Crystal structure and Hirshfeld surface analysis of 5-oxo-7-phenyl-2-(phenyl­amino)-1H-[1,2,4]triazolo[1,5-a]pyridine-6,8-dicarbo­nitrile dimethyl sulfoxide monosolvate

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

doi:10.1107/S2056989023004383

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ISSN: 2056-9890

Volume 79| Part 6| June 2023| Pages 567-570

https://doi.org/10.1107/S2056989023004383

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Crystal structure and Hirshfeld surface analysis of 5-oxo-7-phenyl-2-(phenylamino)-1H-[1,2,4]triazolo[1,5-a]pyridine-6,8-dicarbonitrile dimethyl sulfoxide monosolvate

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

^aFaculty 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, ^dFaculty of Physics, Baku State University, Z. Khalilov str. 23, Az, 1148 Baku, Azerbaijan, ^eDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, and ^fDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 10 May 2023; accepted 20 May 2023; online 26 May 2023)

In the title compound, C₂₀H₁₂N₆O·C₂H₆OS, the [1,2,4]triazolo[1,5-a]pyridine ring system is almost planar and makes dihedral angles of 16.33 (7) and 46.80 (7)°, respectively, with the phenylamino and phenyl rings. In the crystal, molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds into chains along the b-axis direction through the dimethyl sulfoxide solvent molecule, forming C(10)R²₁(6) motifs. These chains are connected via S—O⋯π interactions, π–π stacking interactions between the pyridine rings [centroid-to-centroid distance = 3.6662 (9) Å] and van der Waals interactions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (28.1%), C⋯H/H⋯C (27.2%), N⋯H/H⋯N (19.4%) and O⋯H/H⋯O (9.8%) interactions.

Keywords: crystal structure; [1,2,4]triazolo[1,5-a]pyridine; hydrogen bond; Hirshfeld surface analysis.

CCDC reference: 2264500

1. Chemical context

Diverse carbon–carbon and carbon–heteroatom bond-formation reactions are considered fundamental tools in organic synthesis. The reaction has also been amplified, extending these methods to different fields of chemistry, as well to the synthesis of natural products, in medicinal and pharmaceutical chemistry, material science, supramolecular chemistry etc (Çelik et al., 2023 ; Chalkha et al., 2023 ; Tapera et al., 2022 ; Gurbanov et al., 2020 ; Zubkov et al., 2018 ). Triazolo[1,5-a]pyridines are accessible heterocyclic compounds and α-substituted pyridines are among the most widely used starting materials for their synthesis. The most common synthetic pathways to these compounds are well-reviewed in the literature (Jones & Abarca, 2010 ; Soliman et al., 2014 ; Kotovshchikov et al., 2021 ). The triazolo[1,5-a]pyridine moiety is a widespread structural motif in various synthetic biologically active compounds, possessing cardiovascular, trypanocidal, nitric oxide synthase inhibitor and antimicrobial activity, and in non-hormonal compounds with antifertility activity and leishmanicidal activity (Jones & Abarca, 2010; Mohamed et al., 2013 ; Poustforoosh et al., 2022 ).

A literature survey shows that the title compound 3 was previously synthesized in a two-pot reaction protocol (Barsy et al., 2008 ), wherein the iminophosphorane 1-amino-6-(triphenylphosphoranylideneamino)-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-dicarbonitrile 2 prepared from 1,6-diaminopyridine 1 reacted with phenylisocyanate method to prepare 3 (B pathway, Fig. 1). Herein, we disclose a more straightforward one-pot synthesis method of 3 using the same starting compound 1 at room temperature (A pathway, Fig. 1), but through a different pathway.

Figure 1
The synthesis routes or the title compound 3.

Continuing our investigations of heterocyclic systems with biological activity and in the framework of our ongoing structural studies (Maharramov et al., 2021 , 2022 ; Naghiyev et al., 2020 , 2021 , 2022 ), we report the crystal structure and Hirshfeld surface analysis of the title compound, 5-oxo-7-phenyl-2-(phenylamino)-1,5-dihydro-[1,2,4]triazolo[1,5-a]pyridine-6,8-dicarbonitrile, which crystallized as a DMSO solvate.

