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

Asadov, K.A.; Khrustalev, V.N.; Dobrokhotova, E.V.; Akkurt, M.; Huseynova, A.T.; Akobirshoeva, A.A.; Huseynov, E.Z.

doi:10.1107/S205698902200175X

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ISSN: 2056-9890

Volume 78| Part 3| March 2022| Pages 330-335

https://doi.org/10.1107/S205698902200175X

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

Khammed A. Asadov,^a Victor N. Khrustalev,^b,^c Ekaterina V. Dobrokhotova,^b Mehmet Akkurt,^d Afet T. Huseynova,^a Anzurat A. Akobirshoeva ^e ^* and Elnur Z. Huseynov ^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, and ^eAcad Sci Republ Tadzhikistan, Kh. Yu. Yusufbekov Pamir Biol. Inst., 1 Kholdorova St, Khorog 736002, Gbao, Tajikistan
^*Correspondence e-mail: anzurat2003@mail.ru

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 3 February 2022; accepted 15 February 2022; online 22 February 2022)

The central tetrahydropyridine ring of the title compound, C₁₉H₁₇N₃O₂, adopts a screw-boat conformation. In the crystal, strong C—H⋯O and N—H⋯N hydrogen bonds form dimers with R²₂(14) and R²₂(12) ring motifs, respectively, between consecutive molecules along the c-axis direction. Intermolecular N—H⋯O and C—H⋯O hydrogen bonds connect these dimers, forming a three-dimensional network. C—H⋯π interactions and π–π stacking interactions contribute to the stabilization of the molecular packing. A Hirshfeld surface analysis indicates that the contributions from the most prevalent interactions are H⋯H (47.1%), C⋯H/H⋯C (20.9%), O⋯H/H⋯O (15.3%) and N⋯H/H⋯N (11.4%).

Keywords: crystal structure; tetrahydropyridine; hydrogen bonds; dimers; Hirshfeld surface analysis.

CCDC reference: 2152191

1. Chemical context

Carbon–carbon and carbon–nitrogen bond-forming reactions represent an important synthetic class in organic chemistry (Yadigarov et al., 2009 ; Abdelhamid et al., 2011 ; Yin et al., 2020 ; Khalilov et al., 2021 ). Notably, pyridine derivatives are widely applied in the discovery of biologically active molecules and multifunctional materials (Magerramov et al., 2018 ; Sherman & Murugan, 2015 ; Mamedov et al., 2020 ). On the other hand, the tetrahydropyridine moiety is an essential part of diverse biologically active compounds, food additives and natural products (Mateeva et al., 2005 ).

In the framework of ongoing structural studies (Safavora et al., 2019 ; Naghiyev et al., 2020 ; 2021a ,b ; Maharramov et al., 2021 ), we report here the crystal structure and Hirshfeld surface analysis of the title compound, 2-amino-4-(4-methoxyphenyl)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3- carbonitrile.

2. Structural commentary

The title compound (Fig. 1) crystallizes in the monoclinic space group P2₁/n with Z = 4. The central N1/C2–C6 tetrahydropyridine ring of the molecule adopts a screw-boat conformation with puckering parameters (Cremer & Pople, 1975 ) Q_T = 0.503 (2) Å, θ = 66.1 (2)°, φ = 153.3 (2)°. The C7–C12 phenyl ring, which is attached to N1, is in an equatorial position and makes a dihedral angle of 54.43 (9)° with the mean plane of the tetrahydropyridine ring. The C13–C18 methoxyphenyl ring, which is attached to C4, is in an axial position. The dihedral angle between the C7–C12 phenyl and C13–C18 methoxyphenyl rings is 68.61 (10)°.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

