Crystal structure and Hirshfeld surface analysis of (Z)-2-amino-4-(2,6-di­chloro­phen­yl)-5-(1-hy­droxy­ethyl­idene)-6-oxo-1-phenyl-1,4,5,6-tetra­hydro­pyridine-3-carbo­nitrile

Naghiyev, F.N.; Pavlova, A.V.; Khrustalev, V.N.; Akkurt, M.; Khalilov, A.N.; Akobirshoeva, A.A.; Mamedov, İ.G.

doi:10.1107/S2056989021007994

research communications

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ISSN: 2056-9890

Volume 77| Part 9| September 2021| Pages 930-934

https://doi.org/10.1107/S2056989021007994

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Crystal structure and Hirshfeld surface analysis of (Z)-2-amino-4-(2,6-dichlorophenyl)-5-(1-hydroxyethylidene)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3-carbonitrile

Farid N. Naghiyev,^a Anastasiya V. Pavlova,^b Victor N. Khrustalev,^b,^c Mehmet Akkurt,^d Ali N. Khalilov,^a,^e Anzurat A. Akobirshoeva ^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 ^fAcad. Sci. Republ. Tadzhikistan, Kh. Yu. Yusufbekov Pamir Biol. Inst., 1 Kholdorova St, Khorog 736002, Gbao, Tajikistan
^*Correspondence e-mail: anzurat2003@mail.ru

Edited by C. Schulzke, Universität Greifswald, Germany (Received 6 July 2021; accepted 3 August 2021; online 10 August 2021)

The molecular conformation of the title compound, C₂₀H₁₅Cl₂N₃O₂, is stabilized by an intramolecular O—H⋯O hydrogen bond, forming an S(6) ring motif. The central pyridine ring is almost planar [maximum deviation = 0.074 (3) Å]. It subtends dihedral angles of 86.10 (15) and 87.17 (14)°, respectively, with the phenyl and dichlorophenyl rings, which are at an angle of 21.28 (15)° to each other. The =C(—OH)CH₃ group is coplanar. In the crystal, molecules are linked by intermolecular N—H⋯N and C—H⋯N hydrogen bonds, and N—H⋯π and C—H⋯π interactions, forming a three-dimensional network. The most important contributions to the crystal packing are from H⋯H (33.1%), C⋯H/H⋯C (22.5%), Cl⋯H/H⋯Cl (14.1%), O⋯H/H⋯O (11.9%) and N⋯H/H⋯N (9.7%) interactions.

Keywords: crystal structure; pyridine ring; hydrogen bonds; ring motifs; Hirshfeld surface analysis.

CCDC reference: 2101203

1. Chemical context

The development of effective methods for the construction of small-sized molecules bearing a nitrogen heterocycle is a very important proposition in organic synthesis and catalysis (Abdel-Hafiz et al., 2012 ; Gurbanov et al., 2018 ; Zubkov et al., 2018 ). As members of this family, pyridine derivatives play a key role in flavor chemistry, crystal engineering, and the development of biologically active compounds (Adams & De Kimpe, 2006 ; Mahmoudi et al., 2019 ; Mamedov et al., 2020 ). The pyridine core is a key bioactive fragment of diverse natural products (niacin, pyridoxine, nicotine, NADP⁺) and series of derivatives constitute promising drugs in medicinal chemistry (Mohsin & Ahmad, 2018 ).

In this study, in the framework of our ongoing structural studies (Naghiyev et al., 2020 , 2021a ,b ), we report the crystal structure and Hirshfeld surface analysis of the title compound, (Z)-2-amino-4-(2,6-dichlorophenyl)-5-(1-hydroxyethylidene)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3-carbonitrile, previously mistakenly reported in the E isomeric form (Maharramov et al., 2018 ). This compound was also previously mentioned as transient intermediate but neither isolated nor characterized (Naghiyeva et al., 2019 ).

