Crystal structure of tetra-kis-[μ-3-carboxy-1-(1,2,4-triazol-4-yl)adamantane-κ2 N 1:N 2]tetra-fluoridodi-μ2-oxido-dioxidodisilver(I)divanadium(V) tetra-hydrate.

The crystal structure of the title mol-ecular complex, [Ag2{VO2F2}2(C13H17N3O2)4]·4H2O, supported by the heterofunctional ligand tr-ad-COOH [1-(1,2,4-triazol-4-yl)-3-carb-oxy-adamantane] is reported. Four 1,2,4-triazole groups of the ligand link two AgI atoms, as well as AgI and VV centres, forming the heterobimetallic coordination cluster {AgI 2(VVO2F2)2(tr)4}. VV exists as a vanadium oxofluoride anion and possesses a distorted trigonal-bipyramidal coordination environment [VO2F2N]. A carb-oxy-lic acid functional group of the ligand stays in a neutral form and is involved in hydrogen bonding with solvent water mol-ecules and VO2F2 - ions of adjacent mol-ecules. The extended hydrogen-bonding network is responsible for the crystal packing in the structure.

Chemical context

Heterometallic hybrids incorporating a metal oxide/oxofluoride matrix are of particular inter­est as they exhibit non-trivial magnetic, luminescent (Cui et al., 2012 ▸), optical and catalytic properties (Dolbecq et al., 2010 ▸). Among the broad range of inorganic anions, vanadium oxofluorides (VOFs) stand out for their large number of types and structural motifs from mono- (Aldous et al., 2007 ▸; Stephens et al., 2005 ▸) to polynuclear (Buchholz et al., 1988 ▸; Ninclaus et al., 1997 ▸) ones in the structure as discrete units or incorporated into coordination frameworks (Welk et al., 2007 ▸; Mahenthirarajah et al., 2008 ▸). The AgI/VOF pair is a non-typical combination for classical coordination chemistry, but materials such as Ag4V2O6F2 (Sorensen et al., 2005 ▸; Albrecht et al., 2009 ▸) and Ag3VO2F4 (Chamberlain et al., 2010 ▸) are attractive electrochemically active phases for solid-state batteries.

In the present research we introduce a new ligand [tr-ad-COOH = 1-(1,2,4-triazol-4-yl)-3-carb­oxy­adamantane], whose 1,2,4-triazole and –COOH donor groups can support the formation of the Ag–V heterometallic coordination cluster. It has recently been shown (Senchyk et al., 2012 ▸) that symmetrical 1,2,4-triazoles can selectively bridge these different metals. Considering a possible step-by-step mechanism, it becomes clear that after the formation of the simplest {Ag2(η 2-tr)2(tr)2}2+ binuclear fragment, two N atoms remain uncoordinated and have potential for further inter­actions. In aqueous reaction media, vanadium oxofluorides exist in anionic forms with weakly coordinated water mol­ecules that are very labile toward N-donor ligand substitution. Thus, a combination of an AgI–triazole cation and VOF anions lead to the neutral tetra­nuclear {AgI 2(VVO2F2)2(tr)4} unit, which was found in the structure of the title [Ag2(VO2F2)2(tr-ad-COOH)4]·4H2O complex I (Fig. 1 ▸).

Figure 1

The mol­ecular structure of compound I, showing the atomic labelling scheme [symmetry code: (i) –x, 1 – y, –z]. Displacement ellipsoids are drawn at the 30% probability level. The two symmetry-generated water molecules are omitted.

Structural commentary

The asymmetric unit of the title compound contains one AgI cation, one [VO2F2]− anion, two organic ligands and two solvent water mol­ecules. Two silver ions, two VOF anions and four tr-ad-COOH units constitute the mol­ecular tetra­nuclear cluster, which resides across an inversion centre (Fig. 1 ▸). The AgI atom adopts a distorted tetra­hedral coordination environment [AgN3O] with typical Ag—N(triazole) bond lengths [2.230 (3)–2.262 (3) Å; Table 1 ▸] and an elongated Ag—O bond [2.700 (3) Å]. Two 1,2,4-triazole functional groups link two adjacent silver atoms [the Ag⋯Agi distance is 3.7488 (5) Å; symmetry code: (i) –x, −y + 1, −z], while the other two 1,2,4-triazole groups combine the Ag and V centres [Ag⋯V= 3.5376 (6) Å]. The VV atom possesses a distorted trigonal–bipyramidal coordination environment [VO2F2N] with short V—O bonds [1.627 (2), 1.628 (2) Å], V—F bonds [1.839 (2), 1.850 (2) Å] and an elongated V—N bond [2.152 (3) Å]. The polyhedra can be more precisely described by the Reedijk’s factor τ (Addison et al., 1984 ▸) of 0.72 (for strict square-pyramidal polyhedra τ = 0 and for trigonal–bipyramidal τ = 1).