3. Supramolecular features

As shown in Fig. 2, strong intermolecular C11—H11⋯O1 and N3—H3C⋯N2 hydrogen bonds (Table 1) form dimers with $[R_{2}^{2}]$ (14) and $[R_{2}^{2}]$ (12) ring motifs (Bernstein et al., 1995 ), respectively, between adjacent molecules along the c-axis direction. These dimers are connected by N3—H3D⋯O2 and C14—H14⋯O1 hydrogen bonds, forming a three-dimensional network (Table 1; Fig. 3). Furthermore, C—H⋯π [C10—H10⋯Cg3ⁱⁱⁱ and C18—H18⋯Cg3^v; symmetry codes: (iii) −x + 1, −y + 1, −z + 1; (v) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ .; Cg3 is the centroid of the C13–C18 methoxyphenyl ring; Table 1] and π–π stacking interactions [Cg2⋯Cg2ⁱⁱⁱ = 3.8918 (15) Å and slippage = 1.551 Å; Cg2 is the centroid of the C7–C12 phenyl ring] contribute to the stabilization of the molecular packing (Figs. 4 and 5).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C13–C18 benzene ring of the methoxyphenyl group.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯N2ⁱ	0.91 (2)	2.10 (2)	2.996 (2)	166 (2)
N3—H3D⋯O2ⁱⁱ	0.91 (2)	2.48 (2)	3.152 (2)	131.0 (19)
C11—H11⋯O1ⁱⁱⁱ	0.95	2.55	3.210 (3)	127
C14—H14⋯O1^iv	0.95	2.48	3.199 (2)	133
C10—H10⋯Cg3ⁱⁱⁱ	0.95	2.99	3.813 (3)	146
C18—H18⋯Cg3^v	0.95	2.87	3.716 (2)	150
Symmetry codes: (i) ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) ; (iv) ; (v) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Figure 3
The crystal packing of the title compound, viewed along the b axis, showing the N—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds as dashed lines.

Figure 4
A general view of the C—H⋯π interactions and π–π stacking interactions in the crystal packing of the title compound [symmetry codes: (iii) −x + 1, −y + 1, −z + 1; (v) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ].

Figure 5
The crystal packing of the title compound, viewed along the b axis, showing the C—H⋯π interactions and π–π stacking interactions as dashed lines.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis was performed and the associated two dimensional fingerprint plots generated using Crystal Explorer 17 (Turner et al., 2017 ). The Hirshfeld surface was calculated using a standard (high) surface resolution with the three-dimensional d_norm surface plotted over a fixed colour scale mapped over the range −0.4835 (red) to 1.8469 (blue) a.u. The d_norm mapping indicates that strong hydrogen-bonding interactions, such as N—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds (Tables 1 and 2), appear to be the primary interactions in the structure, seen as a bright-red area in the Hirshfeld surface (Fig. 6).

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

Contact	Distance	Symmetry operation
O1⋯H14	2.48	x, 1 + y, z
H11⋯O1	2.55	1 − x, 1 − y, 1 − z
N2⋯H17	2.70	$[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
O2⋯H3D	2.48 (2)	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z
H3C⋯N2	2.10 (3)	-x, −y, 1 − z
C20⋯C6	3.318 (3)	-x, 1 − y, 1 − z

Figure 6
Hirshfeld surface mapped over d_norm showing the N—H⋯N, N—H⋯O and C—H⋯O intermolecular contacts.

The Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) is shown in Fig. 7. The blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors).

Figure 7
View of the three-dimensional Hirshfeld surface of the title compound, showing the hydrogen-bonding interactions, 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.

The two-dimensional fingerprint plots are illustrated in Fig. 8. H⋯H contacts comprise 47.1% of the total interactions (Fig. 8b), followed by C⋯H/H⋯C (Fig. 8c; 20.9%), O⋯H/H⋯O (Fig. 8d; 15.3%) and N⋯H/H⋯N (Fig. 8e; 11.4%). The percentage contributions of the C⋯C, C⋯N/N⋯C and N⋯N contacts are negligible, at 3.1, 1.4 and 0.8%, respectively. The predominance of H⋯H, C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N contacts indicate that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

Figure 8
(a) The full two-dimensional fingerprint plot for the title compound and those delineated into (b) H⋯H (47.1%), (c) C⋯H/H⋯C (20.9%), (d) O⋯H/H⋯O (15.3%) and (e) N⋯H/H⋯N (11.4%) contacts.

