Synthesis and structure of 6-bromo-2-(di­eth­oxymeth­yl)-2-hy­droxy-3-phenyl-2,3-di­hydro-1H-imidazo[1,2-a]pyridin-4-ium chloride aceto­nitrile monosolvate

Guseinov, F.I.; Samigullina, A.I.; Hökelek, T.; Hamidov, S.Z.; Lasri, J.; Hasanov, K.I.; Javadzade, T.A.; Belay, A.N.

doi:10.1107/S2056989025005778

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 81| Part 8| August 2025| Pages 672-675

https://doi.org/10.1107/S2056989025005778

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Synthesis and structure of 6-bromo-2-(diethoxymethyl)-2-hydroxy-3-phenyl-2,3-dihydro-1H-imidazo[1,2-a]pyridin-4-ium chloride acetonitrile monosolvate

Firudin I. Guseinov,^a,^b Aida I. Samigullina,^b Tuncer Hökelek,^c Sahil Z. Hamidov,^d Jamal Lasri,^e Khudayar I. Hasanov,^f Tahir A. Javadzade ^g and Alebel N. Belay ^h ^*

^aKosygin State University of Russia, 117997 Moscow, Russian Federation, ^bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation, ^cHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, ^dAzerbaijan Technological University, Shah Ismayil Khatai Avenue 103, AZ2011 Ganja, Azerbaijan, ^eDepartment of Chemistry, Rabigh College of Science and Arts, King Abdulaziz University, Jeddah 21589, Saudi Arabia, ^fAzerbaijan Medical University, Scientific Research Centre (SCR), A. Kasumzade St. 14, AZ1022 Baku, Azerbaijan, ^gDepartment of Chemistry and Chemical Engineering, Khazar University, Mahsati St. 41, AZ1096 Baku, Azerbaijan, and ^hDepartment of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 25 March 2025; accepted 25 June 2025; online 4 July 2025)

In the title solvated molecular salt, C₁₈H₂₂BrN₂O₃⁺·Cl⁻·CH₃CN, the imidazole ring is in envelope conformation and the pyridine and phenyl rings are oriented at a dihedral angle of 72.52 (5)°. In the crystal, O—H⋯Cl and N—H⋯Cl hydrogen bonds link the cations and anions into centrosymmetric tetramers enclosing R²₄(12) loops. Short Br⋯Cl [3.2313 (4) Å] and O⋯Cl [3.0490 (10) Å] contacts are observed. A Hirshfeld surface analysis of the structure indicates that the most important contributions for the crystal packing are from H⋯H (52.4%), H⋯C/C⋯H (12.1%), H⋯Br/Br⋯H (11.0%) and H⋯Cl/Cl⋯H (10.2%) interactions.

Keywords: crystal structure; non-covalent interactions; hydrogen bond; imidazole.

CCDC reference: 2467703

1. Chemical context

Nitrogen-containing heterocycles, cyclic molecules with one or more nitrogen atoms in the cyclic scaffold, are ubiquitous in pharmaceutical drugs, agrochemicals, metalloenzymes and biologically active natural products (Li et al., 2023 ). The synthetic chemistry of N-heterocycles is not limited to organic chemistry (Guseinov et al., 2017 , 2020 , 2024 ), they have been well explored in the spectrophotometric determination of metal ions (Alieva et al., 2008 ), synthesis of cyclic carbonates from cycloaddition of CO₂ with epoxides (Aliyeva et al., 2024 ), crystal engineering (Naghiyev et al., 2023 ) and catalysis (Kerimli et al., 2021 ). N-heterocycles have many advantages, such as easy modification and functionalization (Khalilov et al., 2021 ), immobilization on solid materials through supramolecular interactions (Mammadov et al., 2023 ) and crystal growth and design (Hajiyeva et al., 2024 ). As part of our work in this area, we now describe the synthesis and structure of the title solvated molecular salt, C₁₈H₂₂BrN₂O₃⁺·Cl ⁻·C₂H₃N (1).

