Novel three-dimensional coordination polymer of 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethanoic acid with silver(I) tetra­fluoro­borate

A three-dimensional coordination polymer of 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethano­ate with silver(I) tetra­fluoro­borate was fully characterized.

Abstract

An Ag^I-based coordination polymer (CP), namely, poly[[[μ₃-2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethano­ate-κ⁴ N:N′:O,O′]silver(I)] tetra­fluoro­borate], {[Ag(C₉H₁₆N₃O₂P)]BF₄} _n , was synthesized in an aqueous solution of zwitterionic 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethan­o­ate (L) and AgBF₄ with exclusion of light at room temperature. The colourless and light-insensitive CP crystallized in the monoclinic space group Cc. The asymmetric unit consists of an Ag^I cation, the zwitterionic L ligand and a BF₄ ⁻ counter-ion. Each Ag^I ion is coordinated by two carboxyl­ate oxygen atoms in a chelating coordination mode, as well as one of the nitro­gen atoms of two neighbouring L ligands. The crystal structure of the CP was classified as a unique three-dimensional arrangement. The CP was also characterized in aqueous solutions by multinuclear NMR and HRMS spectroscopies and elemental analysis.

Chemical context

The architectures and anti­microbial properties of self-assembled silver-based coordination polymers (CPs) or MOFs (metal–organic frameworks), bridged by phosphaurotropines, have been widely studied (Guerriero et al., 2018 ▸). According to our previous studies, the aqueous reaction of zwitterionic 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethan­o­ate (L) with AgX (X = PF₆, SO₃C₆H₄CH₃, SO₃CF₃) yielded various 1D Ag-based coordination polymers (Udvardy et al., 2021 ▸). The architectures of these Ag^I complexes depend on their counter-ions and the position of the ligand, which contains both rigid and flexible mol­ecular moieties.

Herein, we report the crystal structure of a CP prepared by the aqueous reaction of 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethano­ate and AgBF₄ with the exclusion of light at 278 K (Fig. 1 ▸). The colourless crystals of the CP were isolated by filtration, dissolved in water and characterized by ¹H-, ¹³C- and ³¹P-NMR spectroscopy, ESI mass spectrometry, as well as by elemental analysis.

Figure 1.

Schematic representation of the formation of the title compound.

The chemical shift of the phospho­rus atom in CP (δ = −37.5 ppm in D₂O) was the same as that in the free ligand. Similar to the hexa­fluoro­phosphate, tosyl­ate (tos) and triflate (OTf) derivatives (Udvardy et al., 2021 ▸), the ¹H-NMR spectrum showed differences between the P⁺–CH₂–N and N–CH₂–N signals, which clearly indicated the coordination of the silver ions to the nitro­gen donor atoms of the L ligand.

The most intense ESI–MS signals of the CP (aqueous solution, positive ion mode) were observed at m/z = 252.0878 ([L+Na]⁺, C₉H₁₆N₃NaO₂P, calculated. 252.0872), 336.0026 ([L+Ag]⁺, C₉H₁₆N₃AgO₂P, calculated 336.0026), and 565.1009 ([2L+Ag]⁺, C₁₈H₃₂N₆NaO₄P₂, calculated 565.1005). Similar ions were detected for the CP formed with AgPF₆, AgSO₃C₆H₄CH₃, AgSO₃CF₃ and PTA in aqueous solutions.

Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 2 ▸. The CP crystallized in the monoclinic Cc space group. The asymmetric unit consists of a silver(I) cation, a zwitterionic L ligand and a BF₄ ⁻counter-ion, in which the N,N′,O,O′ coordination mode of the silver(I) ions creates a 3D coordination architecture (Fig. 2 ▸).

Figure 2.

(a) A view of the title CP with atomic labels. Displacement ellipsoids are drawn at the 50% probability level. (b) The coordination architecture of the CP with atomic labels for the coordination sphere. Hydrogen atoms and BF₄ ⁻ ions are omitted for clarity. [Symmetry codes: (1) x, −y,  + z; (2) −  + x, −  − y,  + z; (3) x, −y, −  + z; (4)  + x, −  − y, −  + z.]

