Crystal structure and Hirshfeld surface analysis of 2-(4-bromo­phen­yl)-4-methyl-6-oxo-1-phenyl-1,6-di­hydro­pyridine-3-carbo­nitrile

Naghiyev, F.N.; Khrustalev, V.N.; Dobrokhotova, E.V.; Akkurt, M.; Khalilov, A.N.; Bhattarai, A.; Mamedov, İ.G.

doi:10.1107/S2056989022006466

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ISSN: 2056-9890

Volume 78| Part 8| August 2022| Pages 761-765

https://doi.org/10.1107/S2056989022006466

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Crystal structure and Hirshfeld surface analysis of 2-(4-bromophenyl)-4-methyl-6-oxo-1-phenyl-1,6-dihydropyridine-3-carbonitrile

Farid N. Naghiyev,^a Victor N. Khrustalev,^b,^c Ekaterina V. Dobrokhotova,^c Mehmet Akkurt,^d Ali N. Khalilov,^e,^a Ajaya Bhattarai ^f ^* and İbrahim G. Mamedov ^a

^aDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, Az, 1148, Baku, Azerbaijan, ^bPeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St., 6, Moscow, 117198, Russian Federation, ^cN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow, 119991, Russian Federation, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^e"Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), H. Aliyev str. 135, Az 1063, Baku, Azerbaijan, and ^fDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 15 June 2022; accepted 22 June 2022; online 5 July 2022)

In the title compound, C₁₉H₁₃BrN₂O, the pyridine ring is essentially planar [maximum deviation = 0.024 (4) Å for the N atom] and makes dihedral angles of 74.6 (2) and 65.8 (2)°, respectively, with the phenyl and bromophenyl rings, which subtend a dihedral angle of 63.1 (2)°. In the crystal, molecules are connected along the c-axis direction via C—Br⋯π interactions, generating zigzag chains parallel to the (010) plane. C—H⋯N and C—H⋯O hydrogen-bonding interactions further connect the molecules, forming a three-dimensional network and reinforcing the molecular packing. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (36.2%), C⋯H/H⋯C (21.6%), N⋯H/H⋯N (12.2%), and Br⋯H/H⋯Br (10.8%) interactions.

Keywords: crystal structure; 1,6-dihydropyridine; hydrogen bond; C—Br⋯π interactions; Hirshfeld surface analysis.

CCDC reference: 2181245

1. Chemical context

C—C and C—N bond-forming reactions are a cornerstone of organic synthesis, materials science and medicinal chemistry (Zubkov et al., 2018 ; Shikhaliyev et al., 2019 ; Viswanathan et al., 2019 ; Gurbanov et al., 2020 ). Nitrogen heterocycles, particularly those including the 2-pyridone core, play a key role in medicinal chemistry and natural product synthesis (Sośnicki & Idzik, 2019 ; Duruskari et al., 2020 ; Sangwan et al., 2022 ). We report herein the synthesis of 2-pyridone, 2, on the basis of a one-step reaction of acetoacetanilide with 3-(4-bromophenyl)-3-oxopropanenitrile (Path B). Under two-step reaction conditions (Fig. 1), the interaction of acetoacetanilide with 3-oxo-3-phenylpropanenitrile led to the formation of another 2-pyridone, 1 (Path A), reported in the literature (Wardakhan & Agami, 2001 ).

Figure 1
The reaction of acetoacetanilide with 3-oxo-3-arylpropanenitriles.

Thus, in the framework of our ongoing structural studies (Naghiyev et al., 2020 , 2021 , 2022 ; Khalilov et al., 2022 ), we report the crystal structure and Hirshfeld surface analysis of the title compound, 2-(4-bromophenyl)-4-methyl-6-oxo-1-phenyl-1,6-dihydropyridine-3-carbonitrile.

2. Structural commentary

In the title compound, (Fig. 2), the pyridine ring (N1/C2–C6) is largely planar [maximum deviation = 0.024 (4) Å for N1]. The phenyl and bromophenyl groups are linked to the central pyridine ring in an equatorial arrangement. The pyridine ring subtends dihedral angles of 74.6 (2) and 65.8 (2)° with the phenyl (C7–C12) and bromophenyl (C15–C20) rings, which in turn make a dihedral angle of 63.1 (2)° with each other.