Table 1

Selected geometric parameters (Å, °)

Ag1—N4	2.230 (3)	V1—O2	1.628 (2)
Ag1—N2	2.257 (3)	V1—F2	1.839 (2)
Ag1—N5i	2.262 (3)	V1—F1	1.850 (2)
Ag1—O1	2.700 (3)	V1—N1	2.152 (3)
V1—O1	1.627 (2)
N4—Ag1—N2	121.35 (11)	O1—V1—F1	122.01 (12)
N4—Ag1—N5i	115.91 (10)	O2—V1—F1	122.74 (11)
N2—Ag1—N5i	120.21 (11)	F2—V1—F1	86.60 (10)
N4—Ag1—O1	114.33 (9)	O1—V1—N1	87.04 (11)
N2—Ag1—O1	74.30 (9)	O2—V1—N1	87.42 (12)
N5i—Ag1—O1	97.45 (10)	F2—V1—N1	166.19 (11)
O1—V1—O2	112.52 (13)	F1—V1—N1	79.59 (10)
O1—V1—F2	100.53 (11)	V1—O1—Ag1	107.06 (11)
O2—V1—F2	100.10 (12)

Symmetry code: (i) .

As a result, the heterobimetallic unit {AgI 2(VVO2F2)2(tr)4} is formed. A search in the Cambridge Structural Database (version 5.39, updates of May 2018; Groom et al., 2016 ▸) shows that only three crystal structures containing the AgI/tr/VV fragments are known so far (Senchyk et al., 2012 ▸). While considering heterofunctional ligands, {Cu2(HL)2[Mo4O13]}·2H2O (H2 L = 5-triazole isophthalic acid; Zhu et al., 2012 ▸) is the only known structure where both COO− and triazole groups support the heterometallic Cu⋯Mo connection.

Supra­molecular features

The structure of I is characterized by an extended hydrogen-bonding network. The carb­oxy­lic function of the tr-ad-COOH ligand remains in a neutral form, being uncoordinated. It is involved in hydrogen bonding that leads to a three-dimensional hydrogen-bonded network (Figs. 2 ▸ and 3 ▸). The nearest environment of the mol­ecular fragment complex involved in hydrogen-bonding inter­actions is shown in Fig. 4 ▸. The corres­ponding geometric parameters are given in Table 2 ▸. One carb­oxy­lic group, as a hydrogen-bond donor, forms a contact with a water mol­ecule O3—H1O⋯O2W iv = 2.650 (4) Å [symmetry code: (iv) x, 1 + y, z], while another COOH group, as a hydrogen-bond acceptor, is directed toward the F atom of a {VO2F2} anion [O5—H2O⋯F1v = 2.589 (3) Å; symmetry code: (v) 1 + x, −1 + y, z]. Two water mol­ecules are inter­bonded [O2W—H3W⋯O1W = 2.753 (4) Å] and additionally act as hydrogen-bond donors with O and F atoms from the neighboring {VO2F2} anions and as hydrogen-bond acceptor (in the case of O2W ) with the O3 atom from an adjacent carb­oxy­lic group. Some weak contacts between the triazole C—H groups and F atoms of the VOF anions are also observed.

Figure 2

View of the crystal packing of compound I. Vanadium oxofluoride anions are shown as polyhedra.

Figure 3

Projection on the ab plane showing the crystal packing in the structure. Vanadium oxofluoride anions are shown as polyhedra.

Figure 4

Hydrogen-bonding arrangement in the structure of the title compound. The adamantyl scaffolds are shown in a stick mode omitting the H atoms [symmetry codes: (i) −x, 1 − y, −z; (ii) 1 + x, y, z; (iii) −x, 1 − y, 1 − z; (iv) x, 1 + y, z; (v) 1 + x, −1 + y, z; (vi) x, −1 + y, z; (vii) −1 + x, y, z; (viii) −1 + x, 1 + y, z].

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯F2ii	0.85	1.92	2.763 (4)	169
O1W—H2W⋯O2iii	0.85	2.08	2.910 (4)	166
O2W—H3W⋯O1W	0.85	2.08	2.753 (4)	136
O2W—H4W⋯O1	0.85	2.00	2.813 (4)	161
O3—H1O⋯O2W iv	0.82	1.83	2.650 (4)	178
O5—H2O⋯F1v	0.82	1.77	2.589 (3)	178
C15—H15⋯F1i	0.93	2.19	2.966 (4)	141
C14—H14⋯F2ii	0.93	2.44	3.303 (4)	154

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

Synthesis and crystallization

1-(1,2,4-Triazol-4-yl)-3-carb­oxy­adamantane (tr-ad-COOH) was synthesized in 63% yield 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). Complex I was prepared under hydro­thermal conditions as follows. A mixture of AgOAc (16.7 mg, 0.100 mmol), tr-ad-COOH (12.4 mg, 0.050 mmol), V2O5 (9.1 mg, 0.050 mmol) and 5 mL of water with aqueous HF (50%, 150 µL, 4.33 mmol) was added into a Teflon vessel. Then the components were heated at 423 K for 24 h and slowly cooled to room temperature over 50 h, yielding light-yellow prisms of I (yield 14.8 mg, 78%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The non-H atoms were refined with anisotropic displacement parameters and a soft rigid-bond restraint was applied to C10—C13 in order to improve the refinement stability. C-bound hydrogen atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å (triazole), C—H = 0.97 Å (adamantane CH2), C—H = 0.98 Å (adamantane CH) and with U iso(H) = 1.2U eq(C). O-bound hydrogen atoms were located in a difference-Fourier map and then refined with O—H = 0.82 Å (carb­oxy­lic) or 0.85 Å (H2O) with U iso(H) = 1.5U eq(O).