In the CP, the central Ag⁺ ion is coordinated by an L ligand via two carboxyl­ate oxygen atoms [Ag1²—O11 = 2.594 (9) Å and Ag1²—O12 = 2.298 (8) Å] and two nitro­gen atoms from two adjacent PTA moieties of L [Ag1—N1 = 2.225 (7) Å and Ag1¹—N3 = 2.505 (7) Å]. The N1—Ag—N3³ and O11⁴—Ag—O12⁴ bond angles are 119.6 (3) and 52.9 (2)°, respectively. Selected bond lengths and bond angles are presented in the supporting information. The coordination geometry exhibits a distorted tetra­hedral shape (τ₄ = 0.65 and τ₄’ = 0.66; Yang et al., 2007 ▸; Okuniewski et al., 2015 ▸), in which the Ag^I ion is located at the centre. The space between the 3D polymer backbones is occupied by the BF₄ ⁻ counter-ions (Fig. 3 ▸). The chemical composition was also determined by elemental analysis, which shows a good agreement with the SC-XRD results (see Synthesis and crystallization).

Figure 3.

(a) Packing arrangement of the three-dimensional structure of the CP in the crystal viewed along the crystallographic a axis. The coordination sphere is labelled and highlighted by a ball-and-stick model. Hydrogen atoms are omitted for clarity. (b) Selected hydrogen-bond geometry in the CP showing the weak C—H⋯F and C—H⋯O secondary inter­actions, as well as the Ag1⋯F3 inter­action. For symmetry codes, see Table 1 ▸.

Supra­molecular features

As a result of the lack of primary H-donor groups, no classical hydrogen bonds are found in the crystal structure of the title coordination polymer. The main inter­molecular inter­actions between the mol­ecules in the crystal are weak C—H⋯F and C—H⋯O type hydrogen bonds. The BF₄ ⁻ anion is generally classified as a non-coordinating anion owing to its weak Lewis base properties (Grabowski, 2020 ▸). These secondary inter­actions play a major role in stabilizing the crystal lattice by connecting the mol­ecular units to each other, which results in a 3D coordination polymer. All of the fluorine atoms of a BF₄ ⁻ counter-ion are connected to at least one C—H hydrogen atom by a weak C—H⋯F type hydrogen bond. The shortest C—H⋯F distance is found for the C2—H2B⋯F3 inter­action [C2⋯F3 = 3.183 (13) Å], where the F3 atom of the BF₄ ⁻ counter-ion is also able to coordinate to the central Ag⁺ ion with a distance of 3.010 (11) Å (Fig. 3 ▸). This ionic attraction between the Ag⁺ and BF₄ ⁻ ions is strong enough to affect the arrangement of part of the whole complex mol­ecule and form a bent 3D structure. In comparison, the value of the longest C—H⋯F distance is 3.417 (14) Å (C4—H4B⋯F2, Fig. 3 ▸) owing to the rigid PTA cage, which is unable to change its conformation. There are numerous examples in the literature of where the C—H⋯F distances were investigated in the presence of BF₄ ⁻counter-ions [i.e. BIXBIT03 (Emge et al., 1986 ▸) and SUXHID01 (Albinati et al., 2010 ▸)]. In case of the bis­[μ₂-1,1′-naphthalene-1,8-diyl-bis­(1H-pyrazole)]tris­(aceto­nitrile)­disilver(I) bis­(BF₄) aceto­nitrile solvate structure (OGINOI; Liddle et al., 2009 ▸), it was found that the typical C⋯F distances are between 3.179 (2) and 3.406 (3) Å, which shows a good agreement with our results. The carboxyl­ate oxygen atoms in the title CP are also able to form weak C—H⋯O type inter­actions with the C—H atoms of the complex mol­ecule. Their atomic distances can also be compared to the C—H⋯F secondary inter­actions. An intra­molecular hydrogen bond also helps to form a bent 3D mol­ecular structure for the CP [C2⋯O12 = 2.812 (12) Å]. For selected hydrogen-bond distances and angles see Fig. 3 ▸ b and Table 1 ▸. The considerably high calculated density (2.102 Mg m⁻³) and KPI (Kitaigorodskii packing index) of 74.2% (Spek, 2020 ▸) indicate the tight packing arrangement of the mol­ecules, resulting in no residual solvent-accessible voids in the crystal structure.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯F2	0.97	2.40	3.201 (13)	140
C1—H1B⋯O11i	0.97	2.49	3.213 (12)	131
C2—H2A⋯O11i	0.97	2.56	3.254 (12)	129
C2—H2B⋯F3ii	0.97	2.35	3.183 (13)	143
C2—H2B⋯O12	0.97	2.22	2.812 (12)	118
C3—H3A⋯F4iii	0.97	2.45	3.290 (15)	145
C3—H3B⋯F2	0.97	2.51	3.283 (12)	136
C4—H4A⋯F4iv	0.97	2.43	3.298 (12)	148
C4—H4B⋯F2v	0.97	2.51	3.417 (14)	155
C5—H5A⋯F1	0.97	2.49	3.370 (13)	151
C5—H5B⋯F4iv	0.97	2.54	3.373 (14)	144
C6—H6B⋯F2iv	0.97	2.34	3.314 (13)	177
C7—H7A⋯O11i	0.97	2.48	3.165 (13)	128
C7—H7A⋯F1vi	0.97	2.37	3.137 (12)	135

