Crystal structure and Hirshfeld surface analysis of 6-imino-8-(4-methyl­phen­yl)-1,3,4,6-tetra­hydro-2H-pyrido[1,2-a]pyrimidine-7,9-dicarbo­nitrile

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

doi:10.1107/S2056989024002500

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 80| Part 4| April 2024| Pages 378-382

https://doi.org/10.1107/S2056989024002500

Open

access

Crystal structure and Hirshfeld surface analysis of 6-imino-8-(4-methylphenyl)-1,3,4,6-tetrahydro-2H-pyrido[1,2-a]pyrimidine-7,9-dicarbonitrile

Farid N. Naghiyev,^a Victor N. Khrustalev,^b,^c Mehmet Akkurt,^d ^* Ekaterina V. Dobrokhotova,^b Ajaya Bhattarai,^e ^* Ali N. Khalilov ^f,^a 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, Türkiye, ^eDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal, and ^f"Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), H. Aliyev str. 135, Az 1063, Baku, Azerbaijan
^*Correspondence e-mail: akkurt@erciyes.edu.tr, ajaya.bhattarai@mmamc.tu.edu.np

Edited by X. Hao, Institute of Chemistry, Chinese Academy of Sciences (Received 12 March 2024; accepted 15 March 2024; online 21 March 2024)

In the ten-membered 1,3,4,6-tetrahydro-2H-pyrido[1,2-a]pyrimidine ring system of the title compound, C₁₇H₁₅N₅, the 1,2-dihydropyridine ring is essentially planar (r.m.s. deviation = 0.001 Å), while the 1,3-diazinane ring has a distorted twist-boat conformation. In the crystal, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds, forming a three-dimensional network. In addition, C—H⋯π interactions form layers parallel to the (100) plane. Thus, crystal-structure cohesion is ensured. According to a Hirshfeld surface study, H⋯H (40.4%), N⋯H/H⋯N (28.6%) and C⋯H/H⋯C (24.1%) interactions are the most important contributors to the crystal packing.

Keywords: crystal structure; 1,2-dihydropyridine ring; 1,3-diazinane ring; hydrogen bonds; C–H⋯π interactions; Hirshfeld surface analysis.

CCDC reference: 2340712

1. Chemical context

Heterocyclic compounds are crucial systems, both in terms of frequency of occurrence and consequential importance in different fields (Khalilov et al., 2022 ; Akkurt et al., 2023 ). Heterocyclic systems comprise all nucleic acids, alkaloids, vitamins, sugars, hormones, antibiotics, other drugs, dyes, pesticides, and herbicides. There have been major developments in organic chemistry in recent years with recently developed heterocyclic systems for various research and commercial aims, especially in the pharmaceutical and chemical industries (Maharramov et al., 2022 ; Erenler et al., 2022 ). These compounds have found widespread applications in multiple branches of science, such as coordination chemistry (Gurbanov et al., 2021 ; Mahmoudi et al., 2021 ), medicinal chemistry (Askerova, 2022 ) and materials chemistry (Velásquez et al., 2019 ; Afkhami et al., 2019 ). Pyrido[1,2-a]pyrimidines are simple bicyclic ring systems that contain a nitrogen-bridgehead condensed pyrimidine motif. These derivatives are used for a large range of applications, as well as drugs, ligands, catalysts, materials, etc (Maharramov et al., 2021 , Sobhi & Faisal, 2023 ). Functionalized pyrido[1,2-a]pyrimidines exhibit various biological activities, such as anticancer, antioxidant, cytotoxic, anti-inflammatory, herbicidal, pesticidal, antibacterial (Atalay et al., 2022 ; Donmez & Turkyılmaz, 2022 ). In medical practice, pyrido[1,2-a]pyrimidines are used as tranquilizers, anti-ulcerative agents, antiallergics, anti-asthmatics, analgesics, antipsychotics, protective gastrointestinal, neurotropic, stress-protecting compounds, and anti-HIV agents (Elattar et al., 2017 ). As a result of the wide application of these systems, the efficient and regioselective development of pyrido[1,2-a]pyrimidines has attracted a lot of attention. Thus, in the framework of our studies in heterocyclic chemistry (Naghiyev et al., 2020 , 2021 , 2022 ), herein we report the crystal structure and Hirshfeld surface analysis of the title compound, 6-imino-8-(4-methylphenyl)-1,3,4,6-tetrahydro-2H-pyrido[1,2-a]pyrimidine-7,9-dicarbonitrile.

