Crystal structure of poly[[[μ4-3-(1,2,4-triazol-4-yl)adamantane-1-carboxyl-ato-κ5 N 1:N 2:O 1:O 1,O 1']silver(I)] dihydrate].

The heterobifunctional organic ligand, 3-(1,2,4-triazol-4-yl)adamantane-1-carboxyl-ate (tr-ad-COO- ), was employed for the synthesis of the title silver(I) coordination polymer, {[Ag(C13H16N3O2)]·2H2O} n , crystallizing in the rare ortho-rhom-bic C2221 space group. Alternation of the double μ2-1,2,4-triazole and μ2-η2:η1-COO- (chelating, bridging mode) bridges between AgI cations supports the formation of sinusoidal coordination chains. The AgI centers possess a distorted {N2O3} square-pyramidal arrangement with τ5 = 0.30. The angular organic linkers connect the chains into a tetra-gonal framework with small channels along the c-axis direction occupied by water mol-ecules of crystallization, which are inter-linked via O-H⋯O hydrogen bonds with carboxyl-ate groups, leading to right- and left-handed helical dispositions.

Chemical context

Organic ligands, which contain two different functional groups, such as azole and carb­oxy­lic groups, attract attention in the context of the construction of unusual metal–organic frameworks (MOFs) including heterometallic architectures (Guillerm et al. 2014 ▸). Each ligand function is intended to introduce its coordination ability towards a metal center forming secondary building units (SBUs) based on its peculiarities. For instance, 1,2,4-triazoles (tr) typically serve as short N,N-bridges between two metal ions resulting in polynuclear units and chains (Wang et al. 2007 ▸, Murdock & Jenkins 2014 ▸). In contrast, carboxyl­ate groups offer a much broader variety of coordination modes: mono-, chelate-, bridging- and their combinations; and the number of connected metal ions may differ from one to four (Sun et al. 2004 ▸; Lu et al. 2014 ▸). As shown by Lincke et al. (2011 ▸, 2012 ▸), 1,2,4-triazole­carboxyl­ate ligands are good candidates for the construction of microporous MOFs suitable for gas sorption and separation. Considering the heterofunctional tr/COO ligands, there are two possible roles for them to play. First, the ‘separate’ role, where tr is responsible for di-, tri- or tetra­nuclear cluster formation, whereas the COO group only occupies terminal (non-bridging) positions (Handke et al. 2014 ▸) or it can be involved in the separate coordination to metal centers. In this context, Chen et al. (2011 ▸) used 1,2,4-triazolyl isophthalate as a ligand in the synthesis of a series of AgI–Ln III heterometallic coordination polymers. Second, in the ‘cooperative’ role, tr/COO serves as a heteroleptic bridge between the metal centers (Vasylevs’kyy et al. 2015 ▸).

In present paper, we report the crystal structure of a new silver(I) coordination polymer [Ag(tr-ad-COO)]·2H2O (I) based on the 1-(1,2,4-triazol-4-yl)-3-carb­oxy­adamantane (C13H16N3O2; tr-ad-COOH) ligand.

Structural commentary

The title compound I crystallizes in the ortho­rhom­bic system with the uncommon space group C222. The asymmetric unit contains one AgI cation, one organic ligand and three distinct water mol­ecules of crystallization, one of which (O5) is disordered over two adjacent sites (Fig. 1 ▸). The O3 water mol­ecule is situated on a crystallographic twofold axis passing through the O atom, while the O4 water molecule is statistically disordered over two positions, both possessing an occupancy factor of 0.5. Thus, in the asymmetric unit, the total atom content sums up to two water molecules. The 1,2,4-triazole functional group is coordinated by two AgI centers as a μ2-N,N bridge and the carboxyl­ate group connects two AgI centers in a chelating, bridging mode (μ2-η2:η1), supporting the formation of sinusoidal chains with a periodicity of 13 Å.

