Crystal structure and Hirshfeld surface analysis of 5,7-diphenyl-1,2,3,5,6,7-hexa­hydro­imidazo[1,2-a]pyridine-6,6,8-tricarbo­nitrile methanol mono­solvate

Naghiyev, F.N.; Mammadova, G.Z.; Khalilov, A.N.; Atioğlu, Z.; Akkurt, M.; Akobirshoeva, A.A.; Mamedov, İ.G.

doi:10.1107/S2056989021004655

research communications

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ISSN: 2056-9890

Volume 77| Part 6| June 2021| Pages 600-604

https://doi.org/10.1107/S2056989021004655

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Crystal structure and Hirshfeld surface analysis of 5,7-diphenyl-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-6,6,8-tricarbonitrile methanol monosolvate

Farid N. Naghiyev,^a Gunay Z. Mammadova,^a Ali N. Khalilov,^a,^b Zeliha Atioğlu,^c Mehmet Akkurt,^d Anzurat A. Akobirshoeva ^e ^* and İbrahim G. Mamedov ^a

^aDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, Az, 1148 Baku, Azerbaijan, ^b"Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), H. Aliyev str. 135, Az 1063, Baku, Azerbaijan, ^cDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Turkey, ^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 21 April 2021; accepted 2 May 2021; online 11 May 2021)

In the title compound, C₂₂H₁₇N₅·CH₄O, the imidazolidine ring of the 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine ring system is a twisted envelope, while the 1,2,3,4-tetrahydropyridine ring adopts a twisted boat conformation. In the crystal, pairs of molecules are linked by O—H⋯N and N—H⋯O hydrogen bonds via two methanol molecules, forming a centrosymmetric R⁴₄(16) ring motif. These motifs are connected to each other by C—H⋯N hydrogen bonds and form columns along the a axis. The columns form a stable molecular packing, being connected to each other by van der Waals interactions. A Hirshfeld surface analysis indicates that the most significant contributions to the crystal packing are from H⋯H (43.8%), N⋯H/H⋯N (31.7%) and C⋯H/H⋯C (18.4%) contacts.

Keywords: crystal structure; imidazolidine ring; pyridine ring; hydrogen bond; Hirshfeld surface analysis.

CCDC reference: 2081515

1. Chemical context

Having a great methodological diversity, C—C and C—X (where X is a heteroatom) bond-forming reactions lie at the heart of synthetic organic chemistry (Khalilov et al., 2018a ,b ; Maharramov et al., 2019 ; Cheng & Mankad, 2020 ). They allow the construction of complex molecular structures and the introduction of various substituents. Nowadays, researchers are constantly trying to develop new methods in these directions for the syntheses of structurally diverse valuable molecular entities. These approaches have successfully found application in the building of carbo- and heterocyclic ring systems (Naghiyev et al., 2020 ; Mamedov et al., 2019 ). In heterocyclic ring systems, the use of nitrogen as a bridgehead atom is being assessed widely. Bridgehead nitrogen heterocycles incorporating an imidazole ring are widespread structural motifs in a diverse range of compounds having application in medicinal chemistry, coordination chemistry, catalysis and materials science (Asadov et al., 2016 ; Ma et al., 2017a ,b , 2020 , 2021 ; Maharramov et al., 2010 , 2018 ; Mahmoudi et al., 2017 , 2019 ; Mahmudov et al., 2019 , 2020 ). Various synthetic drugs, such as soraprazan, alpidem, olprinone, saripidem, necopidem, minodronic acid, zolimidine and zolpidem containing the imidazo[1,2-a]pyridine moiety (Fig. 1) have already been used in medical practice (Hosseini & Bayat, 2018 ).

Figure 1
Drugs containing the imidazo[1,2-a]pyridine motif.

In the framework of our ongoing structural studies (Naghiyev et al., 2021 ), herein we report the crystal structure and Hirshfeld surface analysis of the title compound, 5,7-diphenyl-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-6,6,8-tricarbonitrile methanol monosolvate.