2. Structural commentary

The title compound crystallizes in the monoclinic space group P2₁/c with Z = 4, in which the asymmetric unit comprises one molecule. In the molecule (Fig. 1), the central pyridine ring (N1/C2–C6) is almost planar with a maximum deviation of 0.074 (3) Å for C4. The phenyl (C7–C12) and dichlorophenyl (C14–C19) rings are at an angle of 21.28 (15)°. They form dihedral angles of 86.10 (15) and 87.17 (14)°, respectively, with the central pyridine ring. The =C(—OH)CH₃ group is nearly coplanar with the pyridine ring with C2—C3—C1—O2 and C4—C3—C1—C13 torsion angles of only 5.5 (5) and 3.3 (5)°, respectively. A strong intramolecular O2—H2⋯O1 hydrogen bond (Fig. 1, Table 1) stabilizes the molecular conformation of the title molecule, creating an S(6) ring motif (Bernstein et al., 1995 ).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C7–C12 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.86 (4)	1.72 (4)	2.514 (3)	153 (4)
N3—H3A⋯N2ⁱ	0.86 (4)	2.22 (4)	3.032 (4)	159 (3)
C16—H16⋯N2ⁱⁱ	0.95	2.62	3.308 (4)	129
N3—H3B⋯Cg2	0.88 (4)	2.88 (4)	3.581 (3)	138 (3)
C9—H9⋯Cg2ⁱⁱⁱ	0.95	2.70	3.564 (4)	151
Symmetry codes: (i) ; (ii) ; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

Intermolecular N3—H3A⋯N2 hydrogen bonds, which form an R₂²(12) ring motif between pairs of molecules along the b-axis direction and an R₂²(16) ring motif between pairs of molecules along the a-axis direction, together with N3—H3B⋯Cg2 and C9—H9⋯Cg2 interactions (Fig. 2, Tables 1 and 2; Cg2 is the centroid of the C7–C12 phenyl ring) create a three-dimensional network in the crystal (Figs. 2 and 3).

Table 2
Interatomic contacts of the title compound (Å)

Contact	Distance	Symmetry operation
Cl1⋯Cl1	3.6744 (14)	2 − x, 1 − y, 1 − z
H4⋯C20	2.77	1 − x, 1 − y, 1 − z
O1⋯H9	2.54	x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
N2⋯H13C	2.81	x, y, 1 + z
H3A⋯N2	2.22 (4)	1 − x, 1 − y, 2 − z
H16⋯N2	2.62	2 − x, 1 − y, 2 − z
H11⋯H13B	2.54	−1 + x, y, z
H17⋯H3B	2.54	1 + x, y, z
H12⋯C18	2.93	−1 + x, y, −1 + z

Figure 2
A general view of the intra- and intermolecular O—H⋯O, N—H⋯N hydrogen bonding and N—H⋯π and C—H⋯π interactions in the title compound. Symmetry codes: (a) 1 − x, 1 − y, 2 − z; (b) 2 − x, 1 − y, 2 − z; (c) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z.

Figure 3
A view down the a axis of the crystal packing of the title compound based on the intermolecular interactions shown in Fig. 2

The Hirshfeld surfaces were calculated and the two-dimensional fingerprint plots generated using Crystal Explorer 17.5 (Turner et al., 2017 ). The use of various hues and intensities to represent short and long contacts, as well as the relative intensity of the connections, allows Hirshfeld surfaces to depict intermolecular interactions. Fig. 4 shows the three-dimensional Hirshfeld surfaces of the title compound plotted over d_norm (normalized contact distance) in the range of −0.4290 to 1.5192 a.u. The red patches that appear around N2 are caused by the intermolecular N3—H3A⋯N2 and C16—H16⋯N2 interactions, which are important in the packing of the title molecule. Bright red dots near N2 and amine hydrogen atoms H3A and H3B highlight their functions as hydrogen-bonding acceptors and donors, respectively; these also appear as blue and red areas on the Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) in Fig. 5, corresponding to positive and negative potentials. Positive electrostatic potential (hydrogen-bond donors) is shown in blue, whereas negative electrostatic potential is indicated in red (hydrogen-bond acceptors).