Figure 2
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

Fig. 3 shows a general view of the C—H⋯N and C—H⋯O hydrogen bonds (Table 1) and C—Br⋯π interactions in the unit cell of the title compound. In the crystal, molecules are joined along the c-axis direction by C—Br⋯π interactions [C18—Br1⋯Cg1^iv: C18—Br1 = 1.944 (4) Å, Br1⋯Cg1^iv = 3.4788 (18) Å, C18⋯Cg1^iv = 4.283 (5) Å, C18—Br1⋯Cg1^iv = 100.50 (13)°; Cg1 is the centroid of the N1/C2–C6 pyridine ring; symmetry code: (iv) x + $[{3\over 2}]$ , −y − $[{1\over 2}]$ , z], generating zigzag chains parallel to the (010) plane (Figs. 4 and 5). C—H⋯N and C—H⋯O hydrogen bonds link these molecules, establishing a three-dimensional network and strengthening the molecular packing.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯N2ⁱ	0.95	2.55	3.234 (6)	129
C17—H17⋯O1ⁱⁱ	0.95	2.56	3.342 (6)	140
C20—H20⋯O1ⁱⁱⁱ	0.95	2.40	3.256 (6)	150
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ .

Figure 3
A general view of the C—H⋯N, C—H⋯O hydrogen bonds and C—Br⋯π interactions of the title compound. Symmetry codes: (i) x + $[{3\over 2}]$ , −y − $[{1\over 2}]$ , z − 1; (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iii) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (iv) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ + z.

Figure 4
Packing view of the title compound along the a axis showing the C—Br⋯π interactions as dashed lines.

Figure 5
Packing view of the title compound along the b axis with the C—Br⋯π interactions indicated by dashed lines.

CrystalExplorer17.5 (Turner et al., 2017 ) was used to analyse and visualize the intermolecular interactions of the title compound. Fig. 6a,b depicts the front and back sides of the Hirshfeld surface plotted over d_norm in the range of −0.2437 to 1.2589 a.u. The red spots on the Hirshfeld surface indicate C—H⋯N and C—H⋯O interactions (Table 1).

Figure 6
(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 of −0.2437 to 1.2589 a.u.

The overall two-dimensional fingerprint plot for the title compound and those delineated into H⋯H (36.2%, Fig. 7b), C⋯H/H⋯C (21.6%, Fig. 7c), N⋯H/H⋯N (12.2%, Fig. 7d), and Br⋯H/H⋯Br (10.8%, Fig. 7e) interactions, as well as their relative contributions to the Hirshfeld surface, are shown in Fig. 7, while Tables 1 and 2 provide data on the distinct intermolecular contacts. The remaining weak interactions (contribution percentages) are O⋯H/H⋯O (7.2%), Br⋯C/C⋯Br (3.6%), C⋯C (3.0%), Br.·N/N⋯Br (2.2%), O⋯C/C⋯O (2.2%) and Br⋯O/O⋯Br (0.8%), these contacts having little directional influence on the packing.

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

Contact	Distance	Symmetry operation
H19⋯H13B	2.59	$[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ + z
H17⋯O1	2.56	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, z
O1⋯H20	2.40	1 − x, 1 − y, − $[{1\over 2}]$ + z
N2⋯H16	2.55	$[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ + z
C9⋯H11	2.99	1 − x, −y, $[{1\over 2}]$ + z
C10⋯H13A	3.03	x, −1 + y, z

Figure 7
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) N⋯H/H⋯N and (e) Br⋯H/H⋯Br 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].

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.42, updated September 2021; Groom et al., 2016 ) for the basic skeleton of 6-oxo-1,6-dihydropyridine gave five compounds very similar to the title compound.

The cations in the crystal of FONDOC01 (Pérez-Aguirre et al., 2015 ) interact with the anions through O—H⋯O and N—H⋯O hydrogen bonds, forming a three-dimensional supramolecular network.

In the crystal of SECPUN (Thanigaimani et al., 2012 ), an N—H⋯O hydrogen bond connects the cation and anion, while a pair of N—H⋯O hydrogen bonds connects the two anions with an R₂²(8) ring motif. Weak N—H⋯O and C—H⋯O hydrogen bonds connect the aggregates, forming a three-dimensional network.

The ion pairs in the crystal of SUYXIU (Hemamalini & Fun, 2010 ) are linked by O—H⋯O, N—H⋯O, N—H⋯Br and C—H⋯O hydrogen bonds, producing a two-dimensional network parallel to the bc plane.