2. Structural commentary

As seen in Fig. 1, in the ten-membered 1,3,4,6-tetrahydro-2H-pyrido[1,2-a]pyrimidine ring system (N1/N5/C2–C9/C9A) of the title compound, the 1,2-dihydropyridine ring (C11–C16) is essentially planar (r.m.s. deviation = 0.001 Å), while the 1,3-diazinane ring (N1/N5/C2–C4/C9A) has a distorted twist-boat conformation [puckering parameters (Cremer & Pople, 1975 ): Q_T = 0.5085 (14) Å, θ = 122.41 (15)° and φ = 281.45 (17)°]. The plane of the 1,2-dihydropyridine ring makes dihedral angles of 11.49 (6) and 47.52 (6)°, respectively, with the mean plane of the 1,3-diazine and benzene rings. The angle between the mean plane of the 1,3-diazine and benzene rings is 41.40 (6)°. The torsion angles C11—C8—C7—C10, C11—C8—C9—C18 and C8—C7—C6—N6 are 4.73 (19), −4.83 (18) and −179.04 (13) °, respectively. The geometric parameters of the title compound are normal and comparable to those of the related compounds listed in the Database survey section.

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, molecules are linked by N—H⋯N and C–H⋯N hydrogen bonds, forming a three-dimensional network (Table 1; Figs. 2 and 3). In addition, C—H⋯π interactions form layers parallel to the (100) plane (Table 1; Figs. 4 and 5). Thus, crystal-structure cohesion is ensured.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the N5/C6–C9/C9A and C11–C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N18ⁱ	0.892 (18)	2.229 (18)	3.0308 (16)	149.3 (14)
C2—H2B⋯N10ⁱⁱ	0.99	2.60	3.1574 (18)	116
C16—H16⋯N18ⁱⁱⁱ	0.95	2.51	3.3592 (17)	149
C3—H3B⋯Cg3^iv	0.99	2.77	3.5553 (15)	136
C4—H4B⋯Cg3^v	0.99	2.88	3.6750 (14)	138
C17—H17C⋯Cg2^vi	0.98	2.88	3.6306 (16)	134
Symmetry codes: (i) ; (ii) $[x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) ; (iv) ; (v) $[x, -y+{\script{1\over 2}}, z-{\script{3\over 2}}]$ ; (vi) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The packing viewed along the a-axis of the title compound with N—H⋯N and C—H⋯N hydrogen bonds shown as dashed lines.

Figure 3
The packing viewed along the b-axis of the title compound with N—H⋯N and C—H⋯N hydrogen bonds shown as dashed lines.

Figure 4
A view of the packing along the a-axis of the title compound with C—H⋯π interactions shown as dashed lines.

Figure 5
A view of the packing along the b-axis of the title compound with C—H⋯π interactions shown as dashed lines.

In order to quantify the intermolecular interactions in the crystal, Crystal Explorer 17.5 (Spackman et al., 2021 ) was used to generate Hirshfeld surfaces and two-dimensional fingerprint plots. The Hirshfeld surfaces mapped over d_norm are shown in Fig. 6. The bright-red spots indicate their roles as respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the electrostatic potential energy surface (Fig. 7).

Figure 6
(a) Front and (b) back sides of the three-dimensional Hirshfeld surface of the title compound mapped over d_norm.

Figure 7
View of the electrostatic potential energy surface of the title compound calculated using the STO-3G basis set at the Hartree–Fock level of theory.