2. Structural commentary

In the title compound, (Fig. 2), the [1,2,4]triazolo[1,5-a]pyridine ring system (N1/N3/N4/C2/C5–C8/C8A) is almost planar [maximum deviation = 0.043 (2) Å for C5] and subtends dihedral angles of 16.33 (7) and 46.80 (7)°, respectively, with the phenylamino and phenyl rings (C9–C14 and C16–C21). The geometric properties of the title compound are normal and consistent with those of the related compounds listed in the Database survey (Section 4).

Figure 2
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal, molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds into chains along the b-axis direction through the dimethyl sulfoxide solvent molecule, forming C(10) $[R_{1}^{2}]$ (6) motifs (Bernstein et al., 1995 ; Table 1). These chains are connected via S—O⋯π interactions [S1—O2⋯Cg2ⁱ: O2⋯Cg2ⁱ = 3.1775 (14) Å; S1⋯Cg2ⁱ = 4.0054 (8) Å; S1—O2⋯Cg2ⁱ = 111.93 (6)°; symmetry code: (i) 1 − x, 1 − y, 1 − z; Cg2 is the centroid of the pyridine ring (N4/C5–C8/C8A)], π–π stacking interactions [Cg2⋯Cg2ⁱⁱ = 3.6662 (9) Å; slippage = 1.468 Å; symmetry code: (ii) −x, 1 − y, 1 − z] and van der Waals interactions (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.88 (2)	1.84 (2)	2.6249 (16)	146.9 (17)
N2—H2⋯O2	0.90 (2)	2.07 (2)	2.8680 (16)	147.7 (17)
C10—H10⋯N3	0.95	2.39	2.9956 (19)	121
C23—H23B⋯O1ⁱ	0.98	2.44	3.166 (2)	131
C24—H24B⋯N22	0.98	2.53	3.474 (2)	162
Symmetry code: (i) x+1, y+1, z.

Figure 3
A view along the c axis of the N—H⋯O and C—H⋯O bonds in the title compound.

CrystalExplorer17.5 (Spackman et al., 2021 ) was used to compute Hirshfeld surfaces of the title molecule and two-dimensional fingerprints. The Hirshfeld surfaces were mapped over d_norm in the range −0.6769 (red) to +1.1190 (blue) a.u. The interactions given in Table 2 play a key role in the molecular packing of the title compound. The most important interatomic contact is H⋯H as it makes the highest contribution to the crystal packing (28.1%, Fig. 4b). Other major contributors are C⋯H/H⋯C (27.2%, Fig. 4c), N⋯H/H⋯N (19.4%, Fig. 4d) and N⋯H/H⋯N (9.8%, Fig. 4e) interactions. Smaller contributions are made by N⋯C/C⋯N (6.7%), C⋯C (3.6%), O⋯C/C⋯O(1.7%), N⋯N (1.5%), S⋯H/H⋯S (1.0%), O⋯N/N⋯O (0.7%), S⋯C/C⋯S(0.2%) and O⋯S/S⋯O (0.1%) interactions.

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

Contact	Distance	Symmetry operation
O1⋯H23B	2.44	−1 + x, −1 + y, z
H17⋯O1	2.65	−x, 1 − y, 1 − z
O1⋯H24A	2.63	1 − x, 1 − y, 1 − z
H1⋯O2	1.84	x, y, z
H14⋯C21	2.98	1 − x, 1 − y, 1 − z
H19⋯N15	2.73	−x, 1 − y, 2 − z
H18⋯N22	2.82	1 − x, 2 − y, 2 − z
C22⋯H23B	3.08	1 − x, 2 − y, 1 − z
C9⋯H20	3.05	x, y, −1 + z
C11⋯C11	3.53	−x, −y, −z
C12⋯H18	3.05	x, −1 + y, −1 + z
H19⋯H23A	2.54	x, y, 1 + z
H12⋯H24A	2.41	−1 + x, −1 + y, −1 + z
H12⋯S1	3.04	1 − x, 1 − y, −z
H23C⋯H23C	2.43	1 − x, 2 − y, 1 − z

Figure 4
Two-dimensional fingerprint plots for title molecule showing (a) all interactions, and delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) N⋯H/H⋯N and (e) O⋯H/H⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) for the central nine-membered ring system `1,5-dihydro[1,2,4]triazolo[1,5-a]pyridine' yielded three compounds related to the title compound, viz. CSD refcodes HODQEZ (Gumus et al., 2019 ), HODQID (Gumus et al., 2019) and RETCAX (Aydemir et al., 2018 ).