In the crystal of XOZCUL (Shishkina et al., 2009 ), the pyridine-3-carboxylate molecules form layers parallel to (010), which are linked by hydrogen bonds mediated by the bridging solvate molecules.

The asymmetric unit of GIHCOQ (Gupta et al., 2007 ) contains four molecules. The compound forms hydrogen-bonded sheets parallel to the [001] direction via intermolecular N—H⋯O and O—H⋯O hydrogen bonds. Each sheet is made up of linked dimers generated by R₂²(8) N—H⋯O hydrogen-bonded motifs. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds generate sheets parallel to the [001] direction. Each sheet is made up of linked dimers formed by N—H⋯O hydrogen bonds with R₂²(8) motifs.

5. Synthesis and crystallization

To a solution of 3-(4-bromophenyl)-3-oxopropanenitrile (1.14 g; 5.1 mmol) and acetoacetanilide (0.92 g; 5.2 mmol) in methanol (25 mL), methylpyperazine (3 drops) was added and the mixture was stirred at room temperature for 48 h. Then 15 mL of methanol were removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from ethanol/water (1:1) solution (yield 49%; m.p. 484–485 K).

¹H NMR (300 MHz, DMSO-d₆, ppm): 2.21 (s, 3H, CH₃); 6.61 (s, 1H, =CH); 7.19–7.89 (m, 9H, 9Ar—H). ¹³C NMR (75 MHz, DMSO-d₆, ppm): 20.58 (CH₃), 94.75 (=C_quat.), 116.17 (CN), 118.27 (=CH), 120.87 (2CH_arom.), 122.95 (Br—C_arom.), 125.30 (CH_arom.), 127.43 (C_arom.), 129.55 (2CH_arom.), 129.70 (2CH_arom.), 134.09 (2CH_arom.), 138.94 (C_arom.), 143.81 (=C_quat.), 153.68 (=C_quat—N), 165.44 (C=O).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All C-bound H atoms were placed at calculated positions and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, and with U_iso(H) = 1.2 or 1.5U_eq(C). Owing to poor agreement between observed and calculated intensities, nineteen outliers (8 4 0, 17 6 2, 13 9 2, 18 5 0, 9 11 2, 18 2 $[\overline{5}]$ , 17 3 $[\overline{6}]$ , 0 12 4, 4 11 $[\overline{1}]$ , 3 5 0, 18 5 2, 2 0 $[\overline{1}]$ , 5 3 $[\overline{2}]$ , 18 2 5, 15 8 2, 0 10 8, 5 3 2, 0 12 $[\overline{4}]$ and 17 6 1) were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃BrN₂O
M_r	365.21
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	15.58979 (16), 10.33883 (10), 9.91195 (9)
V (Å³)	1597.61 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.55
Crystal size (mm)	0.25 × 0.24 × 0.21

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )
T_min, T_max	0.413, 0.462
No. of measured, independent and observed [I > 2σ(I)] reflections	45325, 3359, 3339
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.099, 1.05
No. of reflections	3359
No. of parameters	209
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.27, −0.89
Absolute structure	Flack x determined using 1531 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	−0.012 (18)
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2181245

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022006466/vm2267sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022006466/vm2267Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022006466/vm2267Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

2-(4-Bromophenyl)-4-methyl-6-oxo-1-phenyl-1,6-dihydropyridine-3-carbonitrile top

Crystal data top

C₁₉H₁₃BrN₂O	D_x = 1.518 Mg m⁻³
M_r = 365.21	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pna2₁	Cell parameters from 35934 reflections
a = 15.58979 (16) Å	θ = 2.7–79.0°
b = 10.33883 (10) Å	µ = 3.55 mm⁻¹
c = 9.91195 (9) Å	T = 100 K
V = 1597.61 (3) Å³	Prism, colourless
Z = 4	0.25 × 0.24 × 0.21 mm
F(000) = 736

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3339 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.047
φ and ω scans	θ_max = 88.3°, θ_min = 5.1°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	h = −19→19
T_min = 0.413, T_max = 0.462	k = −12→12
45325 measured reflections	l = −12→12
3359 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0658P)² + 1.8045P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3359 reflections	Δρ_max = 1.27 e Å⁻³
209 parameters	Δρ_min = −0.89 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1531 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: difference Fourier map	Absolute structure parameter: −0.012 (18)