Figure 1

Fragment of the crystal structure of I. The independent part of the structure is indicated with black bonds and displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i)  − x, − + y,  − z, (ii)  + x, − + y, z, (iii) x, −y, 1 − z]

In the case of compound I an unusual situation with alternation of double triazoles and double carboxyl­ate bridges within the chain is observed. Thus, the tr-ad-COO ligands act in a deprotonated form adopting a μ4-coordination modes (Fig. 2 ▸) that yields a three-dimensional tetra­gonal pattern with open channels along the c-axis direction (Fig. 3 ▸).

Figure 2

Projection on the bc plane showing the inter­connection of sinusoidal AgI coordination chains by means of tr-ad-COO organic ligands into a three-dimensional framework.

Figure 3

View of the channels along the c axis in the structure of I.

The coordination environment of the AgI cation is a very distorted {N2O3} polyhedron with two Ag—N(triazole) [2.291 (3) Å, 2.442 (3) Å] and three elongated Ag—O(carboxyl­ate) [2.437 (3)–2.703 (4) Å] bonds (Table 1 ▸). The geometry of the five-coordinate center can be described by the geometric parameter τ5, which represents the degree of trigonality between two ideal structures – trigonal bipyramid (τ5 = 1) and square pyramid (τ5 = 0) (Addison et al., 1984 ▸). In compound I, the Ag1 center has τ5 = 0.30, indicating a significantly distorted square-pyramidal geometry.

Table 1

Selected geometric parameters (Å, °)

Ag1—N2i	2.291 (3)	Ag1—O2	2.571 (4)
Ag1—O1	2.437 (3)	Ag1—O2iii	2.703 (4)
Ag1—N1ii	2.442 (3)
N2i—Ag1—O1	125.93 (11)	N1ii—Ag1—O2	121.93 (12)
N2i—Ag1—N1ii	92.12 (11)	N2i—Ag1—O2iii	101.35 (11)
O1—Ag1—N1ii	106.84 (11)	O1—Ag1—O2iii	128.04 (11)
N2i—Ag1—O2	145.74 (12)	N1ii—Ag1—O2iii	89.79 (11)
O1—Ag1—O2	51.95 (11)	O2—Ag1—O2iii	77.22 (13)

Symmetry codes: (i) ; (ii) ; (iii) .

Supra­molecular features

The water guest mol­ecules inside the [001] channels are responsible for the extended hydrogen-bonding network (Table 2 ▸). Together with the –COO− groups, they are organized into two types of helices along the c axis – smaller right-handed (A in Fig. 4 ▸) and bigger left-handed (B in Fig. 4 ▸). In addition, weak C—H(triazole)⋯O1(COO) and C—H(triazole)⋯O4(water) contacts are observed. The packig is shown in Fig. 5 ▸.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1W⋯O1	0.85	1.97	2.818 (5)	171
O4—H2W⋯O3	0.85	1.92	2.746 (10)	163
O4—H3W⋯O5A iv	0.85	1.81	2.56 (2)	147
O4—H3W⋯O5B iv	0.85	2.11	2.83 (3)	143
C1—H1⋯O1v	0.94	2.43	3.336 (5)	162
C2—H2⋯O4vi	0.94	2.58	3.516 (12)	171

Symmetry codes: (iv) ; (v) ; (vi) .

Figure 4

Hydrogen-bonding scheme between water mol­ecules and COO− groups showing the formation of right-handed (A) and left-handed (B) helices. Adamantyl fragments are omitted for clarity. [Symmetry codes: (iv)  + x,  − y, 1 − z; (v) −  + x,  − y, 1 − z; (vi) 1 − x, y,  − z; (vii)  − x,  − y,  + z.]

Figure 5

The packing of the right- and left-handed helices in the crystal structure of I (top view). Adamantyl fragments are omitted for clarity.