Table 3

Experimental details

Crystal data
Chemical formula	[Ag2V2F4O4(C13H17N3O2)4]·4H2O
M r	1518.86
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c (Å)	8.2673 (5), 12.6026 (6), 14.6757 (7)
α, β, γ (°)	77.985 (3), 86.535 (2), 83.945 (3)
V (Å3)	1486.05 (14)
Z	1
Radiation type	Mo Kα
μ (mm−1)	1.05
Crystal size (mm)	0.26 × 0.12 × 0.10
Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	Numerical [face indexed (SADABS; Bruker, 2008 ▸)]
T min, T max	0.682, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections	25045, 7659, 4839
R int	0.053
(sin θ/λ)max (Å−1)	0.676
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.112, 1.06
No. of reflections	7659
No. of parameters	397
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.58, −0.70

Computer programs: APEX2 and SAINT (Bruker, 2008 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006844/zq2246sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019006844/zq2246Isup2.hkl

CCDC reference: 1915603

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

[Ag2V2F4O4(C13H17N3O2)4]·4H2O	Z = 1
Mr = 1518.86	F(000) = 776
Triclinic, P1	Dx = 1.697 Mg m−3
a = 8.2673 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.6026 (6) Å	Cell parameters from 25045 reflections
c = 14.6757 (7) Å	θ = 1.7–28.7°
α = 77.985 (3)°	µ = 1.05 mm−1
β = 86.535 (2)°	T = 296 K
γ = 83.945 (3)°	Prism, light-yellow
V = 1486.05 (14) Å3	0.26 × 0.12 × 0.10 mm

Bruker APEXII area-detector diffractometer	4839 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
ω scans	θmax = 28.7°, θmin = 1.7°
Absorption correction: numerical [face indexed (SADABS; Bruker, 2008)]	h = −11→11
Tmin = 0.682, Tmax = 0.890	k = −16→17
25045 measured reflections	l = −19→19
7659 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	Hydrogen site location: mixed
wR(F2) = 0.112	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0428P)2 + 0.1791P] where P = (Fo2 + 2Fc2)/3
7659 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 0.58 e Å−3
1 restraint	Δρmin = −0.70 e Å−3