Figure 4
Hirshfeld surface of the title compound mapped with d_norm.

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions, respectively, around the atoms, corresponding to positive and negative potentials.

In Fig. 6, the overall two-dimensional fingerprint plot for the title compound and those delineated into H⋯H, C⋯H/H⋯C, Cl⋯H/H⋯Cl, O⋯H/H⋯O and N⋯H/H⋯N contacts, as well as their relative contributions to the Hirshfeld surface, are presented, while details of the various contacts are given in Table 2. The percentage contributions to the Hirshfeld surfaces from the various interatomic contacts are as follows: H⋯H (33.1%; Fig. 6b), C⋯H/H⋯C (22.5%; Fig. 6c), Cl⋯H/H⋯Cl (14.1%; Fig. 6d), O⋯H/H⋯O (11.9%; Fig. 6e) and N⋯H/H⋯N (9.7%; Fig. 6f). Other Cl⋯C/C⋯Cl, C⋯C, Cl⋯O/O⋯Cl, Cl⋯N/N⋯Cl, N⋯C/C⋯N, O⋯N/N⋯O, Cl⋯Cl, O⋯C/C⋯O and N⋯N contacts contribute less than 2.1% to Hirshfeld surface mapping and have little directional influence on molecular packing (Table 3).

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
H⋯H	33.1
C⋯H/H⋯C	22.5
Cl⋯H/H⋯Cl	14.1
O⋯H/H⋯O	11.9
N⋯H/H⋯N	9.7
Cl⋯C/C⋯Cl	2.1
C⋯C	1.4
Cl⋯O/O⋯Cl	1.2
Cl⋯N/N⋯Cl	1.1
N⋯C/C⋯N	1.0
O⋯N/N⋯O	0.6
Cl⋯Cl	0.6
O⋯C/C⋯O	0.5
N⋯N	0.1

Figure 6
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) Cl⋯H/H⋯Cl, (e) O⋯H/H⋯O and (f) N⋯H/H⋯N 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 5.39, update of August 2018; Groom et al., 2016 ) using Conquest (Bruno et al., 2002 ) for the tetrahydropyridine unit revealed 1339 hits. Some interesting structures related to the title compound based on their tetrahydropyridine moieties include: ethyl 4-hydroxy-2,6-diphenyl-5-(phenylsulfanyl)pyridine-3-carboxylate (refcode SETWOE: Suresh et al., 2007 ), ethyl 2,6-bis(4-fluorophenyl)-4-hydroxy-5-(4-methylphenylsulfanyl)pyridine-3-carboxylate (SETWUK: Suresh et al., 2007), 2,6-diamino-4-chloropyrimidin-1-ium 2-carboxy-3-nitrobenzoate (JEBRAM: Mohana et al., 2017 ) and 2,6-diamino-4-chloropyrimidin-1-ium 4-methylbenzene-1-sulfonate monohydrate (JEBREQ: Mohana et al., 2017).

The polysubstituted pyridines, SETWOE (space group: P2₁/c) and SETWUK (space group: P2₁/n), adopt nearly planar structures. The crystal structure of SETWOE is stabilized by intermolecular C—H⋯O and C—H⋯π interactions. The C—H⋯O hydrogen bonds generate rings with R²₂(14) and R²₂(20) motifs. The crystal structure of SETWUK is stabilized by intermolecular C—H⋯F and C—H⋯π interactions. The C—H⋯F bond generates a linear chain with a C(14) motif. In addition, in SETWOE and SETWUK, intramolecular O—H⋯O interactions are found, which generate an S(6) graph-set motif. No significant aryl–aryl or π–π interactions exist in these structures. All this bears some resemblance to the title compound.

