5-Phenyl-3-(2-phosphono­eth­yl)-1,2,3-triazol-1-ium chloride

Chachlaki, E.; Choquesillo-Lazarte, D.; Demadis, K.D.

doi:10.1107/S2414314622001894

organic compounds

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ISSN: 2414-3146

Volume 7| Part 2| February 2022| x220189

https://doi.org/10.1107/S2414314622001894

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5-Phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride

Elpiniki Chachlaki,^a Duane Choquesillo-Lazarte ^b and Konstantinos D. Demadis ^a ^*

^aCrystal Engineering, Growth and Design Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Crete, GR-71003, Greece, and ^bLaboratorio de Estudios Cristalográficos, IACT, CSIC-Universidad de Granada, Granada-18100, Spain
^*Correspondence e-mail: demadis@uoc.gr

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 5 February 2022; accepted 17 February 2022; online 25 February 2022)

The new triazole-functionalized phosphonic acid 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride, C₁₀H₁₃N₃O₃P⁺·Cl⁻ (PTEPHCl), was synthesized by the `click' reaction of the alkyl azide diethyl-(2-azidoethyl)phosphonate with phenylacetylene to give the diethyl[2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethyl]phosphonate ester, which was then hydrolyzed under acidic conditions (HCl) to give the `free' phosphonic acid. The use of HCl for the hydrolysis caused protonation of the triazole ring, rendering the compound cationic, charged-balanced by a Cl⁻ anion. There are extensive hydrogen-bonding interactions in the structure of PTEPHCl, involving the phosphonic acid (–PO₃H₂) group, the triazolium ring and the Cl⁻ anion.

Keywords: phosphonate; triazole; hydrogen bonding; click chemistry; crystal structure.

CCDC reference: 2145106

Structure description

The exponential growth of the field of MOFs and coordination polymers over the past few decades is partially due to the design, synthesis and functionalization of appropriate linkers (Zaręba, 2017 ). Although the field was initiated with compounds that were mainly based on polycarboxylate linkers, its continuous development currently embraces virtually all molecules that are able to bind to metals. Among the plethora of ligands, (poly)phosphonic acids stand out because they can construct networks with high thermal and hydrolytic stability (Clearfield & Demadis, 2012 ). The field of metal phosphonates also relies on the availability of proper phosphonate linkers that offer structural diversity and can produce metal phosphonate compounds with attractive properties. Most of the published work on new phosphonic acids is based on two synthetic methodologies: (i) the Arbuzov reaction (Babu et al., 2017 ) and (ii) the Mannich-type (a.k.a. Moedritzer–Irani) reaction (Villemin et al., 2021 ). The Arbuzov reaction can convert an organic halide to a phosphonic acid group, whereas Mannich-type reactions transform an amine group to an aminomethylenephosphonic group. Both synthetic strategies aim at introducing a phosphonic acid moiety to a pre-formed organic fragment. We recently initiated synthetic efforts that are based on `click' chemistry. Specifically, the approach is based on a `reactive' organic molecule that already contains a phosphonic acid group, but can undergo other transformations elsewhere on the backbone.

The reaction of an organic azide with an alkyne to give a triazole is a well-known process (Mukherjee et al., 2013 ). Herein, this transformation was performed on an organic azide that already contains a phosphonate group on its backbone to yield a phosphonate-modified triazole. Specifically, an alkyl azide [diethyl-(2-azidoethyl)phosphonate] was reacted with an aromatic alkyne (phenylacetylene) to give diethyl[2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethyl]phosphonate ester. This ester was then hydrolyzed in acidic conditions to give 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride (PTEPHCl). In the present work, we report the crystal structure of the above-mentioned triazole-functionalized phosphonic acid PTEPHCl.

Molecular structure

Fig. 1 shows the molecular structure of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride. Because HCl was used for the ester hydrolysis, the N3 atom of the triazole ring and the O1 and O2 atoms of the phosphonate group are protonated due to the synthesis of PTEPHCl at low pH, hence a chloride counter-ion (Cl1) is found in the structure.

Figure 1
Molecular structure of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride with the atom-labeling scheme. Displacement ellipsoids are shown at the 50% probability level. Color code: P orange, O red, C black, N blue, Cl green, H white.