5. Database survey

A search of the Cambridge Structural Database (CSD, version 5.42, update of September 2021; Groom et al., 2016 ) found four compounds with the 6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine unit that are similar to the title compound, viz. 5-acetyl-2-amino-4-(4-bromophenyl)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3-carbonitrile (I) (YAXQAT; Mamedov et al., 2022 ), 2-amino-4-(2,6-dichlorophenyl)-5-(1-hydroxyethylidene)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3-carbonitrile (II) (OZAKOS, Naghiyev et al., 2021c ), methyl 6-oxo-4-phenyl-2-[(Z)-2-(pyridin-2-yl)ethenyl]-1,4,5,6-tetrahydropyridine-3-carboxylate (III) (PEDFEL, Smits et al., 2012 ) and ethyl 5-ethoxymethylene-2-methyl-6-oxo-4-phenyl-1,4,5,6-tetrahydropyridine-3-carboxylate (IV) (VAGXAD, Novoa de Armas et al., 2003 ).

Compound (I) crystallizes in the monoclinic space group Pc with Z = 4, and with two molecules, A and B, in the asymmetric unit. These molecules are stereoisomers with an R,R absolute configuration at C3 and C4 in molecule A, whereas the corresponding atoms in B, C23 and C24, have an S configuration. In both molecules, the conformation of the central dihydropyridine ring is close to screw-boat. The molecular conformation is stabilized by N—H⋯O hydrogen bonds, forming a dimer with an $[R_{2}^{2}]$ (16) ring motif. Both molecules of the dimers are connected by intermolecular N—H⋯O and N—H⋯N hydrogen bonds with an R₂³(14) ring motif into chains along the c-axis direction. Furthermore C—Br⋯π and C=O⋯π stacking interactions between these ribbons contribute to the stabilization of the molecular packing.

Compound (II) crystallizes in the monoclinic space group P2₁/c with Z = 4 and the asymmetric unit comprises one molecule. The central tetrahydropyridine ring is almost planar with a maximum deviation of 0.074 (3) Å for C4. The phenyl and dichlorophenyl 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 tetrahydropyridine ring. A strong intramolecular O2—H2⋯O1 hydrogen bond stabilizes the molecular conformation of the molecule, creating an S(6) ring motif. 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.

In molecule (III) (monoclinic space group P2₁/c, Z = 4), the cis configuration of the pyridinyl-vinyl fragment is stabilized by a strong intramolecular N—H⋯N hydrogen bond. The phenyl and pyridine rings are inclined to one another by 77.3 (1)°. In the crystal, inversion dimers are present via pairs of C—H⋯O hydrogen bonds and are further linked by C—H⋯O hydrogen bonds and C—H⋯π interactions.

For compound (IV) (monoclinic space group C2/c, Z = 8), the molecules form dimers by means of a pair of N—H⋯O hydrogen bonds. The 2(1H)-pyridone ring displays a screw-boat conformation.

6. Synthesis and crystallization

To a solution of 2-(4-methoxybenzylidene)malononitrile (0.94 g; 5.1 mmol) and acetoacetanilide (0.92 g; 5.2 mmol) in methanol (25 mL), 3-4 drops of piperidine were added and the mixture was stirred at 328–333 K for 10 min and was kept 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 61%; m.p. 471–472 K).

¹H NMR (300 MHz, DMSO-d₆, ppm.): 2.80 (dd–dd, 1H, CH₂); 3.19 (dd–dd, 1H, CH₂); 3.82 (s, 3H, OCH₃); 3.93 (t, 1H, CH); 5.85 (s, 2H, NH₂); 7.15–7.58 (m, 9H, 2Ar—H). ¹³C NMR (75 MHz, DMSO-d₆, ppm.): 36.06 (CH—Ar), 40.42 (CH₂), 53.78 (OCH₃), 59.05 (C_quat.), 112.89 (2CH_ar), 121.21 (CN), 128.61 (CH_ar.), 128.88 (2CH_ar.), 130.44 (2CH_ar.), 130.51 (2CH_ar.), 136.06 (C_{ar. quat.}), 137.02 (C_{ar. quat.}), 154.59 (C_{ar. quat.}), 155.18 (C_quat.), 168.82 (N—C=O).

