Synthesis, crystal structure and Hirshfeld surface analysis of 3-(4-fluoro­phen­yl)-2-formyl-7-methyl­imidazo[1,2-a]pyridin-1-ium chloride monohydrate

Guseinov, F.I.; Ovsyannikov, V.O.; Sokolovskiy, P.V.; Sebyakin, Y.L.; Samigullina, A.I.; Akkurt, M.; Çelikesir, S.T.; Bhattarai, A.

doi:10.1107/S2056989023007272

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ISSN: 2056-9890

Volume 79| Part 10| October 2023| Pages 899-904

https://doi.org/10.1107/S2056989023007272

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Synthesis, crystal structure and Hirshfeld surface analysis of 3-(4-fluorophenyl)-2-formyl-7-methylimidazo[1,2-a]pyridin-1-ium chloride monohydrate

Firudin I. Guseinov,^a,^b Viacheslav O. Ovsyannikov,^b,^c Pavel V. Sokolovskiy,^b Yurii L. Sebyakin,^c Aida I. Samigullina,^b Mehmet Akkurt,^d Sevim Türktekin Çelikesir ^e and Ajaya Bhattarai ^f ^*

^aKosygin State University of Russia, 117997 Moscow, Russian Federation, ^bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation, ^cMIREA, Russian Technology University, Lomonosov Institute of Fine Chemical Technology, Moscow 119571, Russian Federation, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, ^eDepartment of Physics, Faculty of Science, Erciyes University, 38039 Kayseri, Türkiye, and ^fDepartment of Chemistry, M.M.A.M.C. (Tribhuvan University), Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by J. Reibenspies, Texas A & M University, USA (Received 25 July 2023; accepted 18 August 2023; online 12 September 2023)

In the title salt, C₁₅H₁₂FN₂O⁺·Cl⁻·H₂O, the imidazo[1,2-a]pyridin-1-ium ring system of the cation is almostly planar [maximum deviaition = −0.047 (2) Å for the ring C atom with the attached arene ring] and forms a dihedral angle of 61.81 (6)° with the plane of the fluorophenyl ring. In the crystal, water molecules form an R₂⁴(8) motif parallel to the (100) plane by bonding with the chloride ions via O—H⋯Cl hydrogen bonds. The cations are connected along the b axis via N—H⋯O hydrogen bonds involving the O atoms of water molecules, and C—H⋯O, C—H⋯Cl and π–π interactions [centroid-to-centroid distance = 3.6195 (8) Å] form layers parallel to the (100) plane. Furthermore, these layers are connected via π–π interactions [centroid-to-centroid distance = 3.8051 (9) Å] that further consolidate the crystal structure.

Keywords: crystal structure; imidazo[1,2-a]pyridin-1-ium; hydrogen bonds; π–π interactions; Hirshfeld surface analysis.