There are two `long' P—O bonds [P1—O1 = 1.5526 (16) and P1—O2 = 1.5513 (16) Å] and one `short' P—O bond [P1—O3 = 1.4805 (14) Å]. The `long' P—O bonds correspond to the P—O—H moieties and the `short' P—O bond corresponds to the phosphoryl P=O moiety. All P—O bond lengths have the expected values (Colodrero et al., 2013 ). The bond lengths of the triazolium moiety [N1—N2 = 1.317 (2) Å, N1—C2 = 1.474 (3) Å, N1—C3 = 1.346 (3) Å, N2—N3 = 1.318 (2) Å, N3—C4 = 1.352 (2) Å] are very similar to those in 1,2,4-triazolium chloride (Bujak & Zaleski, 2002 ).

Hydrogen bonding

The phosphonic acid moiety forms four hydrogen-bonding interactions (Fig. 2 and Table 1). Specifically, each of the two P—O—H groups interacts with a different Cl⁻ counter-ion, with contacts O1⋯Cl1 = 2.9521 (16) Å and O2⋯Cl1 = 2.9422 (17) Å. The phosphoryl P=O group forms a hydrogen bond with the N—H portion of the triazolium ring [O3⋯N3 2.610 (2) Å]. Finally, the benzene ring interacts with a phosphonate oxygen through a weak C—H⋯O contact at 3.476 (3) Å (C6⋯O2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1ⁱ	0.82	2.15	2.9521 (16)	167
O2—H2⋯Cl1	0.82	2.16	2.9422 (17)	160
N3—H3⋯O3ⁱⁱ	0.86	1.78	2.610 (2)	162
C6—H6⋯O2ⁱⁱⁱ	0.93	2.58	3.476 (3)	163
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Hydrogen-bonding scheme of the phosphonic acid group in the structure of PTEPHCl.

π–π stacking interactions

There is only one type of very weak π–π stacking interaction in the structure of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride. The centroid-to-centroid distance is 4.0423 (15) Å, with the rings being `shifted' from one another (slippage distance between the rings: 2.222 Å) and parallel.

Crystal packing

Fig. 3 shows the packing along the three axes. The π–π stacking interactions are parallel to the b axis. The chloride anions form corrugated sheets [`short' Cl⋯Cl distances at 4.9455 (12) Å and `long' Cl⋯Cl distances at 6.4564 (9) Å] that are parallel to the bc plane.

Figure 3
Packing of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride along the a- (upper), b- (middle), and c-axes (lower).

Synthesis and crystallization

Reagents and materials

All starting materials were obtained from commercial sources and used without further purification. The reagents diethyl 2-bromoethylphosphonate (97%), phenylacetylene (98+%), copper sulfate pentahydrate (99%), zinc nitrate hexahydrate (98%) and ethylenediaminetetraacetic acid (98%) were from Alfa Aesar. Sodium azide and L-ascorbic acid were from Serva. Sodium sulfate was from Merck. Dichloromethane, tetrahydrofuran (THF), hydrochloric acid (37%) and nitric acid (70%) were from Scharlau. Ion-exchange-column deionized water was used.

Synthesis of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride (PTEPHCl)

Three distinct steps were followed for the syntheses of the ligand PTEP. The first step was the synthesis of diethyl-(2-azidoethyl)phosphonate, following a properly adapted published procedure (Sheikhi et al., 2018 ). Specifically, sodium azide (10.6 g, 163.05 mmol) was added to a solution of diethyl-2-bromoethylphosphonate (10.4 g, 42.44 mmol) in water (50 mL). The reaction mixture was stirred at 338 K for 24 h. Then, extraction was carried out with dichloromethane (4 × 50 mL) and the organic phase was collected and dried over sodium sulfate. After filtration, a yellow oil was obtained, which is diethyl-(2-azidoethyl)phosphonate. The second step included the reaction of diethyl-(2-azidoethyl)phosphonate (3 mL, 2.07 mmol) with phenyl acetylene (895 µL, 1.035 mmol) in THF (67.5 mL), in the presence of copper sulfate (1.198 g 0.64 mmol) and L-ascorbic acid (0.218 g, 1.24 mmol) to produce diethyl[2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethyl]phosphonate ester. The reaction mixture was heated at 313 K under vigorous stirring for 48 h. After filtration, the filtrate was mixed with dichloromethane (50 mL) and an aqueous solution of the Cu²⁺ chelant ethylenediaminetetraacetic acid (50 mL, 0.2 M) and the mixture was stirred for ∼1 h. After extraction with dichloromethane (4 × 50 mL) and evaporation, diethyl[2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethyl]phosphonate ester was obtained in solid form. Finally, the latter (0.5 g) was hydrolyzed with 25 mL of H₂O and 30 mL of HCl at 373 K for 48 h, giving 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride in crystalline form (yield: 0.3 g, 60%). The crystal used for the data collection was handled under inert conditions. It was manipulated while immersed in a perfluoropolyether protecting oil and mounted on a MiTeGen Micromount™.