Synthesis and crystallization

1-(1,2,4-Triazol-4-yl)-3-carb­oxy­adamantane (tr-ad-COOH) was synthesized by refluxing 3-amino-adamantane-1-carb­oxy­lic acid (Wanka et al., 2007 ▸) (3.00 g, 15.4 mmol) and di­methyl­formamide azine (5.46 g, 38.5 mmol) in the presence of toluene­sulfonic acid monohydrate (0.44 g, 2.3 mmol) as catalyst in DMF (30 ml). Yield = 63%.

The synthesis of I was carried out under hydro­thermal conditions as follows. A mixture of AgNO3 (17.0 mg, 0.100 mmol), tr-ad-COOH (12.4 mg, 0.050 mmol) and 5 ml of water was added into a Teflon vessel, which was sealed and heated at 413 K for 24 h and slowly cooled to room temperature over 48 h, yielding colourless needles of I (yield 13.3 mg, 68%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. O4 lies adjacent to a crystallographic twofold axis and is statistically disordered over two positions (O4⋯O4 = 0.60 Å) and O5 is statistically disordered over adjacent locations (O5A⋯O5B = 0.77 Å). CH hydrogen atoms were positioned geometrically and refined as riding, with C—H = 0.94 Å (triazole); C—H = 0.98 Å (adamantane CH2); C—H = 0.99 Å (adamantane CH) and with U iso(H) = 1.2U eq(C). OH hydrogen atoms were located and then refined with O—H = 0.85 Å (H2O) and with U iso(H) = 1.5U eq(O). For one of the disordered water mol­ecules, the H atoms were not located.

Table 3

Experimental details

Crystal data
Chemical formula	[Ag(C13H16N3O2)]·2H2O
M r	390.19
Crystal system, space group	Orthorhombic, C2221
Temperature (K)	213
a, b, c (Å)	12.9321 (9), 17.9056 (10), 12.9695 (9)
V (Å3)	3003.2 (3)
Z	8
Radiation type	Mo Kα
μ (mm−1)	1.36
Crystal size (mm)	0.22 × 0.18 × 0.16
Data collection
Diffractometer	Stoe Image plate diffraction system
Absorption correction	Numerical [X-RED (Stoe & Cie, 2001 ▸) and X-SHAPE (Stoe & Cie, 1999 ▸)]
T min, T max	0.649, 0.689
No. of measured, independent and observed [I > 2σ(I)] reflections	13596, 3617, 3135
R int	0.028
(sin θ/λ)max (Å−1)	0.661
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.025, 0.058, 0.97
No. of reflections	3617
No. of parameters	204
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.89, −0.94
Absolute structure	Flack x determined using 1289 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	−0.060 (9)

Computer programs: IPDS Software (Stoe & Cie, 2000 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019009708/hb7837sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009708/hb7837Isup2.hkl

CCDC reference: 1939097

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ag(C13H16N3O2)]·2H2O	Dx = 1.726 Mg m−3
Mr = 390.19	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C2221	Cell parameters from 13596 reflections
a = 12.9321 (9) Å	θ = 2.8–28.0°
b = 17.9056 (10) Å	µ = 1.36 mm−1
c = 12.9695 (9) Å	T = 213 K
V = 3003.2 (3) Å3	Needle, colourless
Z = 8	0.22 × 0.18 × 0.16 mm
F(000) = 1584

Stoe Image plate diffraction system diffractometer	3135 reflections with I > 2σ(I)
φ oscillation scans	Rint = 0.028
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	θmax = 28.0°, θmin = 2.8°
Tmin = 0.649, Tmax = 0.689	h = −17→17
13596 measured reflections	k = −22→23
3617 independent reflections	l = −17→17