The most important interatomic contact is H⋯H as it makes the highest contribution to the crystal packing (40.4%, Fig. 8b). The other major contributors are the N⋯H/H⋯N (28.6%, Fig. 8c) and C⋯H/H⋯C (24.1%, Fig. 8d) interactions. Other, smaller contributions are made by N⋯H/H⋯N (2.8%), C⋯C (2.7%) and N⋯N (1.4%) interactions.

Figure 8
The two-dimensional fingerprint plots, 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

Five related compounds, which also have the 1,3,4,6-tetrahydro- 2H-pyrido[1,2-a]pyrimidine ring system seen in the title compound, were found in a search of the Cambridge Structural Database (CSD version 5.42, update of November 2020; Groom et al., 2016 ): CSD refcode IQEFOC (Naghiyev et al., 2021), VAMBET (Khodjaniyazov & Ashurov, 2016 ), HECLUZ (Khodjaniyazov et al., 2017 ), LEGLIU (Chen et al., 2012 ) and KUTPEV (Samarov et al., 2010 ).

In IQEFOC, intermolecular N—H⋯N and C—H⋯N hydrogen bonds form molecular sheets parallel to the (110) and ( $[\overline{1}]$ 10) planes, crossing each other. Adjacent molecules are further linked by C—H⋯π interactions, which form zigzag chains propagating parallel to [100]. In the crystal of VAMBET, molecules are linked via C— H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to (101). In the crystal of HECLUZ, hydrogen bonds with 16-membered ring and three chain motifs are generated by N—H⋯N and N—H⋯O contacts. The amino group is located close to the nitrogen atoms, forming hydrogen bonds with R₂¹ (4) and R₂² (12) graph-set motifs. This amino group also forms a hydrogen bond with the C=O oxygen atom of a molecule translated parallel to [100], which links the molecules into R₄⁴ (16) rings. Hydrogen-bonded chains are formed along [100] by alternating R₂² (12) and R₄⁴ (16) rings. These chains are stabilized by intermolecular π–π stacking interactions observed between the pyridine and pyrimidine rings. In LEGLIU, the molecular structure is built up from two fused six-membered rings and one seven-membered ring linked through a spiro C atom. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds between the two N—H groups and the ketone O atoms of the neighbouring molecules. In KUTPEV, water molecules are mutually O—H⋯O hydrogen bonded and form infinite chains propagating parallel to [010]. Neighbouring chains are linked by the quinazoline molecules by means of O—H⋯O=C hydrogen bonds, forming a diperiodic network.

5. Synthesis and crystallization

A solution of 2-(4-methylbenzylidene)malononitrile (6 mmol) and malononitrile (6.1 mmol) in methanol (35 mL) was stirred for 10 min. Then 1,3-diaminopropane (5.3 mol) was added to the reaction mixture and stirred for 72 h. Then 25 mL of methanol were removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from an ethanol/water (1:1) solution (m.p. 501–502 K, yield 36%).

¹H NMR (300 MHz, DMSO-d₆, ppm.): 1.98 (m, 2H, CH₂); 2.39 (s, 3H, CH3-Ar); 3.42 (t, 2H, CH₂, ³J_H–H = 6.9); 3.93 (t, 2H, CH₂, ³J_H–H = 6.9); 4.14 (s, 1H, CH-Ar); 6.41 (s, 2H, NH₂); 7.30–7.42 (m, 4H, 4Ar-H); 7.70 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d₆, ppm.): 19.46 (CH₂), 21.01 (Ar-CH₃), 38.36 (Ar-CH), 39.64 (NCH2), 41.59 (NCH2), 51.64 (=C_quat.), 57.25 (=C_quat.), 120.70 (CN), 121.12 (CN), 128.14 (2CH_arom.), 128.98 (2CH_arom.), 134.92 (C_arom.), 140.77 (C_arom.), 151.15 (=C_quat.), 152.36 (=C_quat.).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed at calculated positions and refined using a riding model, with C—H = 0.95–0.99 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C). The N-bound H atoms were located in difference-Fourier maps [N1—H1 = 0.894 (17) Å, N6—H6 = 0.944 (18) Å] and refined with U_iso(H) = 1.2U_eq(N).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₅N₅
M_r	289.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.2459 (4), 14.1480 (9), 16.2111 (11)
β (°)	92.435 (7)
V (Å³)	1431.23 (16)
Z	4
Radiation type	Synchrotron, λ = 0.74500 Å
μ (mm⁻¹)	0.09
Crystal size (mm)	0.13 × 0.03 × 0.01