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

Database survey

A survey of the Cambridge Structural Database (CSD version 5.42, Sept. 2021 update; Groom et al., 2016 ▸) found zwitterionic 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)eth­ano­ate dihydrate (L) (SIJPOR; Tang et al., 2007 ▸) and three 1D Ag-based coordination polymers containing L, viz. [Ag(μ₃-L-κ³ N:O:O′)] _n (PF₆) _n (UPUCAM; Udvardy et al., 2021 ▸), [Ag(OTf)(μ₃-L-κ³ N:O:O′)] _n (UPUCIU; Udvardy et al., 2021 ▸) and [Ag(tos)(μ₃-L-κ³ N:N:O)] _n ·nH₂O (UPUCEQ; Udvardy et al., 2021 ▸). While in the cases of UPUCAM, UPUCIU and UPUCEQ only 1D polymers were obtained, in the title CP the Ag^I complex is able to form a 3D coordination polymer owing to the relatively small size of the BF₄ ⁻ counter-ion, which is able to occupy a smaller space compared to the PF₆ ⁻, triflate or tosyl­ate anions. These results show how a counter-ion can influence the packing arrangement and the coordination mode of an [(AgL)X] type polymer.

Synthesis and crystallization

Water-soluble PTA (Daigle, 1998 ▸) and 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.1^3,7]decan-7-yl)ethano­ate (L) (Tang et al., 2007 ▸; Udvardy et al., 2021 ▸) were prepared according to literature methods.

CP: With the exclusion of light, 4 mL aqueous solution containing 194.7 mg (1 mmol) AgBF₄ was added to an aqueous solution (4 mL) of L (100 mg, 0.44 mmol). The reaction mixture was stored at 278 K. After two days, the CP was formed as colourless crystals, which were separated by filtration and dried. Yield (based on L) 112 mg, 60%. ¹H NMR (360 MHz, D₂O, 298 K) δ 4.73–4.37 (m, 12H, ⁺P–CH₂–N, N–CH₂–N), 2.58 (dt, J = 24, 7 Hz, 2H, P⁺–CH ₂–CH₂–COO), 2.44–2.22 (m, 2H, P⁺–CH₂–CH ₂–COO) ppm. ¹³C{¹H} NMR (90 MHz, D₂O, 298 K) δ 179.5 (s, COO⁻), 71.5 (d, ³ J _PC = 8 Hz, N–CH₂–N), 49.1 (d, ¹ J _PC = 37 Hz, ⁺P-CH₂–N), 29.0 (d, ² J _PC = 7 Hz, P⁺–CH₂–CH₂–COO⁻), 18.5 (d, ¹ J _PC = 35 Hz, P⁺–CH₂–CH₂–COO⁻) ppm. ³¹P{¹H} NMR (145 MHz, D₂O, 25 °C) δ −37.5 (s) ppm. Elemental analysis: C₉H₁₆AgBF₄N₃O₂P (423.89): calculated C 25.05, H 3.80, N 9.91; found C 25.64, H 4.10, N 9.95.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms of the CP complex were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and U _iso(H) = 1.2U _eq(C).

Table 2. Experimental details.