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025	w = 1/[σ2(Fo2) + (0.037P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.058	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 0.89 e Å−3
3617 reflections	Δρmin = −0.94 e Å−3
204 parameters	Absolute structure: Flack x determined using 1289 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.060 (9)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ag1	0.39032 (3)	0.01581 (2)	0.35981 (2)	0.04198 (10)
O1	0.4141 (3)	0.14822 (17)	0.3962 (2)	0.0474 (8)
O2	0.3185 (3)	0.09152 (19)	0.5123 (3)	0.0581 (9)
N1	0.0616 (2)	0.45845 (17)	0.3648 (3)	0.0318 (6)
N2	0.1451 (2)	0.46474 (17)	0.2982 (2)	0.0316 (7)
N3	0.1946 (2)	0.39903 (16)	0.4325 (2)	0.0231 (6)
C1	0.0930 (3)	0.4190 (2)	0.4435 (3)	0.0282 (8)
H1	0.0514	0.4060	0.5001	0.034*
C2	0.2230 (3)	0.4290 (2)	0.3398 (2)	0.0276 (7)
H2	0.2890	0.4245	0.3102	0.033*
C3	0.3583 (3)	0.1495 (2)	0.4758 (3)	0.0339 (9)
C4	0.2574 (2)	0.3521 (2)	0.5055 (3)	0.0219 (7)
C5	0.2762 (3)	0.27539 (19)	0.4550 (3)	0.0234 (7)
H5A	0.3139	0.2819	0.3900	0.028*
H5B	0.2098	0.2515	0.4396	0.028*
C6	0.3398 (3)	0.2253 (2)	0.5293 (3)	0.0260 (7)
C7	0.2807 (3)	0.2174 (2)	0.6319 (3)	0.0333 (8)
H7A	0.2140	0.1929	0.6196	0.040*
H7B	0.3206	0.1862	0.6796	0.040*
C8	0.2626 (3)	0.2948 (2)	0.6802 (3)	0.0333 (9)
H8	0.2247	0.2887	0.7460	0.040*
C9	0.1977 (3)	0.3427 (2)	0.6064 (3)	0.0278 (8)
H9A	0.1311	0.3184	0.5931	0.033*
H9B	0.1843	0.3917	0.6374	0.033*
C10	0.3616 (3)	0.3907 (2)	0.5253 (3)	0.0287 (8)
H10A	0.3502	0.4401	0.5556	0.034*
H10B	0.3990	0.3970	0.4601	0.034*
C11	0.4256 (3)	0.3416 (2)	0.5999 (3)	0.0326 (8)
H11	0.4930	0.3659	0.6135	0.039*
C12	0.4439 (3)	0.2646 (2)	0.5505 (3)	0.0294 (8)
H12A	0.4859	0.2338	0.5968	0.035*
H12B	0.4819	0.2707	0.4857	0.035*
C13	0.3663 (3)	0.3327 (2)	0.7016 (3)	0.0384 (10)
H13A	0.4069	0.3025	0.7499	0.046*
H13B	0.3547	0.3818	0.7328	0.046*
O3	0.5000	0.2468 (3)	0.2500	0.0630 (13)
H1W	0.4787	0.2190	0.2988	0.094*
O4	0.5231 (6)	0.3992 (4)	0.2479 (18)	0.068 (3)	0.5
H2W	0.5153	0.3530	0.2348	0.102*	0.5
H3W	0.5724	0.4038	0.2909	0.102*	0.5
O5A	0.1318 (13)	0.0398 (10)	0.6097 (11)	0.096 (4)	0.5
O5B	0.1073 (12)	0.0560 (11)	0.5604 (12)	0.100 (5)	0.5

