A novel three-dimensional Ag^I coordination polymer based on mixed naphthalene-1,5-di­sulfonate and amino­acetate ligands

The three-dimensional coordination polymer poly[[bis­(μ₃-2-amino­acetato)di-μ-aqua-μ₃-(naphthalene-1,5-di­sulfonato)-hexa­silver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene-1,5-di­sulfonate (L1) and 2-amino­acetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five-coordinated by three O atoms from one L1 anion, one L2 anion and one water mol­ecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water mol­ecules, and two Ag^I cations in a slightly octa­hedral coordination geometry. Ag3 is four-coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four-coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetra­hedral coordination geometry. In the crystal structure, there are two one-dimensional chains nearly perpendicular to one another (inter­chain angle = 87.0°). The chains are connected by water mol­ecules to give a two-dimensional layer, and the layers are further bridged by L1 anions to generate a novel three-dimensional framework. Moreover, hydrogen-bonding inter­actions consolidate the network.

S1. Introduction

When we were mulling on potential themes for a special issue, we wanted to feature a chemically important compound family wherein the structure plays a palpable effect on reactivity. Perhaps pandering to our own personal experiences, we decided scorpionates would be ideal.

Before 1966 there were only a few examples of poly-substituted boron compounds with B—N bonds with all of them behaving as noncoordinated, spe­cta­tor anions (Krause & Hawes, 1933; Smith & Kraus, 1951). In the seminal report by Trofimenko, a new class of chelating, polypyrazolylborate, specifically tris­pyrazolylborate (Tp), ligands was created by reaction of potassium borohydride with three equivalents of pyrazole. The resulting anion was then observed to coordinate to a large range of divalent metal ions (Trofimenko, 1966).

The first crystal structure with a Tp ligand was reported in 1970, bis­[hydro­tris­(1-pyrazolyl)borato]cobalt(II), which confirmed the D3d symmetric structure for bis-Tp complexes (Churchill et al., 1970) previously theorized based on comparative transition metal complex series colors and molecular modeling (Trofimenko, 1967). In 1978, the first Tp structure to appear in an Acta Crystallographica journal, methyl­[hydro­tris­(1-pyrazolyl)borato]tetra­fluoro­ethyl­eneplatinum , afforded an accurate stereochemical description to elucidate previously observed anomalous couplings in the NMR spectra (Rice & Oliver, 1978). The perfluoro­alkyne analogue was reported four years prior (Davies & Payne, 1974). Both of these platinum structures featured monoligand coordination similar to only a handful of first generation Tp compounds (Thompson et al., 1979; Roundhill et al., 1979).

To combat the formation of bis­ligand complexes, a second generation of Tp ligands was introduced in 1986 wherein the 3-position of the pyrazole has a bulky alkyl or aryl substituent such as t-butyl or phenyl. This modification prevented the inter­digitation observed in bis-Tp complexes and allowed new tetra­hedral complexes to be synthesized (Calabrese et al., 1986).

In a 1993 review, Trofimenko notes the multidentate features of Tp and states, ?Nature provides the closest analogy to these features in the scorpion. This creature grabs its prey with two identical claws and then may proceed to sting it with the sharp point of the curving tail. Therefore, I found it appropriate to coin the term ?scorpionate ligands? ···? (Trofimenko, 1993). While first and second generation scorpionates are still providing bountiful chemistry arising from facile tuning of electronics and sterics, Reger introduced yet another option: third generation scorpionates that are functionalized in the fourth, noncoordinating, back position on the boron atom allowing, for instance, magnetic behavior modification of iron scorpionate complexes (Reger, 2005).