¹H NMR (300 MHz, DMSO-d₆) δ 8.51 (s, 1H), 7.93 (d, 2H), 7.67 (m, 3H), 4.82 (m, 2H), 2.52 (m, 2H). ¹³C NMR (75.5 MHz, DMSO-d₆) δ 146.71, 131.27, 129.38, 128.28, 125.53, 121.87, 45.42, 30.45 (d, J_CP = 134.5 Hz). ³¹P NMR (121.5 MHz, DMSO-d₆) δ 20.17.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₃P⁺·Cl⁻
M_r	289.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.5857 (6), 7.0616 (4), 16.6118 (9)
β (°)	108.222 (2)
V (Å³)	1290.92 (12)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.86
Crystal size (mm)	0.12 × 0.09 × 0.08

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.524, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	11621, 2268, 2048
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.129, 1.11
No. of reflections	2268
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.34
Computer programs: APEX3 (Bruker, 2019 ), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2145106

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622001894/tx4001sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622001894/tx4001Isup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622001894/tx4001Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2414314622001894/tx4001Isup5.mol

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

5-Phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride top

Crystal data top

C₁₀H₁₃N₃O₃P⁺·Cl⁻	F(000) = 600
M_r = 289.65	D_x = 1.490 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 11.5857 (6) Å	Cell parameters from 9685 reflections
b = 7.0616 (4) Å	θ = 4.0–66.7°
c = 16.6118 (9) Å	µ = 3.86 mm⁻¹
β = 108.222 (2)°	T = 298 K
V = 1290.92 (12) Å³	Plate, colourless
Z = 4	0.12 × 0.09 × 0.08 mm

Data collection top

Bruker D8 Venture diffractometer	2048 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 66.7°, θ_min = 4.0°
T_min = 0.524, T_max = 0.753	h = −12→13
11621 measured reflections	k = −8→8
2268 independent reflections	l = −18→19

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0842P)² + 0.2113P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.21 e Å⁻³
2268 reflections	Δρ_min = −0.34 e Å⁻³
166 parameters	Extinction correction: SHELXL2019/1 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0086 (14)

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.

Refinement. All hydrogen atoms were located in difference Fourier maps and included as fixed contributions riding on attached atoms with isotropic thermal displacement parameters 1.2 or 1.5 times those of the respective atom.