	U11	U22	U33	U12	U13	U23
Ag1	0.04963 (17)	0.03609 (16)	0.04023 (15)	0.01122 (15)	−0.00959 (15)	−0.01749 (13)
O1	0.063 (2)	0.0348 (16)	0.0446 (17)	0.0145 (14)	−0.0012 (14)	−0.0141 (12)
O2	0.064 (2)	0.0231 (18)	0.087 (3)	0.0013 (17)	0.005 (2)	−0.0047 (15)
N1	0.0325 (15)	0.0318 (15)	0.0311 (14)	0.0098 (12)	−0.0019 (15)	−0.0012 (14)
N2	0.0379 (17)	0.0292 (17)	0.0275 (14)	0.0059 (13)	−0.0028 (12)	0.0018 (12)
N3	0.0255 (15)	0.0201 (15)	0.0239 (14)	0.0042 (12)	−0.0023 (11)	0.0004 (11)
C1	0.0258 (19)	0.0321 (19)	0.0266 (17)	0.0057 (15)	0.0039 (14)	0.0016 (13)
C2	0.0290 (17)	0.0307 (19)	0.0231 (17)	0.0050 (15)	0.0002 (13)	0.0037 (13)
C3	0.037 (2)	0.019 (2)	0.045 (2)	0.0076 (16)	−0.0134 (16)	−0.0061 (17)
C4	0.0260 (15)	0.022 (2)	0.0176 (13)	0.0035 (15)	−0.0030 (14)	0.0009 (11)
C5	0.0261 (16)	0.0211 (17)	0.0229 (15)	0.0034 (14)	−0.0023 (13)	−0.0028 (13)
C6	0.0317 (18)	0.0184 (17)	0.0280 (17)	0.0040 (15)	−0.0026 (13)	−0.0024 (13)
C7	0.0394 (18)	0.0290 (19)	0.0315 (18)	0.0046 (15)	0.0011 (17)	0.0080 (16)
C8	0.042 (2)	0.039 (2)	0.0196 (15)	0.0089 (17)	0.0015 (15)	0.0045 (14)
C9	0.0321 (19)	0.0278 (19)	0.0235 (16)	0.0076 (15)	0.0039 (13)	0.0010 (13)
C10	0.0305 (19)	0.0208 (19)	0.0349 (19)	−0.0023 (14)	−0.0063 (13)	−0.0024 (15)
C11	0.0323 (19)	0.0275 (19)	0.0380 (19)	0.0011 (15)	−0.0147 (15)	−0.0050 (15)
C12	0.0272 (18)	0.029 (2)	0.0321 (19)	0.0056 (16)	−0.0059 (14)	−0.0003 (15)
C13	0.052 (3)	0.037 (2)	0.0266 (17)	0.0087 (18)	−0.0121 (16)	−0.0052 (15)
O3	0.067 (3)	0.060 (3)	0.062 (3)	0.000	0.001 (3)	0.000
O4	0.051 (9)	0.068 (4)	0.085 (5)	−0.008 (4)	−0.018 (10)	0.000 (6)
O5A	0.089 (10)	0.109 (9)	0.091 (10)	−0.005 (7)	0.009 (7)	−0.018 (8)
O5B	0.060 (7)	0.128 (12)	0.110 (11)	0.003 (8)	−0.005 (8)	−0.045 (10)