In the crystal of HODQEZ, pairs of N—H⋯N hydrogen bonds link the molecules, forming inversion dimers with an R₂²(8) ring motif. The dimers are linked by C—H⋯π and C—Br⋯π interactions, forming layers parallel to the bc plane. In the crystal of HODQID, molecules are linked by N—H⋯N and C—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction. In the crystal of RETCAX, N—H⋯N hydrogen bonds link the molecules into supramolecular chains propagating along the c-axis direction.

5. Synthesis and crystallization

To a solution of 1,6-diamino-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-dicarbonitrile (0.82 g, 5.1 mmol) in DMF (25 mL) was added 10 mL of an aqueous solution of potassium hydroxide (0.28 g, 5.1 mmol). The mixture was stirred at room temperature for 2 h. Then an equimolar amount of phenylisothiocyanate (0.51 g, 5.2 mmol) was added to the vigorously stirred reaction mixture and left overnight. After completion of the reaction, monitored by TLC, the reaction mixture was acidified by adding conc. HCl (4 mL). The precipitated solids were separated by filtration and recrystallized from an ethanol/water (1:1) solution (yield 80%; m.p. 557–558 K). Single crystals were grown from a DMSO solution.

¹H NMR (300 MHz, DMSO-d₆, p.p.m.): 4.3 (s, 1H, NH); 6.9 (t, 1H, CH_arom, ³J_H—H = 7.5 MHz); 7.3 (t, 2H, CH_arom, ³J_H—H = 7.5 MHz); 7.5 (m, 5H, CH_arom); 7.7 (d, 2H, CH_arom, ³J_H—H = 8.1 MHz); 9.6 (s, 1H, NH); ¹³C NMR (75 MHz, DMSO-d₆, p.p.m.): 76.4 (C_quat), 83.9 (C_quat), 117.0 (CH_arom), 117.5 (CN), 118.9 (CN), 120.7 (CH_arom), 128.9 (CH_arom), 129.0 (CH_arom), 129.2 (CH_arom), 129.9 (CH_arom), 136.3 (C_arom), 141.4 (C_arom), 152.2 (C_quat), 154.9 (C_quat), 156.2 (C_quat), 161.1 (C=O).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The NH H atoms were located in a difference-Fourier map [N1—H1 = 0.88 (2) Å and N2—H2 = 0.90 (2) Å] and refined with U_iso(H) = 1.2U_eq(N). Carbon-bound H atoms were positioned geometrically [C—H = 0.95–0.98 Å;] and were included in the refinement in the riding-model approximation with U_iso(H) = 1.2 or 1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₂₀H₁₂N₆O·C₂H₆OS
M_r	430.48
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.87885 (12), 10.46018 (13), 11.48307 (12)
α, β, γ (°)	100.9305 (10), 105.3054 (11), 112.6790 (12)
V (Å³)	997.81 (2)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	1.73
Crystal size (mm)	0.22 × 0.16 × 0.12

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.660, 0.781
No. of measured, independent and observed [I > 2σ(I)] reflections	22299, 4314, 4124
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.08
No. of reflections	4314
No. of parameters	289
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.51
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2264500

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004383/tx2068sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004383/tx2068Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023004383/tx2068Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.41.117a (Rigaku OD, 2021); cell refinement: CrysAlis PRO 1.171.41.117a (Rigaku OD, 2021); data reduction: CrysAlis PRO 1.171.41.117a (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

5-Oxo-7-phenyl-2-(phenylamino)-1H-[1,2,4]triazolo[1,5-a]pyridine-6,8-dicarbonitrile dimethyl sulfoxide monosolvate top