2. Structural commentary

In the title compound, (Fig. 2), the imidazolidine ring (N1/N2/C1–C3) of the 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine ring system (N1/N2/C1–C7) is a twisted envelope [with puckering parameters (Cremer & Pople, 1975 ) Q(2) = 0.2844 (16) Å and φ(2) = 226.3 (3)°], while the 1,2,3,4-tetrahydropyridine ring (N1/C3–C7) adopts a twisted boat conformation with Q_T = 0.5368 (14) Å, θ = 135.38 (15)°, φ = 82.6 (2)°. The C9–C14 and C17–C22 phenyl rings, which are attached to C5 and C7, respectively, are in equatorial positions (Fig. 2) and make dihedral angles of 64.00 (7) and 65.90 (7)°, respectively, with the mean plane of the 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine ring system. The dihedral angle between the phenyl rings is 61.43 (8)°. The molecular conformation of the title compound is stabilized by an N2—H2N⋯O1 hydrogen bond (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—HO1⋯N3ⁱ	0.92 (3)	2.02 (3)	2.907 (2)	161 (2)
N2—H2N⋯O1	0.887 (18)	2.004 (18)	2.870 (2)	165.0 (16)
C7—H7⋯N3ⁱⁱ	0.98	2.52	3.3742 (19)	146
Symmetry codes: (i) ; (ii) .

Figure 2
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a N—H⋯O hydrogen bond.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, pairs of molecules are linked by O—H⋯N, C—H⋯N and N—H⋯O hydrogen bonds via two methanol molecules, forming a centrosymmetric R₄⁴(16) ring motif (Bernstein et al., 1995 ; Table 1; Fig. 3). These motifs are connected to each other by C—H⋯N hydrogen bonds and form columns along the a-axis direction (Figs. 4 and 5). The columns form a stable molecular packing, being connected to each other by van der Waals interactions.

Figure 3
Details of the O—H⋯N, C—H⋯N and N—H⋯O hydrogen bonds (dashed lines) in the unit cell of the title compound. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 1.]

Figure 4
A view along the a axis of the columns that are formed by the O—H⋯N, C—H⋯N and N—H⋯O hydrogen bonds (dashed lines) in the title compound. H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 5
A part of view along the b axis of the columns shown in Fig. 4

. H atoms not involved in hydrogen bonding have been omitted for clarity. Dashed lines indicate hydrogen bonds.

To further investigate and visualize the intermolecular interactions of the title compound, the CrystalExplorer program (Turner et al., 2017 ) was used. The interactions between the corresponding donor and acceptor atoms are visualized as bright-red spots on the Hirshfeld surface mapped over d_norm (Fig. 6), corresponding to O1—HO1⋯N3, C7—H7⋯N3 and N2—H2N⋯O1 hydrogen bonds. The other red spots correspond to weaker van der Waals interactions, of which the details are listed in Table 2.

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

Contact	Distance	Symmetry operation
H2N⋯O1	2.00	x, y, z
H7⋯N3	2.52	1 − x, 1 − y, 1 − z
N3⋯H18	2.75	−1 + x, y, z
N3⋯HO1	2.02	−x, 1 − y, 1 − z
N5⋯H1B	2.75	− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
N5⋯H23B	2.77	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
H12⋯H12	2.54	−x, 1 − y, −z
C20⋯H2B	3.02	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
H5⋯O1	2.79	1 − x, 1 − y, 1 − z
H12⋯C23	3.07	x, y, −1 + z

Figure 6
The three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.5585 to +1.5646 a.u. The O—H⋯N, C—H⋯O and N—H⋯O hydrogen bonds are shown as dashed lines.

The overall two-dimensional fingerprint plot of the title structure and H⋯H, N⋯H/H⋯N and C⋯H/H⋯C contacts are illustrated in Fig. 7a–d). The greatest contribution to the overall Hirshfeld surface results from H⋯H contacts with a 43.8% contribution (Fig. 7b). The relative contributions of the other interactions in descending order are: N⋯H/H⋯N (31.7%), C⋯H/H⋯C (18.4%), O⋯H/H⋯O (2.6%), C⋯C (2.4%), N⋯O/O⋯N (0.1%) and C⋯O/O⋯C (0.1%). The large contributions of H⋯H, N⋯H/H⋯N and C⋯H/H⋯C interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

Figure 7
The two-dimensional fingerprint plots of the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) N⋯H/H⋯N, and (d) C⋯H/H⋯C 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 survey of the Cambridge Structural Database (CSD version 5.41, update of March 2020; Groom et al., 2016 ) reveals two related compounds having the 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine ring system of the title compound: ethyl 8-benzoyl-5-oxo-7-phenyl-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-6-carboxylate (refcode ADETUZ; Yu et al., 2006 ) and 1-[(6-chloropyridin-3-yl)methyl]-5-ethoxy-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine (BUDZAC; Tian et al., 2009 ).