CCDC reference: 2289534

1. Chemical context

Imidazo[1,2-a]pyridine is considered to be the most important derivative in the imidazopyridine system, with many important biological activities (Ribeiro et al., 1998 ; Khalilov et al., 2021 ). These derivatives exhibit a number of interesting properties, such as anticancer, antifungal, anti-inflammatory, antibacterial, antiprotozoal, antipyretic and anti-infective, as well as analgesic and pain relief and sedative properties (Ribeiro et al., 1998; Almirante et al., 1965 ; Safavora et al., 2019 ). Imidazo[1,2-a]pyridine is present in various pharmaceutical products, such as zolpidem (used to treat insomnia), alpidem (sedative) (Lacerda et al., 2014 ), zolimidine (used to treat peptic ulcers) (Tyagi et al., 2012 ; Martins et al., 2017 ), olprinone (acute heart failure), saripidem (sedative), necopidem (sedative), soraprazan, miroprofen and minodronic acid (Kielesiński et al., 2015 ). Due to its importance in the pharmaceutical industry, much effort has been devoted to this heterocycle in order to develop an efficient, feasible and low-cost synthesis of imidazo[1,2-a]pyridine derivatives (Ribeiro et al., 1998). Besides their biological activity, the transition-metal complexes of imidazole ligands have been found to possess a wide variety of functional properties, for example, as catalysts, supramolecular building blocks, analytical reagents, etc. (Gurbanov et al., 2020a ,b ; Kopylovich et al., 2011 ; Mahmudov et al., 2010 , 2012 ). By the functionalization of the imidazole synthon their functional properties can be improved (Gurbanov et al., 2022 ; Mahmoudi et al., 2017a ,b , 2019 ). In addition, the functional groups on the imidazole ring can participate in various types of intermolecular interactions (Mahmudov et al., 2022 ). Acetal-containing 2-chloro-2-(diethoxymethyl)-3-(4-fluorophenyl)oxirane (1) or 1-chloro-3,3-diethoxy-1-(4-fluorophenyl)propan-2-one (2) in reactions with bi- and polyfunctional nucleophiles (Fig. 1) turned out to be convenient in the molecular design of various heterocyclic systems, in particular, heterocyclic carbaldehydes and their derivatives (Guseinov et al., 1994 , 1995 , 1998 , 2006 , 2017 , 2020 ; Pistsov et al., 2017 ). We have found that electrophilic reagents (1 or 2) react with 2-amino-4-methylpyridine under certain conditions to transform into 3-(4-fluorophenyl)-2-formyl-7-methylimidazo[1,2-a]pyridin-1-ium chloride (3) whose structure has been determined by NMR spectroscopy and X-ray diffraction methods (Fig. 1).

Figure 1
Reaction mechanism of the title compound.

2. Structural commentary

In the title salt (Fig. 2), the imidazo[1,2-a]pyridin-1-ium ring system (atoms N1/N4/C2/C3/C5–C8/C8A) of the cation is almost planar [maximum deviaition = −0.047 (2) Å for atom C3] and forms a dihedral angle of 61.81 (6)° with the plane of the fluorophenyl ring (C11–C16).

Figure 2
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

The bond lengths and angles in the molecule of the title salt are comparable with those of closely related structures detailed in Section 4 (Database survey).

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, water molecules form an $[R_{2}^{4}]$ (8) motif (Bernstein et al., 1995 ) parallel to the (100) plane by bonding with the chloride ions via O—H⋯Cl hydrogen bonds (Table 1 and Figs. 3 and 4). The cations are also connected along the b axis via N—H⋯O hydrogen bonds involving the O atoms of the water molecules, and C—H⋯O, C—H⋯Cl and π–π interactions [Cg2⋯Cg2^iv = 3.6195 (8) Å; symmetry code: (iv) −x + 1, −y + 1, −z + 1; Cg2 is a centroid of the six-membered ring (N4/C5–C8/C8A) of the imidazo[1,2-a]pyridin-1-ium ring system (N1/N4/C2/C3/C5–C8/C8A)] form layers parallel to the (100) plane (Fig. 5). Furthermore, these layers are connected to each other via π–π interactions [Cg3⋯Cg3^vii = 3.8051 (9) Å; symmetry code: (vii) −x + 1, −y, −z + 2; Cg3 is a centroid of the fluorophenyl ring (C11–C16)] that consolidate the crystal structure (Fig. 6).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O18ⁱ	0.91 (2)	1.77 (2)	2.6754 (16)	174 (2)
O18—H18A⋯Cl1ⁱⁱ	0.87 (2)	2.24 (2)	3.1070 (11)	175 (2)
O18—H18B⋯Cl1ⁱⁱⁱ	0.87 (2)	2.24 (2)	3.1142 (11)	178.0 (19)
C8—H8⋯Cl1^iv	0.95	2.69	3.6431 (15)	176
C12—H12⋯Cl1^v	0.95	2.71	3.5610 (16)	150
C13—H13⋯O10^vi	0.95	2.41	3.057 (2)	125
Symmetry codes: (i) ; (ii) x+1, y+1, z; (iii) ; (iv) ; (v) x+1, y, z; (vi) .