Crystal data top

C₂₀H₁₂N₆O·C₂H₆OS	Z = 2
M_r = 430.48	F(000) = 448
Triclinic, P1	D_x = 1.433 Mg m⁻³
a = 9.87885 (12) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.46018 (13) Å	Cell parameters from 15870 reflections
c = 11.48307 (12) Å	θ = 4.8–79.3°
α = 100.9305 (10)°	µ = 1.73 mm⁻¹
β = 105.3054 (11)°	T = 100 K
γ = 112.6790 (12)°	Prism, colourless
V = 997.81 (2) Å³	0.22 × 0.16 × 0.12 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	4124 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.037
φ and ω scans	θ_max = 79.5°, θ_min = 4.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	h = −12→9
T_min = 0.660, T_max = 0.781	k = −12→13
22299 measured reflections	l = −14→14
4314 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0554P)² + 0.554P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
4314 reflections	Δρ_max = 0.41 e Å⁻³
289 parameters	Δρ_min = −0.51 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: 0.0029 (4)

Special details top

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

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O1	−0.06967 (12)	0.20611 (11)	0.42668 (10)	0.0214 (2)
N1	0.37412 (14)	0.55891 (13)	0.44627 (11)	0.0171 (2)
H1	0.465 (2)	0.635 (2)	0.4612 (18)	0.021*
C2	0.29261 (16)	0.44403 (15)	0.33251 (13)	0.0163 (3)
N2	0.35694 (14)	0.44663 (14)	0.24222 (12)	0.0189 (3)
H2	0.453 (2)	0.523 (2)	0.2678 (18)	0.023*
N3	0.15858 (14)	0.34368 (13)	0.32865 (11)	0.0178 (2)
N4	0.15615 (14)	0.40235 (12)	0.44782 (11)	0.0159 (2)
C5	0.03861 (16)	0.32893 (15)	0.49174 (14)	0.0177 (3)
C6	0.06152 (16)	0.41513 (15)	0.61676 (13)	0.0176 (3)
C7	0.19229 (16)	0.55162 (15)	0.69078 (13)	0.0174 (3)
C8	0.30798 (16)	0.61215 (15)	0.63984 (13)	0.0172 (3)
C8A	0.28510 (16)	0.53211 (15)	0.51784 (13)	0.0167 (3)
C9	0.29501 (17)	0.34391 (15)	0.11906 (13)	0.0179 (3)
C10	0.13802 (18)	0.23723 (17)	0.06025 (15)	0.0227 (3)
H10	0.0659	0.2308	0.1023	0.027*
C11	0.08828 (19)	0.13987 (18)	−0.06143 (15)	0.0262 (3)
H11	−0.0189	0.0670	−0.1026	0.031*
C12	0.19282 (19)	0.14769 (18)	−0.12345 (15)	0.0265 (3)
H12	0.1581	0.0794	−0.2056	0.032*
C13	0.34888 (19)	0.25654 (18)	−0.06421 (15)	0.0242 (3)
H13	0.4208	0.2634	−0.1065	0.029*
C14	0.39982 (17)	0.35488 (17)	0.05611 (14)	0.0211 (3)
H14	0.5062	0.4298	0.0958	0.025*
C15	−0.06863 (17)	0.35194 (15)	0.65539 (13)	0.0186 (3)
N15	−0.18041 (15)	0.29648 (14)	0.67726 (13)	0.0235 (3)
C16	0.21011 (16)	0.63048 (16)	0.82000 (13)	0.0178 (3)
C17	0.25352 (17)	0.78044 (16)	0.85674 (14)	0.0202 (3)
H17	0.2689	0.8319	0.7977	0.024*
C18	0.27428 (18)	0.85436 (16)	0.97909 (14)	0.0223 (3)
H18	0.3041	0.9563	1.0037	0.027*
C19	0.25145 (17)	0.77930 (17)	1.06577 (14)	0.0218 (3)
H19	0.2658	0.8301	1.1495	0.026*
C20	0.20758 (17)	0.62989 (17)	1.03002 (14)	0.0215 (3)
H20	0.1913	0.5788	1.0892	0.026*
C21	0.18757 (17)	0.55538 (16)	0.90782 (14)	0.0195 (3)