In ADETUZ, the six-membered ring adopts a twist-boat conformation. The molecules form dimeric associations via inversion-generated pairs of N—H⋯O hydrogen bonds. In BUDZAC, the fused pyridine ring adopts a twisted sofa conformation. The molecular structure features close intramolecular C—H⋯N and C—H⋯O hydrogen bonding.

5. Synthesis and crystallization

To a solution of benzylidenemalononitrile (0.78 g; 5.1 mmol) in ethanol (30 mL), ethylenediamine (0.31 g; 5.2 mmol) was added and the mixture was refluxed for 7 h. Then 25 mL of ethanol were removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from methanol (yield 47%; m.p. 443–444 K).

¹H NMR (300 MHz, DMSO-d₆): 3.18 (t, 2H, NCH₂); 3.42 (t, 2H, NCH₂); 4.79 (s, 1H, CH-Ar); 5.19 (s, 1H, CH-Ar); 7.41–7.58 (m, 10H, 10Ar-H); 7.70 (s, 1H, NH).¹³C NMR (75 MHz, DMSO-d₆): 42.04 (NCH₂), 47.67 (CH-Ar), 48.41 (C_quart), 48.64 (=C_quart), 49.05 (NCH₂), 63.46 (CH-Ar), 112.91 (CN), 113.69 (CN), 121.24 (CN), 129.03 (4CH_arom), 129.42 (2CH_arom), 129.72 (CH_arom), 129.96 (2CH_arom), 130.85 (CH_arom), 133.25 (C_arom),135.90 (C_ar.), 162.08 (=C_quart).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and refined as riding with U_iso(H) = 1.2 or 1.5U_eq(C). The H atoms of the amine and hydroxyl groups were located in a difference map [N2—H2N = 0.887 (18) Å and O1—HO1 = 0.92 (3) Å] and were refined with the constraint U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	C₂₂H₁₇N₅·CH₄O
M_r	383.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.5517 (10), 18.781 (2), 13.1925 (14)
β (°)	99.757 (4)
V (Å³)	2088.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.28 × 0.26 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	33652, 4239, 3656
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.123, 1.03
No. of reflections	4239
No. of parameters	269
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23
Computer programs: APEX2 (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: 2081515

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989021004655/vm2248sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021004655/vm2248Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021004655/vm2248Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (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).

5,7-Diphenyl-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-6,6,8-tricarbonitrile methanol monosolvate top