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.981, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	16784, 3956, 3119
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.692

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.113, 1.04
No. of reflections	3956
No. of parameters	206
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.24
Computer programs: Marccd (Doyle, 2011 ), iMosflm (Battye et al., 2011 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2340712

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024002500/nx2006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024002500/nx2006Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024002500/nx2006Isup3.cml

checkCIF report

Computing details top

6-Imino-8-(4-methylphenyl)-1,3,4,6-tetrahydro-2H-pyrido[1,2-a]pyrimidine-7,9-dicarbonitrile top

Crystal data top

C₁₇H₁₅N₅	F(000) = 608
M_r = 289.34	D_x = 1.343 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.74500 Å
a = 6.2459 (4) Å	Cell parameters from 600 reflections
b = 14.1480 (9) Å	θ = 2.6–26.0°
c = 16.2111 (11) Å	µ = 0.09 mm⁻¹
β = 92.435 (7)°	T = 100 K
V = 1431.23 (16) Å³	Needle, yellow
Z = 4	0.13 × 0.03 × 0.01 mm

Data collection top

Rayonix SX165 CCD diffractometer	3119 reflections with I > 2σ(I)
/f scan	R_int = 0.049
Absorption correction: multi-scan (Scala; Evans, 2006)	θ_max = 31.0°, θ_min = 2.6°
T_min = 0.981, T_max = 0.989	h = −8→8
16784 measured reflections	k = −19→19
3956 independent reflections	l = −22→22