H21	0.1587	0.4537	0.8839	0.023*
C22	0.44758 (17)	0.74971 (16)	0.70142 (14)	0.0191 (3)
N22	0.56198 (16)	0.85887 (14)	0.74045 (13)	0.0251 (3)
S1	0.73840 (4)	0.86862 (4)	0.42677 (3)	0.01894 (11)
O2	0.63433 (12)	0.71002 (11)	0.41226 (10)	0.0215 (2)
C23	0.6060 (2)	0.94489 (18)	0.39068 (19)	0.0328 (4)
H23A	0.5447	0.9058	0.2985	0.049*
H23B	0.6662	1.0518	0.4170	0.049*
H23C	0.5340	0.9190	0.4366	0.049*
C24	0.83449 (19)	0.96161 (17)	0.59410 (15)	0.0249 (3)
H24A	0.9001	0.9187	0.6319	0.037*
H24B	0.7551	0.9518	0.6326	0.037*
H24C	0.9013	1.0657	0.6101	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0204 (5)	0.0187 (5)	0.0200 (5)	0.0048 (4)	0.0082 (4)	0.0039 (4)
N1	0.0170 (6)	0.0169 (5)	0.0174 (6)	0.0073 (5)	0.0079 (4)	0.0045 (4)
C2	0.0179 (6)	0.0170 (6)	0.0160 (6)	0.0096 (5)	0.0072 (5)	0.0054 (5)
N2	0.0173 (6)	0.0196 (6)	0.0181 (6)	0.0065 (5)	0.0089 (5)	0.0037 (5)
N3	0.0193 (6)	0.0192 (6)	0.0162 (6)	0.0087 (5)	0.0095 (5)	0.0049 (5)
N4	0.0174 (6)	0.0156 (5)	0.0157 (5)	0.0075 (5)	0.0080 (4)	0.0046 (4)
C5	0.0187 (6)	0.0193 (6)	0.0191 (7)	0.0108 (5)	0.0086 (5)	0.0083 (5)
C6	0.0195 (7)	0.0199 (7)	0.0177 (7)	0.0109 (6)	0.0091 (5)	0.0081 (5)
C7	0.0198 (7)	0.0198 (7)	0.0178 (7)	0.0128 (6)	0.0077 (5)	0.0080 (5)
C8	0.0181 (6)	0.0175 (6)	0.0172 (7)	0.0089 (5)	0.0073 (5)	0.0058 (5)
C8A	0.0175 (6)	0.0187 (6)	0.0178 (7)	0.0109 (5)	0.0075 (5)	0.0076 (5)
C9	0.0204 (7)	0.0190 (6)	0.0161 (6)	0.0102 (5)	0.0077 (5)	0.0058 (5)
C10	0.0210 (7)	0.0257 (7)	0.0210 (7)	0.0090 (6)	0.0106 (6)	0.0063 (6)
C11	0.0227 (7)	0.0272 (8)	0.0200 (7)	0.0057 (6)	0.0072 (6)	0.0032 (6)
C12	0.0298 (8)	0.0277 (8)	0.0168 (7)	0.0104 (7)	0.0088 (6)	0.0025 (6)
C13	0.0263 (8)	0.0301 (8)	0.0211 (7)	0.0144 (6)	0.0138 (6)	0.0085 (6)
C14	0.0197 (7)	0.0253 (7)	0.0202 (7)	0.0107 (6)	0.0093 (6)	0.0082 (6)
C15	0.0214 (7)	0.0187 (6)	0.0173 (7)	0.0105 (6)	0.0075 (5)	0.0058 (5)
N15	0.0241 (6)	0.0250 (6)	0.0239 (6)	0.0114 (5)	0.0123 (5)	0.0083 (5)
C16	0.0170 (6)	0.0211 (7)	0.0170 (7)	0.0100 (5)	0.0070 (5)	0.0058 (5)
C17	0.0222 (7)	0.0216 (7)	0.0206 (7)	0.0115 (6)	0.0105 (6)	0.0080 (6)
C18	0.0230 (7)	0.0212 (7)	0.0221 (7)	0.0107 (6)	0.0090 (6)	0.0039 (6)
C19	0.0209 (7)	0.0273 (7)	0.0174 (7)	0.0122 (6)	0.0079 (6)	0.0041 (6)
C20	0.0213 (7)	0.0266 (7)	0.0195 (7)	0.0122 (6)	0.0093 (6)	0.0087 (6)
C21	0.0187 (6)	0.0207 (7)	0.0199 (7)	0.0096 (5)	0.0078 (5)	0.0066 (6)
C22	0.0231 (7)	0.0216 (7)	0.0179 (6)	0.0130 (6)	0.0108 (6)	0.0072 (5)
N22	0.0255 (7)	0.0221 (6)	0.0252 (7)	0.0082 (5)	0.0114 (5)	0.0053 (5)
S1	0.01723 (18)	0.01879 (19)	0.01979 (19)	0.00657 (14)	0.00849 (13)	0.00567 (13)
O2	0.0199 (5)	0.0174 (5)	0.0244 (5)	0.0061 (4)	0.0091 (4)	0.0048 (4)
C23	0.0242 (8)	0.0246 (8)	0.0444 (10)	0.0123 (7)	0.0037 (7)	0.0111 (7)
C24	0.0269 (8)	0.0197 (7)	0.0224 (7)	0.0085 (6)	0.0062 (6)	0.0038 (6)