2. Structural commentary

The molecular structure of (1) is illustrated in Fig. 1. In the cation, the five-membered imidazole N1/N2/C3/C8A/C10 ring is non-planar due to the substituents bonded to atoms C3 and C10. It adopts an envelope conformation with puckering parameter φ = 137.38 (5)° where atom C10 is at the flap position and is displaced by −0.4138 (13) Å from the best least-squares plane of the other four atoms. The pyridine N2/C5–C8/C8a and phenyl C16–C21 rings are oriented at a dihedral angle of 72.52 (5)°. Atom Br6 is displaced by −0.0523 (1) Å from the best least-squares plane of the pyridine ring. The pendant C12 ethoxymethyl group has a gauche–anti conformation as indicated by the following torsion angles: C10—C9—O10—C11 = 75.76 (15)°; C9—O10—C11—C12 = 170.67 (13)°. Conversely, the C15 chain is anti–anti: C10—C9—O13—C14 = 163.79 (11)°; C9—O13—C14—C15 = −176.75 (12)°. Atom N1 of the imidazole ring is anti to O13 [N1—C10—C9—O13 = 178.28 (10)°] and gauche to O10 [N1—C10—C9—O10 = 51.69 (14)°]. Atoms C3 and C10 of the cation are stereogenic centres: in the arbitrarily chosen asymmetric unit, they both have R configurations, but crystal symmetry generates a racemic mixture.

Figure 1
The asymmetric unit of the title compound with 50% probability ellipsoids. Only one part of the disordered atoms is shown for clarity. The O—H⋯Cl hydrogen bond is shown as a dashed line.

3. Supramolecular features

In the crystal, the cation and the anion are linked by a strong O—H⋯Cl hydrogen bond (Table 1). The chloride ion also accepts an N—H⋯Cl hydrogen bond from another cation, which generates centrosymmetric tetramers (two cations, two anions) enclosing R₄²(12) loops (Fig. 2). Various weak C—H⋯N, C—H⋯O and C—H⋯Cl hydrogen bonds are also observed (Table 1). Short Br6⋯Cl1 [3.2313 (4) Å, compared to a van der Waals separation of about 3.60 Å] and O2⋯Cl1 [3.0490 (10), 3.27 Å] contacts occur.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯Cl1	0.80 (2)	2.25 (2)	3.0489 (10)	177 (2)
N1—H1⋯Cl1ⁱ	0.86 (2)	2.37 (2)	3.1829 (12)	157.0 (17)
C7—H7⋯N22Aⁱⁱ	0.95	2.51	3.410 (15)	157
C24A—H24F⋯O13	0.98	2.34	3.260 (12)	156
C3—H3⋯Cl1ⁱⁱⁱ	1.00	2.62	3.6125 (13)	171
C9—H9⋯Cl1ⁱⁱⁱ	1.00	2.72	3.6643 (14)	157
C17—H17⋯Cl1	0.95	2.70	3.6259 (15)	165
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
A partial packing diagram with O—H⋯Cl and N—H⋯Cl hydrogen bonds shown as dashed lines. The other hydrogen atoms have been omitted for clarity.

4. Hirshfeld surface analysis

To visualize the intermolecular interactions in the crystal a Hirshfeld surface (HS) analysis was carried out using Crystal Explorer 17.5 (Spackman et al., 2021 ) following the protocol of Tan et al. (2019 ) after removal of the disordered acetonitrile solvent molecule. In the surface plotted over d_norm (Fig. 3), the contact distances equal, shorter and longer with respect to the sum of van der Waals radii are shown by the white, red and blue colours, respectively, where the bright-red spots correspond to the respective donors and/or acceptors. The overall two-dimensional fingerprint plot, Fig. 4a, and those delineated into the different contact types are illustrated in Fig. 4b–n, together with their relative contributions to the HS.The most important contributors to the surface are H⋯H (52.4%) H⋯C/C⋯H (12.1%), H⋯Br/Br⋯H (11.0%) and H⋯Cl/Cl⋯H (10.2%) contacts. The remaining contacts have a very low density of points.