Crystal data
Chemical formula	[Ag(C9H16N3O2P)]BF4
M r	423.90
Crystal system, space group	Monoclinic, C c
Temperature (K)	293
a, b, c (Å)	10.116 (5), 12.186 (5), 10.979 (5)
β (°)	98.260 (5)
V (Å3)	1339.4 (11)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.68
Crystal size (mm)	0.35 × 0.2 × 0.15
Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968 ▸)
T min, T max	0.558, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	1358, 1313, 1299
R int	0.009
(sin θ/λ)max (Å−1)	0.605
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.048, 0.123, 1.13
No. of reflections	1313
No. of parameters	190
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	1.20, −1.54
Absolute structure	Classical Flack method preferred over Parsons because s.u. lower
Absolute structure parameter	0.13 (6)

Computer programs: MACH3/PC (Enraf–Nonius, 1992 ▸), PROFIT (Streltsov & Zavodnik, 1989 ▸), SIR97 (Burla et al., 2007 ▸), SHELXL (Sheldrick, 2015 ▸), OLEX2 (Dolomanov et al., 2009 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

CCDC reference: 2143743

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

supplementary crystallographic information

Crystal data

[Ag(C9H16N3O2P)]BF4	F(000) = 840
Mr = 423.90	Dx = 2.102 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 10.116 (5) Å	Cell parameters from 25 reflections
b = 12.186 (5) Å	θ = 9.1–17.2°
c = 10.979 (5) Å	µ = 1.68 mm−1
β = 98.260 (5)°	T = 293 K
V = 1339.4 (11) Å3	Prism, colourless
Z = 4	0.35 × 0.2 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.009
profiled ω/2θ scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: ψ scan (North et al., 1968)	h = 0→12
Tmin = 0.558, Tmax = 0.755	k = 0→14
1358 measured reflections	l = −13→13
1313 independent reflections	3 standard reflections every 184 reflections
1299 reflections with I > 2σ(I)	intensity decay: 2%

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.048	w = 1/[σ2(Fo2) + (0.0873P)2 + 4.2725P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 1.20 e Å−3
1313 reflections	Δρmin = −1.54 e Å−3
190 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower
2 restraints	Absolute structure parameter: 0.13 (6)
Primary atom site location: structure-invariant direct methods