Ag1—N2i	2.291 (3)	C6—C12	1.544 (5)
Ag1—O1	2.437 (3)	C7—C8	1.538 (5)
Ag1—N1ii	2.442 (3)	C7—H7A	0.9800
Ag1—O2	2.571 (4)	C7—H7B	0.9800
Ag1—O2iii	2.703 (4)	C8—C13	1.529 (6)
O1—C3	1.259 (5)	C8—C9	1.536 (5)
O2—C3	1.251 (5)	C8—H8	0.9900
N1—C1	1.305 (5)	C9—H9A	0.9800
N1—N2	1.387 (4)	C9—H9B	0.9800
N1—Ag1iv	2.442 (3)	C10—C11	1.548 (5)
N2—C2	1.310 (5)	C10—H10A	0.9800
N2—Ag1v	2.291 (3)	C10—H10B	0.9800
N3—C2	1.366 (4)	C11—C13	1.533 (6)
N3—C1	1.369 (5)	C11—C12	1.538 (5)
N3—C4	1.505 (4)	C11—H11	0.9900
C1—H1	0.9400	C12—H12A	0.9800
C2—H2	0.9400	C12—H12B	0.9800
C3—C6	1.544 (5)	C13—H13A	0.9800
C4—C9	1.530 (5)	C13—H13B	0.9800
C4—C10	1.535 (5)	O3—H1W	0.8500
C4—C5	1.541 (5)	O4—O4vi	0.601 (16)
C5—C6	1.552 (5)	O4—H2W	0.8500
C5—H5A	0.9800	O4—H3W	0.8500
C5—H5B	0.9800	O5A—O5B	0.770 (16)
C6—C7	1.542 (5)
N2i—Ag1—O1	125.93 (11)	C3—C6—C5	108.1 (3)
N2i—Ag1—N1ii	92.12 (11)	C8—C7—C6	110.1 (3)
O1—Ag1—N1ii	106.84 (11)	C8—C7—H7A	109.6
N2i—Ag1—O2	145.74 (12)	C6—C7—H7A	109.6
O1—Ag1—O2	51.95 (11)	C8—C7—H7B	109.6
N1ii—Ag1—O2	121.93 (12)	C6—C7—H7B	109.6
N2i—Ag1—O2iii	101.35 (11)	H7A—C7—H7B	108.2
O1—Ag1—O2iii	128.04 (11)	C13—C8—C9	110.1 (3)
N1ii—Ag1—O2iii	89.79 (11)	C13—C8—C7	110.0 (3)
O2—Ag1—O2iii	77.22 (13)	C9—C8—C7	109.5 (3)
C3—O1—Ag1	96.0 (3)	C13—C8—H8	109.1
C3—O2—Ag1	89.9 (3)	C9—C8—H8	109.1
C1—N1—N2	106.7 (3)	C7—C8—H8	109.1
C1—N1—Ag1iv	122.0 (2)	C4—C9—C8	108.5 (3)
N2—N1—Ag1iv	130.9 (2)	C4—C9—H9A	110.0
C2—N2—N1	107.6 (3)	C8—C9—H9A	110.0
C2—N2—Ag1v	135.8 (2)	C4—C9—H9B	110.0
N1—N2—Ag1v	115.7 (2)	C8—C9—H9B	110.0
C2—N3—C1	104.3 (3)	H9A—C9—H9B	108.4
C2—N3—C4	128.9 (3)	C4—C10—C11	108.6 (3)
C1—N3—C4	126.8 (3)	C4—C10—H10A	110.0
N1—C1—N3	111.0 (3)	C11—C10—H10A	110.0
N1—C1—H1	124.5	C4—C10—H10B	110.0
N3—C1—H1	124.5	C11—C10—H10B	110.0
N2—C2—N3	110.3 (3)	H10A—C10—H10B	108.4
N2—C2—H2	124.8	C13—C11—C12	110.0 (3)
N3—C2—H2	124.8	C13—C11—C10	109.2 (3)
O2—C3—O1	122.1 (4)	C12—C11—C10	109.3 (3)
O2—C3—C6	119.7 (4)	C13—C11—H11	109.4
O1—C3—C6	118.2 (4)	C12—C11—H11	109.4
N3—C4—C9	109.1 (3)	C10—C11—H11	109.4
N3—C4—C10	109.1 (3)	C11—C12—C6	110.4 (3)
C9—C4—C10	110.5 (3)	C11—C12—H12A	109.6