Figure 3
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm.

Figure 4
The two-dimensional fingerprint plots for the title compound, showing (a) all interactions and (b)–(n) different contact types. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface. Both disordered components of the acetonitrile molecule were omitted.

5. Synthesis and crystallization

A solution of 2-chloro-2-(diethoxymethyl)-3-phenyloxirane (128 mg, 0.5 mmol) and 5-bromopyridin-2-amine (82 mg, 0.5 mmol) in 20 ml of ethanol (95%) was boiled for 1 h. The solvent was distilled off in vacuo and the remaining powder was recrystallized from acetonitrile solution. Yield: 166 mg (79%), m.p. 485–487 K. Analysis calculated (%) for C₂₀H₂₅BrClN₃O₃: C 51.02, H 5.35, N 8.93; found C 51.00, H 5.32, N 8.91. ¹H NMR (300 MHz, DMSO-d₆): 1.22 (6H), 2.07 (3H), 3.63–3.94 (4H), 4.77 (1H), 6.43 (1H), 6.89 (OH), 7.43–7.93 (8H), 8.25 (NH), ¹³C NMR (200 MHz, DMSO-d⁶): 1.03, 15.55, 63.56, 76.28, 101.78, 104.25, 111.25, 117.90, 125.58, 126.77, 128.88, 129.25, 143.89, 147.25, 151.26, 160.99.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The OH and NH hydrogen atoms were located in a difference-Fourier map and refined isotropically. The C-bound hydrogen-atom positions were calculated geometrically at distances of 0.95–1.00 Å depending on hybridization and refined using a riding model by applying the constraints of U_iso = 1.2U_eq(C) or 1.5U_eq(methyl C). Atoms N22 and C24 and its attached H atoms of the acetonitrile solvent molecule are disordered over two adjacent orientations, and they were refined with an occupancy ratio of 0.443 (19):0.557 (19).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₂₂BrN₂O₃⁺·Cl⁻·C₂H₃N
M_r	470.79
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.59344 (7), 11.07365 (13), 13.73164 (16)
α, β, γ (°)	75.4564 (10), 85.3656 (8), 88.4658 (8)
V (Å³)	1113.98 (2)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	3.82
Crystal size (mm)	0.29 × 0.22 × 0.18

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.345, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	28449, 4661, 4621
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.632

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.058, 1.07
No. of reflections	4661
No. of parameters	273
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2467703

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005778/hb8130sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005778/hb8130Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025005778/hb8130Isup3.cml

checkCIF report

Computing details top

6-Bromo-2-(diethoxymethyl)-2-hydroxy-3-phenyl-2,3-dihydro-1H-imidazo[1,2-a]pyridin-4-ium chloride acetonitrile monosolvate top

Crystal data top

C₁₈H₂₂BrN₂O₃⁺·Cl⁻·C₂H₃N	Z = 2
M_r = 470.79	F(000) = 484
Triclinic, P1	D_x = 1.404 Mg m⁻³
a = 7.59344 (7) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.07365 (13) Å	Cell parameters from 22359 reflections
c = 13.73164 (16) Å	θ = 3.3–76.8°
α = 75.4564 (10)°	µ = 3.82 mm⁻¹
β = 85.3656 (8)°	T = 100 K
γ = 88.4658 (8)°	Prism, colorless
V = 1113.98 (2) Å³	0.29 × 0.22 × 0.18 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	4661 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	4621 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.0°, θ_min = 3.3°
ω scans	h = −9→8
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2023)	k = −13→13
T_min = 0.345, T_max = 1.000	l = −17→17
28449 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0263P)² + 0.6353P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.002
4661 reflections	Δρ_max = 0.34 e Å⁻³
273 parameters	Δρ_min = −0.36 e Å⁻³
2 restraints	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.00204 (13)