In both the related salts, JEBRAM (space group: P $[\overline{1}]$ ) and JEBREQ (space group: P $[\overline{1}]$ ) , the N atom in the 1-position of the pyrimidine ring is protonated. In JEBRAM, the protonated N atom and the amino group of the pyrimidinium cation interact with the carboxylate group of the anion through N—H⋯O hydrogen bonds, forming a heterosynthon with an R²₂(8) ring motif. In the hydrated salt JEBREQ, the presence of the water molecule prevents the formation of the familiar R₂²(8) ring motif. Instead, an expanded ring [i.e. R³₂(8)] is formed involving the sulfonate group, the pyrimidinium cation and the water molecule. Both salts form a supramolecular homosynthon [ R₂²(8) ring motif] through N—H⋯N hydrogen bonds. The molecular structures are further stabilized by π–π stacking, and C=O⋯π, C—H⋯O and C—H⋯Cl interactions. None of these are found in the crystal packing of the title compound. It appears that the protonation state of the pyrimidine ring influences the intermolecular interactions within the crystal lattices to a substantial extent.

5. Synthesis and crystallization

The title compound was synthesized using our previously reported procedure (Maharramov et al., 2018), and colorless prisms were obtained upon recrystallization from its methanol solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The positional parameters of the H atoms of the hydroxy and amine groups were determined from difference electron-density maps and were refined freely [O2—H2 = 0.86 (4) Å, N3—H3A = 0.86 (4) Å and N3—H3B = 0.88 (4) Å]. Their isotropic displacement parameters were refined using a riding model with U_iso(H) set to either 1.2U_eq(N) for the NH₂ group or 1.5U_eq(O) for the OH group. The C-bound H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C) for the methyl group and U_iso(H) = 1.2U_eq(C) for aromatic and methine H atoms.

Table 4
Experimental details

Crystal data
Chemical formula	C₂₀H₁₅Cl₂N₃O₂
M_r	400.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.662 (1), 27.010 (3), 7.4782 (8)
β (°)	111.571 (2)
V (Å³)	1814.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.38
Crystal size (mm)	0.24 × 0.21 × 0.02

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.864, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	27440, 4180, 2631
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.126, 1.01
No. of reflections	4180
No. of parameters	255
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.37
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2013 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2101203

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021007994/yz2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021007994/yz2010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021007994/yz2010Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

(Z)-2-Amino-4-(2,6-dichlorophenyl)-5-(1-hydroxyethylidene)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3-carbonitrile top

Crystal data top

C₂₀H₁₅Cl₂N₃O₂	F(000) = 824
M_r = 400.25	D_x = 1.465 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.662 (1) Å	Cell parameters from 2887 reflections
b = 27.010 (3) Å	θ = 2.3–25.6°
c = 7.4782 (8) Å	µ = 0.38 mm⁻¹
β = 111.571 (2)°	T = 100 K
V = 1814.9 (3) Å³	Plate, colourless
Z = 4	0.24 × 0.21 × 0.02 mm

Data collection top

Bruker D8 QUEST PHOTON-III CCD diffractometer	2631 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.099
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.5°, θ_min = 2.3°
T_min = 0.864, T_max = 0.986	h = −12→12
27440 measured reflections	k = −35→35
4180 independent reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0387P)² + 2.0157P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
4180 reflections	Δρ_max = 0.50 e Å⁻³
255 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.0024 (2)