Crystal data top

C₂₂H₁₇N₅·CH₄O	F(000) = 808
M_r = 383.45	D_x = 1.220 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9885 reflections
a = 8.5517 (10) Å	θ = 3.1–26.4°
b = 18.781 (2) Å	µ = 0.08 mm⁻¹
c = 13.1925 (14) Å	T = 296 K
β = 99.757 (4)°	Block, colourless
V = 2088.2 (4) Å³	0.28 × 0.26 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.033
φ and ω scans	θ_max = 26.4°, θ_min = 2.7°
33652 measured reflections	h = −10→10
4239 independent reflections	k = −23→23
3656 reflections with I > 2σ(I)	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0553P)² + 0.5899P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
4239 reflections	Δρ_max = 0.31 e Å⁻³
269 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.60712 (14)	0.34477 (6)	0.50461 (8)	0.0455 (3)
N2	0.42807 (17)	0.38674 (7)	0.59278 (9)	0.0554 (4)
N3	0.16518 (16)	0.50048 (7)	0.42172 (10)	0.0564 (4)
N4	0.77545 (19)	0.37704 (11)	0.17841 (12)	0.0818 (7)
N5	0.43619 (17)	0.24442 (8)	0.29156 (13)	0.0687 (5)
C1	0.6680 (2)	0.32722 (10)	0.61313 (11)	0.0610 (5)
O1	0.15621 (16)	0.45171 (9)	0.65565 (10)	0.0796 (5)
C2	0.5187 (2)	0.33436 (11)	0.66018 (13)	0.0728 (6)
C3	0.47744 (16)	0.38817 (7)	0.50125 (10)	0.0416 (4)
C4	0.41241 (15)	0.42550 (7)	0.41462 (9)	0.0400 (4)
C5	0.49374 (15)	0.42867 (7)	0.32123 (9)	0.0400 (3)
C6	0.60291 (14)	0.36144 (7)	0.32248 (9)	0.0396 (4)
C7	0.71275 (15)	0.35675 (7)	0.43062 (10)	0.0406 (3)
C8	0.27705 (16)	0.46706 (7)	0.41791 (10)	0.0430 (4)
C9	0.38002 (16)	0.43787 (7)	0.22050 (10)	0.0435 (4)
C10	0.24007 (17)	0.39947 (9)	0.19806 (11)	0.0529 (5)
C11	0.14001 (19)	0.40923 (12)	0.10485 (13)	0.0698 (6)
C12	0.1790 (2)	0.45789 (13)	0.03484 (12)	0.0768 (7)
C13	0.3160 (3)	0.49685 (11)	0.05680 (13)	0.0726 (7)
C14	0.4164 (2)	0.48700 (9)	0.14907 (12)	0.0567 (5)
C15	0.70149 (17)	0.36934 (9)	0.24146 (11)	0.0519 (4)
C16	0.50897 (16)	0.29533 (7)	0.30346 (11)	0.0456 (4)
C17	0.84126 (15)	0.30107 (7)	0.43683 (10)	0.0422 (4)
C18	0.99408 (17)	0.32313 (8)	0.43065 (13)	0.0555 (5)
C19	1.11587 (18)	0.27445 (10)	0.43609 (15)	0.0650 (6)
C20	1.08799 (19)	0.20309 (9)	0.44872 (14)	0.0622 (6)
C21	0.93680 (19)	0.18065 (8)	0.45511 (14)	0.0615 (5)
C22	0.81374 (17)	0.22886 (8)	0.44866 (12)	0.0519 (4)
C23	0.1184 (3)	0.4273 (2)	0.74675 (18)	0.1210 (12)
H1A	0.74920	0.36056	0.64351	0.0730*
H1B	0.71018	0.27920	0.62033	0.0730*
H2A	0.46245	0.28943	0.65878	0.0870*
H2B	0.54270	0.35144	0.73049	0.0870*
H2N	0.334 (2)	0.4024 (10)	0.6028 (14)	0.0660*
H5	0.56337	0.47045	0.32956	0.0480*
H7	0.76386	0.40317	0.44550	0.0490*
H10	0.21323	0.36709	0.24562	0.0640*
H11	0.04673	0.38302	0.08952	0.0840*
H12	0.11175	0.46428	−0.02770	0.0920*
H13	0.34110	0.52988	0.00955	0.0870*
H14	0.50947	0.51345	0.16372	0.0680*
H18	1.01463	0.37126	0.42275	0.0670*
H19	1.21761	0.28995	0.43119	0.0780*
H20	1.17047	0.17038	0.45289	0.0750*
H21	0.91735	0.13251	0.46387	0.0740*
H22	0.71184	0.21295	0.45224	0.0620*
HO1	0.061 (3)	0.4657 (15)	0.617 (2)	0.1190*
H23A	0.21254	0.42549	0.79796	0.1810*
H23B	0.07336	0.38048	0.73674	0.1810*
H23C	0.04282	0.45890	0.76915	0.1810*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0484 (6)	0.0509 (6)	0.0359 (6)	0.0044 (5)	0.0037 (5)	0.0042 (5)
N2	0.0646 (8)	0.0647 (8)	0.0388 (6)	0.0088 (6)	0.0142 (6)	0.0043 (5)
N3	0.0557 (7)	0.0551 (7)	0.0591 (8)	0.0089 (6)	0.0120 (6)	−0.0015 (6)
N4	0.0656 (9)	0.1250 (15)	0.0605 (9)	0.0014 (9)	0.0267 (8)	0.0042 (9)
N5	0.0602 (8)	0.0552 (8)	0.0845 (10)	−0.0080 (7)	−0.0053 (7)	−0.0160 (7)
C1	0.0707 (10)	0.0703 (10)	0.0390 (7)	0.0103 (8)	0.0004 (7)	0.0099 (7)
O1	0.0639 (7)	0.1204 (12)	0.0577 (7)	0.0139 (8)	0.0191 (6)	0.0105 (7)
C2	0.0933 (13)	0.0838 (12)	0.0428 (8)	0.0176 (10)	0.0161 (8)	0.0159 (8)
C3	0.0469 (7)	0.0407 (6)	0.0369 (6)	−0.0037 (5)	0.0067 (5)	−0.0032 (5)
C4	0.0432 (7)	0.0391 (6)	0.0373 (6)	−0.0009 (5)	0.0057 (5)	−0.0018 (5)
C5	0.0414 (6)	0.0390 (6)	0.0396 (6)	−0.0032 (5)	0.0067 (5)	0.0017 (5)
C6	0.0377 (6)	0.0438 (7)	0.0370 (6)	−0.0019 (5)	0.0051 (5)	−0.0007 (5)
C7	0.0397 (6)	0.0399 (6)	0.0400 (6)	−0.0044 (5)	0.0009 (5)	−0.0008 (5)
C8	0.0499 (7)	0.0397 (7)	0.0393 (6)	−0.0026 (6)	0.0076 (5)	−0.0017 (5)
C9	0.0451 (7)	0.0480 (7)	0.0381 (6)	0.0099 (6)	0.0095 (5)	0.0036 (5)
C10	0.0431 (7)	0.0721 (10)	0.0434 (7)	0.0063 (7)	0.0067 (6)	0.0015 (7)
C11	0.0436 (8)	0.1130 (15)	0.0509 (9)	0.0185 (9)	0.0027 (7)	−0.0113 (9)
C12	0.0699 (11)	0.1208 (16)	0.0386 (8)	0.0531 (12)	0.0064 (7)	0.0081 (9)
C13	0.0874 (13)	0.0836 (12)	0.0502 (9)	0.0394 (11)	0.0218 (9)	0.0238 (8)
C14	0.0666 (9)	0.0564 (9)	0.0501 (8)	0.0135 (7)	0.0182 (7)	0.0125 (7)
C15	0.0445 (7)	0.0657 (9)	0.0455 (7)	0.0031 (6)	0.0076 (6)	0.0017 (6)
C16	0.0407 (7)	0.0467 (7)	0.0466 (7)	0.0017 (6)	−0.0004 (5)	−0.0075 (6)
C17	0.0387 (6)	0.0444 (7)	0.0412 (7)	−0.0035 (5)	−0.0002 (5)	−0.0002 (5)
C18	0.0436 (7)	0.0490 (8)	0.0716 (10)	−0.0085 (6)	0.0034 (7)	0.0044 (7)
C19	0.0385 (7)	0.0712 (11)	0.0841 (12)	−0.0037 (7)	0.0074 (7)	0.0060 (9)
C20	0.0488 (8)	0.0629 (10)	0.0731 (11)	0.0106 (7)	0.0052 (7)	0.0055 (8)
C21	0.0582 (9)	0.0453 (8)	0.0798 (11)	0.0022 (7)	0.0080 (8)	0.0084 (7)
C22	0.0418 (7)	0.0462 (7)	0.0663 (9)	−0.0052 (6)	0.0053 (6)	0.0051 (6)
C23	0.0825 (15)	0.205 (3)	0.0758 (14)	−0.0012 (18)	0.0142 (12)	0.0563 (18)