The first book on scorpionates, ?Scorpionates: The Coordination Chemistry of Polypyrazolylbolrate Ligands?, intended to provide a 32-year comprehensive coverage of Tp chemistry up to 1998 (including some 1999 papers), was published in 1999 (reprinted in 2005) with 1568 references cited (Trofimenko, 1999). The second book, ?Scorpionates II: Chelating Borate Ligands? was published in 2008 to cover research from 1999 to 2008, a much shorter nine year period, with 1710 references cited (Pettinari, 2008)! A study of common ligand metrics display that Tp ligands had the largest population, at the time the study was conducted, for fac-coordinating, tris­kelion (ie. tripodal) ligands and second largest only to cyclo­penta­dienide ligands for all tridentate ligands (Aguila, 2009). While much of Tp research, as to be expected, is within the realm of classical chemistry, scorpionates could even be found in more general scientific endeavors. A recent paper shows a palladium scorpionate used in positron emission tomography (Lee et al., 2011). A search on scorpionate structures in the Cambridge Sructural Database (version 5.34 May 2013) (Allen, 2002) yields 3480 hits, of which 59 appear in Acta Crystallographica journals. We can confidently say that scorpionates are clearly valuable, prolific, ?work-horse? ligands. In his final remarks in the first scorpionate book, Trofimenko concludes with a sentiment which rings true even today, ?In the final analysis, the scorpionate field is wide open, and can be extended in almost any direction, being restricted only by the creativity of the scientist.? (Trofimenko, 1999).

Allow us to comment on the cover art at this point. The background is composed of a representative IR spectrum of the first metal scorpionates (Trofimenko, 1967). The top molecule was generated from atomic coordinates from the first scorpionate to appear in an Acta Crystallographica journal (Rice & Oliver, 1978). The lower molecule is one of the most recent scorpionates, that is to say, a molecule from this issue!

Tony Linden, our esteemed Section Editor, instructed us to scour the scientific community to look for ?contributions that have something special to say.? We believe we have persuaded some of the best authors in the field of Tp chemistry - or chemistry, in general, for that matter - many of whom haven?t submitted to a Acta Crystallographica journal previously. Together with our expert authors, we are pleased and honored to feature the chemistry of scorpionates and their kin in our first special issue of Acta Crystallographica C.

S2. Experimental

S2.1. Synthesis and crystallization

An aqueous solution (25 ml) of sodium naphthalene-1,5-di­sulfonate (0.052 g, 0.3 mmol) and amino­acetic acid (0.023 g, 0.3 mmol) was added to solid AgNO₃ (0.10 g, 0.6 mmol) and stirred for several minutes, and a white precipitate formed. The precipitate was dissolved by dropwise addition of an aqueous solution of NH₃ (14 M) until no further CO₂ was given off. The filtrate was kept for 7 d in a dark room to produce single crystals of (I) suitable for X-ray analysis (78% yield). Elemental analysis, found: C 16.57, N 4.32, H 2.29%; calculated for C₉H₁₅Ag₃N₂O₉S: C 16.61, N 4.30, H 2.32%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically, with C—H = 0.93 or 0.97 Å for aromatic or methyl­ene H atoms, respectively, and refined using a riding model, with U_iso = 1.2U_eq(C). O- and N-bound H atoms were located in a difference map and were refined with distance restraints of O/N—H = 0.85 Å and U_iso = 1.5U_eq(O,N).

S3. Results and discussion

The asymmetric unit of (I) has four Ag^I cations (two of them in general positions and two on inversion centres), two L2 anions, one L1 anion lying on an independent inversion centre, and one coordinated and one uncoordinated water molecule.

As shown in Fig. 1, atom Ag1 is five-coordinated by one N atom (from an NH₂ group of one L2 anion), three O atoms (from one sulfonate group of one L1 anion, one carboxyl­ate group from another L2 anion and one water molecule) and one Ag^I cation, defining a distorted trigonal–bipyramidal coordination geometry (Fig. 1 and Table 2).

Atom Ag2 lies on an inversion centre and is coordinated in a slightly distorted o­cta­hedral coordination geometry by two O atoms from the carboxyl­ate groups of two L2 anions, two water molecules (the base) and two apical Ag^I cations [cis bond angles around Ag2 = 90±5.87 (8)° (basal) and ranging from 90±10.24 (7) to 90±11.30 (8)° (apical)].

The Ag3 centre also lies on an inversion centre and is four-coordinated by two O atoms from the carboxyl­ate groups of two L2 anions and two Ag^I cations in a slightly distorted (though strictly planar) square geometry [cis bond angles around Ag3 = 90±8.05 (6)°].

Atom Ag4 is also four-coordinated by two O atoms (from one sulfonate group of one L1 anion and one carboxyl­ate group of an L2 anion), one N atom from the NH₂ group (from another L2 anion) and one Ag^I cation, exhibiting a distorted tetra­hedral coordination geometry.