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0455P)² + 0.6432P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3956 reflections	Δρ_max = 0.30 e Å⁻³
206 parameters	Δρ_min = −0.24 e Å⁻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
N1	1.22846 (18)	0.85962 (8)	0.43598 (6)	0.0203 (2)
H1	1.338 (3)	0.8968 (12)	0.4519 (10)	0.024*
C2	1.2417 (2)	0.80620 (10)	0.35940 (7)	0.0218 (2)
H2A	1.303447	0.742845	0.370787	0.026*
H2B	1.334227	0.839650	0.320792	0.026*
C3	1.0165 (2)	0.79718 (10)	0.32220 (7)	0.0217 (2)
H3A	1.018198	0.760667	0.270134	0.026*
H3B	0.957031	0.860657	0.309545	0.026*
C4	0.8787 (2)	0.74716 (9)	0.38329 (8)	0.0220 (3)
H4A	0.726345	0.751480	0.364155	0.026*
H4B	0.918397	0.679453	0.385898	0.026*
N5	0.90562 (17)	0.78939 (8)	0.46706 (6)	0.0188 (2)
C6	0.7437 (2)	0.76717 (9)	0.52209 (7)	0.0196 (2)
N6	0.60252 (19)	0.70637 (8)	0.49720 (7)	0.0246 (2)
H6	0.504 (3)	0.6963 (13)	0.5390 (11)	0.030*
C7	0.7591 (2)	0.81478 (9)	0.60171 (7)	0.0191 (2)
C8	0.91651 (19)	0.88052 (9)	0.62207 (7)	0.0181 (2)
C9	1.07340 (19)	0.89846 (9)	0.56422 (7)	0.0184 (2)
C9A	1.07054 (19)	0.84860 (9)	0.48773 (7)	0.0177 (2)
C10	0.6013 (2)	0.78674 (9)	0.65782 (8)	0.0218 (3)
N10	0.4674 (2)	0.75999 (9)	0.69863 (8)	0.0291 (3)
C11	0.91976 (19)	0.93141 (9)	0.70229 (7)	0.0185 (2)
C12	1.1058 (2)	0.93959 (9)	0.75279 (7)	0.0206 (2)
H12	1.235238	0.911116	0.736637	0.025*
C13	1.1016 (2)	0.98949 (10)	0.82682 (8)	0.0224 (3)
H13	1.228854	0.994184	0.860790	0.027*
C14	0.9150 (2)	1.03264 (9)	0.85215 (8)	0.0219 (3)
C15	0.7295 (2)	1.02285 (9)	0.80184 (8)	0.0220 (3)
H15	0.599979	1.050941	0.818303	0.026*
C16	0.7307 (2)	0.97293 (9)	0.72833 (7)	0.0204 (2)
H16	0.602065	0.966821	0.695323	0.025*
C17	0.9088 (2)	1.09051 (11)	0.92991 (8)	0.0285 (3)
H17A	1.047423	1.086173	0.960301	0.043*
H17B	0.795831	1.066382	0.964407	0.043*
H17C	0.878970	1.156666	0.915642	0.043*
C18	1.2316 (2)	0.96948 (9)	0.57532 (7)	0.0190 (2)
N18	1.36293 (18)	1.02717 (8)	0.57859 (7)	0.0228 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0197 (5)	0.0226 (5)	0.0188 (5)	−0.0025 (4)	0.0026 (4)	−0.0023 (4)
C2	0.0240 (6)	0.0227 (6)	0.0189 (5)	−0.0004 (5)	0.0036 (4)	−0.0017 (5)
C3	0.0249 (6)	0.0227 (6)	0.0174 (5)	0.0001 (5)	0.0010 (4)	−0.0015 (4)
C4	0.0236 (6)	0.0229 (6)	0.0195 (5)	−0.0021 (5)	0.0007 (4)	−0.0035 (4)
N5	0.0193 (5)	0.0199 (5)	0.0173 (4)	−0.0008 (4)	0.0011 (4)	−0.0010 (4)
C6	0.0186 (5)	0.0207 (6)	0.0195 (5)	−0.0004 (5)	0.0011 (4)	0.0016 (4)
N6	0.0240 (5)	0.0264 (6)	0.0236 (5)	−0.0055 (5)	0.0023 (4)	−0.0015 (4)
C7	0.0195 (5)	0.0194 (6)	0.0186 (5)	−0.0006 (5)	0.0021 (4)	0.0010 (4)
C8	0.0182 (5)	0.0188 (6)	0.0173 (5)	0.0027 (5)	0.0004 (4)	0.0013 (4)
C9	0.0179 (5)	0.0191 (6)	0.0181 (5)	−0.0012 (5)	0.0000 (4)	0.0003 (4)
C9A	0.0170 (5)	0.0175 (5)	0.0184 (5)	0.0014 (4)	−0.0004 (4)	0.0019 (4)
C10	0.0235 (6)	0.0216 (6)	0.0203 (5)	−0.0012 (5)	0.0015 (5)	−0.0013 (4)
N10	0.0315 (6)	0.0284 (6)	0.0278 (6)	−0.0052 (5)	0.0082 (5)	−0.0006 (5)
C11	0.0195 (6)	0.0188 (5)	0.0173 (5)	−0.0009 (5)	0.0016 (4)	0.0008 (4)
C12	0.0204 (6)	0.0214 (6)	0.0200 (5)	0.0002 (5)	0.0013 (4)	0.0020 (4)
C13	0.0216 (6)	0.0246 (6)	0.0208 (6)	−0.0029 (5)	−0.0011 (4)	0.0009 (5)
C14	0.0256 (6)	0.0210 (6)	0.0191 (5)	−0.0024 (5)	0.0023 (5)	−0.0009 (4)
C15	0.0218 (6)	0.0211 (6)	0.0233 (6)	0.0018 (5)	0.0029 (4)	−0.0003 (5)
C16	0.0190 (6)	0.0215 (6)	0.0207 (5)	−0.0008 (5)	0.0003 (4)	0.0009 (4)
C17	0.0328 (7)	0.0293 (7)	0.0232 (6)	0.0009 (6)	−0.0002 (5)	−0.0077 (5)
C18	0.0204 (5)	0.0213 (6)	0.0154 (5)	0.0022 (5)	0.0004 (4)	−0.0001 (4)
N18	0.0223 (5)	0.0250 (5)	0.0211 (5)	−0.0020 (5)	−0.0003 (4)	−0.0004 (4)