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	0.86090 (9)	0.51416 (3)	0.60657 (12)	0.0256 (2)
Cl2	0.73128 (9)	0.32459 (3)	0.75788 (12)	0.0262 (2)
O1	0.3936 (2)	0.32320 (9)	0.2910 (3)	0.0280 (5)
O2	0.5668 (3)	0.34472 (9)	0.1210 (3)	0.0286 (6)
H2	0.502 (4)	0.3295 (15)	0.155 (6)	0.043*
N1	0.3832 (3)	0.36887 (10)	0.5389 (4)	0.0190 (6)
N2	0.6028 (3)	0.51570 (10)	0.8819 (4)	0.0213 (6)
N3	0.3468 (3)	0.41829 (11)	0.7719 (4)	0.0216 (6)
H3A	0.376 (4)	0.4411 (13)	0.857 (5)	0.026*
H3B	0.275 (4)	0.3976 (13)	0.763 (5)	0.026*
C1	0.6193 (3)	0.38087 (12)	0.2516 (4)	0.0222 (7)
C2	0.4484 (3)	0.35814 (12)	0.4048 (4)	0.0215 (7)
C3	0.5700 (3)	0.38792 (12)	0.3994 (4)	0.0190 (7)
C4	0.6393 (3)	0.42841 (12)	0.5454 (4)	0.0185 (7)
H4	0.6402	0.4592	0.4717	0.022*
C5	0.5438 (3)	0.43903 (11)	0.6633 (4)	0.0178 (6)
C6	0.4288 (3)	0.40975 (12)	0.6622 (4)	0.0190 (6)
C7	0.2636 (3)	0.33754 (11)	0.5457 (4)	0.0182 (6)
C8	0.2954 (3)	0.29874 (12)	0.6757 (4)	0.0225 (7)
H8	0.3954	0.2923	0.7572	0.027*
C9	0.1808 (4)	0.26931 (12)	0.6866 (5)	0.0247 (7)
H9	0.2018	0.2428	0.7762	0.030*
C10	0.0355 (4)	0.27893 (12)	0.5655 (5)	0.0254 (7)
H10	−0.0431	0.2588	0.5722	0.030*
C11	0.0039 (3)	0.31762 (12)	0.4351 (5)	0.0233 (7)
H11	−0.0959	0.3239	0.3526	0.028*
C12	0.1182 (3)	0.34720 (12)	0.4251 (4)	0.0219 (7)
H12	0.0970	0.3739	0.3362	0.026*
C13	0.7339 (4)	0.41270 (13)	0.2175 (5)	0.0262 (7)
H13A	0.7588	0.3988	0.1121	0.039*
H13B	0.8235	0.4139	0.3346	0.039*
H13C	0.6943	0.4462	0.1834	0.039*
C14	0.8003 (3)	0.41904 (12)	0.6829 (4)	0.0168 (6)
C15	0.9070 (3)	0.45717 (12)	0.7254 (4)	0.0206 (7)
C16	1.0502 (3)	0.45270 (13)	0.8591 (5)	0.0237 (7)
H16	1.1177	0.4797	0.8851	0.028*
C17	1.0934 (3)	0.40785 (13)	0.9546 (4)	0.0252 (7)
H17	1.1915	0.4041	1.0469	0.030*
C18	0.9949 (3)	0.36865 (13)	0.9164 (5)	0.0238 (7)
H18	1.0255	0.3378	0.9793	0.029*
C19	0.8510 (3)	0.37491 (12)	0.7852 (4)	0.0194 (7)
C20	0.5773 (3)	0.48144 (12)	0.7841 (4)	0.0190 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0223 (4)	0.0243 (4)	0.0291 (4)	−0.0013 (3)	0.0083 (3)	0.0025 (4)
Cl2	0.0236 (4)	0.0258 (4)	0.0260 (4)	−0.0006 (3)	0.0056 (3)	0.0049 (4)
O1	0.0271 (12)	0.0342 (14)	0.0240 (12)	−0.0085 (11)	0.0108 (10)	−0.0124 (11)
O2	0.0296 (13)	0.0394 (15)	0.0171 (12)	−0.0043 (11)	0.0091 (10)	−0.0072 (11)
N1	0.0169 (13)	0.0243 (15)	0.0161 (13)	−0.0028 (11)	0.0063 (10)	−0.0035 (11)
N2	0.0213 (14)	0.0210 (14)	0.0200 (14)	−0.0026 (11)	0.0058 (11)	−0.0030 (12)
N3	0.0199 (14)	0.0270 (15)	0.0196 (14)	−0.0071 (12)	0.0095 (11)	−0.0081 (12)
C1	0.0210 (16)	0.0286 (18)	0.0135 (15)	0.0038 (13)	0.0022 (12)	−0.0012 (14)
C2	0.0200 (15)	0.0275 (18)	0.0160 (15)	0.0009 (13)	0.0053 (12)	−0.0023 (14)
C3	0.0174 (15)	0.0225 (17)	0.0152 (15)	−0.0002 (12)	0.0038 (12)	−0.0001 (13)
C4	0.0157 (15)	0.0228 (17)	0.0166 (15)	0.0014 (12)	0.0055 (12)	−0.0020 (13)
C5	0.0172 (15)	0.0207 (16)	0.0139 (15)	0.0005 (12)	0.0037 (12)	−0.0014 (13)
C6	0.0162 (14)	0.0237 (17)	0.0135 (15)	0.0036 (12)	0.0012 (12)	−0.0002 (13)
C7	0.0175 (15)	0.0185 (16)	0.0184 (15)	−0.0037 (12)	0.0062 (12)	−0.0048 (13)
C8	0.0201 (16)	0.0264 (18)	0.0174 (16)	0.0015 (13)	0.0026 (13)	−0.0003 (14)
C9	0.0275 (17)	0.0219 (17)	0.0254 (18)	0.0030 (14)	0.0106 (14)	0.0049 (14)
C10	0.0228 (16)	0.0245 (18)	0.0310 (19)	−0.0028 (14)	0.0124 (14)	−0.0042 (15)
C11	0.0177 (15)	0.0259 (18)	0.0223 (17)	0.0019 (13)	0.0024 (13)	0.0013 (14)
C12	0.0230 (16)	0.0224 (17)	0.0177 (16)	0.0031 (13)	0.0044 (13)	0.0001 (13)
C13	0.0264 (17)	0.033 (2)	0.0206 (17)	0.0037 (15)	0.0107 (14)	0.0041 (15)
C14	0.0152 (14)	0.0241 (16)	0.0126 (14)	0.0025 (12)	0.0070 (11)	−0.0011 (12)
C15	0.0200 (15)	0.0254 (17)	0.0179 (16)	0.0040 (13)	0.0088 (13)	0.0024 (14)
C16	0.0185 (15)	0.0315 (19)	0.0222 (17)	−0.0020 (13)	0.0089 (13)	−0.0035 (14)
C17	0.0162 (15)	0.042 (2)	0.0173 (16)	0.0027 (14)	0.0063 (13)	−0.0010 (15)
C18	0.0219 (16)	0.0307 (19)	0.0196 (16)	0.0047 (14)	0.0087 (13)	0.0047 (14)
C19	0.0174 (15)	0.0266 (17)	0.0150 (15)	−0.0009 (13)	0.0066 (12)	−0.0022 (13)
C20	0.0110 (14)	0.0270 (18)	0.0193 (16)	0.0044 (12)	0.0058 (12)	0.0062 (14)