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	Occ. (<1)
Br6	0.71051 (2)	−0.02116 (2)	0.40214 (2)	0.02342 (6)
O2	0.63388 (13)	0.39419 (9)	0.70984 (7)	0.01627 (19)
H2	0.555 (3)	0.369 (2)	0.6849 (16)	0.034 (5)*
O10	0.90770 (13)	0.59295 (9)	0.65996 (7)	0.01821 (19)
O13	0.94075 (12)	0.41038 (9)	0.78971 (7)	0.01768 (19)
N1	0.77063 (15)	0.44100 (11)	0.54370 (8)	0.0156 (2)
H1	0.735 (2)	0.5163 (19)	0.5181 (14)	0.023 (4)*
N2	0.79268 (14)	0.23811 (10)	0.55778 (8)	0.0148 (2)
C3	0.86257 (17)	0.25545 (12)	0.65138 (10)	0.0149 (2)
H3	0.994348	0.259107	0.640632	0.018*
C5	0.78508 (17)	0.12883 (13)	0.53030 (10)	0.0174 (3)
H5	0.818893	0.052418	0.574201	0.021*
C6	0.72782 (18)	0.13148 (13)	0.43832 (11)	0.0184 (3)
C7	0.67733 (18)	0.24541 (14)	0.37389 (10)	0.0191 (3)
H7	0.637428	0.246615	0.309840	0.023*
C8	0.68567 (17)	0.35439 (13)	0.40341 (10)	0.0177 (3)
H8	0.650962	0.431486	0.360816	0.021*
C8A	0.74689 (17)	0.34921 (12)	0.49836 (10)	0.0150 (2)
C9	0.93386 (17)	0.46309 (12)	0.68605 (10)	0.0153 (2)
H9	1.049840	0.445590	0.652129	0.018*
C10	0.79212 (17)	0.39016 (12)	0.65150 (10)	0.0143 (2)
C11	0.7717 (2)	0.64392 (14)	0.71812 (13)	0.0272 (3)
H11A	0.785968	0.611957	0.791164	0.033*
H11B	0.653457	0.619906	0.704179	0.033*
C12	0.7906 (3)	0.78235 (16)	0.68768 (17)	0.0405 (4)
H12A	0.781124	0.812412	0.614806	0.061*
H12B	0.906170	0.805053	0.704541	0.061*
H12C	0.697028	0.820516	0.723683	0.061*
C14	1.09708 (19)	0.44236 (15)	0.83005 (11)	0.0238 (3)
H14A	1.100746	0.533414	0.823262	0.029*
H14B	1.204216	0.417686	0.793453	0.029*
C15	1.0887 (2)	0.37254 (18)	0.94002 (13)	0.0331 (4)
H15A	1.085856	0.282624	0.945606	0.050*
H15B	0.981776	0.397466	0.975210	0.050*
H15C	1.193030	0.392261	0.970583	0.050*
C16	0.81484 (18)	0.15009 (12)	0.74240 (10)	0.0170 (3)
C17	0.64230 (19)	0.10643 (13)	0.76702 (11)	0.0204 (3)
H17	0.550314	0.143950	0.726404	0.024*
C18	0.6051 (2)	0.00806 (15)	0.85096 (12)	0.0287 (3)
H18	0.487323	−0.021077	0.868097	0.034*
C19	0.7394 (3)	−0.04782 (16)	0.90987 (13)	0.0360 (4)
H19	0.713307	−0.114718	0.967518	0.043*
C20	0.9118 (2)	−0.00599 (16)	0.88460 (13)	0.0338 (4)
H20	1.003978	−0.045215	0.924294	0.041*
C21	0.9496 (2)	0.09330 (14)	0.80120 (11)	0.0239 (3)
H21	1.067421	0.122388	0.784344	0.029*
Cl1	0.33366 (4)	0.30609 (3)	0.61057 (2)	0.01733 (8)
N22	0.602 (7)	0.357 (3)	1.1158 (12)	0.046 (3)	0.443 (19)
N22A	0.594 (5)	0.331 (2)	1.1255 (9)	0.046 (3)	0.557 (19)
C24	0.611 (2)	0.2884 (16)	0.9482 (9)	0.0410 (19)	0.443 (19)
H24A	0.686904	0.347333	0.898044	0.061*	0.443 (19)
H24B	0.493588	0.288120	0.923808	0.061*	0.443 (19)