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.0444 (9)	−0.2414 (7)	−0.2977 (8)	0.0266 (16)
H1A	0.0509	−0.2557	−0.2849	0.032*
H1B	−0.0820	−0.2737	−0.3758	0.032*
C2	−0.2914 (9)	−0.2548 (7)	−0.2148 (9)	0.0302 (19)
H2A	−0.3323	−0.2870	−0.2918	0.036*
H2B	−0.3444	−0.2743	−0.1511	0.036*
C3	−0.0546 (9)	−0.2182 (7)	−0.0445 (8)	0.0284 (17)
H3A	−0.0975	−0.2365	0.0265	0.034*
H3B	0.0408	−0.2298	−0.0232	0.034*
C4	−0.2157 (10)	−0.1011 (7)	−0.3251 (9)	0.0317 (19)
H4A	−0.2311	−0.0233	−0.3392	0.038*
H4B	−0.2532	−0.1397	−0.3994	0.038*
C5	−0.0139 (9)	−0.0704 (7)	−0.1840 (8)	0.0269 (16)
H5A	0.0798	−0.0897	−0.1646	0.032*
H5B	−0.0192	0.0087	−0.1934	0.032*
C6	−0.2256 (10)	−0.0841 (8)	−0.1135 (10)	0.035 (2)
H6A	−0.2706	−0.1113	−0.0472	0.042*
H6B	−0.2418	−0.0057	−0.1203	0.042*
C7	−0.0690 (9)	−0.4434 (7)	−0.1593 (9)	0.0311 (19)
H7A	−0.1281	−0.4868	−0.2178	0.037*
H7B	0.0201	−0.4492	−0.1815	0.037*
C8	−0.0676 (11)	−0.4934 (8)	−0.0308 (9)	0.0340 (19)
H8A	−0.0322	−0.5674	−0.0306	0.041*
H8B	−0.0084	−0.4506	0.0285	0.041*
C9	−0.2032 (10)	−0.4967 (8)	0.0078 (8)	0.0298 (18)
N1	−0.0681 (7)	−0.1216 (6)	−0.3016 (6)	0.0253 (14)
N2	−0.2837 (7)	−0.1355 (6)	−0.2263 (8)	0.0323 (17)
N3	−0.0822 (8)	−0.1022 (6)	−0.0806 (7)	0.0278 (15)
O11	−0.2377 (9)	−0.5691 (6)	0.0750 (8)	0.0444 (17)
O12	−0.2793 (8)	−0.4175 (6)	−0.0319 (7)	0.0408 (16)
P1	−0.1202 (2)	−0.30412 (17)	−0.1746 (2)	0.0234 (4)
B1	0.3222 (13)	−0.2721 (10)	−0.1875 (11)	0.039 (2)
Ag1	0.03866 (7)	−0.03737 (7)	−0.43859 (7)	0.0488 (3)
F1	0.2885 (9)	−0.1691 (6)	−0.2226 (8)	0.062 (2)
F2	0.2229 (8)	−0.3155 (7)	−0.1250 (9)	0.066 (2)
F3	0.4361 (8)	−0.2745 (9)	−0.1032 (10)	0.082 (3)
F4	0.3319 (16)	−0.3351 (7)	−0.2846 (9)	0.104 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.025 (4)	0.023 (4)	0.033 (4)	0.002 (3)	0.013 (3)	−0.004 (3)
C2	0.022 (4)	0.022 (4)	0.047 (5)	0.005 (3)	0.006 (4)	0.005 (4)
C3	0.029 (4)	0.027 (4)	0.029 (4)	0.007 (3)	0.003 (3)	0.001 (3)
C4	0.028 (5)	0.027 (4)	0.040 (5)	−0.001 (3)	0.001 (4)	0.008 (3)
C5	0.029 (4)	0.025 (4)	0.027 (4)	−0.004 (3)	0.008 (3)	−0.003 (3)
C6	0.031 (5)	0.028 (4)	0.049 (5)	0.010 (4)	0.019 (4)	−0.001 (4)
C7	0.026 (4)	0.029 (4)	0.042 (5)	−0.001 (3)	0.016 (4)	0.000 (4)
C8	0.040 (5)	0.031 (4)	0.030 (4)	0.004 (4)	0.001 (4)	0.009 (4)
C9	0.033 (5)	0.026 (4)	0.028 (4)	−0.001 (4)	−0.002 (3)	0.002 (4)
N1	0.023 (3)	0.025 (3)	0.027 (3)	−0.001 (3)	0.003 (3)	0.005 (3)
N2	0.023 (4)	0.027 (4)	0.048 (5)	0.001 (3)	0.008 (3)	0.005 (3)
N3	0.030 (4)	0.021 (3)	0.033 (4)	0.001 (3)	0.009 (3)	−0.002 (3)
O11	0.049 (4)	0.034 (3)	0.052 (4)	−0.002 (3)	0.013 (3)	0.016 (3)
O12	0.042 (4)	0.037 (3)	0.046 (4)	0.011 (3)	0.016 (3)	0.012 (3)
P1	0.0211 (10)	0.0193 (9)	0.0306 (10)	0.0024 (8)	0.0065 (8)	0.0009 (8)
B1	0.043 (7)	0.038 (6)	0.037 (5)	0.009 (5)	0.012 (5)	0.008 (5)
Ag1	0.0465 (4)	0.0623 (5)	0.0407 (4)	−0.0149 (4)	0.0167 (3)	0.0099 (4)
F1	0.059 (4)	0.037 (3)	0.090 (6)	0.000 (3)	0.007 (4)	0.016 (3)
F2	0.040 (4)	0.064 (5)	0.096 (6)	−0.004 (3)	0.016 (4)	0.024 (4)
F3	0.038 (4)	0.114 (8)	0.091 (6)	0.013 (5)	−0.003 (4)	0.020 (6)
F4	0.205 (14)	0.049 (4)	0.065 (5)	0.025 (6)	0.047 (7)	−0.003 (4)

Geometric parameters (Å, º)