Geometric parameters (Å, º) top

N1—C1	1.4754 (18)	C17—C22	1.390 (2)
N1—C3	1.3710 (18)	C17—C18	1.387 (2)
N1—C7	1.4554 (17)	C18—C19	1.379 (2)
N2—C2	1.458 (2)	C19—C20	1.376 (3)
N2—C3	1.3453 (18)	C20—C21	1.376 (2)
N3—C8	1.1524 (19)	C21—C22	1.380 (2)
N4—C15	1.136 (2)	C1—H1A	0.9700
N5—C16	1.137 (2)	O1—HO1	0.92 (3)
C1—C2	1.517 (2)	C1—H1B	0.9700
O1—C23	1.375 (3)	C2—H2A	0.9700
N2—H2N	0.887 (18)	C2—H2B	0.9700
C3—C4	1.3753 (18)	C5—H5	0.9800
C4—C8	1.4029 (19)	C7—H7	0.9800
C4—C5	1.5151 (17)	C10—H10	0.9300
C5—C6	1.5687 (18)	C11—H11	0.9300
C5—C9	1.5177 (18)	C12—H12	0.9300
C6—C7	1.5720 (18)	C13—H13	0.9300
C6—C16	1.4770 (19)	C14—H14	0.9300
C6—C15	1.4767 (19)	C18—H18	0.9300
C7—C17	1.5091 (19)	C19—H19	0.9300
C9—C14	1.391 (2)	C20—H20	0.9300
C9—C10	1.386 (2)	C21—H21	0.9300
C10—C11	1.386 (2)	C22—H22	0.9300
C11—C12	1.380 (3)	C23—H23A	0.9600
C12—C13	1.370 (3)	C23—H23B	0.9600
C13—C14	1.378 (3)	C23—H23C	0.9600