H24C	0.663150	0.204517	0.959064	0.061*	0.443 (19)
C24A	0.5848 (18)	0.3253 (13)	0.9381 (7)	0.0410 (19)	0.557 (19)
H24D	0.517870	0.398668	0.904347	0.061*	0.557 (19)
H24E	0.524540	0.249411	0.934754	0.061*	0.557 (19)
H24F	0.703877	0.327211	0.904437	0.061*	0.557 (19)
C23	0.5968 (2)	0.32604 (18)	1.04328 (13)	0.0337 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br6	0.02516 (9)	0.02146 (9)	0.02878 (9)	−0.00157 (6)	−0.00279 (6)	−0.01548 (6)
O2	0.0129 (4)	0.0182 (5)	0.0193 (5)	−0.0019 (3)	−0.0004 (4)	−0.0077 (4)
O10	0.0188 (5)	0.0135 (4)	0.0231 (5)	−0.0011 (3)	−0.0015 (4)	−0.0059 (4)
O13	0.0174 (5)	0.0188 (5)	0.0175 (5)	−0.0031 (4)	−0.0041 (4)	−0.0047 (4)
N1	0.0177 (5)	0.0134 (5)	0.0162 (5)	−0.0005 (4)	−0.0033 (4)	−0.0038 (4)
N2	0.0138 (5)	0.0148 (5)	0.0163 (5)	−0.0006 (4)	−0.0013 (4)	−0.0045 (4)
C3	0.0150 (6)	0.0143 (6)	0.0164 (6)	−0.0010 (5)	−0.0025 (5)	−0.0054 (5)
C5	0.0167 (6)	0.0145 (6)	0.0220 (7)	−0.0004 (5)	0.0007 (5)	−0.0072 (5)
C6	0.0169 (6)	0.0184 (6)	0.0224 (7)	−0.0025 (5)	0.0009 (5)	−0.0106 (5)
C7	0.0169 (6)	0.0241 (7)	0.0175 (6)	−0.0030 (5)	−0.0001 (5)	−0.0075 (5)
C8	0.0168 (6)	0.0192 (6)	0.0164 (6)	−0.0018 (5)	−0.0013 (5)	−0.0030 (5)
C8A	0.0119 (6)	0.0148 (6)	0.0178 (6)	−0.0015 (4)	0.0008 (5)	−0.0038 (5)
C9	0.0152 (6)	0.0142 (6)	0.0174 (6)	−0.0012 (5)	−0.0022 (5)	−0.0050 (5)
C10	0.0138 (6)	0.0139 (6)	0.0154 (6)	−0.0010 (4)	−0.0010 (5)	−0.0038 (5)
C11	0.0204 (7)	0.0205 (7)	0.0425 (9)	0.0018 (5)	0.0010 (6)	−0.0125 (6)
C12	0.0440 (10)	0.0218 (8)	0.0572 (12)	−0.0017 (7)	0.0097 (9)	−0.0166 (8)
C14	0.0205 (7)	0.0283 (7)	0.0244 (7)	−0.0030 (6)	−0.0086 (6)	−0.0075 (6)
C15	0.0329 (9)	0.0399 (9)	0.0268 (8)	−0.0021 (7)	−0.0124 (7)	−0.0056 (7)
C16	0.0214 (7)	0.0136 (6)	0.0168 (6)	0.0009 (5)	−0.0020 (5)	−0.0049 (5)
C17	0.0218 (7)	0.0159 (6)	0.0228 (7)	−0.0004 (5)	−0.0025 (5)	−0.0034 (5)
C18	0.0308 (8)	0.0215 (7)	0.0293 (8)	−0.0035 (6)	0.0028 (6)	0.0005 (6)
C19	0.0466 (10)	0.0263 (8)	0.0271 (8)	0.0012 (7)	−0.0019 (7)	0.0076 (6)
C20	0.0390 (9)	0.0311 (9)	0.0271 (8)	0.0068 (7)	−0.0113 (7)	0.0027 (7)
C21	0.0241 (7)	0.0234 (7)	0.0241 (7)	0.0030 (6)	−0.0062 (6)	−0.0046 (6)
Cl1	0.01411 (14)	0.01354 (14)	0.02489 (16)	−0.00020 (10)	−0.00402 (11)	−0.00502 (11)
N22	0.046 (3)	0.065 (9)	0.026 (2)	−0.015 (7)	0.003 (3)	−0.010 (4)
N22A	0.046 (3)	0.065 (9)	0.026 (2)	−0.015 (7)	0.003 (3)	−0.010 (4)
C24	0.028 (4)	0.071 (7)	0.0266 (18)	−0.010 (3)	0.0026 (16)	−0.018 (3)
C24A	0.028 (4)	0.071 (7)	0.0266 (18)	−0.010 (3)	0.0026 (16)	−0.018 (3)
C23	0.0292 (8)	0.0458 (10)	0.0243 (8)	−0.0118 (7)	0.0026 (6)	−0.0056 (7)