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
Ag1	−0.00385 (4)	0.54697 (2)	0.11326 (2)	0.04628 (11)
V1	−0.30899 (7)	0.54308 (4)	0.29331 (4)	0.03150 (14)
F1	−0.3693 (3)	0.67346 (15)	0.21335 (14)	0.0467 (5)
F2	−0.5052 (3)	0.49964 (18)	0.26987 (17)	0.0604 (6)
O1	−0.1839 (3)	0.44852 (18)	0.26017 (19)	0.0480 (7)
O2	−0.3264 (3)	0.5279 (2)	0.40630 (16)	0.0465 (6)
O3	0.1863 (4)	1.1178 (2)	0.3251 (2)	0.0763 (10)
H1O	0.1652	1.1836	0.3210	0.114*
O4	0.2087 (4)	1.1221 (2)	0.4731 (2)	0.0697 (9)
O5	0.7345 (4)	−0.1354 (2)	0.1879 (2)	0.0763 (10)
H2O	0.7008	−0.1957	0.1971	0.114*
O6	0.4929 (4)	−0.0858 (2)	0.1313 (2)	0.0754 (10)
N1	−0.0998 (3)	0.6295 (2)	0.29829 (18)	0.0340 (6)
N2	0.0147 (4)	0.6413 (2)	0.2265 (2)	0.0422 (7)
N3	0.0900 (3)	0.7190 (2)	0.33460 (18)	0.0324 (6)
N4	0.2080 (4)	0.4410 (2)	0.0703 (2)	0.0412 (7)
N5	0.2061 (4)	0.4050 (2)	−0.0112 (2)	0.0444 (8)
N6	0.4209 (4)	0.3254 (2)	0.06259 (18)	0.0356 (7)
C1	−0.0521 (4)	0.6773 (3)	0.3618 (2)	0.0374 (8)
H1	−0.1086	0.6817	0.4178	0.045*
C2	0.1274 (5)	0.6938 (3)	0.2511 (2)	0.0425 (9)
H2	0.2212	0.7114	0.2153	0.051*
C3	0.1904 (4)	0.7734 (2)	0.3894 (2)	0.0290 (7)
C4	0.1587 (5)	0.7283 (3)	0.4921 (2)	0.0385 (8)
H4A	0.1819	0.6497	0.5054	0.046*
H4B	0.0455	0.7457	0.5095	0.046*
C5	0.2693 (5)	0.7795 (3)	0.5474 (3)	0.0496 (10)
H5	0.2521	0.7500	0.6141	0.059*
C6	0.4463 (5)	0.7555 (3)	0.5197 (3)	0.0600 (12)
H6A	0.5146	0.7876	0.5560	0.072*
H6B	0.4752	0.6773	0.5322	0.072*
C7	0.4743 (4)	0.8014 (3)	0.4181 (3)	0.0475 (10)
H7	0.5890	0.7852	0.4003	0.057*
C8	0.3671 (4)	0.7488 (3)	0.3614 (3)	0.0472 (10)
H8A	0.3852	0.7775	0.2954	0.057*
H8B	0.3953	0.6706	0.3731	0.057*
C9	0.1443 (4)	0.8964 (2)	0.3674 (2)	0.0352 (8)
H9A	0.0301	0.9124	0.3837	0.042*
H9B	0.1622	0.9251	0.3013	0.042*
C10	0.2513 (4)	0.9494 (3)	0.4246 (3)	0.0380 (8)
C11	0.2249 (5)	0.9011 (3)	0.5283 (2)	0.0461 (9)
H11A	0.2915	0.9345	0.5646	0.055*
H11B	0.1118	0.9165	0.5471	0.055*
C12	0.4305 (4)	0.9237 (3)	0.3956 (3)	0.0415 (9)
H12A	0.4475	0.9512	0.3292	0.050*
H12B	0.4999	0.9590	0.4287	0.050*
C13	0.2125 (5)	1.0721 (3)	0.4106 (3)	0.0514 (10)
C14	0.3380 (5)	0.3922 (3)	0.1122 (2)	0.0423 (9)
H14	0.3691	0.4026	0.1693	0.051*
C15	0.3337 (5)	0.3364 (3)	−0.0129 (3)	0.0519 (10)
H15	0.3613	0.2993	−0.0610	0.062*
C16	0.5697 (4)	0.2489 (2)	0.0852 (2)	0.0328 (7)
C17	0.6483 (5)	0.2732 (3)	0.1687 (3)	0.0447 (9)
H17A	0.5725	0.2647	0.2223	0.054*
H17B	0.6772	0.3476	0.1550	0.054*
C18	0.8018 (5)	0.1935 (3)	0.1904 (3)	0.0467 (9)
H18	0.8533	0.2085	0.2442	0.056*
C19	0.7547 (5)	0.0767 (3)	0.2133 (2)	0.0421 (9)
H19A	0.6806	0.0671	0.2675	0.050*
H19B	0.8511	0.0263	0.2275	0.050*
C20	0.6725 (4)	0.0529 (3)	0.1294 (2)	0.0376 (8)
C21	0.5206 (4)	0.1337 (2)	0.1075 (2)	0.0337 (7)
H21A	0.4677	0.1192	0.0547	0.040*
H21B	0.4442	0.1251	0.1607	0.040*
C22	0.6886 (5)	0.2630 (3)	0.0006 (3)	0.0471 (9)
H22A	0.7184	0.3373	−0.0144	0.057*
H22B	0.6376	0.2488	−0.0528	0.057*
C23	0.8418 (5)	0.1830 (3)	0.0231 (3)	0.0516 (10)
H23	0.9186	0.1920	−0.0308	0.062*
C24	0.9208 (5)	0.2080 (3)	0.1068 (3)	0.0599 (12)
H24A	1.0189	0.1592	0.1209	0.072*
H24B	0.9507	0.2822	0.0923	0.072*
C25	0.7922 (5)	0.0670 (3)	0.0448 (3)	0.0464 (9)
H25A	0.8878	0.0156	0.0578	0.056*
H25B	0.7414	0.0525	−0.0087	0.056*
C26	0.6226 (5)	−0.0622 (3)	0.1493 (3)	0.0476 (9)
O1W	0.2476 (3)	0.4641 (2)	0.4048 (2)	0.0595 (7)
H1W	0.3296	0.4786	0.3682	0.089*
H2W	0.2773	0.4552	0.4606	0.089*
O2W	0.1186 (3)	0.33128 (19)	0.3067 (2)	0.0564 (7)
H3W	0.1261	0.3502	0.3585	0.085*
H4W	0.0243	0.3540	0.2866	0.085*