Geometric parameters (Å, º) top

N1—C9A	1.3310 (16)	C8—C11	1.4859 (16)
N1—C2	1.4587 (16)	C9—C18	1.4155 (17)
N1—H1	0.894 (17)	C9—C9A	1.4259 (16)
C2—C3	1.5123 (18)	C10—N10	1.1524 (18)
C2—H2A	0.9900	C11—C12	1.3974 (17)
C2—H2B	0.9900	C11—C16	1.4002 (17)
C3—C4	1.5150 (18)	C12—C13	1.3936 (17)
C3—H3A	0.9900	C12—H12	0.9500
C3—H3B	0.9900	C13—C14	1.3929 (19)
C4—N5	1.4865 (15)	C13—H13	0.9500
C4—H4A	0.9900	C14—C15	1.3947 (18)
C4—H4B	0.9900	C14—C17	1.5050 (18)
N5—C9A	1.3586 (16)	C15—C16	1.3855 (17)
N5—C6	1.4120 (16)	C15—H15	0.9500
C6—N6	1.2847 (17)	C16—H16	0.9500
C6—C7	1.4555 (17)	C17—H17A	0.9800
N6—H6	0.944 (18)	C17—H17B	0.9800
C7—C8	1.3833 (17)	C17—H17C	0.9800
C7—C10	1.4252 (17)	C18—N18	1.1567 (17)
C8—C9	1.4080 (17)

C9A—N1—C2	123.11 (11)	C9—C8—C11	120.77 (11)
C9A—N1—H1	117.8 (10)	C8—C9—C18	123.04 (11)
C2—N1—H1	118.7 (11)	C8—C9—C9A	120.44 (11)
N1—C2—C3	107.31 (10)	C18—C9—C9A	116.40 (11)
N1—C2—H2A	110.3	N1—C9A—N5	119.41 (11)
C3—C2—H2A	110.3	N1—C9A—C9	120.53 (11)
N1—C2—H2B	110.3	N5—C9A—C9	120.06 (11)
C3—C2—H2B	110.3	N10—C10—C7	174.99 (14)
H2A—C2—H2B	108.5	C12—C11—C16	118.66 (11)
C2—C3—C4	108.88 (10)	C12—C11—C8	122.20 (11)
C2—C3—H3A	109.9	C16—C11—C8	119.13 (11)
C4—C3—H3A	109.9	C13—C12—C11	120.05 (12)
C2—C3—H3B	109.9	C13—C12—H12	120.0
C4—C3—H3B	109.9	C11—C12—H12	120.0
H3A—C3—H3B	108.3	C14—C13—C12	121.50 (12)
N5—C4—C3	111.35 (10)	C14—C13—H13	119.2
N5—C4—H4A	109.4	C12—C13—H13	119.2
C3—C4—H4A	109.4	C13—C14—C15	117.94 (11)
N5—C4—H4B	109.4	C13—C14—C17	122.48 (12)
C3—C4—H4B	109.4	C15—C14—C17	119.56 (12)
H4A—C4—H4B	108.0	C16—C15—C14	121.27 (12)
C9A—N5—C6	122.49 (10)	C16—C15—H15	119.4
C9A—N5—C4	121.90 (10)	C14—C15—H15	119.4
C6—N5—C4	115.55 (10)	C15—C16—C11	120.55 (12)
N6—C6—N5	116.82 (11)	C15—C16—H16	119.7
N6—C6—C7	127.35 (12)	C11—C16—H16	119.7
N5—C6—C7	115.81 (11)	C14—C17—H17A	109.5
C6—N6—H6	109.5 (11)	C14—C17—H17B	109.5
C8—C7—C10	122.59 (11)	H17A—C17—H17B	109.5
C8—C7—C6	122.82 (11)	C14—C17—H17C	109.5
C10—C7—C6	114.58 (11)	H17A—C17—H17C	109.5
C7—C8—C9	118.05 (11)	H17B—C17—H17C	109.5
C7—C8—C11	121.18 (11)	N18—C18—C9	175.26 (13)