Geometric parameters (Å, º) top

Br6—C6	1.8882 (13)	C12—H12B	0.9800
O2—H2	0.80 (2)	C12—H12C	0.9800
O2—C10	1.3954 (16)	C14—H14A	0.9900
O10—C9	1.4047 (16)	C14—H14B	0.9900
O10—C11	1.4438 (18)	C14—C15	1.511 (2)
O13—C9	1.4010 (16)	C15—H15A	0.9800
O13—C14	1.4383 (16)	C15—H15B	0.9800
N1—H1	0.86 (2)	C15—H15C	0.9800
N1—C8A	1.3413 (18)	C16—C17	1.395 (2)
N1—C10	1.4664 (16)	C16—C21	1.392 (2)
N2—C3	1.4867 (16)	C17—H17	0.9500
N2—C5	1.3590 (17)	C17—C18	1.389 (2)
N2—C8A	1.3487 (17)	C18—H18	0.9500
C3—H3	1.0000	C18—C19	1.387 (2)
C3—C10	1.5715 (18)	C19—H19	0.9500
C3—C16	1.5072 (18)	C19—C20	1.388 (3)
C5—H5	0.9500	C20—H20	0.9500
C5—C6	1.362 (2)	C20—C21	1.391 (2)
C6—C7	1.411 (2)	C21—H21	0.9500
C7—H7	0.9500	N22—C23	1.132 (12)
C7—C8	1.371 (2)	N22A—C23	1.141 (9)
C8—H8	0.9500	C24—H24A	0.9800
C8—C8A	1.4065 (19)	C24—H24B	0.9800
C9—H9	1.0000	C24—H24C	0.9800
C9—C10	1.5352 (17)	C24—C23	1.462 (11)
C11—H11A	0.9900	C24A—H24D	0.9800
C11—H11B	0.9900	C24A—H24E	0.9800
C11—C12	1.492 (2)	C24A—H24F	0.9800
C12—H12A	0.9800	C24A—C23	1.457 (8)