	U11	U22	U33	U12	U13	U23
Ag1	0.0503 (2)	0.05347 (19)	0.03972 (17)	0.00170 (14)	−0.00405 (13)	−0.02286 (13)
V1	0.0352 (3)	0.0265 (3)	0.0343 (3)	−0.0065 (2)	−0.0035 (2)	−0.0074 (2)
F1	0.0587 (14)	0.0416 (11)	0.0383 (12)	−0.0013 (10)	−0.0061 (10)	−0.0051 (9)
F2	0.0451 (14)	0.0697 (15)	0.0759 (17)	−0.0204 (11)	−0.0034 (12)	−0.0285 (13)
O1	0.0462 (16)	0.0342 (13)	0.0697 (18)	−0.0062 (11)	−0.0050 (13)	−0.0227 (12)
O2	0.0495 (17)	0.0532 (15)	0.0348 (14)	−0.0085 (12)	−0.0027 (12)	−0.0022 (12)
O3	0.118 (3)	0.0406 (16)	0.068 (2)	−0.0068 (17)	−0.011 (2)	−0.0057 (15)
O4	0.073 (2)	0.0575 (18)	0.091 (2)	−0.0061 (15)	−0.0108 (18)	−0.0400 (17)
O5	0.071 (2)	0.0330 (15)	0.122 (3)	−0.0048 (14)	−0.033 (2)	−0.0003 (16)
O6	0.087 (3)	0.0415 (16)	0.098 (3)	−0.0194 (16)	−0.042 (2)	0.0033 (16)
N1	0.0354 (16)	0.0372 (15)	0.0336 (15)	−0.0097 (12)	−0.0004 (13)	−0.0142 (12)
N2	0.0450 (19)	0.0518 (18)	0.0386 (17)	−0.0174 (14)	0.0052 (14)	−0.0247 (14)
N3	0.0341 (16)	0.0340 (14)	0.0333 (15)	−0.0084 (12)	0.0039 (12)	−0.0151 (12)
N4	0.0451 (19)	0.0443 (17)	0.0383 (17)	0.0040 (14)	−0.0067 (14)	−0.0205 (14)
N5	0.051 (2)	0.0509 (18)	0.0333 (16)	0.0055 (15)	−0.0092 (14)	−0.0176 (14)
N6	0.0435 (18)	0.0344 (15)	0.0306 (15)	0.0008 (13)	−0.0052 (13)	−0.0112 (12)
C1	0.033 (2)	0.048 (2)	0.0373 (19)	−0.0148 (16)	0.0065 (15)	−0.0199 (16)
C2	0.044 (2)	0.057 (2)	0.0333 (19)	−0.0212 (18)	0.0093 (16)	−0.0190 (17)
C3	0.0270 (17)	0.0314 (16)	0.0320 (17)	−0.0067 (13)	−0.0010 (13)	−0.0122 (13)
C4	0.045 (2)	0.0367 (18)	0.0353 (19)	−0.0130 (16)	−0.0025 (16)	−0.0052 (15)
C5	0.062 (3)	0.056 (2)	0.034 (2)	−0.022 (2)	−0.0089 (18)	−0.0061 (17)
C6	0.053 (3)	0.045 (2)	0.084 (3)	−0.0065 (19)	−0.035 (2)	−0.004 (2)
C7	0.026 (2)	0.047 (2)	0.074 (3)	−0.0029 (16)	−0.0016 (19)	−0.023 (2)
C8	0.034 (2)	0.045 (2)	0.071 (3)	−0.0073 (16)	0.0059 (19)	−0.0302 (19)
C9	0.036 (2)	0.0297 (17)	0.041 (2)	−0.0064 (14)	−0.0068 (15)	−0.0066 (14)
C10	0.0318 (19)	0.0296 (16)	0.055 (2)	−0.0063 (14)	−0.0107 (16)	−0.0106 (16)
C11	0.038 (2)	0.064 (2)	0.047 (2)	−0.0129 (18)	0.0019 (17)	−0.0321 (19)
C12	0.035 (2)	0.047 (2)	0.048 (2)	−0.0184 (16)	0.0010 (16)	−0.0160 (17)
C13	0.047 (2)	0.046 (2)	0.064 (3)	−0.0117 (18)	−0.009 (2)	−0.013 (2)
C14	0.049 (2)	0.045 (2)	0.036 (2)	0.0040 (17)	−0.0082 (17)	−0.0179 (16)
C15	0.059 (3)	0.062 (2)	0.038 (2)	0.014 (2)	−0.0126 (19)	−0.0252 (19)
C16	0.038 (2)	0.0290 (16)	0.0316 (18)	−0.0041 (14)	−0.0039 (15)	−0.0060 (13)
C17	0.048 (2)	0.040 (2)	0.051 (2)	−0.0030 (17)	−0.0113 (18)	−0.0186 (17)
C18	0.043 (2)	0.048 (2)	0.054 (2)	−0.0046 (17)	−0.0159 (19)	−0.0179 (18)
C19	0.047 (2)	0.043 (2)	0.0346 (19)	−0.0016 (17)	−0.0086 (17)	−0.0043 (16)
C20	0.048 (2)	0.0289 (17)	0.0357 (19)	−0.0026 (15)	−0.0043 (16)	−0.0056 (14)
C21	0.040 (2)	0.0335 (17)	0.0282 (17)	−0.0083 (14)	−0.0034 (15)	−0.0059 (14)
C22	0.051 (2)	0.040 (2)	0.045 (2)	−0.0083 (17)	0.0041 (19)	0.0047 (17)
C23	0.041 (2)	0.056 (2)	0.051 (2)	−0.0020 (19)	0.0122 (19)	−0.0001 (19)
C24	0.038 (2)	0.051 (2)	0.087 (3)	−0.0087 (19)	−0.007 (2)	−0.002 (2)
C25	0.050 (2)	0.043 (2)	0.044 (2)	0.0071 (17)	0.0032 (18)	−0.0120 (17)
C26	0.057 (3)	0.040 (2)	0.046 (2)	−0.0025 (19)	−0.0149 (19)	−0.0088 (17)
O1W	0.0571 (19)	0.0644 (18)	0.0593 (19)	−0.0086 (14)	−0.0060 (14)	−0.0151 (14)
O2W	0.0617 (19)	0.0372 (14)	0.0679 (19)	0.0009 (13)	−0.0066 (15)	−0.0072 (13)