Special details top

Experimental. CrysAlisPro 1.171.41.117a (Rigaku OD, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Br1	0.84710 (3)	−0.04550 (4)	0.63282 (7)	0.02494 (16)
O1	0.4307 (2)	0.4948 (4)	0.3074 (4)	0.0278 (7)
N1	0.5437 (2)	0.4161 (4)	0.4275 (4)	0.0188 (7)
N2	0.7885 (2)	0.6147 (4)	0.6339 (5)	0.0294 (7)
C2	0.4948 (3)	0.5231 (5)	0.3709 (4)	0.0216 (10)
C3	0.5263 (3)	0.6562 (5)	0.3980 (4)	0.0238 (9)
H3	0.4934	0.7271	0.3657	0.029*
C4	0.5993 (3)	0.6812 (4)	0.4665 (4)	0.0215 (8)
C5	0.6468 (3)	0.5678 (5)	0.5140 (5)	0.0222 (10)
C6	0.6185 (3)	0.4373 (4)	0.4937 (4)	0.0188 (8)
C7	0.5051 (3)	0.2830 (4)	0.4247 (4)	0.0205 (8)
C8	0.4705 (3)	0.2349 (5)	0.5395 (5)	0.0237 (9)
H8	0.4733	0.2837	0.6205	0.028*
C9	0.4295 (3)	0.1103 (5)	0.5393 (5)	0.0263 (9)
H9	0.4052	0.0789	0.6209	0.032*
C10	0.4243 (3)	0.0354 (5)	0.4255 (5)	0.0268 (10)
H10	0.3970	−0.0467	0.4261	0.032*
C11	0.4602 (3)	0.0848 (5)	0.3123 (5)	0.0290 (10)
H11	0.4587	0.0354	0.2315	0.035*
C12	0.5005 (3)	0.2097 (5)	0.3110 (5)	0.0260 (9)
H12	0.5243	0.2417	0.2293	0.031*
C13	0.6315 (3)	0.8212 (5)	0.4893 (5)	0.0274 (10)
H13A	0.5887	0.8824	0.4551	0.041*
H13B	0.6857	0.8338	0.4412	0.041*
H13C	0.6403	0.8359	0.5859	0.041*
C14	0.7262 (3)	0.5907 (4)	0.5820 (5)	0.0233 (9)
C15	0.6711 (3)	0.3187 (4)	0.5311 (4)	0.0174 (8)
C16	0.7071 (3)	0.2397 (4)	0.4329 (4)	0.0201 (8)
H16	0.6956	0.2589	0.3409	0.024*
C17	0.7600 (3)	0.1318 (4)	0.4629 (4)	0.0214 (8)
H17	0.7843	0.0813	0.3924	0.026*
C18	0.7751 (3)	0.1027 (4)	0.5913 (4)	0.0205 (8)
C19	0.7397 (3)	0.1793 (5)	0.6909 (4)	0.0232 (9)
H19	0.7505	0.1587	0.7828	0.028*
C20	0.6878 (3)	0.2878 (4)	0.6599 (4)	0.0230 (9)
H20	0.6647	0.3389	0.7307	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0283 (2)	0.0232 (3)	0.0233 (2)	0.00633 (14)	−0.0028 (2)	0.0055 (2)
O1	0.0269 (16)	0.0306 (17)	0.0260 (16)	0.0013 (15)	−0.0068 (13)	0.0022 (14)
N1	0.0179 (16)	0.0204 (18)	0.0182 (17)	0.0037 (15)	−0.0015 (13)	0.0042 (14)
N2	0.0286 (17)	0.0326 (19)	0.0270 (17)	0.0030 (14)	−0.003 (2)	−0.009 (2)
C2	0.0214 (19)	0.027 (3)	0.016 (2)	0.0027 (19)	0.0010 (16)	0.0020 (17)
C3	0.024 (2)	0.024 (2)	0.024 (2)	0.0070 (18)	0.0013 (16)	0.0046 (18)
C4	0.026 (2)	0.020 (2)	0.0187 (19)	0.0013 (17)	0.0017 (16)	−0.0013 (15)
C5	0.024 (2)	0.024 (2)	0.019 (2)	0.0049 (16)	−0.0004 (16)	−0.0031 (18)
C6	0.021 (2)	0.023 (2)	0.0128 (18)	0.0052 (17)	0.0003 (15)	0.0013 (15)
C7	0.0197 (19)	0.022 (2)	0.019 (2)	0.0020 (17)	−0.0003 (15)	0.0009 (17)
C8	0.023 (2)	0.029 (2)	0.0188 (18)	0.0036 (17)	0.0015 (16)	0.0010 (17)
C9	0.027 (2)	0.028 (2)	0.023 (2)	0.0004 (18)	0.0009 (17)	0.0042 (18)
C10	0.026 (2)	0.023 (2)	0.031 (3)	0.0001 (17)	0.0013 (19)	−0.0009 (18)
C11	0.033 (2)	0.028 (2)	0.026 (2)	0.001 (2)	0.0016 (19)	−0.004 (2)
C12	0.027 (2)	0.033 (3)	0.0172 (19)	−0.0010 (19)	0.0026 (16)	−0.0004 (18)
C13	0.031 (2)	0.020 (2)	0.031 (2)	0.0041 (19)	−0.0016 (19)	0.0007 (18)
C14	0.029 (2)	0.021 (2)	0.0199 (18)	0.0020 (18)	0.0007 (16)	−0.0028 (17)
C15	0.0170 (17)	0.017 (2)	0.018 (2)	0.0035 (16)	−0.0027 (15)	−0.0001 (16)
C16	0.025 (2)	0.022 (2)	0.0131 (18)	0.0017 (16)	0.0016 (15)	0.0015 (15)
C17	0.0219 (19)	0.025 (2)	0.0174 (19)	0.0030 (16)	0.0019 (15)	−0.0021 (16)
C18	0.0228 (19)	0.019 (2)	0.0196 (19)	0.0006 (16)	−0.0029 (14)	0.0030 (15)
C19	0.026 (2)	0.028 (2)	0.0150 (18)	0.0051 (18)	−0.0014 (16)	−0.0002 (17)
C20	0.028 (2)	0.027 (2)	0.014 (2)	0.0015 (17)	−0.0006 (15)	−0.0017 (15)