C10—O2—H2	109.4 (15)	C11—C12—H12B	109.5
C9—O10—C11	117.69 (11)	C11—C12—H12C	109.5
C9—O13—C14	113.71 (10)	H12A—C12—H12B	109.5
C8A—N1—H1	121.0 (12)	H12A—C12—H12C	109.5
C8A—N1—C10	110.85 (11)	H12B—C12—H12C	109.5
C10—N1—H1	123.7 (12)	O13—C14—H14A	110.3
C5—N2—C3	126.31 (11)	O13—C14—H14B	110.3
C8A—N2—C3	110.27 (11)	O13—C14—C15	106.88 (12)
C8A—N2—C5	123.28 (12)	H14A—C14—H14B	108.6
N2—C3—H3	108.0	C15—C14—H14A	110.3
N2—C3—C10	101.08 (10)	C15—C14—H14B	110.3
N2—C3—C16	112.88 (10)	C14—C15—H15A	109.5
C10—C3—H3	108.0	C14—C15—H15B	109.5
C16—C3—H3	108.0	C14—C15—H15C	109.5
C16—C3—C10	118.46 (11)	H15A—C15—H15B	109.5
N2—C5—H5	120.8	H15A—C15—H15C	109.5
N2—C5—C6	118.41 (13)	H15B—C15—H15C	109.5
C6—C5—H5	120.8	C17—C16—C3	122.00 (12)
C5—C6—Br6	118.27 (11)	C21—C16—C3	118.21 (13)
C5—C6—C7	120.32 (13)	C21—C16—C17	119.76 (13)
C7—C6—Br6	121.38 (10)	C16—C17—H17	120.0
C6—C7—H7	119.9	C18—C17—C16	119.93 (14)
C8—C7—C6	120.20 (13)	C18—C17—H17	120.0
C8—C7—H7	119.9	C17—C18—H18	119.9
C7—C8—H8	120.8	C19—C18—C17	120.21 (15)
C7—C8—C8A	118.33 (13)	C19—C18—H18	119.9
C8A—C8—H8	120.8	C18—C19—H19	120.0
N1—C8A—N2	110.41 (12)	C18—C19—C20	120.01 (15)
N1—C8A—C8	130.13 (13)	C20—C19—H19	120.0
N2—C8A—C8	119.46 (12)	C19—C20—H20	120.0
O10—C9—H9	107.4	C19—C20—C21	120.04 (15)
O10—C9—C10	113.93 (11)	C21—C20—H20	120.0
O13—C9—O10	114.38 (11)	C16—C21—H21	120.0
O13—C9—H9	107.4	C20—C21—C16	120.04 (15)
O13—C9—C10	105.91 (10)	C20—C21—H21	120.0
C10—C9—H9	107.4	H24A—C24—H24B	109.5
O2—C10—N1	111.60 (10)	H24A—C24—H24C	109.5
O2—C10—C3	115.02 (10)	H24B—C24—H24C	109.5
O2—C10—C9	109.37 (10)	C23—C24—H24A	109.5
N1—C10—C3	100.50 (10)	C23—C24—H24B	109.5
N1—C10—C9	110.23 (10)	C23—C24—H24C	109.5
C9—C10—C3	109.84 (10)	H24D—C24A—H24E	109.5
O10—C11—H11A	110.3	H24D—C24A—H24F	109.5
O10—C11—H11B	110.3	H24E—C24A—H24F	109.5
O10—C11—C12	107.15 (13)	C23—C24A—H24D	109.5
H11A—C11—H11B	108.5	C23—C24A—H24E	109.5
C12—C11—H11A	110.3	C23—C24A—H24F	109.5
C12—C11—H11B	110.3	N22—C23—C24	174 (3)
C11—C12—H12A	109.5	N22A—C23—C24A	175 (2)