Ag1—N4	2.230 (3)	C8—H8A	0.9700
Ag1—N2	2.257 (3)	C8—H8B	0.9700
Ag1—N5i	2.262 (3)	C9—C10	1.543 (4)
Ag1—O1	2.700 (3)	C9—H9A	0.9700
V1—O1	1.627 (2)	C9—H9B	0.9700
V1—O2	1.628 (2)	C10—C13	1.519 (5)
V1—F2	1.839 (2)	C10—C11	1.529 (5)
V1—F1	1.850 (2)	C10—C12	1.536 (5)
V1—N1	2.152 (3)	C11—H11A	0.9700
O3—C13	1.288 (5)	C11—H11B	0.9700
O3—H1O	0.8200	C12—H12A	0.9700
O4—C13	1.214 (5)	C12—H12B	0.9700
O5—C26	1.301 (4)	C14—H14	0.9300
O5—H2O	0.8200	C15—H15	0.9300
O6—C26	1.201 (5)	C16—C21	1.513 (4)
N1—C1	1.309 (4)	C16—C17	1.521 (4)
N1—N2	1.368 (4)	C16—C22	1.528 (5)
N2—C2	1.306 (4)	C17—C18	1.539 (5)
N3—C2	1.339 (4)	C17—H17A	0.9700
N3—C1	1.342 (4)	C17—H17B	0.9700
N3—C3	1.496 (4)	C18—C24	1.519 (6)
N4—C14	1.301 (4)	C18—C19	1.526 (5)
N4—N5	1.367 (4)	C18—H18	0.9800
N5—C15	1.293 (4)	C19—C20	1.539 (5)
N5—Ag1i	2.262 (3)	C19—H19A	0.9700
N6—C15	1.334 (4)	C19—H19B	0.9700
N6—C14	1.335 (4)	C20—C26	1.514 (5)
N6—C16	1.489 (4)	C20—C25	1.533 (5)
C1—H1	0.9300	C20—C21	1.536 (5)
C2—H2	0.9300	C21—H21A	0.9700
C3—C8	1.512 (4)	C21—H21B	0.9700
C3—C4	1.513 (4)	C22—C23	1.540 (5)
C3—C9	1.529 (4)	C22—H22A	0.9700
C4—C5	1.531 (5)	C22—H22B	0.9700
C4—H4A	0.9700	C23—C25	1.525 (5)
C4—H4B	0.9700	C23—C24	1.528 (6)
C5—C11	1.509 (5)	C23—H23	0.9800
C5—C6	1.512 (6)	C24—H24A	0.9700
C5—H5	0.9800	C24—H24B	0.9700
C6—C7	1.496 (6)	C25—H25A	0.9700
C6—H6A	0.9700	C25—H25B	0.9700
C6—H6B	0.9700	O1W—H1W	0.8500
C7—C12	1.517 (5)	O1W—H2W	0.8500
C7—C8	1.535 (5)	O2W—H3W	0.8499
C7—H7	0.9800	O2W—H4W	0.8500
N4—Ag1—N2	121.35 (11)	C11—C10—C9	109.4 (3)
N4—Ag1—N5i	115.91 (10)	C12—C10—C9	108.4 (3)
N2—Ag1—N5i	120.21 (11)	C5—C11—C10	110.3 (3)
N4—Ag1—O1	114.33 (9)	C5—C11—H11A	109.6
N2—Ag1—O1	74.30 (9)	C10—C11—H11A	109.6
N5i—Ag1—O1	97.45 (10)	C5—C11—H11B	109.6
O1—V1—O2	112.52 (13)	C10—C11—H11B	109.6
O1—V1—F2	100.53 (11)	H11A—C11—H11B	108.1
O2—V1—F2	100.10 (12)	C7—C12—C10	109.5 (3)
O1—V1—F1	122.01 (12)	C7—C12—H12A	109.8
O2—V1—F1	122.74 (11)	C10—C12—H12A	109.8
F2—V1—F1	86.60 (10)	C7—C12—H12B	109.8
O1—V1—N1	87.04 (11)	C10—C12—H12B	109.8
O2—V1—N1	87.42 (12)	H12A—C12—H12B	108.2
F2—V1—N1	166.19 (11)	O4—C13—O3	123.5 (4)
F1—V1—N1	79.59 (10)	O4—C13—C10	123.6 (4)
V1—O1—Ag1	107.06 (11)	O3—C13—C10	112.9 (3)
C13—O3—H1O	109.5	N4—C14—N6	111.3 (3)
C26—O5—H2O	109.5	N4—C14—H14	124.3
C1—N1—N2	107.1 (3)	N6—C14—H14	124.3
C1—N1—V1	131.9 (2)	N5—C15—N6	111.9 (3)
N2—N1—V1	120.97 (19)	N5—C15—H15	124.0
C2—N2—N1	106.5 (3)	N6—C15—H15	124.0
C2—N2—Ag1	134.6 (2)	N6—C16—C21	108.4 (3)
N1—N2—Ag1	117.65 (19)	N6—C16—C17	109.7 (3)
C2—N3—C1	104.9 (3)	C21—C16—C17	110.0 (3)
C2—N3—C3	127.8 (3)	N6—C16—C22	108.9 (3)
C1—N3—C3	127.2 (3)	C21—C16—C22	109.9 (3)
C14—N4—N5	106.5 (3)	C17—C16—C22	110.0 (3)