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms bonded to nitrogen were located in a difference-Fourier map, and only their positional parameters were refined [N3—H3C = 0.91 (2) and N3—H3D = 0.91 (2) Å with U_iso(H) = 1.2U_eq(N)]. C-bound H atoms were positioned geometrically, with C—H = 0.95–1.00 Å, and were refined with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₉H₁₇N₃O₂
M_r	319.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.910 (3), 6.3200 (13), 21.170 (4)
β (°)	106.48 (3)
V (Å³)	1656.3 (7)
Z	4
Radiation type	Synchrotron, λ = 0.80246 Å
μ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.15 × 0.07

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA;Evans, 2006 )
T_min, T_max	0.950, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	26143, 3603, 3125
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.143, 1.05
No. of reflections	3603
No. of parameters	225
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.27
Computer programs: Marccd (Doyle, 2011 ), iMosflm (Battye et al., 2011 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2152191

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902200175X/vm2260sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902200175X/vm2260Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902200175X/vm2260Isup3.cml

checkCIF report

Computing details top

Data collection: Marccd (Doyle, 2011); cell refinement: iMosflm (Battye et al., 2011); data reduction: iMosflm (Battye et al., 2011); 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-Amino-4-(4-methoxyphenyl)-6-oxo-1-phenyl-1,4,5,6-tetrahydropyridine-3-carbonitrile top

Crystal data top

C₁₉H₁₇N₃O₂	F(000) = 672
M_r = 319.36	D_x = 1.281 Mg m⁻³
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.80246 Å
a = 12.910 (3) Å	Cell parameters from 600 reflections
b = 6.3200 (13) Å	θ = 2.4–30.0°
c = 21.170 (4) Å	µ = 0.11 mm⁻¹
β = 106.48 (3)°	T = 100 K
V = 1656.3 (7) Å³	Prism, colourless
Z = 4	0.40 × 0.15 × 0.07 mm

Data collection top

Rayonix SX165 CCD diffractometer	3125 reflections with I > 2σ(I)
/f scan	R_int = 0.049
Absorption correction: multi-scan (Scala;Evans, 2006)	θ_max = 31.1°, θ_min = 2.3°
T_min = 0.950, T_max = 0.985	h = −16→16
26143 measured reflections	k = −8→7
3603 independent reflections	l = −27→27