Figure 3
View of the molecular packing along the a axis. N—H⋯O and O—H⋯Cl hydrogen bonds are shown as dashed lines.

Figure 4
View of the molecular packing along the b axis. Hydrogen bonds are depicted as in Fig. 3

Figure 5
View of the molecular packing along the c axis. Hydrogen bonds are depicted as in Fig. 3

Figure 6
View of the π–π stacking interactions along the b axis in the unit cell.

The Hirshfeld surface mapped over d_norm was generated using CrystalExplorer17.5 (Spackman et al., 2021 ) with a colour scale from −0.7283 a.u. for red to +1.3376 a.u. for blue. The front and rear views of the Hirshfeld surface mapped over d_norm are depicted in Fig. 7. The bright-red circular spots on d_norm indicate the presence of intermolecular N1—H1⋯O18ⁱ, C8—H8⋯Cl1^iv, C12—H12⋯Cl1^v and C13—H13⋯O10^vi interactions (Table 1). The percentage contributions from different intermolecular interactions towards the formation of a three-dimensional Hirshfeld surface were computed using two-dimensional fingerprint calculations (Fig. 8).

Figure 7
(a) Front and (b) back sides of the three-dimensional Hirshfeld surface of the title compound mapped over d_norm, with a fixed colour scale from −0.7283 to 1.3376 a.u.

Figure 8
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O and (e) F⋯H/H⋯F interactions. d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively.

Fig. 8 shows the full two-dimensional fingerprint plots for the molecule and those delineated into the major contacts. H⋯H interactions [Fig. 8(b)] are the major contributor (35.2%) to the crystal packing, with C⋯H/H⋯C [Fig. 8(c); 19.0%], O⋯H/H⋯O [Fig. 8(d); 15.5%] and F⋯H/H⋯F [Fig. 8(e); 9.9%] interactions representing the next highest contributions. The percentage contributions of comparatively weaker interactions are C⋯C (4.6%), N⋯H/H⋯N (2.8%), F⋯O/O⋯F (1.5%), Cl⋯C/C⋯Cl (1.3%), Cl⋯H/H⋯Cl (1.3%), N⋯C/C⋯N (1.3%), F⋯F (1.2%), F⋯C/C⋯F (1.1%) and O⋯O (0.1%). Relevant short intermolecular atomic contacts are summarized in Table 2.

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
H13⋯O10	2.41	x + 1, y − 1, z
F1⋯H17C	2.78	x, y − 1, z + 1
H9⋯F1	2.79	−x + 1, −y, −z + 2
H9⋯O10	2.71	−x, −y + 1, −z + 2
H16⋯Cl1	3.04	x, y, z
H17B⋯C2	3.02	−x + 1, −y + 1, −z + 1
H5⋯C6	3.02	−x + 1, −y, −z + 1
H17A⋯O18	2.78	−x + 1, −y + 1, −z + 1
H8⋯Cl1	2.69	−x, −y + 1, −z + 1
H15⋯C9	3.08	−x, −y, −z + 2
H12⋯Cl1	2.71	x + 1, y, z
H5⋯O18	2.76	x, y − 1, z
Cl1⋯H6	2.94	−x + 1, −y, −z + 1
H18A⋯Cl1	2.24	x + 1, y + 1, z
O18⋯H1	1.77	x + 1, y, z

The results show that the H⋯H (35.2%) contacts give the major contribution to the crystal packing, and that the C⋯H/H⋯C (19.0%), O⋯H/H⋯O (15.5%) and F⋯H/H⋯F (9.9%) contacts also give a significant contribution to the total area of the Hirshfeld surface.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) for compounds most closely related to the imidazo[1,2-a]pyridin-1-ium unit of the title compound gave the following hits: refcodes LESMAZ (Yin, 2013 ), UREPIR (Nichol et al., 2011 ), ABAJOE (Rybakov & Babaev, 2011 ), BIZWAI02 (Airoldi et al., 2015 ), UREYIA (Türkyılmaz et al., 2011 ) and NEQPOP (Qiao et al., 2006 ).