Br6—C6—C7—C8	177.82 (10)	C7—C8—C8A—N2	−1.00 (19)
O10—C9—C10—O2	−71.36 (13)	C8A—N1—C10—O2	−97.51 (13)
O10—C9—C10—N1	51.69 (14)	C8A—N1—C10—C3	24.90 (13)
O10—C9—C10—C3	161.53 (10)	C8A—N1—C10—C9	140.75 (11)
O13—C9—C10—O2	55.23 (13)	C8A—N2—C3—C10	17.62 (13)
O13—C9—C10—N1	178.28 (10)	C8A—N2—C3—C16	145.19 (11)
O13—C9—C10—C3	−71.88 (13)	C8A—N2—C5—C6	−0.23 (19)
N2—C3—C10—O2	95.88 (12)	C9—O10—C11—C12	170.67 (13)
N2—C3—C10—N1	−24.09 (11)	C9—O13—C14—C15	−176.75 (12)
N2—C3—C10—C9	−140.24 (10)	C10—N1—C8A—N2	−15.17 (15)
N2—C3—C16—C17	−49.31 (17)	C10—N1—C8A—C8	165.20 (13)
N2—C3—C16—C21	128.79 (13)	C10—C3—C16—C17	68.46 (17)
N2—C5—C6—Br6	−178.08 (9)	C10—C3—C16—C21	−113.43 (14)
N2—C5—C6—C7	−0.2 (2)	C11—O10—C9—O13	−46.27 (16)
C3—N2—C5—C6	−175.57 (12)	C11—O10—C9—C10	75.76 (15)
C3—N2—C8A—N1	−2.82 (15)	C14—O13—C9—O10	−69.90 (14)
C3—N2—C8A—C8	176.85 (11)	C14—O13—C9—C10	163.79 (11)
C3—C16—C17—C18	179.20 (13)	C16—C3—C10—O2	−27.96 (16)
C3—C16—C21—C20	−178.63 (14)	C16—C3—C10—N1	−147.93 (11)
C5—N2—C3—C10	−166.53 (12)	C16—C3—C10—C9	95.92 (13)
C5—N2—C3—C16	−38.96 (17)	C16—C17—C18—C19	−0.7 (2)
C5—N2—C8A—N1	−178.82 (11)	C17—C16—C21—C20	−0.5 (2)
C5—N2—C8A—C8	0.85 (19)	C17—C18—C19—C20	−0.4 (3)
C5—C6—C7—C8	0.0 (2)	C18—C19—C20—C21	1.1 (3)
C6—C7—C8—C8A	0.6 (2)	C19—C20—C21—C16	−0.6 (3)
C7—C8—C8A—N1	178.60 (13)	C21—C16—C17—C18	1.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl1	0.80 (2)	2.25 (2)	3.0489 (10)	177 (2)
N1—H1···Cl1ⁱ	0.86 (2)	2.37 (2)	3.1829 (12)	157.0 (17)
C7—H7···N22Aⁱⁱ	0.95	2.51	3.410 (15)	157
C24A—H24F···O13	0.98	2.34	3.260 (12)	156
C3—H3···Cl1ⁱⁱⁱ	1.00	2.62	3.6125 (13)	171
C9—H9···Cl1ⁱⁱⁱ	1.00	2.72	3.6643 (14)	157
C17—H17···Cl1	0.95	2.70	3.6259 (15)	165

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

Acknowledgements

The crystal structure determination was performed in the Department of Structural Studies of Zelinsky Institute of Organic Chemistry, Moscow. This work was supported by the Azerbaijan Technological University (Azerbaijan), Azerbaijan Medical University (Azerbaijan) and Khazar University (Azerbaijan). TH is also grateful to Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004). The authors contributions are as follows. Conceptualization, FIG, TH and ANB; synthesis, FIG and SZH; X-ray analysis, AIS; Hirshfeld surface analysis, TH; writing (review and editing of the manuscript), JL, TH and KIH; funding acquisition, KIH and TAJ; supervision, FIG, TH and ANB.

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