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.059P)² + 1.3785P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3603 reflections	Δρ_max = 0.29 e Å⁻³
225 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.033 (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
O1	0.33220 (11)	0.8608 (2)	0.55256 (7)	0.0332 (3)
O2	0.55206 (12)	0.1472 (3)	0.79862 (7)	0.0413 (4)
N1	0.24126 (11)	0.5628 (2)	0.50951 (7)	0.0269 (3)
N2	−0.03015 (13)	0.1368 (3)	0.56257 (8)	0.0321 (4)
N3	0.12078 (12)	0.3027 (3)	0.45307 (8)	0.0300 (4)
H3C	0.0857 (18)	0.177 (4)	0.4520 (11)	0.036*
H3D	0.1458 (19)	0.336 (4)	0.4183 (12)	0.036*
C2	0.26361 (14)	0.7307 (3)	0.55371 (9)	0.0272 (4)
C3	0.19790 (14)	0.7407 (3)	0.60221 (9)	0.0287 (4)
H3A	0.1284	0.8122	0.5814	0.034*
H3B	0.2372	0.8254	0.6409	0.034*
C4	0.17589 (14)	0.5196 (3)	0.62495 (9)	0.0277 (4)
H4	0.1221	0.5339	0.6506	0.033*
C5	0.12391 (13)	0.3942 (3)	0.56355 (9)	0.0268 (4)
C6	0.15916 (13)	0.4149 (3)	0.50888 (9)	0.0262 (4)
C7	0.30690 (13)	0.5355 (3)	0.46514 (9)	0.0279 (4)
C8	0.31570 (15)	0.6969 (3)	0.42287 (9)	0.0338 (4)
H8	0.2765	0.8249	0.4215	0.041*
C9	0.38256 (17)	0.6690 (4)	0.38261 (11)	0.0408 (5)
H9	0.3906	0.7800	0.3541	0.049*
C10	0.43779 (17)	0.4806 (4)	0.38357 (11)	0.0421 (5)
H10	0.4827	0.4624	0.3554	0.051*
C11	0.42768 (16)	0.3194 (4)	0.42533 (10)	0.0379 (5)
H11	0.4651	0.1898	0.4256	0.045*
C12	0.36267 (15)	0.3466 (3)	0.46698 (9)	0.0314 (4)
H12	0.3564	0.2370	0.4964	0.038*
C13	0.27801 (14)	0.4188 (3)	0.66992 (9)	0.0266 (4)
C14	0.32417 (14)	0.2403 (3)	0.65102 (9)	0.0274 (4)
H14	0.2927	0.1822	0.6085	0.033*
C15	0.41514 (15)	0.1438 (3)	0.69241 (9)	0.0298 (4)
H15	0.4443	0.0197	0.6787	0.036*
C16	0.46259 (15)	0.2306 (3)	0.75379 (9)	0.0316 (4)
C17	0.41891 (15)	0.4125 (3)	0.77340 (9)	0.0333 (4)
H17	0.4520	0.4735	0.8153	0.040*
C18	0.32761 (15)	0.5043 (3)	0.73205 (9)	0.0301 (4)
H18	0.2980	0.6273	0.7460	0.036*
C19	0.5911 (2)	−0.0507 (4)	0.78134 (12)	0.0535 (6)
H19A	0.6153	−0.0321	0.7418	0.080*
H19B	0.5329	−0.1558	0.7726	0.080*
H19C	0.6517	−0.0995	0.8178	0.080*
C20	0.03871 (13)	0.2533 (3)	0.56225 (9)	0.0268 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0328 (7)	0.0278 (7)	0.0408 (7)	−0.0063 (5)	0.0132 (6)	−0.0045 (6)
O2	0.0378 (7)	0.0485 (9)	0.0319 (7)	0.0068 (6)	0.0005 (6)	0.0031 (6)
N1	0.0262 (7)	0.0245 (7)	0.0304 (7)	−0.0025 (6)	0.0086 (6)	−0.0026 (6)
N2	0.0318 (8)	0.0294 (8)	0.0348 (8)	−0.0028 (6)	0.0093 (6)	0.0009 (7)
N3	0.0311 (8)	0.0297 (8)	0.0288 (8)	−0.0072 (6)	0.0079 (6)	−0.0025 (6)
C2	0.0272 (8)	0.0218 (8)	0.0310 (9)	0.0010 (6)	0.0058 (7)	0.0001 (7)
C3	0.0300 (8)	0.0248 (8)	0.0319 (9)	0.0000 (7)	0.0096 (7)	−0.0022 (7)
C4	0.0267 (8)	0.0268 (9)	0.0305 (9)	−0.0005 (7)	0.0098 (7)	−0.0023 (7)
C5	0.0240 (8)	0.0255 (8)	0.0300 (9)	−0.0003 (6)	0.0060 (6)	0.0015 (7)
C6	0.0233 (7)	0.0228 (8)	0.0303 (8)	−0.0006 (6)	0.0040 (6)	0.0003 (7)
C7	0.0243 (8)	0.0310 (9)	0.0278 (8)	−0.0053 (7)	0.0064 (6)	−0.0040 (7)
C8	0.0319 (9)	0.0351 (10)	0.0331 (9)	−0.0054 (8)	0.0072 (7)	0.0005 (8)
C9	0.0395 (10)	0.0479 (12)	0.0366 (10)	−0.0109 (9)	0.0135 (8)	0.0021 (9)
C10	0.0368 (10)	0.0531 (13)	0.0404 (11)	−0.0106 (9)	0.0173 (9)	−0.0088 (10)
C11	0.0304 (9)	0.0418 (11)	0.0426 (11)	−0.0044 (8)	0.0122 (8)	−0.0118 (9)
C12	0.0296 (9)	0.0313 (9)	0.0329 (9)	−0.0019 (7)	0.0083 (7)	−0.0033 (8)
C13	0.0279 (8)	0.0239 (8)	0.0286 (8)	−0.0032 (6)	0.0089 (7)	−0.0008 (7)
C14	0.0276 (8)	0.0259 (8)	0.0278 (8)	−0.0031 (7)	0.0067 (7)	−0.0011 (7)
C15	0.0308 (8)	0.0283 (9)	0.0312 (9)	0.0005 (7)	0.0105 (7)	0.0018 (7)
C16	0.0300 (9)	0.0356 (10)	0.0273 (9)	−0.0003 (7)	0.0047 (7)	0.0052 (7)
C17	0.0347 (9)	0.0368 (10)	0.0269 (9)	−0.0047 (8)	0.0063 (7)	−0.0033 (8)
C18	0.0342 (9)	0.0280 (9)	0.0290 (9)	−0.0020 (7)	0.0106 (7)	−0.0030 (7)
C19	0.0529 (13)	0.0586 (15)	0.0408 (12)	0.0229 (12)	0.0002 (10)	0.0033 (11)
C20	0.0264 (8)	0.0245 (8)	0.0280 (8)	0.0024 (7)	0.0054 (6)	0.0005 (7)