In the crystal of LESMAZ, the cations and anions are linked into chains parallel to [021] by O—H⋯Cl and N—H⋯Cl hydrogen bonds. In the crystal of UREPIR, N—H⋯O interactions form a one-dimensional chain, which propagates in the b-axis direction. C—H⋯O interactions are also found in the crystal packing. The crystal structure of ABAJOE is consolidated by weak C—H⋯O and C—H⋯Cl interactions involving the `olate' O atom and the Cl atom attached to the benzoyl group as acceptors. In the crystal of BIZWAI02, molecules are linked by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, and π–π interactions [centroid-to-centroid distance = 3.5822 (11) Å], forming a three-dimensional structure. In the crystal of UREYIA, the components are linked by N—H⋯O and C—H⋯O hydrogen bonds and π–π stacking interactions [centroid–centroid separation = 3.642 (3) Å]. In the crystal of NEQPOP, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into two-dimensional layers.

5. Synthesis and crystallization

A solution of equimolar amounts of 2-aminopyridine (410 mg, 3.8 mmol) and 2-chloro-2-(diethoxymethyl)-3-(4-fluorophenyl)oxirane (1) or 1-chloro-3,3-diethoxy-1-(4-fluorophenyl) propan-2-one (2) (1.05 g, 3.8 mmol) in 25 ml of 95% aqueous ethanol was heated at reflux for 8 h. The solvent was removed in vacuo. After purification by column chromatography using a chloroform/ethyl acetate mixture (3:1 v/v), 2-(diethoxymethyl)-3-(4-fluorophenyl)imidazo[1,2-a]pyridine was obtained as a white powder. Gaseous HCl was passed through a solution of 2-(diethoxymethyl)-3-(4-fluorophenyl)imidazo[1,2-a]pyridine in chloroform, leading to the main product, 3-(4-fluorophenyl)-2-formyl-7-methylimidazo[1,2-a]pyridin-1-ium chloride (3) in the form of a white precipitate; this was insoluble in chloroform and was filtered off and recrystallized from acetonitrile (Fig. 1). Yield 0.61 g (55%); m.p. 509–510 K. Analysis calculated (%) for C₁₅H₁₂ClFN₂O: C 70.58, H 4.74, F 7.44, N 10.97, O 6.27; found: C 70.60, H 4.78, F 7.42, N 10.93, O 6.27. ¹H NMR (300 MHz, DMSO-d₆): δ 2.54 (s, 3H, CH₃), 7.28 (d, J = 6.6 Hz, 1H, 6CH), 7.55 (dd, J = 8.8, 5.5 Hz, 2H, Ar), 7.75 (s, 1H, NH), 7.90 (dd, J = 8.6, 5.5 Hz, 2H, Ar), 8.35 (s, 1H, 8CH), 8.47 (d, J = 7.1 Hz, 1H, 5CH), 9.85 (s, 1H, CHO). ¹³C NMR (200 MHz, DMSO-d₆): δ 21.27, 111.92, 116.44, 116.87, 119.67, 120.02, 126.18, 130.39, 131.39, 133.59 (d, J = 35 Hz, CF), 141.40, 147.07, 161.11, 166.06, 182.45. ESI–MS: m/z: 255.0928 [M + H]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The N-bound H atom and the H atoms of the water molecule were located in a difference Fourier map and refined freely along with their isotropic displacement parameters. C-bound H atoms were included in calculated positions and treated as riding atoms (C—H = 0.95–0.98 Å), with U_iso(H) = 1.2U_eq(C) for aromatic H atoms and 1.5U_eq(C) for methyl H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₅H₁₂FN₂O⁺·Cl⁻·H₂O
M_r	308.73
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.45681 (13), 8.41737 (10), 12.8928 (2)
α, β, γ (°)	74.0382 (12), 73.7634 (14), 72.7034 (13)
V (Å³)	725.40 (2)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.50
Crystal size (mm)	0.33 × 0.19 × 0.15