One type of {Ag^I}₃ cluster (Fig. 2), consisting of one Ag3 and two Ag1 atoms, is linked by L2 ligands to give a novel one-dimensional chain (denoted chain A). Meanwhile, another type of {Ag^I}₃ cluster (Fig. 2), consisting of one Ag2 and two Ag4 atoms, is linked by L2 ligands to form another one-dimensional chain (chain B), which is nearly perpendicular to chain A, making an angle of 87.0°. Inter­estingly, the water molecule bridges the two Ag^I cations of adjacent chains A and B to generate a novel two-dimensional layer (Fig. 2). Furthermore, adjacent sheets are connected by L1 ligands to give a fascinating three-dimensional pillared framework (Fig. 3).

In addition, the water molecule, the coordinated amino group of the L2 anion and the sulfonate group of the L1 anion are involved in the formation of hydrogen-bonding inter­actions, consolidating the three-dimensional structure of (I) (Fig. 4 and Table 2). It is inter­esting to note that the coordinated and solvent water molecules arrange themselves to form a hydrogen-bonded water (H₂O)₂ dimer with an O1W···O2W distance of 2.852 (5) Å, and this supra­molecular water dimer is associated with the L1 and L2 ligands by hydrogen bonds, strengthening the three-dimensional framework.

Related literature

For related literature, see: Aguila et al. (2009); Allen (2002); Calabrese et al. (1986); Churchill et al. (1970); Davies & Payne (1974); Krause & Hawes (1933); Lee et al. (2011); Pettinari (2008); Reger et al. (2005); Rice & Oliver (1978); Roundhill et al. (1979); Smith & Kraus (1951); Thompson et al. (1979); Trofimenko (1966, 1967, 1993, 1999).

Computing details

Data collection: SMART; cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SHELXS97; program(s) used to refine structure: SHELXL97; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures

	Fig. 1. A displacement ellipsoid plot (30% probability level) of (I), showing the coordination environment around the Ag atoms. [Symmetry codes: (#1) x - 1, y, z; (#2) -x + 1, -y + 2, -z; (#3) -x + 2, -y + 2, -z + 1; (#4) -x + 1, -y + 2, -z + 1; (#5) x - 1, y, z.]
	Fig. 2. The two-dimensional layer structure of (I). H atoms and uncoordinated water molecules have been omitted for clarity.
	Fig. 3. The three-dimensional framework of (I). H atoms and uncoordinated water molecules have been omitted for clarity.
	Fig. 4. The most significant hydrogen bonds in (I) (dashed lines). [Symmetry codes: (iii) x, y + 1, z; (iv) x - 1, y + 1, z; (v) -x + 1, -y + 2, -z + 1.]

Poly[[bis(µ₃-2-aminoacetato)di-µ-aqua-µ₃-(naphthalene-1,5-disulfonato)-hexasilver(I)] dihydrate]

Crystal data

[Ag6(C10H6S2O6)(C2H4NO2)4(H2O)2]·2H2O	Z = 1
Mr = 1301.80	F(000) = 624
Triclinic, P1	Dx = 2.758 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4864 (15) Å	Cell parameters from 3429 reflections
b = 8.1555 (16) Å	θ = 2.7–27.5°
c = 14.136 (3) Å	µ = 3.89 mm^−1
α = 78.47 (3)°	T = 293 K
β = 74.99 (3)°	Block, colourless
γ = 71.43 (3)°	0.24 × 0.22 × 0.19 mm
V = 783.7 (3) Å^3