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

	x	y	z	U_iso*/U_eq
P1	0.81725 (4)	0.61394 (8)	0.26679 (3)	0.0473 (2)
O1	0.91887 (15)	0.4728 (3)	0.26434 (10)	0.0660 (5)
H1	0.946479	0.421812	0.310754	0.099*
O2	0.78145 (14)	0.7154 (3)	0.17962 (10)	0.0663 (5)
H2	0.838534	0.711018	0.160392	0.099*
O3	0.70907 (13)	0.5261 (2)	0.28078 (9)	0.0570 (4)
N1	0.68960 (15)	0.9187 (2)	0.35631 (11)	0.0480 (4)
N2	0.59278 (15)	0.9687 (3)	0.29376 (10)	0.0497 (4)
N3	0.50156 (14)	0.9160 (2)	0.32010 (10)	0.0446 (4)
H3	0.426572	0.931250	0.290694	0.054*
C1	0.88515 (18)	0.7829 (3)	0.34778 (14)	0.0530 (5)
H1A	0.902609	0.720386	0.402270	0.064*
H1B	0.962183	0.821985	0.341559	0.064*
C2	0.8107 (2)	0.9598 (3)	0.34921 (17)	0.0626 (6)
H2A	0.855085	1.038465	0.396689	0.075*
H2B	0.801074	1.031479	0.297697	0.075*
C3	0.66201 (18)	0.8378 (3)	0.42134 (13)	0.0468 (5)
H3A	0.716089	0.792849	0.471680	0.056*
C4	0.53734 (17)	0.8355 (3)	0.39786 (12)	0.0406 (4)
C5	0.45429 (18)	0.7694 (2)	0.44224 (12)	0.0419 (5)
C6	0.4974 (2)	0.7322 (3)	0.52898 (13)	0.0509 (5)
H6	0.579280	0.748521	0.558805	0.061*
C7	0.4176 (3)	0.6708 (3)	0.57037 (15)	0.0634 (6)
H7	0.446686	0.644005	0.628029	0.076*
C8	0.2960 (3)	0.6489 (3)	0.52761 (18)	0.0678 (7)
H8	0.242943	0.611045	0.556500	0.081*
C9	0.2534 (2)	0.6829 (4)	0.44228 (18)	0.0727 (7)
H9	0.171424	0.665745	0.412999	0.087*
C10	0.3319 (2)	0.7427 (3)	0.39929 (16)	0.0573 (6)
H10	0.302340	0.765053	0.341264	0.069*
Cl1	0.94890 (5)	0.76568 (8)	0.07972 (3)	0.0583 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0364 (3)	0.0693 (4)	0.0365 (4)	0.0015 (2)	0.0118 (2)	0.0013 (2)
O1	0.0610 (10)	0.0914 (12)	0.0490 (9)	0.0254 (8)	0.0223 (7)	0.0080 (8)
O2	0.0475 (9)	0.1068 (13)	0.0442 (9)	0.0135 (8)	0.0136 (7)	0.0171 (8)
O3	0.0468 (8)	0.0797 (10)	0.0457 (8)	−0.0157 (7)	0.0163 (6)	−0.0101 (7)
N1	0.0392 (9)	0.0508 (9)	0.0543 (10)	−0.0028 (7)	0.0150 (7)	−0.0041 (7)
N2	0.0458 (9)	0.0583 (10)	0.0469 (10)	0.0002 (7)	0.0174 (8)	0.0004 (7)
N3	0.0383 (8)	0.0560 (9)	0.0385 (9)	0.0008 (7)	0.0104 (6)	−0.0007 (7)
C1	0.0325 (10)	0.0742 (14)	0.0510 (12)	−0.0047 (9)	0.0110 (9)	−0.0007 (10)
C2	0.0422 (11)	0.0659 (14)	0.0816 (16)	−0.0130 (10)	0.0220 (11)	−0.0053 (12)
C3	0.0401 (10)	0.0492 (10)	0.0470 (11)	−0.0016 (8)	0.0076 (8)	−0.0018 (8)
C4	0.0419 (9)	0.0394 (9)	0.0384 (10)	0.0006 (7)	0.0097 (7)	−0.0037 (7)
C5	0.0470 (11)	0.0379 (9)	0.0414 (11)	0.0027 (7)	0.0145 (8)	−0.0006 (7)
C6	0.0610 (13)	0.0468 (11)	0.0419 (11)	0.0008 (9)	0.0118 (9)	−0.0026 (8)
C7	0.1016 (19)	0.0488 (12)	0.0472 (12)	0.0034 (12)	0.0339 (12)	0.0020 (9)
C8	0.0832 (18)	0.0559 (13)	0.0814 (18)	0.0002 (12)	0.0503 (15)	0.0100 (12)
C9	0.0525 (13)	0.0751 (16)	0.094 (2)	−0.0061 (12)	0.0289 (13)	0.0171 (14)
C10	0.0476 (12)	0.0685 (14)	0.0525 (13)	−0.0047 (9)	0.0110 (10)	0.0134 (10)
Cl1	0.0507 (4)	0.0795 (4)	0.0435 (4)	0.0062 (2)	0.0130 (3)	−0.0025 (2)

Geometric parameters (Å, º) top

P1—O1	1.5526 (16)	C2—H2B	0.9700
P1—O2	1.5513 (16)	C3—H3A	0.9300
P1—O3	1.4805 (14)	C3—C4	1.373 (3)
P1—C1	1.786 (2)	C4—C5	1.460 (3)
O1—H1	0.8200	C5—C6	1.394 (3)
O2—H2	0.8200	C5—C10	1.386 (3)
N1—N2	1.317 (2)	C6—H6	0.9300
N1—C2	1.474 (3)	C6—C7	1.383 (3)
N1—C3	1.346 (3)	C7—H7	0.9300
N2—N3	1.318 (2)	C7—C8	1.373 (4)
N3—H3	0.8600	C8—H8	0.9300
N3—C4	1.352 (2)	C8—C9	1.368 (4)
C1—H1A	0.9700	C9—H9	0.9300
C1—H1B	0.9700	C9—C10	1.387 (3)
C1—C2	1.522 (3)	C10—H10	0.9300
C2—H2A	0.9700