C1—H1A	0.9700	C6—N2	1.436 (14)
C1—H1B	0.9700	C6—N3	1.460 (12)
C1—N1	1.479 (11)	C7—H7A	0.9700
C1—P1	1.815 (9)	C7—H7B	0.9700
C2—H2A	0.9700	C7—C8	1.534 (13)
C2—H2B	0.9700	C7—P1	1.775 (9)
C2—N2	1.461 (11)	C8—H8A	0.9700
C2—P1	1.826 (9)	C8—H8B	0.9700
C3—H3A	0.9700	C8—C9	1.494 (15)
C3—H3B	0.9700	C9—O11	1.233 (12)
C3—N3	1.484 (11)	C9—O12	1.272 (12)
C3—P1	1.818 (9)	N1—Ag1	2.225 (7)
C4—H4A	0.9700	N3—Ag1i	2.505 (7)
C4—H4B	0.9700	O11—Ag1ii	2.594 (9)
C4—N1	1.499 (12)	O12—Ag1ii	2.298 (8)
C4—N2	1.428 (13)	B1—F1	1.343 (14)
C5—H5A	0.9700	B1—F2	1.399 (14)
C5—H5B	0.9700	B1—F3	1.370 (15)
C5—N1	1.467 (10)	B1—F4	1.328 (16)
C5—N3	1.464 (12)	Ag1—N3iii	2.505 (7)
C6—H6A	0.9700	Ag1—O11iv	2.594 (9)
C6—H6B	0.9700	Ag1—O12iv	2.298 (8)
H1A—C1—H1B	108.1	C7—C8—H8B	109.1
N1—C1—H1A	109.5	H8A—C8—H8B	107.8
N1—C1—H1B	109.5	C9—C8—C7	112.6 (8)
N1—C1—P1	110.7 (6)	C9—C8—H8A	109.1
P1—C1—H1A	109.5	C9—C8—H8B	109.1
P1—C1—H1B	109.5	O11—C9—C8	122.7 (9)
H2A—C2—H2B	108.6	O11—C9—O12	122.6 (10)
N2—C2—H2A	110.4	O12—C9—C8	114.7 (8)
N2—C2—H2B	110.4	C1—N1—C4	108.8 (7)
N2—C2—P1	106.7 (6)	C1—N1—Ag1	112.5 (5)
P1—C2—H2A	110.4	C4—N1—Ag1	112.0 (5)
P1—C2—H2B	110.4	C5—N1—C1	110.9 (6)
H3A—C3—H3B	108.5	C5—N1—C4	108.6 (7)
N3—C3—H3A	110.2	C5—N1—Ag1	104.0 (5)
N3—C3—H3B	110.2	C4—N2—C2	113.3 (7)
N3—C3—P1	107.8 (6)	C4—N2—C6	110.2 (8)
P1—C3—H3A	110.2	C6—N2—C2	112.3 (8)
P1—C3—H3B	110.2	C3—N3—Ag1i	115.1 (5)
H4A—C4—H4B	107.7	C5—N3—C3	111.6 (7)
N1—C4—H4A	108.9	C5—N3—Ag1i	93.4 (5)
N1—C4—H4B	108.9	C6—N3—C3	110.6 (7)
N2—C4—H4A	108.9	C6—N3—C5	109.4 (7)
N2—C4—H4B	108.9	C6—N3—Ag1i	115.4 (5)
N2—C4—N1	113.4 (7)	C9—O11—Ag1ii	85.8 (6)
H5A—C5—H5B	107.6	C9—O12—Ag1ii	98.7 (6)
N1—C5—H5A	108.7	C1—P1—C2	99.7 (4)
N1—C5—H5B	108.7	C1—P1—C3	101.4 (4)
N3—C5—H5A	108.7	C3—P1—C2	103.1 (4)
N3—C5—H5B	108.7	C7—P1—C1	108.9 (4)
N3—C5—N1	114.2 (7)	C7—P1—C2	126.3 (4)
H6A—C6—H6B	107.6	C7—P1—C3	114.0 (4)
N2—C6—H6A	108.6	F1—B1—F2	108.8 (9)
N2—C6—H6B	108.6	F1—B1—F3	111.6 (11)
N2—C6—N3	114.6 (7)	F3—B1—F2	104.7 (9)
N3—C6—H6A	108.6	F4—B1—F1	110.8 (10)
N3—C6—H6B	108.6	F4—B1—F2	108.4 (11)
H7A—C7—H7B	107.5	F4—B1—F3	112.2 (12)
C8—C7—H7A	108.4	N1—Ag1—N3iii	119.6 (3)
C8—C7—H7B	108.4	N1—Ag1—O11iv	134.1 (3)