Data collection

Bruker SMART 1K CCD area-detector diffractometer	3429 independent reflections
Radiation source: fine-focus sealed tube	2975 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8.192 pixels mm^-1	θmax = 27.6°, θmin = 2.7°
thin–slice ω scans	h = −9→8
Absorption correction: multi-scan (SADABS)	k = −10→10
Tmin = 0.413, Tmax = 0.481	l = −18→18
6978 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 0.1885P] where P = (Fo^2 + 2Fc^2)/3
3429 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.52 e Å^−3
12 restraints	Δρmin = −0.71 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 > 2σ(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	0.25416 (3)	0.88378 (4)	0.32668 (2)	0.03670 (9)
Ag2	0.5000	1.0000	0.0000	0.04027 (11)
Ag3	1.0000	1.0000	0.5000	0.04701 (12)
Ag4	0.44128 (3)	0.67753 (4)	0.09918 (2)	0.04336 (9)
C1	0.1430 (5)	0.4266 (4)	0.3787 (3)	0.0308 (6)
C2	0.0128 (5)	0.3725 (4)	0.3496 (3)	0.0350 (7)
H2	0.0473	0.3270	0.2900	0.042*
C3	−0.1715 (5)	0.3844 (5)	0.4081 (3)	0.0383 (8)
H3	−0.2582	0.3465	0.3874	0.046*
C4	−0.2240 (5)	0.4509 (4)	0.4946 (3)	0.0322 (7)
H4	−0.3481	0.4609	0.5321	0.039*
C5	−0.0941 (4)	0.5055 (4)	0.5294 (2)	0.0285 (6)
C6	0.6700 (4)	0.8665 (4)	0.3211 (2)	0.0293 (7)
H6A	0.6545	0.9412	0.2594	0.035*
H6B	0.7085	0.7467	0.3076	0.035*
C7	0.8316 (4)	0.8963 (4)	0.3556 (2)	0.0269 (6)
C8	0.8340 (4)	0.7275 (4)	0.0822 (2)	0.0279 (6)
C9	1.0401 (4)	0.6530 (4)	0.0984 (3)	0.0321 (7)
H9AA	1.0358	0.5991	0.1663	0.038*
H9BA	1.1085	0.5622	0.0563	0.038*
N1	1.1487 (4)	0.7802 (4)	0.0783 (3)	0.0406 (7)
HN1A	1.148 (7)	0.835 (5)	0.0215 (19)	0.061*
HN1B	1.097 (6)	0.863 (5)	0.116 (3)	0.061*
N2	0.4834 (4)	0.8991 (4)	0.3899 (2)	0.0292 (6)
HN2A	0.452 (6)	1.001 (3)	0.402 (3)	0.044*
HN2B	0.498 (6)	0.828 (4)	0.442 (2)	0.044*
O1	0.4212 (3)	0.5675 (3)	0.28913 (19)	0.0395 (6)
O2	0.5048 (4)	0.2633 (3)	0.3541 (2)	0.0488 (7)
O3	0.3660 (4)	0.3616 (4)	0.2089 (2)	0.0496 (7)
O4	0.8018 (3)	0.9268 (3)	0.44112 (17)	0.0339 (5)
O5	0.9850 (3)	0.8879 (4)	0.2926 (2)	0.0483 (7)
O6	0.7697 (3)	0.8857 (3)	0.06105 (19)	0.0379 (6)
O7	0.7463 (3)	0.6135 (3)	0.0922 (2)	0.0420 (6)
S1	0.37675 (11)	0.40272 (11)	0.30243 (7)	0.03310 (18)
O1W	0.2790 (4)	1.0908 (4)	0.1605 (2)	0.0481 (7)
