1^iii—Ag3—Ag1	139.03 (8)	C21—C22—C23	121.4 (10)
S1—Ag3—Ag1	54.65 (7)	C21—C22—H22A	119.3
O2—Ag3—Ag1	63.92 (18)	C23—C22—H22A	119.3
Ag2—Ag3—Ag1	58.93 (3)	C22—C23—C24	120.3 (11)
Ag4^ii—Ag3—Ag1	146.98 (4)	C22—C23—H23A	119.8
N1—Ag4—O2	142.4 (3)	C24—C23—H23A	119.8
N1—Ag4—S1^iv	116.9 (3)	C23—C24—C25	120.0 (10)
O2—Ag4—S1^iv	98.9 (2)	C23—C24—H24A	120.0
N1—Ag4—S2	92.6 (2)	C25—C24—H24A	120.0
O2—Ag4—S2	89.06 (19)	C24—C25—C26	117.9 (10)
S1^iv—Ag4—S2	104.49 (9)	C24—C25—H25A	121.0
N1—Ag4—Ag3^iii	148.9 (2)	C26—C25—H25A	121.0
O2—Ag4—Ag3^iii	65.49 (19)	C21—C26—C25	122.1 (10)
S1^iv—Ag4—Ag3^iii	48.25 (6)	C21—C26—C27	121.7 (9)
S2—Ag4—Ag3^iii	70.42 (6)	C25—C26—C27	116.2 (10)
N1—Ag4—Ag1	86.8 (2)	O3—C27—O4	127.4 (12)
O2—Ag4—Ag1	65.74 (19)	O3—C27—C26	117.4 (11)
S1^iv—Ag4—Ag1	148.22 (7)	O4—C27—C26	115.2 (10)
S2—Ag4—Ag1	50.47 (6)	C1—N1—Ag4	119.9 (7)
Ag3^iii—Ag4—Ag1	100.49 (3)	C1—N1—H1C	107.3
C11—S1—Ag3^ii	103.7 (4)	Ag4—N1—H1C	107.3
C11—S1—Ag3	91.7 (3)	C1—N1—H1D	107.3
Ag3^ii—S1—Ag3	89.18 (9)	Ag4—N1—H1D	107.3
C11—S1—Ag1	123.3 (4)	H1C—N1—H1D	106.9
Ag3^ii—S1—Ag1	130.56 (11)	C2—N2—Ag1	121.7 (7)
Ag3—S1—Ag1	76.22 (8)	C2—N2—H2C	106.9
C11—S1—Ag4^i	110.5 (4)	Ag1—N2—H2C	106.9
Ag3^ii—S1—Ag4^i	76.14 (8)	C2—N2—H2D	106.9
Ag3—S1—Ag4^i	155.60 (12)	Ag1—N2—H2D	106.9
Ag1—S1—Ag4^i	98.47 (9)	H2C—N2—H2D	106.7
C21—S2—Ag2	104.3 (4)	C17—O2—Ag4	110.3 (7)
C21—S2—Ag2^iii	104.1 (4)	C17—O2—Ag3	118.8 (7)
Ag2—S2—Ag2^iii	90.84 (9)	Ag4—O2—Ag3	117.6 (3)
C21—S2—Ag1	101.4 (4)	C27—O3—Ag1^iv	128.9 (8)
Ag2—S2—Ag1	73.01 (8)	C27—O4—Ag2^iv	122.7 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22A···O4^i	0.93	2.54	3.449 (13)	165
N1—H1C···O3	0.90	2.17	2.942 (12)	143
N1—H1D···O1^v	0.90	2.16	3.007 (12)	156
N2—H2C···O1	0.90	2.17	3.019 (12)	157
N2—H2D···O1^vi	0.90	2.42	3.233 (12)	151

Symmetry codes: (i) x, y+1, z; (v) −x+1, y−1/2, −z+3/2; (vi) −x+1, y+1/2, −z+3/2.