C14—N4—Ag1	133.2 (2)	C16—C17—C18	108.7 (3)
N5—N4—Ag1	119.9 (2)	C16—C17—H17A	110.0
C15—N5—N4	106.3 (3)	C18—C17—H17A	110.0
C15—N5—Ag1i	129.4 (2)	C16—C17—H17B	110.0
N4—N5—Ag1i	124.1 (2)	C18—C17—H17B	110.0
C15—N6—C14	103.9 (3)	H17A—C17—H17B	108.3
C15—N6—C16	125.8 (3)	C24—C18—C19	109.8 (3)
C14—N6—C16	130.2 (3)	C24—C18—C17	109.7 (3)
N1—C1—N3	110.4 (3)	C19—C18—C17	109.5 (3)
N1—C1—H1	124.8	C24—C18—H18	109.3
N3—C1—H1	124.8	C19—C18—H18	109.3
N2—C2—N3	111.0 (3)	C17—C18—H18	109.3
N2—C2—H2	124.5	C18—C19—C20	109.5 (3)
N3—C2—H2	124.5	C18—C19—H19A	109.8
N3—C3—C8	107.8 (2)	C20—C19—H19A	109.8
N3—C3—C4	108.5 (2)	C18—C19—H19B	109.8
C8—C3—C4	110.8 (3)	C20—C19—H19B	109.8
N3—C3—C9	109.8 (3)	H19A—C19—H19B	108.2
C8—C3—C9	109.8 (3)	C26—C20—C25	109.0 (3)
C4—C3—C9	110.1 (3)	C26—C20—C21	109.1 (3)
C3—C4—C5	108.1 (3)	C25—C20—C21	109.3 (3)
C3—C4—H4A	110.1	C26—C20—C19	111.2 (3)
C5—C4—H4A	110.1	C25—C20—C19	109.0 (3)
C3—C4—H4B	110.1	C21—C20—C19	109.1 (3)
C5—C4—H4B	110.1	C16—C21—C20	109.5 (3)
H4A—C4—H4B	108.4	C16—C21—H21A	109.8
C11—C5—C6	109.7 (3)	C20—C21—H21A	109.8
C11—C5—C4	108.6 (3)	C16—C21—H21B	109.8
C6—C5—C4	110.9 (3)	C20—C21—H21B	109.8
C11—C5—H5	109.2	H21A—C21—H21B	108.2
C6—C5—H5	109.2	C16—C22—C23	109.2 (3)
C4—C5—H5	109.2	C16—C22—H22A	109.8
C7—C6—C5	109.6 (3)	C23—C22—H22A	109.8
C7—C6—H6A	109.7	C16—C22—H22B	109.8
C5—C6—H6A	109.7	C23—C22—H22B	109.8
C7—C6—H6B	109.7	H22A—C22—H22B	108.3
C5—C6—H6B	109.7	C25—C23—C24	110.7 (3)
H6A—C6—H6B	108.2	C25—C23—C22	108.8 (3)
C6—C7—C12	111.3 (3)	C24—C23—C22	108.8 (3)
C6—C7—C8	109.2 (3)	C25—C23—H23	109.5
C12—C7—C8	108.2 (3)	C24—C23—H23	109.5
C6—C7—H7	109.3	C22—C23—H23	109.5
C12—C7—H7	109.3	C18—C24—C23	109.4 (3)
C8—C7—H7	109.3	C18—C24—H24A	109.8
C3—C8—C7	109.2 (3)	C23—C24—H24A	109.8
C3—C8—H8A	109.8	C18—C24—H24B	109.8
C7—C8—H8A	109.8	C23—C24—H24B	109.8
C3—C8—H8B	109.8	H24A—C24—H24B	108.2
C7—C8—H8B	109.8	C23—C25—C20	109.5 (3)
H8A—C8—H8B	108.3	C23—C25—H25A	109.8
C3—C9—C10	108.1 (3)	C20—C25—H25A	109.8
C3—C9—H9A	110.1	C23—C25—H25B	109.8
C10—C9—H9A	110.1	C20—C25—H25B	109.8
C3—C9—H9B	110.1	H25A—C25—H25B	108.2
C10—C9—H9B	110.1	O6—C26—O5	122.0 (4)
H9A—C9—H9B	108.4	O6—C26—C20	124.2 (4)
C13—C10—C11	107.8 (3)	O5—C26—C20	113.8 (3)
C13—C10—C12	109.3 (3)	H1W—O1W—H2W	108.4
C11—C10—C12	109.1 (3)	H3W—O2W—H4W	108.4
C13—C10—C9	112.9 (3)
O2—V1—O1—Ag1	−138.31 (12)	C11—C10—C13—O4	19.2 (5)
F2—V1—O1—Ag1	116.01 (11)	C12—C10—C13—O4	−99.3 (5)
F1—V1—O1—Ag1	23.43 (16)	C9—C10—C13—O4	140.1 (4)
N1—V1—O1—Ag1	−52.34 (11)	C11—C10—C13—O3	−161.8 (3)
C1—N1—N2—C2	1.2 (4)	C12—C10—C13—O3	79.8 (4)
V1—N1—N2—C2	−178.1 (2)	C9—C10—C13—O3	−40.9 (5)
C1—N1—N2—Ag1	170.6 (2)	N5—N4—C14—N6	−0.5 (4)
V1—N1—N2—Ag1	−8.7 (3)	Ag1—N4—C14—N6	171.8 (2)