Geometric parameters (Å, º) top

Cl1—C15	1.751 (3)	C7—C12	1.387 (4)
Cl2—C19	1.747 (3)	C8—C9	1.390 (4)
O1—C2	1.250 (4)	C8—H8	0.9500
O2—C1	1.342 (4)	C9—C10	1.387 (4)
O2—H2	0.86 (4)	C9—H9	0.9500
N1—C2	1.397 (4)	C10—C11	1.385 (5)
N1—C6	1.401 (4)	C10—H10	0.9500
N1—C7	1.448 (4)	C11—C12	1.387 (4)
N2—C20	1.149 (4)	C11—H11	0.9500
N3—C6	1.354 (4)	C12—H12	0.9500
N3—H3A	0.86 (4)	C13—H13A	0.9800
N3—H3B	0.88 (4)	C13—H13B	0.9800
C1—C3	1.368 (4)	C13—H13C	0.9800
C1—C13	1.496 (4)	C14—C19	1.404 (4)
C2—C3	1.437 (4)	C14—C15	1.408 (4)
C3—C4	1.516 (4)	C15—C16	1.382 (4)
C4—C5	1.519 (4)	C16—C17	1.390 (5)
C4—C14	1.538 (4)	C16—H16	0.9500
C4—H4	1.0000	C17—C18	1.382 (5)
C5—C6	1.361 (4)	C17—H17	0.9500
C5—C20	1.421 (4)	C18—C19	1.386 (4)
C7—C8	1.385 (4)	C18—H18	0.9500