Geometric parameters (Å, º) top

O1—C2	1.214 (2)	C8—H8	0.9500
O2—C16	1.375 (2)	C9—C10	1.385 (3)
O2—C19	1.434 (3)	C9—H9	0.9500
N1—C2	1.390 (2)	C10—C11	1.379 (3)
N1—C6	1.410 (2)	C10—H10	0.9500
N1—C7	1.443 (2)	C11—C12	1.390 (3)
N2—C20	1.156 (2)	C11—H11	0.9500
N3—C6	1.346 (2)	C12—H12	0.9500
N3—H3C	0.91 (2)	C13—C14	1.387 (2)
N3—H3D	0.91 (2)	C13—C18	1.398 (3)
C2—C3	1.507 (2)	C14—C15	1.391 (3)
C3—C4	1.530 (2)	C14—H14	0.9500
C3—H3A	0.9900	C15—C16	1.383 (3)
C3—H3B	0.9900	C15—H15	0.9500
C4—C5	1.508 (2)	C16—C17	1.395 (3)
C4—C13	1.529 (2)	C17—C18	1.381 (3)
C4—H4	1.0000	C17—H17	0.9500
C5—C6	1.365 (2)	C18—H18	0.9500
C5—C20	1.410 (2)	C19—H19A	0.9800
C7—C8	1.383 (3)	C19—H19B	0.9800
C7—C12	1.389 (3)	C19—H19C	0.9800
C8—C9	1.386 (3)

C16—O2—C19	116.44 (16)	C8—C9—H9	119.7
C2—N1—C6	121.62 (15)	C11—C10—C9	120.19 (19)
C2—N1—C7	118.78 (14)	C11—C10—H10	119.9
C6—N1—C7	119.55 (14)	C9—C10—H10	119.9
C6—N3—H3C	122.5 (15)	C10—C11—C12	119.9 (2)
C6—N3—H3D	117.7 (15)	C10—C11—H11	120.0
H3C—N3—H3D	118 (2)	C12—C11—H11	120.0
O1—C2—N1	121.14 (16)	C7—C12—C11	119.35 (19)
O1—C2—C3	122.71 (16)	C7—C12—H12	120.3
N1—C2—C3	116.16 (15)	C11—C12—H12	120.3
C2—C3—C4	111.53 (14)	C14—C13—C18	117.78 (17)
C2—C3—H3A	109.3	C14—C13—C4	121.64 (16)
C4—C3—H3A	109.3	C18—C13—C4	120.58 (16)
C2—C3—H3B	109.3	C13—C14—C15	122.01 (17)
C4—C3—H3B	109.3	C13—C14—H14	119.0
H3A—C3—H3B	108.0	C15—C14—H14	119.0
C5—C4—C13	114.33 (15)	C16—C15—C14	119.18 (17)
C5—C4—C3	106.59 (15)	C16—C15—H15	120.4
C13—C4—C3	111.84 (14)	C14—C15—H15	120.4
C5—C4—H4	108.0	O2—C16—C15	123.92 (18)
C13—C4—H4	108.0	O2—C16—C17	116.22 (17)
C3—C4—H4	108.0	C15—C16—C17	119.86 (17)
C6—C5—C20	119.33 (16)	C18—C17—C16	120.13 (17)
C6—C5—C4	120.46 (15)	C18—C17—H17	119.9
C20—C5—C4	120.21 (16)	C16—C17—H17	119.9
N3—C6—C5	124.45 (16)	C17—C18—C13	121.01 (18)
N3—C6—N1	116.48 (16)	C17—C18—H18	119.5
C5—C6—N1	119.07 (16)	C13—C18—H18	119.5
C8—C7—C12	121.01 (17)	O2—C19—H19A	109.5
C8—C7—N1	120.29 (17)	O2—C19—H19B	109.5
C12—C7—N1	118.68 (16)	H19A—C19—H19B	109.5
C7—C8—C9	118.95 (19)	O2—C19—H19C	109.5
C7—C8—H8	120.5	H19A—C19—H19C	109.5
C9—C8—H8	120.5	H19B—C19—H19C	109.5
C10—C9—C8	120.5 (2)	N2—C20—C5	178.6 (2)
C10—C9—H9	119.7