C14—N4—N5—C15	0.5 (4)	C15—N6—C14—N4	0.2 (4)
Ag1—N4—N5—C15	−173.0 (3)	C16—N6—C14—N4	−175.9 (3)
C14—N4—N5—Ag1i	176.9 (2)	N4—N5—C15—N6	−0.4 (5)
Ag1—N4—N5—Ag1i	3.4 (4)	Ag1i—N5—C15—N6	−176.5 (2)
N2—N1—C1—N3	−0.5 (4)	C14—N6—C15—N5	0.1 (5)
V1—N1—C1—N3	178.6 (2)	C16—N6—C15—N5	176.5 (3)
C2—N3—C1—N1	−0.3 (4)	C15—N6—C16—C21	−68.7 (4)
C3—N3—C1—N1	−175.8 (3)	C14—N6—C16—C21	106.7 (4)
N1—N2—C2—N3	−1.4 (4)	C15—N6—C16—C17	171.2 (4)
Ag1—N2—C2—N3	−168.2 (2)	C14—N6—C16—C17	−13.4 (5)
C1—N3—C2—N2	1.1 (4)	C15—N6—C16—C22	50.7 (5)
C3—N3—C2—N2	176.5 (3)	C14—N6—C16—C22	−133.8 (4)
C2—N3—C3—C8	−26.6 (4)	N6—C16—C17—C18	−179.8 (3)
C1—N3—C3—C8	147.8 (3)	C21—C16—C17—C18	61.1 (4)
C2—N3—C3—C4	−146.7 (3)	C22—C16—C17—C18	−60.0 (4)
C1—N3—C3—C4	27.8 (4)	C16—C17—C18—C24	60.2 (4)
C2—N3—C3—C9	92.9 (4)	C16—C17—C18—C19	−60.4 (4)
C1—N3—C3—C9	−92.6 (4)	C24—C18—C19—C20	−60.6 (4)
N3—C3—C4—C5	176.8 (3)	C17—C18—C19—C20	59.9 (4)
C8—C3—C4—C5	58.6 (4)	C18—C19—C20—C26	−179.6 (3)
C9—C3—C4—C5	−63.0 (4)	C18—C19—C20—C25	60.2 (4)
C3—C4—C5—C11	62.2 (4)	C18—C19—C20—C21	−59.2 (4)
C3—C4—C5—C6	−58.4 (4)	N6—C16—C21—C20	179.0 (2)
C11—C5—C6—C7	−59.7 (4)	C17—C16—C21—C20	−61.1 (4)
C4—C5—C6—C7	60.2 (4)	C22—C16—C21—C20	60.1 (4)
C5—C6—C7—C12	59.4 (4)	C26—C20—C21—C16	−178.7 (3)
C5—C6—C7—C8	−60.1 (4)	C25—C20—C21—C16	−59.6 (3)
N3—C3—C8—C7	−178.7 (3)	C19—C20—C21—C16	59.6 (4)
C4—C3—C8—C7	−60.1 (4)	N6—C16—C22—C23	−179.2 (3)
C9—C3—C8—C7	61.7 (4)	C21—C16—C22—C23	−60.6 (4)
C6—C7—C8—C3	60.1 (4)	C17—C16—C22—C23	60.5 (4)
C12—C7—C8—C3	−61.3 (4)	C16—C22—C23—C25	60.5 (4)
N3—C3—C9—C10	−179.6 (3)	C16—C22—C23—C24	−60.2 (4)
C8—C3—C9—C10	−61.2 (4)	C19—C18—C24—C23	59.4 (4)
C4—C3—C9—C10	61.0 (3)	C17—C18—C24—C23	−61.0 (4)
C3—C9—C10—C13	−178.2 (3)	C25—C23—C24—C18	−58.8 (4)
C3—C9—C10—C11	−58.2 (3)	C22—C23—C24—C18	60.7 (4)
C3—C9—C10—C12	60.6 (3)	C24—C23—C25—C20	59.0 (4)
C6—C5—C11—C10	60.2 (4)	C22—C23—C25—C20	−60.6 (4)
C4—C5—C11—C10	−61.2 (4)	C26—C20—C25—C23	179.3 (3)
C13—C10—C11—C5	−177.3 (3)	C21—C20—C25—C23	60.1 (4)
C12—C10—C11—C5	−58.8 (4)	C19—C20—C25—C23	−59.1 (4)
C9—C10—C11—C5	59.6 (4)	C25—C20—C26—O6	−104.9 (5)
C6—C7—C12—C10	−58.3 (4)	C21—C20—C26—O6	14.5 (5)
C8—C7—C12—C10	61.7 (4)	C19—C20—C26—O6	134.9 (4)
C13—C10—C12—C7	174.6 (3)	C25—C20—C26—O5	74.7 (4)
C11—C10—C12—C7	57.0 (4)	C21—C20—C26—O5	−166.0 (3)
C9—C10—C12—C7	−62.0 (4)	C19—C20—C26—O5	−45.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···F2ii	0.85	1.92	2.763 (4)	169
O1W—H2W···O2iii	0.85	2.08	2.910 (4)	166
O2W—H3W···O1W	0.85	2.08	2.753 (4)	136
O2W—H4W···O1	0.85	2.00	2.813 (4)	161
O3—H1O···O2Wiv	0.82	1.83	2.650 (4)	178
O5—H2O···F1v	0.82	1.77	2.589 (3)	178
C15—H15···F1i	0.93	2.19	2.966 (4)	141
C14—H14···F2ii	0.93	2.44	3.303 (4)	154