Geometric parameters (Å, º) top

Br1—C18	1.944 (4)	C9—H9	0.9500
O1—C2	1.217 (6)	C10—C11	1.354 (7)
N1—C6	1.356 (6)	C10—H10	0.9500
N1—C2	1.456 (6)	C11—C12	1.436 (7)
N1—C7	1.503 (6)	C11—H11	0.9500
N2—C14	1.127 (6)	C12—H12	0.9500
C2—C3	1.485 (7)	C13—H13A	0.9800
C3—C4	1.352 (7)	C13—H13B	0.9800
C3—H3	0.9500	C13—H13C	0.9800
C4—C5	1.464 (7)	C15—C20	1.342 (6)
C4—C13	1.548 (6)	C15—C16	1.389 (6)
C5—C14	1.429 (6)	C16—C17	1.420 (6)
C5—C6	1.433 (7)	C16—H16	0.9500
C6—C15	1.520 (6)	C17—C18	1.329 (6)
C7—C8	1.353 (6)	C17—H17	0.9500
C7—C12	1.360 (6)	C18—C19	1.380 (6)
C8—C9	1.437 (7)	C19—C20	1.417 (6)
C8—H8	0.9500	C19—H19	0.9500
C9—C10	1.371 (7)	C20—H20	0.9500

C6—N1—C2	121.0 (4)	C10—C11—H11	119.1
C6—N1—C7	120.1 (4)	C12—C11—H11	119.1
C2—N1—C7	118.6 (3)	C7—C12—C11	121.1 (4)
O1—C2—N1	116.5 (4)	C7—C12—H12	119.5
O1—C2—C3	126.0 (4)	C11—C12—H12	119.5
N1—C2—C3	117.5 (4)	C4—C13—H13A	109.5
C4—C3—C2	123.2 (4)	C4—C13—H13B	109.5
C4—C3—H3	118.4	H13A—C13—H13B	109.5
C2—C3—H3	118.4	C4—C13—H13C	109.5
C3—C4—C5	115.7 (4)	H13A—C13—H13C	109.5
C3—C4—C13	121.7 (4)	H13B—C13—H13C	109.5
C5—C4—C13	122.6 (4)	N2—C14—C5	176.7 (5)
C14—C5—C6	119.2 (4)	C20—C15—C16	116.6 (4)
C14—C5—C4	117.1 (4)	C20—C15—C6	121.9 (4)
C6—C5—C4	123.6 (4)	C16—C15—C6	121.4 (4)
N1—C6—C5	118.9 (4)	C15—C16—C17	123.4 (4)
N1—C6—C15	116.8 (4)	C15—C16—H16	118.3
C5—C6—C15	124.0 (4)	C17—C16—H16	118.3
C8—C7—C12	118.1 (4)	C18—C17—C16	118.8 (4)
C8—C7—N1	118.7 (4)	C18—C17—H17	120.6
C12—C7—N1	123.1 (4)	C16—C17—H17	120.6
C7—C8—C9	120.4 (4)	C17—C18—C19	119.0 (4)
C7—C8—H8	119.8	C17—C18—Br1	118.9 (3)
C9—C8—H8	119.8	C19—C18—Br1	122.1 (3)
C10—C9—C8	122.2 (4)	C18—C19—C20	121.8 (4)
C10—C9—H9	118.9	C18—C19—H19	119.1
C8—C9—H9	118.9	C20—C19—H19	119.1
C11—C10—C9	116.4 (4)	C15—C20—C19	120.4 (4)
C11—C10—H10	121.8	C15—C20—H20	119.8
C9—C10—H10	121.8	C19—C20—H20	119.8
C10—C11—C12	121.8 (5)