HW1A	0.318 (6)	1.167 (5)	0.173 (4)	0.072*
HW1B	0.168 (4)	1.132 (6)	0.151 (4)	0.072*
O2W	0.8867 (5)	0.2530 (4)	0.1473 (3)	0.0628 (8)
HW2A	0.843 (8)	0.360 (4)	0.132 (4)	0.094*
HW2B	0.815 (7)	0.211 (6)	0.190 (4)	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.02155 (12)	0.05184 (17)	0.04348 (16)	−0.01321 (11)	−0.00694 (10)	−0.01650 (13)
Ag2	0.02500 (17)	0.0388 (2)	0.0554 (3)	−0.00647 (15)	−0.01708 (16)	0.00469 (17)
Ag3	0.02978 (18)	0.0831 (3)	0.0406 (2)	−0.02164 (19)	−0.00653 (15)	−0.0276 (2)
Ag4	0.02312 (13)	0.04585 (17)	0.0630 (2)	−0.01533 (11)	−0.01816 (12)	0.00983 (13)
C1	0.0290 (14)	0.0324 (16)	0.0348 (17)	−0.0143 (13)	−0.0120 (13)	0.0035 (13)
C2	0.0366 (17)	0.0397 (19)	0.0367 (18)	−0.0169 (15)	−0.0166 (14)	−0.0013 (15)
C3	0.0345 (17)	0.048 (2)	0.044 (2)	−0.0219 (15)	−0.0195 (15)	0.0005 (16)
C4	0.0296 (15)	0.0346 (17)	0.0392 (18)	−0.0165 (13)	−0.0143 (14)	0.0016 (14)
C5	0.0281 (15)	0.0288 (15)	0.0331 (16)	−0.0117 (12)	−0.0143 (13)	0.0025 (13)
C6	0.0201 (13)	0.0367 (17)	0.0351 (17)	−0.0098 (12)	−0.0078 (12)	−0.0082 (14)
C7	0.0221 (13)	0.0303 (16)	0.0323 (17)	−0.0100 (12)	−0.0094 (12)	−0.0042 (13)
C8	0.0171 (12)	0.0380 (18)	0.0277 (16)	−0.0061 (12)	−0.0050 (11)	−0.0045 (13)
C9	0.0217 (14)	0.0361 (17)	0.0393 (18)	−0.0078 (13)	−0.0127 (13)	0.0009 (14)
N1	0.0251 (13)	0.0384 (16)	0.062 (2)	−0.0120 (12)	−0.0188 (14)	0.0025 (14)
N2	0.0220 (12)	0.0356 (15)	0.0336 (15)	−0.0104 (11)	−0.0067 (11)	−0.0074 (12)
O1	0.0406 (13)	0.0297 (12)	0.0471 (15)	−0.0154 (10)	−0.0021 (11)	−0.0026 (11)
O2	0.0348 (13)	0.0326 (13)	0.084 (2)	−0.0102 (11)	−0.0266 (13)	0.0006 (13)
O3	0.0412 (14)	0.0649 (18)	0.0507 (17)	−0.0216 (13)	−0.0038 (12)	−0.0219 (15)
O4	0.0240 (10)	0.0477 (14)	0.0356 (13)	−0.0102 (10)	−0.0091 (9)	−0.0139 (11)
O5	0.0270 (12)	0.088 (2)	0.0382 (14)	−0.0272 (13)	−0.0019 (10)	−0.0168 (14)
O6	0.0252 (11)	0.0381 (14)	0.0509 (16)	−0.0058 (10)	−0.0150 (10)	−0.0029 (11)
O7	0.0199 (10)	0.0456 (14)	0.0625 (17)	−0.0121 (10)	−0.0120 (11)	−0.0021 (13)
S1	0.0274 (4)	0.0294 (4)	0.0453 (5)	−0.0096 (3)	−0.0096 (3)	−0.0057 (3)
O1W	0.0511 (15)	0.0553 (17)	0.0433 (15)	−0.0181 (14)	−0.0110 (13)	−0.0120 (13)
O2W	0.0595 (19)	0.0514 (18)	0.073 (2)	−0.0148 (15)	−0.0182 (17)	0.0069 (17)

