Novel three-dimensional coordination polymer of 2-(1,3,5-tri­aza-7-phospho­niatri­cyclo­[3.3.1.13,7]decan-7-yl)ethanoic acid with silver(I) tetra­fluoro­borate

Udvardy, A.; Kathó, Á.; Papp, G.; Joó, F.; Gál, G.T.

doi:10.1107/S2056989022000767

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 78| Part 3| March 2022| Pages 251-254

https://doi.org/10.1107/S2056989022000767

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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

Antal Udvardy,^a ^* Ágnes Kathó,^a Gábor Papp,^a Ferenc Joó ^a,^b and Gyula Tamás Gál ^a ^*

^aDepartment of Physical Chemistry, University of Debrecen, Debrecen, Hungary, and ^bMTA-DE Redox and Homogeneous Catalytic Reaction Mechanisms Research Group, Department of Physical Chemistry, University of Debrecen, Debrecen, Hungary
^*Correspondence e-mail: udvardya@unideb.hu, gal.tamas@science.unideb.hu

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 21 December 2021; accepted 21 January 2022; online 1 February 2022)

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-κ⁴N: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.

Keywords: crystal structure; coordination polymer; silver; phosphabetaine; tetrafluoroborate.

CCDC reference: 2143743

1. 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.

2. 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, $[{1\over 2}]$ + z; (2) − $[{1\over 2}]$ + x, − $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (3) x, −y, − $[{1\over 2}]$ + z; (4) $[{1\over 2}]$ + x, − $[{1\over 2}]$ − y, − $[{1\over 2}]$ + 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

3. 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. 3b 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⋯F4^iv	0.97	2.43	3.298 (12)	148
C4—H4B⋯F2^v	0.97	2.51	3.417 (14)	155
C5—H5A⋯F1	0.97	2.49	3.370 (13)	151
C5—H5B⋯F4^iv	0.97	2.54	3.373 (14)	144
C6—H6B⋯F2^iv	0.97	2.34	3.314 (13)	177
C7—H7A⋯O11ⁱ	0.97	2.48	3.165 (13)	128
C7—H7A⋯F1^vi	0.97	2.37	3.137 (12)	135
Symmetry codes: (i) $[x, -y-1, z-{\script{1\over 2}}]$ ; (ii) ; (iii) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

4. 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-κ³N:O:O′)]_n(PF₆)_n (UPUCAM; Udvardy et al., 2021), [Ag(OTf)(μ₃-L-κ³N:O:O′)]_n (UPUCIU; Udvardy et al., 2021) and [Ag(tos)(μ₃-L-κ³N: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.

5. 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⁺–CH₂–CH₂–COO), 2.44–2.22 (m, 2H, P⁺–CH₂–CH₂–COO) ppm. ¹³C{¹H} NMR (90 MHz, D₂O, 298 K) δ 179.5 (s, COO⁻), 71.5 (d, ³J_PC = 8 Hz, N–CH₂–N), 49.1 (d, ¹J_PC = 37 Hz, ⁺P-CH₂–N), 29.0 (d, ²J_PC = 7 Hz, P⁺–CH₂–CH₂–COO⁻), 18.5 (d, ¹J_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.

6. 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, Cc
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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC reference: 2143743

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022000767/ex2052sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022000767/ex2052Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022000767/ex2052Isup3.mol

Cover letter. DOI: https://doi.org/10.1107/S2056989022000767/ex2052sup4.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989022000767/ex2052sup5.docx

Supporting information file. DOI: https://doi.org/10.1107/S2056989022000767/ex2052sup6.pdf

Cover letter. DOI: https://doi.org/10.1107/S2056989022000767/ex2052sup7.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989022000767/ex2052sup8.pdf

checkCIF report

Computing details top

Data collection: MACH3/PC (Enraf–Nonius, 1992); cell refinement: MACH3/PC (Enraf–Nonius, 1992); data reduction: PROFIT (Streltsov & Zavodnik, 1989); program(s) used to solve structure: SIR97 (Burla et al., 2007); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Poly[[[µ₃-2-(1,3,5-triaza-7-phosphoniatricyclo[3.3.1.1^3,7]decan-7-yl)ethanoate-κ⁴N:N':O,O']silver(I)] tetrafluoroborate] top

Crystal data top

[Ag(C₉H₁₆N₃O₂P)]BF₄	F(000) = 840
M_r = 423.90	D_x = 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 top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.009
profiled ω/2θ scans	θ_max = 25.5°, θ_min = 3.1°
Absorption correction: ψ scan (North et al., 1968)	h = 0→12
T_min = 0.558, T_max = 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 top

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(F_o²) + (0.0873P)² + 4.2725P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.13	Δρ_max = 1.20 e Å⁻³
1313 reflections	Δρ_min = −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 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
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 (Å²) top

	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) top

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—O11^iv	2.594 (9)
C6—H6B	0.9700	Ag1—O12^iv	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—O11^iv	134.1 (3)
C8—C7—P1	115.5 (7)	N1—Ag1—O12^iv	133.5 (3)
P1—C7—H7A	108.4	N3ⁱⁱⁱ—Ag1—O11^iv	92.3 (3)
P1—C7—H7B	108.4	O12^iv—Ag1—N3ⁱⁱⁱ	103.6 (3)
C7—C8—H8A	109.1	O12^iv—Ag1—O11^iv	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) top

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···O11^v	0.97	2.49	3.213 (12)	131
C2—H2A···O11^v	0.97	2.56	3.254 (12)	129
C2—H2B···F3^vi	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···F4^vii	0.97	2.43	3.298 (12)	148
C4—H4B···F2^viii	0.97	2.51	3.417 (14)	155
C5—H5A···F1	0.97	2.49	3.370 (13)	151
C5—H5B···F4^vii	0.97	2.54	3.373 (14)	144
C6—H6B···F2^vii	0.97	2.34	3.314 (13)	177
C7—H7A···O11^v	0.97	2.48	3.165 (13)	128
C7—H7A···F1^ix	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.

Acknowledgements

The authors thank Ms Cynthia Nóra Nagy (University of Debrecen) for the HRMS measurements and Dr Attila Kiss for the elemental analysis measurements. We are also grateful to Dr Attila Bényei (University of Debrecen) for recording the diffraction data.

Funding information

The financial support of the Hungarian National Research, Development and Innovation Office (FK-128333) is greatly acknowledged. Project No. TKP2020-NKA-04 has been implemented with support provided from the National Research, Development and Innovation Fund of Hungary, financed under the 2020–4.1.1-TKP2020 funding scheme. The research was supported by the EU and co-financed by the European Regional Development Fund under the projects GINOP-2.3.3–15-2016–00004 and GINOP 2.3.2–15-2016–00008.

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