C6—N1—C2—O1	176.5 (4)	C2—N1—C7—C12	75.3 (5)
C7—N1—C2—O1	−10.1 (6)	C12—C7—C8—C9	−0.5 (6)
C6—N1—C2—C3	−4.8 (6)	N1—C7—C8—C9	177.2 (4)
C7—N1—C2—C3	168.5 (4)	C7—C8—C9—C10	0.5 (7)
O1—C2—C3—C4	−178.3 (5)	C8—C9—C10—C11	0.2 (7)
N1—C2—C3—C4	3.2 (7)	C9—C10—C11—C12	−0.9 (7)
C2—C3—C4—C5	−0.2 (7)	C8—C7—C12—C11	−0.1 (7)
C2—C3—C4—C13	178.2 (4)	N1—C7—C12—C11	−177.8 (4)
C3—C4—C5—C14	177.5 (4)	C10—C11—C12—C7	0.9 (7)
C13—C4—C5—C14	−0.8 (7)	N1—C6—C15—C20	−117.6 (5)
C3—C4—C5—C6	−1.4 (7)	C5—C6—C15—C20	68.0 (6)
C13—C4—C5—C6	−179.8 (4)	N1—C6—C15—C16	65.0 (6)
C2—N1—C6—C5	3.4 (6)	C5—C6—C15—C16	−109.5 (5)
C7—N1—C6—C5	−169.9 (4)	C20—C15—C16—C17	−0.8 (6)
C2—N1—C6—C15	−171.3 (4)	C6—C15—C16—C17	176.8 (4)
C7—N1—C6—C15	15.4 (6)	C15—C16—C17—C18	1.3 (7)
C14—C5—C6—N1	−179.1 (4)	C16—C17—C18—C19	−0.9 (7)
C4—C5—C6—N1	−0.2 (7)	C16—C17—C18—Br1	179.7 (3)
C14—C5—C6—C15	−4.8 (7)	C17—C18—C19—C20	0.1 (7)
C4—C5—C6—C15	174.1 (4)	Br1—C18—C19—C20	179.5 (3)
C6—N1—C7—C8	71.1 (5)	C16—C15—C20—C19	−0.1 (7)
C2—N1—C7—C8	−102.3 (5)	C6—C15—C20—C19	−177.6 (4)
C6—N1—C7—C12	−111.3 (5)	C18—C19—C20—C15	0.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N2ⁱ	0.95	2.55	3.234 (6)	129
C17—H17···O1ⁱⁱ	0.95	2.56	3.342 (6)	140
C20—H20···O1ⁱⁱⁱ	0.95	2.40	3.256 (6)	150

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

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

Contact	Distance	Symmetry operation
H19···H13B	2.59	3/2 - x, -1/2 + y, 1/2 + z
H17···O1	2.56	1/2 + x, 1/2 - y, z
O1···H20	2.40	1 - x, 1 - y, -1/2 + z
N2···H16	2.55	3/2 - x, 1/2 + y, 1/2 + z
C9···H11	2.99	1 - x, -y, 1/2 + z
C10···H13A	3.03	x, -1 + y, z

Acknowledgements

Author contributions are as follows. Conceptualization, ANK and IGM; methodology, ANK and IGM; investigation, FNN, ANK, MA and EVD; writing (original draft), MA and ANK; writing (review and editing of the manuscript), MA and ANK; visualization, MA, ANK and IGM; funding acquisition, VNK, AB and ANK; resources, AB, VNK and EVD; supervision, ANK and MA.