Geometric parameters (Å, º)

Ag1—N2	2.176 (3)	C5—C1^iv	1.428 (5)
Ag1—O5^i	2.179 (2)	C6—N2	1.460 (4)
Ag1—O1	2.579 (2)	C6—C7	1.516 (4)
Ag1—O1W	2.606 (3)	C6—H6A	0.9700
Ag2—O6^ii	2.252 (2)	C6—H6B	0.9700
Ag2—O6	2.252 (2)	C7—O4	1.233 (4)
Ag2—O1W	2.526 (3)	C7—O5	1.249 (4)
Ag2—O1W^ii	2.526 (3)	C8—O6	1.229 (4)
Ag3—O4^iii	2.157 (2)	C8—O7	1.267 (4)
Ag3—O4	2.157 (2)	C8—C9	1.527 (4)
Ag4—O7	2.154 (2)	C9—N1	1.455 (4)
Ag4—N1^i	2.157 (3)	C9—H9AA	0.9700
Ag4—O1	2.637 (3)	C9—H9BA	0.9700
Ag1—Ag3^i	2.8084 (11)	N1—HN1A	0.84 (3)
Ag2—Ag4^ii	2.8316 (9)	N1—HN1B	0.87 (2)
C1—C2	1.368 (4)	N2—HN2A	0.83 (2)
C1—C5^iv	1.428 (5)	N2—HN2B	0.85 (2)
C1—S1	1.775 (3)	O1—S1	1.450 (2)
C2—C3	1.397 (5)	O2—S1	1.443 (3)
C2—H2	0.9300	O3—S1	1.455 (3)
C3—C4	1.351 (5)	O1W—HW1A	0.83 (3)
C3—H3	0.9300	O1W—HW1B	0.83 (2)
C4—C5	1.413 (4)	O2W—HW2A	0.84 (3)
C4—H4	0.9300	O2W—HW2B	0.80 (3)
C5—C5^iv	1.423 (6)
N2—Ag1—O5^i	167.73 (9)	N2—C6—C7	115.6 (2)
N2—Ag1—O1	94.40 (10)	N2—C6—H6A	108.4
O5^i—Ag1—O1	93.23 (10)	C7—C6—H6A	108.4
N2—Ag1—Ag3^i	86.59 (7)	N2—C6—H6B	108.4
O5^i—Ag1—Ag3^i	81.15 (7)	C7—C6—H6B	108.4
O1—Ag1—Ag3^i	128.35 (6)	H6A—C6—H6B	107.4
O6^ii—Ag2—O6	180.00 (12)	O4—C7—O5	125.9 (3)
O6^ii—Ag2—O1W	84.11 (10)	O4—C7—C6	118.5 (3)
O6—Ag2—O1W	95.89 (10)	O5—C7—C6	115.6 (3)
O6^ii—Ag2—O1W^ii	95.89 (10)	O6—C8—O7	126.6 (3)
O6—Ag2—O1W^ii	84.11 (10)	O6—C8—C9	119.4 (3)
O1W—Ag2—O1W^ii	180.0	O7—C8—C9	114.0 (3)
O6^ii—Ag2—Ag4^ii	79.76 (7)	N1—C9—C8	114.7 (3)
O6—Ag2—Ag4^ii	100.24 (7)	N1—C9—H9AA	108.6
O1W—Ag2—Ag4^ii	101.28 (7)	C8—C9—H9AA	108.6
O1W^ii—Ag2—Ag4^ii	78.72 (7)	N1—C9—H9BA	108.6
O6^ii—Ag2—Ag4	100.24 (7)	C8—C9—H9BA	108.6
O6—Ag2—Ag4	79.76 (7)	H9AA—C9—H9BA	107.6
O1W—Ag2—Ag4	78.72 (7)	C9—N1—Ag4^vi	115.4 (2)
O1W^ii—Ag2—Ag4	101.28 (7)	C9—N1—HN1A	111 (3)
Ag4^ii—Ag2—Ag4	180.0	Ag4^vi—N1—HN1A	109 (3)
O4^iii—Ag3—O4	180.000 (1)	C9—N1—HN1B	113 (3)
O4^iii—Ag3—Ag1^v	81.95 (6)	Ag4^vi—N1—HN1B	104 (3)
O4—Ag3—Ag1^v	98.05 (6)	HN1A—N1—HN1B	103 (3)
O4^iii—Ag3—Ag1^vi	98.05 (6)	C6—N2—Ag1	112.69 (19)
O4—Ag3—Ag1^vi	81.95 (6)	C6—N2—HN2A	108 (3)
Ag1^v—Ag3—Ag1^vi	180.000 (1)	Ag1—N2—HN2A	106 (3)
O7—Ag4—N1^i	167.72 (12)	C6—N2—HN2B	107 (3)
O7—Ag4—Ag2	81.87 (8)	Ag1—N2—HN2B	113 (3)
N1^i—Ag4—Ag2	87.13 (9)	HN2A—N2—HN2B	110 (3)
C2—C1—C5^iv	120.5 (3)	S1—O1—Ag1	139.43 (14)
C2—C1—S1	118.7 (3)	C7—O4—Ag3	124.37 (19)