C1—O2—H2	105 (3)	C8—C9—H9	120.3
C2—N1—C6	121.3 (3)	C11—C10—C9	120.6 (3)
C2—N1—C7	118.7 (2)	C11—C10—H10	119.7
C6—N1—C7	120.0 (2)	C9—C10—H10	119.7
C6—N3—H3A	118 (2)	C10—C11—C12	120.0 (3)
C6—N3—H3B	118 (2)	C10—C11—H11	120.0
H3A—N3—H3B	123 (3)	C12—C11—H11	120.0
O2—C1—C3	122.6 (3)	C11—C12—C7	119.5 (3)
O2—C1—C13	113.5 (3)	C11—C12—H12	120.2
C3—C1—C13	123.8 (3)	C7—C12—H12	120.2
O1—C2—N1	117.1 (3)	C1—C13—H13A	109.5
O1—C2—C3	123.3 (3)	C1—C13—H13B	109.5
N1—C2—C3	119.6 (3)	H13A—C13—H13B	109.5
C1—C3—C2	118.4 (3)	C1—C13—H13C	109.5
C1—C3—C4	119.4 (3)	H13A—C13—H13C	109.5
C2—C3—C4	122.1 (3)	H13B—C13—H13C	109.5
C3—C4—C5	110.7 (2)	C19—C14—C15	114.7 (3)
C3—C4—C14	115.6 (2)	C19—C14—C4	124.6 (3)
C5—C4—C14	108.9 (2)	C15—C14—C4	120.5 (3)
C3—C4—H4	107.1	C16—C15—C14	123.7 (3)
C5—C4—H4	107.1	C16—C15—Cl1	116.4 (3)
C14—C4—H4	107.1	C14—C15—Cl1	120.0 (2)
C6—C5—C20	117.8 (3)	C15—C16—C17	118.7 (3)
C6—C5—C4	123.7 (3)	C15—C16—H16	120.7
C20—C5—C4	118.4 (3)	C17—C16—H16	120.7
N3—C6—C5	123.7 (3)	C18—C17—C16	120.5 (3)
N3—C6—N1	114.8 (3)	C18—C17—H17	119.8
C5—C6—N1	121.4 (3)	C16—C17—H17	119.8
C8—C7—C12	120.6 (3)	C17—C18—C19	119.2 (3)
C8—C7—N1	119.5 (3)	C17—C18—H18	120.4
C12—C7—N1	119.9 (3)	C19—C18—H18	120.4
C7—C8—C9	119.9 (3)	C18—C19—C14	123.2 (3)
C7—C8—H8	120.1	C18—C19—Cl2	115.9 (3)
C9—C8—H8	120.1	C14—C19—Cl2	120.9 (2)
C10—C9—C8	119.5 (3)	N2—C20—C5	179.2 (3)
C10—C9—H9	120.3