C1—N1—C3	108.34 (11)	C17—C22—C21	120.35 (14)
C1—N1—C7	121.89 (12)	N1—C1—H1A	112.00
C3—N1—C7	118.49 (11)	N1—C1—H1B	112.00
C2—N2—C3	110.22 (13)	C2—C1—H1A	112.00
N1—C1—C2	101.20 (13)	C2—C1—H1B	112.00
N2—C2—C1	101.97 (14)	H1A—C1—H1B	109.00
C3—N2—H2N	123.9 (12)	C23—O1—HO1	105.2 (17)
C2—N2—H2N	122.3 (12)	N2—C2—H2B	111.00
N1—C3—C4	122.75 (12)	C1—C2—H2A	111.00
N2—C3—C4	127.72 (13)	C1—C2—H2B	111.00
N1—C3—N2	109.53 (12)	H2A—C2—H2B	109.00
C5—C4—C8	119.88 (11)	N2—C2—H2A	111.00
C3—C4—C5	121.27 (12)	C4—C5—H5	107.00
C3—C4—C8	118.52 (12)	C9—C5—H5	107.00
C6—C5—C9	113.12 (10)	C6—C5—H5	107.00
C4—C5—C9	113.71 (11)	N1—C7—H7	108.00
C4—C5—C6	108.31 (10)	C17—C7—H7	108.00
C5—C6—C15	108.86 (11)	C6—C7—H7	108.00
C5—C6—C16	111.67 (10)	C9—C10—H10	120.00
C7—C6—C16	109.34 (11)	C11—C10—H10	120.00
C15—C6—C16	108.80 (11)	C12—C11—H11	120.00
C7—C6—C15	109.63 (11)	C10—C11—H11	120.00
C5—C6—C7	108.52 (10)	C11—C12—H12	120.00
C6—C7—C17	113.94 (11)	C13—C12—H12	120.00
N1—C7—C6	105.90 (10)	C14—C13—H13	120.00
N1—C7—C17	112.68 (11)	C12—C13—H13	120.00
N3—C8—C4	178.94 (14)	C9—C14—H14	120.00
C10—C9—C14	118.99 (13)	C13—C14—H14	120.00
C5—C9—C10	122.00 (12)	C19—C18—H18	120.00
C5—C9—C14	119.01 (13)	C17—C18—H18	120.00
C9—C10—C11	120.11 (15)	C18—C19—H19	120.00
C10—C11—C12	119.91 (16)	C20—C19—H19	120.00
C11—C12—C13	120.48 (16)	C21—C20—H20	120.00
C12—C13—C14	119.84 (18)	C19—C20—H20	120.00
C9—C14—C13	120.66 (17)	C20—C21—H21	120.00
N4—C15—C6	178.24 (18)	C22—C21—H21	120.00
N5—C16—C6	178.13 (16)	C17—C22—H22	120.00
C7—C17—C18	118.34 (12)	C21—C22—H22	120.00
C18—C17—C22	118.52 (13)	O1—C23—H23A	109.00
C7—C17—C22	123.14 (12)	O1—C23—H23B	109.00
C17—C18—C19	120.67 (14)	O1—C23—H23C	109.00
C18—C19—C20	120.48 (15)	H23A—C23—H23B	109.00
C19—C20—C21	119.31 (15)	H23A—C23—H23C	109.00
C20—C21—C22	120.66 (14)	H23B—C23—H23C	109.00