C9A—N1—C2—C3	38.85 (16)	C6—N5—C9A—N1	173.71 (11)
N1—C2—C3—C4	−59.02 (13)	C4—N5—C9A—N1	−9.17 (18)
C2—C3—C4—N5	48.56 (14)	C6—N5—C9A—C9	−6.41 (18)
C3—C4—N5—C9A	−14.66 (16)	C4—N5—C9A—C9	170.71 (11)
C3—C4—N5—C6	162.65 (11)	C8—C9—C9A—N1	−174.37 (11)
C9A—N5—C6—N6	−176.32 (12)	C18—C9—C9A—N1	9.52 (17)
C4—N5—C6—N6	6.39 (17)	C8—C9—C9A—N5	5.75 (18)
C9A—N5—C6—C7	2.43 (17)	C18—C9—C9A—N5	−170.36 (11)
C4—N5—C6—C7	−174.86 (11)	C7—C8—C11—C12	132.01 (13)
N6—C6—C7—C8	−179.04 (13)	C9—C8—C11—C12	−48.44 (17)
N5—C6—C7—C8	2.36 (18)	C7—C8—C11—C16	−48.17 (17)
N6—C6—C7—C10	2.2 (2)	C9—C8—C11—C16	131.37 (13)
N5—C6—C7—C10	−176.36 (11)	C16—C11—C12—C13	−0.95 (18)
C10—C7—C8—C9	175.72 (12)	C8—C11—C12—C13	178.86 (12)
C6—C7—C8—C9	−2.91 (18)	C11—C12—C13—C14	−0.42 (19)
C10—C7—C8—C11	−4.73 (19)	C12—C13—C14—C15	1.33 (19)
C6—C7—C8—C11	176.65 (11)	C12—C13—C14—C17	−177.21 (13)
C7—C8—C9—C18	174.72 (11)	C13—C14—C15—C16	−0.88 (19)
C11—C8—C9—C18	−4.83 (18)	C17—C14—C15—C16	177.71 (12)
C7—C8—C9—C9A	−1.12 (18)	C14—C15—C16—C11	−0.48 (19)
C11—C8—C9—C9A	179.33 (11)	C12—C11—C16—C15	1.40 (18)
C2—N1—C9A—N5	−4.15 (18)	C8—C11—C16—C15	−178.42 (12)
C2—N1—C9A—C9	175.97 (11)

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of the N5/C6–C9/C9A and C11–C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N18ⁱ	0.892 (18)	2.229 (18)	3.0308 (16)	149.3 (14)
C2—H2B···N10ⁱⁱ	0.99	2.60	3.1574 (18)	116
C16—H16···N18ⁱⁱⁱ	0.95	2.51	3.3592 (17)	149
C3—H3B···Cg3^iv	0.99	2.77	3.5553 (15)	136
C4—H4B···Cg3^v	0.99	2.88	3.6750 (14)	138
C17—H17C···Cg2^vi	0.98	2.88	3.6306 (16)	134