C6—N1—C2—O1	−174.8 (3)	C6—N1—C7—C8	−86.5 (4)
C7—N1—C2—O1	3.5 (4)	C2—N1—C7—C12	−86.2 (4)
C6—N1—C2—C3	3.4 (4)	C6—N1—C7—C12	92.2 (3)
C7—N1—C2—C3	−178.2 (3)	C12—C7—C8—C9	−0.4 (5)
O2—C1—C3—C2	−5.5 (5)	N1—C7—C8—C9	178.3 (3)
C13—C1—C3—C2	173.5 (3)	C7—C8—C9—C10	0.5 (5)
O2—C1—C3—C4	177.7 (3)	C8—C9—C10—C11	−0.3 (5)
C13—C1—C3—C4	−3.3 (5)	C9—C10—C11—C12	−0.1 (5)
O1—C2—C3—C1	6.4 (5)	C10—C11—C12—C7	0.3 (5)
N1—C2—C3—C1	−171.7 (3)	C8—C7—C12—C11	0.0 (5)
O1—C2—C3—C4	−176.9 (3)	N1—C7—C12—C11	−178.7 (3)
N1—C2—C3—C4	5.0 (4)	C3—C4—C14—C19	−48.4 (4)
C1—C3—C4—C5	165.1 (3)	C5—C4—C14—C19	76.9 (4)
C2—C3—C4—C5	−11.6 (4)	C3—C4—C14—C15	136.5 (3)
C1—C3—C4—C14	−70.5 (4)	C5—C4—C14—C15	−98.2 (3)
C2—C3—C4—C14	112.8 (3)	C19—C14—C15—C16	−1.0 (4)
C3—C4—C5—C6	11.6 (4)	C4—C14—C15—C16	174.6 (3)
C14—C4—C5—C6	−116.5 (3)	C19—C14—C15—Cl1	179.1 (2)
C3—C4—C5—C20	−169.4 (3)	C4—C14—C15—Cl1	−5.3 (4)
C14—C4—C5—C20	62.5 (4)	C14—C15—C16—C17	1.4 (5)
C20—C5—C6—N3	−1.3 (5)	Cl1—C15—C16—C17	−178.7 (2)
C4—C5—C6—N3	177.7 (3)	C15—C16—C17—C18	0.0 (5)
C20—C5—C6—N1	176.3 (3)	C16—C17—C18—C19	−1.7 (5)
C4—C5—C6—N1	−4.7 (5)	C17—C18—C19—C14	2.2 (5)
C2—N1—C6—N3	174.1 (3)	C17—C18—C19—Cl2	−176.1 (2)
C7—N1—C6—N3	−4.2 (4)	C15—C14—C19—C18	−0.8 (4)
C2—N1—C6—C5	−3.6 (4)	C4—C14—C19—C18	−176.2 (3)
C7—N1—C6—C5	178.0 (3)	C15—C14—C19—Cl2	177.3 (2)
C2—N1—C7—C8	95.1 (3)	C4—C14—C19—Cl2	1.9 (4)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C7–C12 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.86 (4)	1.72 (4)	2.514 (3)	153 (4)
N3—H3A···N2ⁱ	0.86 (4)	2.22 (4)	3.032 (4)	159 (3)
C16—H16···N2ⁱⁱ	0.95	2.62	3.308 (4)	129
N3—H3B···Cg2	0.88 (4)	2.88 (4)	3.581 (3)	138 (3)
C9—H9···Cg2ⁱⁱⁱ	0.95	2.70	3.564 (4)	151

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

Interatomic contacts of the title compound (Å) top

Contact	Distance	Symmetry operation
Cl1···Cl1	3.6744 (14)	2 - x, 1 - y, 1 - z
H4···C20	2.77	1 - x, 1 - y, 1 - z
O1···H9	2.54	x, 1/2 - y, -1/2 + z
N2···H13C	2.81	x, y, 1 + z
H3A···N2	2.22 (4)	1 - x, 1 - y, 2 - z
H16···N2	2.62	2 - x, 1 - y, 2 - z
H11···H13B	2.54	-1 + x, y, z
H17···H3B	2.54	1 + x, y, z
H12···C18	2.93	-1 + x, y, -1 + z

Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound top

Contact	Percentage contribution
H···H	33.1
C···H/H···C	22.5
Cl···H/H···Cl	14.1
O···H/H···O	11.9
N···H/H···N	9.7
Cl···C/C···Cl	2.1
C···C	1.4
Cl···O/O···Cl	1.2
Cl···N/N···Cl	1.1
N···C/C···N	1.0
O···N/N···O	0.6
Cl···Cl	0.6
O···C/C···O	0.5
N···N	0.1

Acknowledgements

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

Funding information

This work was supported by Baku State University and RUDN University Strategic Academic Leadership Program.

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