Crystal structure of poly[[[μ4-3-(1,2,4-triazol-4-yl)adamantane-1-carboxyl­ato-κ5N1:N2:O1:O1,O1′]silver(I)] dihydrate]

Senchyk, G.A.; Krautscheid, H.; Domasevitch, K.V.

doi:10.1107/S2056989019009708

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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1145-1148

https://doi.org/10.1107/S2056989019009708

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Crystal structure of poly[[[μ₄-3-(1,2,4-triazol-4-yl)adamantane-1-carboxylato-κ⁵N¹:N²:O¹:O¹,O^1′]silver(I)] dihydrate]

Ganna A. Senchyk,^a ^* Harald Krautscheid ^b and Kostiantyn V. Domasevitch ^a

^aInorganic Chemistry Department, Taras Shevchenko National University of Kyiv, Volodymyrska Street, 64, Kyiv 01033, Ukraine, and ^bInstitut für Anorganische Chemie, Universitat Leipzig, Johannisallee 29, D-04103, Leipzig, Germany
^*Correspondence e-mail: senchyk.ganna@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 28 June 2019; accepted 8 July 2019; online 12 July 2019)

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

Keywords: 1,2,4-triazolyl carboxylate; silver(I) metal-organic framework; hydrogen bonding; crystal structure.

CCDC reference: 1939097

1. 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 Ag^I–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)]_n·2H₂O (I) based on the 1-(1,2,4-triazol-4-yl)-3-carboxyadamantane (C₁₃H₁₆N₃O₂; tr-ad-COOH) ligand.

2. Structural commentary

The title compound I crystallizes in the orthorhombic system with the uncommon space group C222₁. The asymmetric unit contains one Ag^I 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 Ag^I centers as a μ₂-N,N bridge and the carboxylate group connects two Ag^I 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) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z, (ii) $[{1\over 2}]$ + x, − $[{1\over 2}]$ + 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 Ag^I 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 Ag^I 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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) x, -y, -z+1.

3. 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⋯O1^v	0.94	2.43	3.336 (5)	162
C2—H2⋯O4^vi	0.94	2.58	3.516 (12)	171
Symmetry codes: (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (vi) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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) $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z; (v) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z; (vi) 1 − x, y, $[{1\over 2}]$ − z; (vii) $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + 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.

4. 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%).

5. 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[F² > 2σ(F²)], wR(F²), S	0.025, 0.058, 0.97
No. of reflections	3617
No. of parameters	204
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 1939097

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009708/hb7837sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009708/hb7837Isup2.hkl

checkCIF report

Computing details top

Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Poly[[[µ₄-3-(1,2,4-triazol-4-yl)adamantane-1-carboxylato-κ⁵N¹:N²:O¹:O¹,O^1']silver(I)] dihydrate] top

Crystal data top

[Ag(C₁₃H₁₆N₃O₂)]·2H₂O	D_x = 1.726 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.037P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.058	(Δ/σ)_max = 0.001
S = 0.97	Δρ_max = 0.89 e Å⁻³
3617 reflections	Δρ_min = −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)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—Ag1^iv	2.442 (3)	C10—C11	1.548 (5)
N2—C2	1.310 (5)	C10—H10A	0.9800
N2—Ag1^v	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—O4^vi	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—Ag1^iv	122.0 (2)	C4—C9—C8	108.5 (3)
N2—N1—Ag1^iv	130.9 (2)	C4—C9—H9A	110.0
C2—N2—N1	107.6 (3)	C8—C9—H9A	110.0
C2—N2—Ag1^v	135.8 (2)	C4—C9—H9B	110.0
N1—N2—Ag1^v	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)	O4^vi—O4—H2W	84.2
C12—C6—C3	110.2 (3)	O4^vi—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)
Ag1^iv—N1—N2—C2	173.7 (3)	O1—C3—C6—C5	65.8 (4)
C1—N1—N2—Ag1^v	171.1 (2)	C4—C5—C6—C7	58.0 (4)
Ag1^iv—N1—N2—Ag1^v	−15.1 (4)	C4—C5—C6—C12	−60.0 (4)
N2—N1—C1—N3	0.4 (4)	C4—C5—C6—C3	−179.3 (3)
Ag1^iv—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)
Ag1^v—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)

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

Hydrogen-bond geometry (Å, º) top

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^vii	0.85	1.81	2.56 (2)	147
O4—H3W···O5B^vii	0.85	2.11	2.83 (3)	143
C1—H1···O1^viii	0.94	2.43	3.336 (5)	162
C2—H2···O4^vi	0.94	2.58	3.516 (12)	171

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

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 19BF037-05).

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