C3—N1—C1—C2	26.59 (16)	C9—C5—C6—C7	−179.03 (10)
C7—N1—C1—C2	169.55 (13)	C9—C5—C6—C15	61.71 (14)
C7—N1—C3—N2	−158.46 (12)	C4—C5—C6—C15	−171.28 (11)
C1—N1—C7—C6	171.10 (12)	C16—C6—C7—N1	−57.45 (13)
C1—N1—C3—N2	−14.05 (16)	C16—C6—C7—C17	66.96 (14)
C3—N1—C7—C17	−174.68 (11)	C15—C6—C7—C17	−52.24 (15)
C1—N1—C3—C4	166.57 (13)	C5—C6—C7—N1	64.58 (12)
C7—N1—C3—C4	22.16 (19)	C5—C6—C7—C17	−171.02 (10)
C1—N1—C7—C17	45.91 (17)	C15—C6—C7—N1	−176.64 (11)
C3—N1—C7—C6	−49.49 (14)	N1—C7—C17—C18	−137.73 (13)
C3—N2—C2—C1	22.03 (17)	N1—C7—C17—C22	42.12 (18)
C2—N2—C3—C4	173.60 (14)	C6—C7—C17—C18	101.58 (15)
C2—N2—C3—N1	−5.74 (17)	C6—C7—C17—C22	−78.57 (16)
N1—C1—C2—N2	−28.10 (16)	C5—C9—C10—C11	−179.63 (15)
N1—C3—C4—C5	−8.3 (2)	C14—C9—C10—C11	1.2 (2)
N1—C3—C4—C8	178.32 (12)	C5—C9—C14—C13	−179.97 (16)
N2—C3—C4—C5	172.44 (13)	C10—C9—C14—C13	−0.8 (2)
N2—C3—C4—C8	−0.9 (2)	C9—C10—C11—C12	−0.8 (3)
C3—C4—C5—C6	24.53 (16)	C10—C11—C12—C13	−0.1 (3)
C8—C4—C5—C6	−162.18 (11)	C11—C12—C13—C14	0.6 (3)
C8—C4—C5—C9	−35.51 (17)	C12—C13—C14—C9	−0.1 (3)
C3—C4—C5—C9	151.19 (12)	C7—C17—C18—C19	179.89 (15)
C4—C5—C6—C7	−52.02 (13)	C22—C17—C18—C19	0.0 (2)
C9—C5—C6—C16	−58.43 (14)	C7—C17—C22—C21	−179.19 (14)
C4—C5—C9—C10	−43.99 (18)	C18—C17—C22—C21	0.7 (2)
C4—C5—C9—C14	135.18 (14)	C17—C18—C19—C20	−0.6 (3)
C6—C5—C9—C10	80.12 (16)	C18—C19—C20—C21	0.5 (3)
C6—C5—C9—C14	−100.71 (15)	C19—C20—C21—C22	0.2 (3)
C4—C5—C6—C16	68.57 (13)	C20—C21—C22—C17	−0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···N3ⁱ	0.92 (3)	2.02 (3)	2.907 (2)	161 (2)
N2—H2N···O1	0.887 (18)	2.004 (18)	2.870 (2)	165.0 (16)
C7—H7···N3ⁱⁱ	0.98	2.52	3.3742 (19)	146

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

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

Contact	Distance	Symmetry operation
H2N···O1	2.00	x, y, z
H7···N3	2.52	1 - x, 1 - y, 1 - z
N3···H18	2.75	-1 + x, y, z
N3···HO1	2.02	-x, 1 - y, 1 - z
N5···H1B	2.75	-1/2 + x, 1/2 - y, -1/2 + z
N5···H23B	2.77	1/2 + x, 1/2 - y, -1/2 + z
H12···H12	2.54	-x, 1 - y, -z
C20···H2B	3.02	1/2 + x, 1/2 - y, -1/2 + z
H5···O1	2.79	1 - x, 1 - y, 1 - z
H12···C23	3.07	x, y, -1 + z

Acknowledgements

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

Funding information

This work was supported by Baku State University and UNEC Research Program.