O1—P1—C1	106.83 (10)	H2A—C2—H2B	107.7
O2—P1—O1	104.80 (9)	N1—C3—H3A	127.2
O2—P1—C1	108.71 (11)	N1—C3—C4	105.65 (18)
O3—P1—O1	114.92 (11)	C4—C3—H3A	127.2
O3—P1—O2	110.35 (9)	N3—C4—C3	104.31 (17)
O3—P1—C1	110.89 (9)	N3—C4—C5	124.28 (17)
P1—O1—H1	109.5	C3—C4—C5	131.39 (18)
P1—O2—H2	109.5	C6—C5—C4	120.16 (19)
N2—N1—C2	118.78 (18)	C10—C5—C4	120.86 (18)
N2—N1—C3	112.94 (16)	C10—C5—C6	119.0 (2)
C3—N1—C2	128.26 (18)	C5—C6—H6	120.2
N1—N2—N3	103.64 (15)	C7—C6—C5	119.6 (2)
N2—N3—H3	123.3	C7—C6—H6	120.2
N2—N3—C4	113.45 (16)	C6—C7—H7	119.5
C4—N3—H3	123.3	C8—C7—C6	121.0 (2)
P1—C1—H1A	108.2	C8—C7—H7	119.5
P1—C1—H1B	108.2	C7—C8—H8	120.2
H1A—C1—H1B	107.4	C9—C8—C7	119.7 (2)
C2—C1—P1	116.22 (15)	C9—C8—H8	120.2
C2—C1—H1A	108.2	C8—C9—H9	119.8
C2—C1—H1B	108.2	C8—C9—C10	120.3 (2)
N1—C2—C1	113.42 (18)	C10—C9—H9	119.8
N1—C2—H2A	108.9	C5—C10—C9	120.4 (2)
N1—C2—H2B	108.9	C5—C10—H10	119.8
C1—C2—H2A	108.9	C9—C10—H10	119.8
C1—C2—H2B	108.9

P1—C1—C2—N1	56.6 (3)	C2—N1—C3—C4	178.52 (19)
O1—P1—C1—C2	167.10 (17)	C3—N1—N2—N3	−0.6 (2)
O2—P1—C1—C2	54.50 (19)	C3—N1—C2—C1	65.1 (3)
O3—P1—C1—C2	−67.0 (2)	C3—C4—C5—C6	14.3 (3)
N1—N2—N3—C4	0.6 (2)	C3—C4—C5—C10	−165.7 (2)
N1—C3—C4—N3	0.0 (2)	C4—C5—C6—C7	179.59 (18)
N1—C3—C4—C5	−178.62 (18)	C4—C5—C10—C9	−178.9 (2)
N2—N1—C2—C1	−116.9 (2)	C5—C6—C7—C8	−1.1 (3)
N2—N1—C3—C4	0.4 (2)	C6—C5—C10—C9	1.0 (3)
N2—N3—C4—C3	−0.4 (2)	C6—C7—C8—C9	1.9 (4)
N2—N3—C4—C5	178.37 (17)	C7—C8—C9—C10	−1.2 (4)
N3—C4—C5—C6	−164.07 (18)	C8—C9—C10—C5	−0.2 (4)
N3—C4—C5—C10	15.9 (3)	C10—C5—C6—C7	−0.4 (3)
C2—N1—N2—N3	−178.94 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.82	2.15	2.9521 (16)	167
O2—H2···Cl1	0.82	2.16	2.9422 (17)	160
N3—H3···O3ⁱⁱ	0.86	1.78	2.610 (2)	162
C6—H6···O2ⁱⁱⁱ	0.93	2.58	3.476 (3)	163

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z+1/2.

Funding information

Funding for this research was provided for the research project `Innovative Materials and Applications' (INNOVAMAT, KA 10694) by the Special Account for Research Grants.

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