C8—C7—P1	115.5 (7)	N1—Ag1—O12iv	133.5 (3)
P1—C7—H7A	108.4	N3iii—Ag1—O11iv	92.3 (3)
P1—C7—H7B	108.4	O12iv—Ag1—N3iii	103.6 (3)
C7—C8—H8A	109.1	O12iv—Ag1—O11iv	52.9 (2)
C7—C8—C9—O11	148.3 (10)	N2—C6—N3—C5	53.5 (10)
C7—C8—C9—O12	−33.2 (12)	N2—C6—N3—Ag1i	157.2 (6)
C8—C7—P1—C1	153.3 (7)	N3—C3—P1—C1	51.8 (7)
C8—C7—P1—C2	−88.5 (8)	N3—C3—P1—C2	−51.1 (7)
C8—C7—P1—C3	40.9 (8)	N3—C3—P1—C7	168.7 (6)
C8—C9—O11—Ag1ii	177.7 (9)	N3—C5—N1—C1	−66.7 (9)
C8—C9—O12—Ag1ii	−177.7 (7)	N3—C5—N1—C4	52.8 (9)
N1—C1—P1—C2	54.5 (7)	N3—C5—N1—Ag1	172.2 (6)
N1—C1—P1—C3	−51.1 (7)	N3—C6—N2—C2	71.6 (10)
N1—C1—P1—C7	−171.6 (6)	N3—C6—N2—C4	−55.7 (10)
N1—C4—N2—C2	−71.1 (10)	O11—C9—O12—Ag1ii	0.8 (11)
N1—C4—N2—C6	55.6 (10)	O12—C9—O11—Ag1ii	−0.7 (10)
N1—C5—N3—C3	70.1 (9)	P1—C1—N1—C4	−60.8 (8)
N1—C5—N3—C6	−52.7 (9)	P1—C1—N1—C5	58.5 (8)
N1—C5—N3—Ag1i	−171.2 (6)	P1—C1—N1—Ag1	174.5 (4)
N2—C2—P1—C1	−53.2 (7)	P1—C2—N2—C4	64.6 (9)
N2—C2—P1—C3	51.0 (7)	P1—C2—N2—C6	−61.0 (8)
N2—C2—P1—C7	−175.5 (6)	P1—C3—N3—C5	−62.5 (8)
N2—C4—N1—C1	66.6 (10)	P1—C3—N3—C6	59.5 (8)
N2—C4—N1—C5	−54.2 (9)	P1—C3—N3—Ag1i	−167.4 (3)
N2—C4—N1—Ag1	−168.4 (6)	P1—C7—C8—C9	62.9 (10)
N2—C6—N3—C3	−69.8 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F2	0.97	2.40	3.201 (13)	140
C1—H1B···O11v	0.97	2.49	3.213 (12)	131
C2—H2A···O11v	0.97	2.56	3.254 (12)	129
C2—H2B···F3vi	0.97	2.35	3.183 (13)	143
C2—H2B···O12	0.97	2.22	2.812 (12)	118
C3—H3A···F4ii	0.97	2.45	3.290 (15)	145
C3—H3B···F2	0.97	2.51	3.283 (12)	136
C4—H4A···F4vii	0.97	2.43	3.298 (12)	148
C4—H4B···F2viii	0.97	2.51	3.417 (14)	155
C5—H5A···F1	0.97	2.49	3.370 (13)	151
C5—H5B···F4vii	0.97	2.54	3.373 (14)	144
C6—H6B···F2vii	0.97	2.34	3.314 (13)	177
C7—H7A···O11v	0.97	2.48	3.165 (13)	128
C7—H7A···F1ix	0.97	2.37	3.137 (12)	135

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

Funding Statement

This work was funded by Hungarian National Research, Development and Innovation Office grant FK-128333; Development and Innovation Fund of Hungary grant 2020-4.1.1-TKP2020, TKP2020-NKA-04; European Regional Development Fund grants GINOP-2.3.3-15-2016-00004 and GINOP 2.3.2-15-2016-00008.