C6—N1—C2—O1	−177.75 (16)	C12—C7—C8—C9	−0.9 (3)
C7—N1—C2—O1	4.8 (3)	N1—C7—C8—C9	177.59 (17)
C6—N1—C2—C3	2.1 (2)	C7—C8—C9—C10	1.5 (3)
C7—N1—C2—C3	−175.40 (15)	C8—C9—C10—C11	−0.8 (3)
O1—C2—C3—C4	−143.36 (18)	C9—C10—C11—C12	−0.6 (3)
N1—C2—C3—C4	36.8 (2)	C8—C7—C12—C11	−0.4 (3)
C2—C3—C4—C5	−54.71 (18)	N1—C7—C12—C11	−178.91 (16)
C2—C3—C4—C13	70.92 (19)	C10—C11—C12—C7	1.1 (3)
C13—C4—C5—C6	−84.4 (2)	C5—C4—C13—C14	7.1 (2)
C3—C4—C5—C6	39.7 (2)	C3—C4—C13—C14	−114.15 (18)
C13—C4—C5—C20	95.23 (19)	C5—C4—C13—C18	−172.53 (16)
C3—C4—C5—C20	−140.67 (16)	C3—C4—C13—C18	66.2 (2)
C20—C5—C6—N3	−2.7 (3)	C18—C13—C14—C15	1.7 (3)
C4—C5—C6—N3	176.95 (17)	C4—C13—C14—C15	−177.99 (16)
C20—C5—C6—N1	177.30 (15)	C13—C14—C15—C16	−1.4 (3)
C4—C5—C6—N1	−3.1 (2)	C19—O2—C16—C15	−5.2 (3)
C2—N1—C6—N3	159.46 (16)	C19—O2—C16—C17	174.22 (19)
C7—N1—C6—N3	−23.1 (2)	C14—C15—C16—O2	179.53 (17)
C2—N1—C6—C5	−20.5 (2)	C14—C15—C16—C17	0.1 (3)
C7—N1—C6—C5	156.97 (16)	O2—C16—C17—C18	−178.57 (17)
C2—N1—C7—C8	−57.2 (2)	C15—C16—C17—C18	0.9 (3)
C6—N1—C7—C8	125.25 (18)	C16—C17—C18—C13	−0.6 (3)
C2—N1—C7—C12	121.29 (18)	C14—C13—C18—C17	−0.6 (3)
C6—N1—C7—C12	−56.3 (2)	C4—C13—C18—C17	179.03 (17)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C13–C18 benzene ring of the methoxyphenyl group.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N2ⁱ	0.91 (2)	2.10 (2)	2.996 (2)	166 (2)
N3—H3D···O2ⁱⁱ	0.91 (2)	2.48 (2)	3.152 (2)	131.0 (19)
C11—H11···O1ⁱⁱⁱ	0.95	2.55	3.210 (3)	127
C14—H14···O1^iv	0.95	2.48	3.199 (2)	133
C10—H10···Cg3ⁱⁱⁱ	0.95	2.99	3.813 (3)	146
C18—H18···Cg3^v	0.95	2.87	3.716 (2)	150

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

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

Contact	Distance	Symmetry operation
O1···H14	2.48	x, 1 + y, z
H11···O1	2.55	1 - x, 1 - y, 1 - z
N2···H17	2.70	1/2 - x, -1/2 + y, 3/2 - z
O2···H3D	2.48 (2)	1/2 + x, 1/2 - y, 1/2 + z
H3C···N2	2.10 (3)	-x, -y, 1 - z
C20···C6	3.318 (3)	-x, 1 - y, 1 - z

Acknowledgements

Authors' contributions are as follows. Conceptualization, KAA and EZH; methodology, EZH and KAA; investigation, KAA, MA and EVD; writing (original draft), MA and KAA; writing (review and editing of the manuscript), MA and EZH; visualization, MA, EZH and KAA; funding acquisition, VNK, ATH and AAA; resources, AAA, VNK and KAA; supervision, KAA and MA.

Funding information

This work was supported by the Baku State University and the Ministry of Science and Higher Education of the Russian Federation.

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