References

Asadov, Z. H., Rahimov, R. A., Ahmadova, G. A., Mammadova, K. A. & Gurbanov, A. V. (2016). J. Surfactants Deterg. 19, 145–153. Web of Science CrossRef CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2018). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheng, L.-J. & Mankad, N. P. (2020). Chem. Soc. Rev. 49, 8036–8064. Web of Science CrossRef CAS PubMed Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science 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
Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). IUCrJ, 2, 563–574. Web of Science CSD CrossRef CAS PubMed IUCr Journals Google Scholar
Hosseini, H. & Bayat, M. (2018). RSC Adv. 8, 41218–41225. Web of Science CrossRef CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Maharramov, A. M., Nagiyev, F. N. & Brito, I. (2018a). Z. Kristallogr. NCS 233, 1019–1020. CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Nagiyev, F. N. & Brito, I. (2018b). Z. Kristallogr. New Cryst. Struct. 233, 947–948. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Maharramov, A. M., Guseinov, F. I., Kopylovich, M. N., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2017a). J. Mol. Catal. A Chem. 426, 526–533. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Sutradhar, M., Kopylovich, M. N., Mahmudov, K. T., Maharramov, A. M., Guseinov, F. I., Zubkov, F. I. & Pombeiro, A. J. L. (2017b). Mol. Catal. 428, 17–23. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Coord. Chem. Rev. 437, 213859. Web of Science CrossRef Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 423, 213482. Web of Science CrossRef Google Scholar
Maharramov, A. M., Aliyeva, R. A., Aliyev, I. A., Pashaev, F. G., Gasanov, A. G., Azimova, S. I., Askerov, R. K., Kurbanov, A. V. & Mahmudov, K. T. (2010). Dyes Pigments, 85, 1–6. Web of Science CSD CrossRef CAS Google Scholar
Maharramov, A. M., Duruskari, G. S., Mammadova, G. Z., Khalilov, A. N., Aslanova, J. M., Cisterna, J., Cárdenas, A. & Brito, I. (2019). J. Chil. Chem. Soc. 64, 4441–4447. Web of Science CSD CrossRef CAS Google Scholar
Maharramov, A. M., Shikhaliyev, N. Q., Suleymanova, G. T., Gurbanov, A. V., Babayeva, G. V., Mammadova, G. Z., Zubkov, F. I., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Dyes Pigments, 159, 135–141. Web of Science CrossRef CAS Google Scholar
Mahmoudi, G., Dey, L., Chowdhury, H., Bauzá, A., Ghosh, B. K., Kirillov, A. M., Seth, S. K., Gurbanov, A. V. & Frontera, A. (2017). Inorg. Chim. Acta, 461, 192–205. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Khandar, A. A., Afkhami, F. A., Miroslaw, B., Gurbanov, A. V., Zubkov, F. I., Kennedy, A., Franconetti, A. & Frontera, A. (2019). CrystEngComm, 21, 108–117. Web of Science CSD CrossRef CAS Google Scholar
Mahmudov, K. T., Gurbanov, A. V., Aliyeva, V. A., Resnati, G. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 418, 213381. Web of Science CrossRef Google Scholar
Mahmudov, K. T., Gurbanov, A. V., Guseinov, F. I. & Guedes da Silva, M. F. C. (2019). Coord. Chem. Rev. 387, 32–46. Web of Science CrossRef CAS Google Scholar
Mamedov, I. G., Khrustalev, V. N., Dorovatovskii, P. V., Naghiev, F. N. & Maharramov, A. M. (2019). Mendeleev Commun. 29, 232–233. Web of Science CSD CrossRef CAS Google Scholar
Naghiyev, F. N., Cisterna, J., Khalilov, A. N., Maharramov, A. M., Askerov, R. K., Asadov, K. A., Mamedov, I. G., Salmanli, K. S., Cárdenas, A. & Brito, I. (2020). Molecules, 25, 2235–2248. Web of Science CSD CrossRef CAS Google Scholar
Naghiyev, F. N., Grishina, M. M., Khrustalev, V. N., Khalilov, A. N., Akkurt, M., Akobirshoeva, A. A. & Mamedov, İ. G. (2021). Acta Cryst. E77, 195–199. Web of Science CSD CrossRef IUCr Journals 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
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Tian, Z., Li, D. & Li, Z. (2009). Acta Cryst. E65, o2517. Web of Science 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. Google Scholar
Yu, C.-Y., Yan, S.-J. & Huang, Z.-T. (2006). Acta Cryst. E62, o2731–o2733. Web of Science CSD CrossRef IUCr Journals Google Scholar

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