Data collection
Diffractometer	Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.404, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15845, 3082, 3033
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.03
No. of reflections	3082
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.24
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT2019 (Sheldrick, 2015a ), SHELXL2019 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2289534

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007272/jy2034sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007272/jy2034Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023007272/jy2034Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2023); cell refinement: CrysAlis PRO (Rigaku OD, 2023); data reduction: CrysAlis PRO (Rigaku OD, 2023); program(s) used to solve structure: SHELXT2019 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

3-(4-Fluorophenyl)-2-formyl-7-methylimidazo[1,2-a]pyridin-1-ium chloride monohydrate top

Crystal data top

C₁₅H₁₂FN₂O⁺·Cl⁻·H₂O	Z = 2
M_r = 308.73	F(000) = 320
Triclinic, P1	D_x = 1.413 Mg m⁻³
a = 7.45681 (13) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.41737 (10) Å	Cell parameters from 11896 reflections
c = 12.8928 (2) Å	θ = 3.6–77.3°
α = 74.0382 (12)°	µ = 2.50 mm⁻¹
β = 73.7634 (14)°	T = 100 K
γ = 72.7034 (13)°	Prism, colorless
V = 725.40 (2) Å³	0.33 × 0.19 × 0.15 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	3082 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3033 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.9°, θ_min = 3.7°
ω scans	h = −9→9
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2023)	k = −10→9
T_min = 0.404, T_max = 1.000	l = −16→16
15845 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: mixed
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0415P)² + 0.4038P] where P = (F_o² + 2F_c²)/3
3082 reflections	(Δ/σ)_max = 0.001
203 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