N3—C4—C5	108.4 (3)	C6—C12—H12A	109.6
C9—C4—C5	110.2 (3)	C11—C12—H12B	109.6
C10—C4—C5	109.5 (3)	C6—C12—H12B	109.6
C4—C5—C6	109.5 (3)	H12A—C12—H12B	108.1
C4—C5—H5A	109.8	C8—C13—C11	109.2 (3)
C6—C5—H5A	109.8	C8—C13—H13A	109.8
C4—C5—H5B	109.8	C11—C13—H13A	109.8
C6—C5—H5B	109.8	C8—C13—H13B	109.8
H5A—C5—H5B	108.2	C11—C13—H13B	109.8
C7—C6—C12	108.7 (3)	H13A—C13—H13B	108.3
C7—C6—C3	112.6 (3)	O4vi—O4—H2W	84.2
C12—C6—C3	110.2 (3)	O4vi—O4—H3W	133.4
C7—C6—C5	109.1 (3)	H2W—O4—H3W	108.4
C12—C6—C5	108.1 (3)
C1—N1—N2—C2	−0.1 (4)	O2—C3—C6—C5	−114.4 (4)
Ag1iv—N1—N2—C2	173.7 (3)	O1—C3—C6—C5	65.8 (4)
C1—N1—N2—Ag1v	171.1 (2)	C4—C5—C6—C7	58.0 (4)
Ag1iv—N1—N2—Ag1v	−15.1 (4)	C4—C5—C6—C12	−60.0 (4)
N2—N1—C1—N3	0.4 (4)	C4—C5—C6—C3	−179.3 (3)
Ag1iv—N1—C1—N3	−174.1 (2)	C12—C6—C7—C8	58.8 (4)
C2—N3—C1—N1	−0.5 (4)	C3—C6—C7—C8	−178.8 (3)
C4—N3—C1—N1	−178.4 (3)	C5—C6—C7—C8	−58.8 (4)
N1—N2—C2—N3	−0.2 (4)	C6—C7—C8—C13	−60.3 (4)
Ag1v—N2—C2—N3	−168.8 (3)	C6—C7—C8—C9	60.7 (4)
C1—N3—C2—N2	0.4 (4)	N3—C4—C9—C8	180.0 (3)
C4—N3—C2—N2	178.3 (3)	C10—C4—C9—C8	−60.1 (4)
Ag1—O2—C3—O1	−4.0 (4)	C5—C4—C9—C8	61.1 (4)
Ag1—O2—C3—C6	176.3 (3)	C13—C8—C9—C4	59.9 (4)
Ag1—O1—C3—O2	4.2 (4)	C7—C8—C9—C4	−61.1 (4)
Ag1—O1—C3—C6	−176.0 (3)	N3—C4—C10—C11	−179.7 (3)
C2—N3—C4—C9	170.9 (3)	C9—C4—C10—C11	60.4 (4)
C1—N3—C4—C9	−11.7 (5)	C5—C4—C10—C11	−61.2 (4)
C2—N3—C4—C10	50.1 (5)	C4—C10—C11—C13	−60.1 (4)
C1—N3—C4—C10	−132.5 (3)	C4—C10—C11—C12	60.4 (4)
C2—N3—C4—C5	−69.0 (4)	C13—C11—C12—C6	59.3 (4)
C1—N3—C4—C5	108.3 (4)	C10—C11—C12—C6	−60.6 (4)
N3—C4—C5—C6	−179.3 (3)	C7—C6—C12—C11	−58.4 (4)
C9—C4—C5—C6	−60.0 (3)	C3—C6—C12—C11	177.8 (3)
C10—C4—C5—C6	61.8 (4)	C5—C6—C12—C11	59.8 (4)
O2—C3—C6—C7	6.2 (5)	C9—C8—C13—C11	−60.8 (4)
O1—C3—C6—C7	−173.6 (3)	C7—C8—C13—C11	59.9 (4)
O2—C3—C6—C12	127.7 (4)	C12—C11—C13—C8	−59.4 (4)
O1—C3—C6—C12	−52.1 (4)	C10—C11—C13—C8	60.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1W···O1	0.85	1.97	2.818 (5)	171
O4—H2W···O3	0.85	1.92	2.746 (10)	163
O4—H3W···O5Avii	0.85	1.81	2.56 (2)	147
O4—H3W···O5Bvii	0.85	2.11	2.83 (3)	143
C1—H1···O1viii	0.94	2.43	3.336 (5)	162
C2—H2···O4vi	0.94	2.58	3.516 (12)	171