Funding information

This study was supported by Baku State University and the Ministry of Science and Higher Education of the Russian Federation [award No. 075–03–2020-223 (FSSF-2020–0017)].

References

Duruskari, G. S., Asgarova, A. R., Aliyeva, K. N., Musayeva, S. A. & Maharramov, A. M. (2020). Russ. J. Org. Chem. 56, 712–715. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gupta, S., Long, S. & Li, T. (2007). Acta Cryst. E63, o2784. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Demukhamedova, S. D., Alieva, I. N., Godjaev, N. M., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2020). CrystEngComm, 22, 628–633. Web of Science CSD CrossRef CAS Google Scholar
Hemamalini, M. & Fun, H.-K. (2010). Acta Cryst. E66, o2246–o2247. Web of Science CSD CrossRef IUCr Journals Google Scholar
Khalilov, A. N., Khrustalev, V. N., Tereshina, T. A., Akkurt, M., Rzayev, R. M., Akobirshoeva, A. A. & Mamedov, İ. G. (2022). Acta Cryst. E78, 525–529. Web of Science CSD CrossRef IUCr Journals Google Scholar
Naghiyev, F. N., Akkurt, M., Askerov, R. K., Mamedov, I. G., Rzayev, R. M., Chyrka, T. & Maharramov, A. M. (2020). Acta Cryst. E76, 720–723. Web of Science CSD CrossRef IUCr Journals Google Scholar
Naghiyev, F. N., Khrustalev, V. N., Novikov, A. P., Akkurt, M., Rzayev, R. M., Akobirshoeva, A. A. & Mamedov, I. G. (2022). Acta Cryst. E78, 554–558. CSD CrossRef IUCr Journals Google Scholar
Naghiyev, F. N., Tereshina, T. A., Khrustalev, V. N., Akkurt, M., Rzayev, R. M., Akobirshoeva, A. A. & Mamedov, İ. G. (2021). Acta Cryst. E77, 516–521. Web of Science CSD CrossRef IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Pérez-Aguirre, R., Pérez-Yáñez, S., Beobide, G., Castillo, O., Gutiérrez-Zorrilla, J. M. & Luque, A. (2015). Acta Cryst. E71, m238–m239. CSD CrossRef IUCr Journals Google Scholar
Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan. Google Scholar
Sangwan, S., Yadav, N., Kumar, R., Chauhan, S., Dhanda, V., Walia, P. & Duhan, A. (2022). Eur. J. Med. Chem. 232, 114199. Web of Science CrossRef PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shikhaliyev, N. Q., Kuznetsov, M. L., Maharramov, A. M., Gurbanov, A. V., Ahmadova, N. E., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. L. (2019). CrystEngComm, 21, 5032–5038. Web of Science CSD CrossRef CAS Google Scholar
Shishkina, S. V., Shishkin, O. V., Ukrainets, I. V., Tkach, A. A. & Grinevich, L. A. (2009). Acta Cryst. E65, o1984. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sośnicki, J. G. & Idzik, T. J. (2019). Synthesis, 51, 3369–3396. Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Thanigaimani, K., Farhadikoutenaei, A., Khalib, N. C., Arshad, S. & Razak, I. A. (2012). Acta Cryst. E68, o3151–o3152. CSD CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://Hirshfeldsurface.net Google Scholar
Viswanathan, A., Kute, D., Musa, A., Konda Mani, S., Sipilä, V., Emmert-Streib, F., Zubkov, F. I., Gurbanov, A. V., Yli-Harja, O. & Kandhavelu, M. (2019). Eur. J. Med. Chem. 166, 291–303. Web of Science CrossRef CAS PubMed Google Scholar
Wardakhan, W. W. & Agami, S. M. (2001). Egypt. J. Chem. 44, 315–333. CAS Google Scholar
Zubkov, F. I., Mertsalov, D. F., Zaytsev, V. P., Varlamov, A. V., Gurbanov, A. V., Dorovatovskii, P. V., Timofeeva, T. V., Khrustalev, V. N. & Mahmudov, K. T. (2018). J. Mol. Liq. 249, 949–952. Web of Science CSD CrossRef CAS Google Scholar

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