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
Cl1	0.01542 (4)	0.11097 (4)	0.64700 (3)	0.02403 (11)
F1	0.56045 (14)	−0.35098 (11)	1.02878 (8)	0.0367 (2)
O18	0.90723 (15)	0.80467 (12)	0.61002 (9)	0.0241 (2)
N4	0.37156 (15)	0.27422 (14)	0.62115 (9)	0.0190 (2)
N1	0.14182 (17)	0.49767 (15)	0.65794 (10)	0.0215 (2)
C8A	0.26290 (18)	0.42655 (16)	0.57537 (11)	0.0196 (3)
C11	0.37885 (19)	0.08741 (17)	0.81151 (11)	0.0210 (3)
C5	0.51012 (19)	0.17210 (16)	0.55569 (12)	0.0214 (3)
H5	0.586532	0.067821	0.587952	0.026*
C12	0.5714 (2)	0.03302 (17)	0.81846 (11)	0.0233 (3)
H12	0.660070	0.098082	0.773040	0.028*
C3	0.30886 (19)	0.24618 (17)	0.73582 (11)	0.0208 (3)
C7	0.4192 (2)	0.37812 (17)	0.39448 (11)	0.0228 (3)
C2	0.16899 (19)	0.38788 (17)	0.75689 (11)	0.0217 (3)
C8	0.28524 (19)	0.48118 (17)	0.46032 (11)	0.0215 (3)
H8	0.209704	0.586666	0.428855	0.026*
C14	0.5015 (2)	−0.20644 (18)	0.95627 (12)	0.0267 (3)
C16	0.2482 (2)	−0.00887 (19)	0.87709 (12)	0.0271 (3)
H16	0.117247	0.027457	0.871462	0.032*
C6	0.5351 (2)	0.22342 (17)	0.44449 (12)	0.0232 (3)
H6	0.631903	0.154967	0.398747	0.028*
C13	0.6343 (2)	−0.11584 (18)	0.89146 (12)	0.0256 (3)
H13	0.765513	−0.154250	0.896619	0.031*
C17	0.4406 (2)	0.4222 (2)	0.27152 (12)	0.0295 (3)
H17A	0.374708	0.355153	0.250243	0.044*
H17B	0.577414	0.396555	0.235805	0.044*
H17C	0.383705	0.543651	0.248116	0.044*
C15	0.3103 (2)	−0.1578 (2)	0.95051 (12)	0.0303 (3)
H15	0.223073	−0.224471	0.995677	0.036*
C9	0.0719 (2)	0.4320 (2)	0.86403 (12)	0.0305 (3)
H9	0.092957	0.349329	0.929217	0.037*
H18A	0.937 (3)	0.887 (3)	0.6243 (19)	0.046 (6)*
H18B	0.926 (3)	0.830 (3)	0.538 (2)	0.045 (6)*
H1	0.059 (3)	0.602 (3)	0.6466 (17)	0.042 (5)*
O10	−0.0336 (2)	0.56891 (18)	0.87279 (11)	0.0572 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02505 (17)	0.02388 (17)	0.02491 (17)	−0.00803 (12)	−0.00593 (12)	−0.00495 (12)
F1	0.0455 (6)	0.0280 (5)	0.0283 (5)	−0.0034 (4)	−0.0120 (4)	0.0055 (4)
O18	0.0284 (5)	0.0197 (5)	0.0241 (5)	−0.0053 (4)	−0.0058 (4)	−0.0045 (4)
N4	0.0200 (5)	0.0177 (5)	0.0196 (5)	−0.0050 (4)	−0.0035 (4)	−0.0047 (4)
N1	0.0221 (5)	0.0188 (5)	0.0217 (6)	−0.0011 (4)	−0.0052 (4)	−0.0050 (4)
C8A	0.0195 (6)	0.0174 (6)	0.0228 (6)	−0.0051 (5)	−0.0046 (5)	−0.0048 (5)
C11	0.0231 (6)	0.0203 (6)	0.0189 (6)	−0.0031 (5)	−0.0039 (5)	−0.0057 (5)
C5	0.0201 (6)	0.0178 (6)	0.0265 (7)	−0.0047 (5)	−0.0032 (5)	−0.0068 (5)
C12	0.0236 (6)	0.0232 (6)	0.0216 (6)	−0.0041 (5)	−0.0030 (5)	−0.0060 (5)
C3	0.0214 (6)	0.0215 (6)	0.0205 (6)	−0.0060 (5)	−0.0045 (5)	−0.0048 (5)
C7	0.0267 (7)	0.0225 (6)	0.0220 (6)	−0.0126 (5)	−0.0023 (5)	−0.0048 (5)
C2	0.0218 (6)	0.0223 (6)	0.0202 (6)	−0.0044 (5)	−0.0047 (5)	−0.0036 (5)
C8	0.0245 (6)	0.0187 (6)	0.0227 (6)	−0.0070 (5)	−0.0064 (5)	−0.0031 (5)
C14	0.0356 (8)	0.0216 (7)	0.0194 (6)	−0.0015 (6)	−0.0077 (6)	−0.0026 (5)
C16	0.0249 (7)	0.0286 (7)	0.0261 (7)	−0.0068 (6)	−0.0051 (5)	−0.0032 (6)
C6	0.0242 (6)	0.0218 (6)	0.0247 (7)	−0.0073 (5)	−0.0006 (5)	−0.0094 (5)
C13	0.0260 (7)	0.0250 (7)	0.0235 (7)	0.0007 (5)	−0.0069 (5)	−0.0075 (5)
C17	0.0375 (8)	0.0301 (7)	0.0219 (7)	−0.0135 (6)	−0.0021 (6)	−0.0054 (6)
C15	0.0330 (8)	0.0305 (8)	0.0244 (7)	−0.0113 (6)	−0.0036 (6)	0.0006 (6)
C9	0.0306 (7)	0.0321 (8)	0.0227 (7)	0.0010 (6)	−0.0039 (6)	−0.0073 (6)
O10	0.0698 (10)	0.0467 (8)	0.0304 (6)	0.0263 (7)	−0.0082 (6)	−0.0152 (6)