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

Acknowledgements

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

Funding information

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

References

Afkhami, F. A., Mahmoudi, G., Khandar, A. A., Franconetti, A., Zangrando, E., Qureshi, N., Lipkowski, J., Gurbanov, A. V. & Frontera, A. (2019). Eur. J. Inorg. Chem. pp. 262–270. Web of Science CSD CrossRef Google Scholar
Akkurt, M., Maharramov, A. M., Shikhaliyev, N. G., Qajar, A. M., Atakishiyeva, G., Shikhaliyeva, I. M., Niyazova, A. A. & Bhattarai, A. (2023). UNEC J. Eng. Appl. Sci. 3, 33–39. CrossRef Google Scholar
Askerova, U. F. (2022). UNEC J. Eng. Appl. Sci, 2, 58–64. Google Scholar
Atalay, V. E., Atish, I. S., Shahin, K. F., Kashikchi, E. S. & Karahan, M. (2022). UNEC J. Eng. Appl. Sci. 2, 33–40. Google Scholar
Battye, T. G. G., Kontogiannis, L., Johnson, O., Powell, H. R. & Leslie, A. G. W. (2011). Acta Cryst. D67, 271–281. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chen, S., Shi, D., Liu, M. & Li, J. (2012). Acta Cryst. E68, o2546. CSD CrossRef IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Donmez, M. & Turkyılmaz, M. (2022). UNEC J. Eng. Appl. Sci, 2, 43–48. Google Scholar
Doyle, R. A. (2011). MarCCD software manual. Rayonix LLC, Evanston, IL 60201, USA. Google Scholar
Elattar, K. M., Rabie, R. & Hammouda, M. M. (2017). Monatsh. Chem. 148, 601–627. Web of Science CrossRef CAS Google Scholar
Erenler, R., Dag, B. & Ozbek, B. B. (2022). UNEC J. Eng. Appl. Sci. 2, 26–32. Google Scholar
Evans, P. (2006). Acta Cryst. D62, 72–82. Web of Science CrossRef CAS IUCr Journals 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
Gurbanov, A. V., Mertsalov, D. F., Zubkov, F. I., Nadirova, M. A., Nikitina, E. V., Truong, H. H., Grigoriev, M. S., Zaytsev, V. P., Mahmudov, K. T. & Pombeiro, A. J. L. (2021). Crystals, 11, 112. Web of Science CSD CrossRef 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
Khodjaniyazov, Kh. U. & Ashurov, J. M. (2016). Acta Cryst. E72, 452–455. Web of Science CSD CrossRef IUCr Journals Google Scholar
Khodjaniyazov, K. U., Makhmudov, U. S., Turgunov, K. K. & Elmuradov, B. Z. (2017). Acta Cryst. E73, 1497–1500. Web of Science CSD CrossRef IUCr Journals Google Scholar
Maharramov, A. M., Shikhaliyev, N. G., Zeynalli, N. R., Niyazova, A. A., Garazade, Kh. A. & Shikhaliyeva, I. M. (2021). UNEC J. Eng. Appl. Sci. 1, 5–11. Google Scholar
Maharramov, A. M., Suleymanova, G. T., Qajar, A. M., Niyazova, A. A., Ahmadova, N. E., Shikhaliyeva, I. M., Garazade, Kh. A., Nenajdenko, V. G. & Shikaliyev, N. G. (2022). UNEC J. Eng. Appl. Sci. 2, 64–73. Google Scholar
Mahmoudi, G., Zangrando, E., Miroslaw, B., Gurbanov, A. V., Babashkina, M. G., Frontera, A. & Safin, D. A. (2021). Inorg. Chim. Acta, 519, 120279. Web of Science CSD CrossRef 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. Web of Science 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
Samarov, Z. U., Okmanov, R. Y., Turgunov, K. K., Tashkhodjaev, B. & Shakhidoyatov, K. M. (2010). Acta Cryst. E66, o890. 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
Sobhi, R. M. & Faisal, R. M. (2023). UNEC J. Eng. Appl. Sci. 3, 21–32. Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Velásquez, J. D., Mahmoudi, G., Zangrando, E., Gurbanov, A. V., Zubkov, F. I., Zorlu, Y., Masoudiasl, A. & Echeverría, J. (2019). CrystEngComm, 21, 6018–6025. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.