C5^iv—C1—S1	120.8 (2)	C7—O5—Ag1^vi	123.7 (2)
C1—C2—C3	120.9 (3)	C8—O6—Ag2	121.5 (2)
C1—C2—H2	119.5	C8—O7—Ag4	123.1 (2)
C3—C2—H2	119.5	O2—S1—O1	112.49 (15)
C4—C3—C2	120.2 (3)	O2—S1—O3	113.24 (18)
C4—C3—H3	119.9	O1—S1—O3	110.85 (17)
C2—C3—H3	119.9	O2—S1—C1	105.82 (17)
C3—C4—C5	121.3 (3)	O1—S1—C1	107.89 (15)
C3—C4—H4	119.3	O3—S1—C1	106.08 (16)
C5—C4—H4	119.3	Ag2—O1W—HW1A	104 (4)
C4—C5—C5^iv	119.2 (4)	Ag2—O1W—HW1B	108 (4)
C4—C5—C1^iv	123.0 (3)	HW1A—O1W—HW1B	111 (4)
C5^iv—C5—C1^iv	117.8 (3)	HW2A—O2W—HW2B	114 (4)
O6^ii—Ag2—Ag4—O7	162.46 (10)	O5—C7—O4—Ag3	6.5 (5)
O6—Ag2—Ag4—O7	−17.54 (10)	C6—C7—O4—Ag3	−173.1 (2)
O1W—Ag2—Ag4—O7	−115.73 (10)	Ag1^v—Ag3—O4—C7	166.0 (2)
O1W^ii—Ag2—Ag4—O7	64.27 (10)	Ag1^vi—Ag3—O4—C7	−14.0 (2)
O6^ii—Ag2—Ag4—N1^i	−12.06 (12)	O4—C7—O5—Ag1^vi	10.4 (5)
O6—Ag2—Ag4—N1^i	167.94 (12)	C6—C7—O5—Ag1^vi	−169.9 (2)
O1W—Ag2—Ag4—N1^i	69.76 (12)	O7—C8—O6—Ag2	−14.8 (5)
O1W^ii—Ag2—Ag4—N1^i	−110.24 (12)	C9—C8—O6—Ag2	164.8 (2)
C5^iv—C1—C2—C3	0.9 (5)	O1W—Ag2—O6—C8	100.9 (3)
S1—C1—C2—C3	178.4 (3)	O1W^ii—Ag2—O6—C8	−79.1 (3)
C1—C2—C3—C4	0.3 (6)	Ag4^ii—Ag2—O6—C8	−156.4 (2)
C2—C3—C4—C5	−1.6 (6)	Ag4—Ag2—O6—C8	23.6 (2)
C3—C4—C5—C5^iv	1.7 (6)	O6—C8—O7—Ag4	−11.3 (5)
C3—C4—C5—C1^iv	−178.8 (3)	C9—C8—O7—Ag4	169.1 (2)
N2—C6—C7—O4	7.5 (5)	N1^i—Ag4—O7—C8	49.3 (7)
N2—C6—C7—O5	−172.2 (3)	Ag2—Ag4—O7—C8	22.6 (3)
O6—C8—C9—N1	−5.0 (5)	Ag1—O1—S1—O2	−124.6 (2)
O7—C8—C9—N1	174.6 (3)	Ag1—O1—S1—O3	107.4 (2)
C8—C9—N1—Ag4^vi	−179.4 (2)	Ag1—O1—S1—C1	−8.3 (3)
C7—C6—N2—Ag1	172.9 (2)	C2—C1—S1—O2	−108.0 (3)
O5^i—Ag1—N2—C6	−173.6 (5)	C5^iv—C1—S1—O2	69.5 (3)
O1—Ag1—N2—C6	58.1 (2)	C2—C1—S1—O1	131.4 (3)
Ag3^i—Ag1—N2—C6	−173.6 (2)	C5^iv—C1—S1—O1	−51.1 (3)
N2—Ag1—O1—S1	131.8 (2)	C2—C1—S1—O3	12.5 (3)
O5^i—Ag1—O1—S1	−38.6 (3)	C5^iv—C1—S1—O3	−170.0 (3)
Ag3^i—Ag1—O1—S1	42.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—HW1A···O3^vii	0.83 (3)	1.92 (3)	2.742 (4)	171 (4)
O1W—HW1B···O2W^viii	0.83 (2)	2.03 (3)	2.848 (4)	171 (5)
O2W—HW2A···O7	0.83 (2)	1.98 (2)	2.810 (4)	177 (5)
N2—HN2A···O2^vii	0.83 (3)	2.24 (3)	2.961 (4)	145 (5)
N2—HN2A···O4^v	0.83 (3)	2.55 (5)	3.009 (3)	116 (4)
N1—HN1A···O6^ix	0.84 (3)	2.52 (4)	3.157 (4)	133 (4)
N1—HN1B···O5	0.87 (4)	2.45 (4)	3.147 (5)	138 (3)

Symmetry codes: (v) −x+1, −y+2, −z+1; (vii) x, y+1, z; (viii) x−1, y+1, z; (ix) −x+2, −y+2, −z.