Geometric parameters (Å, º) top

F1—C14	1.3542 (16)	C7—C8	1.3734 (19)
O18—H18A	0.86 (2)	C7—C6	1.428 (2)
O18—H18B	0.87 (2)	C7—C17	1.4988 (19)
N4—C8A	1.3719 (17)	C2—C9	1.4605 (19)
N4—C5	1.3791 (17)	C8—H8	0.9500
N4—C3	1.3955 (17)	C14—C13	1.377 (2)
N1—C8A	1.3411 (17)	C14—C15	1.379 (2)
N1—C2	1.3811 (17)	C16—H16	0.9500
N1—H1	0.92 (2)	C16—C15	1.389 (2)
C8A—C8	1.4042 (19)	C6—H6	0.9500
C11—C12	1.3920 (19)	C13—H13	0.9500
C11—C3	1.4709 (18)	C17—H17A	0.9800
C11—C16	1.3973 (19)	C17—H17B	0.9800
C5—H5	0.9500	C17—H17C	0.9800
C5—C6	1.354 (2)	C15—H15	0.9500
C12—H12	0.9500	C9—H9	0.9500
C12—C13	1.387 (2)	C9—O10	1.2011 (19)
C3—C2	1.3654 (19)

H18A—O18—H18B	103 (2)	C8A—C8—H8	120.9
C8A—N4—C5	121.11 (12)	C7—C8—C8A	118.26 (12)
C8A—N4—C3	108.76 (11)	C7—C8—H8	120.9
C5—N4—C3	130.04 (11)	F1—C14—C13	118.85 (13)
C8A—N1—C2	108.37 (11)	F1—C14—C15	118.03 (13)
C8A—N1—H1	123.1 (13)	C13—C14—C15	123.12 (13)
C2—N1—H1	128.5 (13)	C11—C16—H16	120.1
N4—C8A—C8	121.05 (12)	C15—C16—C11	119.86 (13)
N1—C8A—N4	108.00 (11)	C15—C16—H16	120.1
N1—C8A—C8	130.92 (12)	C5—C6—C7	121.48 (12)
C12—C11—C3	121.05 (12)	C5—C6—H6	119.3
C12—C11—C16	120.14 (13)	C7—C6—H6	119.3
C16—C11—C3	118.81 (12)	C12—C13—H13	120.9
N4—C5—H5	120.7	C14—C13—C12	118.22 (13)
C6—C5—N4	118.69 (12)	C14—C13—H13	120.9
C6—C5—H5	120.7	C7—C17—H17A	109.5
C11—C12—H12	119.9	C7—C17—H17B	109.5
C13—C12—C11	120.26 (13)	C7—C17—H17C	109.5
C13—C12—H12	119.9	H17A—C17—H17B	109.5
N4—C3—C11	123.90 (11)	H17A—C17—H17C	109.5
C2—C3—N4	105.71 (11)	H17B—C17—H17C	109.5
C2—C3—C11	130.28 (12)	C14—C15—C16	118.39 (14)
C8—C7—C6	119.34 (13)	C14—C15—H15	120.8
C8—C7—C17	121.11 (13)	C16—C15—H15	120.8
C6—C7—C17	119.51 (13)	C2—C9—H9	118.8
N1—C2—C9	122.80 (12)	O10—C9—C2	122.45 (14)
C3—C2—N1	109.06 (12)	O10—C9—H9	118.8
C3—C2—C9	127.88 (13)

F1—C14—C13—C12	−179.27 (12)	C12—C11—C3—N4	62.54 (18)
F1—C14—C15—C16	179.42 (13)	C12—C11—C3—C2	−121.88 (16)
N4—C8A—C8—C7	−0.07 (19)	C12—C11—C16—C15	1.0 (2)
N4—C5—C6—C7	−1.2 (2)	C3—N4—C8A—N1	3.08 (14)
N4—C3—C2—N1	1.89 (15)	C3—N4—C8A—C8	−175.22 (12)
N4—C3—C2—C9	−172.39 (14)	C3—N4—C5—C6	175.22 (12)
N1—C8A—C8—C7	−177.93 (13)	C3—C11—C12—C13	179.08 (12)
N1—C2—C9—O10	−2.3 (3)	C3—C11—C16—C15	−178.93 (13)
C8A—N4—C5—C6	−1.22 (18)	C3—C2—C9—O10	171.26 (17)
C8A—N4—C3—C11	173.45 (12)	C2—N1—C8A—N4	−1.87 (15)
C8A—N4—C3—C2	−3.04 (14)	C2—N1—C8A—C8	176.21 (13)
C8A—N1—C2—C3	−0.05 (15)	C8—C7—C6—C5	3.0 (2)
C8A—N1—C2—C9	174.58 (13)	C16—C11—C12—C13	−0.8 (2)
C11—C12—C13—C14	−0.2 (2)	C16—C11—C3—N4	−117.56 (15)
C11—C3—C2—N1	−174.29 (13)	C16—C11—C3—C2	58.0 (2)
C11—C3—C2—C9	11.4 (2)	C6—C7—C8—C8A	−2.29 (19)
C11—C16—C15—C14	−0.1 (2)	C13—C14—C15—C16	−1.0 (2)
C5—N4—C8A—N1	−179.80 (11)	C17—C7—C8—C8A	175.47 (12)
C5—N4—C8A—C8	1.90 (18)	C17—C7—C6—C5	−174.78 (13)
C5—N4—C3—C11	−3.3 (2)	C15—C14—C13—C12	1.2 (2)
C5—N4—C3—C2	−179.83 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O18ⁱ	0.91 (2)	1.77 (2)	2.6754 (16)	174 (2)
O18—H18A···Cl1ⁱⁱ	0.87 (2)	2.24 (2)	3.1070 (11)	175 (2)
O18—H18B···Cl1ⁱⁱⁱ	0.87 (2)	2.24 (2)	3.1142 (11)	178.0 (19)
C8—H8···Cl1^iv	0.95	2.69	3.6431 (15)	176
C12—H12···Cl1^v	0.95	2.71	3.5610 (16)	150
C13—H13···O10^vi	0.95	2.41	3.057 (2)	125

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

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
H13···O10	2.41	x+1, y-1, z
F1···H17C	2.78	x, y-1, z+1
H9···F1	2.79	-x+1, -y, -z+2
H9···O10	2.71	-x, -y+1, -z+2
H16···Cl1	3.04	x, y, z
H17B···C2	3.02	-x+1, -y+1, -z+1
H5···C6	3.02	-x+1, -y, -z+1
H17A···O18	2.78	-x+1, -y+1, -z+1
H8···Cl1	2.69	-x, -y+1, -z+1
H15···C9	3.08	-x, -y, -z+2
H12···Cl1	2.71	x+1, y, z
H5···O18	2.76	x, y-1, z
Cl1···H6	2.94	-x+1, -y, -z+1
H18A···Cl1	2.24	x+1, y+1, z
O18···H1	1.77	x+1, y, z

Acknowledgements

The author's contributions are as follows: conceptualization by FIG, MA and AB; synthesis by VOO, PVS, YLS and AIS; X-ray analysis by PVS, AIS and STÇ; writing (review and editing of the manuscript) by FIG, MA and AB; supervision by FIG, MA and AB.

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