Geometric parameters (Å, º) top

O1—C5	1.2277 (18)	C13—C14	1.384 (2)
N1—C8A	1.3439 (18)	C13—H13	0.9500
N1—C2	1.3792 (18)	C14—H14	0.9500
N1—H1	0.88 (2)	C15—N15	1.152 (2)
C2—N3	1.3178 (18)	C16—C17	1.399 (2)
C2—N2	1.3508 (18)	C16—C21	1.403 (2)
N2—C9	1.4102 (18)	C17—C18	1.388 (2)
N2—H2	0.90 (2)	C17—H17	0.9500
N3—N4	1.4000 (16)	C18—C19	1.392 (2)
N4—C8A	1.3504 (18)	C18—H18	0.9500
N4—C5	1.4003 (18)	C19—C20	1.393 (2)
C5—C6	1.4510 (19)	C19—H19	0.9500
C6—C7	1.403 (2)	C20—C21	1.391 (2)
C6—C15	1.4297 (19)	C20—H20	0.9500
C7—C8	1.4088 (19)	C21—H21	0.9500
C7—C16	1.4829 (19)	C22—N22	1.151 (2)
C8—C8A	1.3988 (19)	S1—O2	1.5253 (10)
C8—C22	1.429 (2)	S1—C24	1.7764 (16)
C9—C10	1.390 (2)	S1—C23	1.7788 (16)
C9—C14	1.394 (2)	C23—H23A	0.9800
C10—C11	1.394 (2)	C23—H23B	0.9800
C10—H10	0.9500	C23—H23C	0.9800
C11—C12	1.388 (2)	C24—H24A	0.9800
C11—H11	0.9500	C24—H24B	0.9800
C12—C13	1.391 (2)	C24—H24C	0.9800
C12—H12	0.9500

C8A—N1—C2	106.74 (12)	C14—C13—H13	119.9
C8A—N1—H1	130.6 (12)	C12—C13—H13	119.9
C2—N1—H1	122.6 (12)	C13—C14—C9	119.96 (14)
N3—C2—N2	128.74 (13)	C13—C14—H14	120.0
N3—C2—N1	112.99 (12)	C9—C14—H14	120.0
N2—C2—N1	118.26 (13)	N15—C15—C6	175.03 (16)
C2—N2—C9	128.42 (13)	C17—C16—C21	119.42 (13)
C2—N2—H2	113.3 (12)	C17—C16—C7	120.65 (13)
C9—N2—H2	118.3 (12)	C21—C16—C7	119.90 (13)
C2—N3—N4	102.08 (11)	C18—C17—C16	120.31 (13)
C8A—N4—N3	112.16 (11)	C18—C17—H17	119.8
C8A—N4—C5	124.35 (12)	C16—C17—H17	119.8
N3—N4—C5	123.34 (11)	C17—C18—C19	120.05 (14)
O1—C5—N4	121.08 (13)	C17—C18—H18	120.0
O1—C5—C6	126.58 (13)	C19—C18—H18	120.0
N4—C5—C6	112.33 (12)	C18—C19—C20	120.12 (14)
C7—C6—C15	122.14 (13)	C18—C19—H19	119.9
C7—C6—C5	124.47 (13)	C20—C19—H19	119.9
C15—C6—C5	113.26 (12)	C21—C20—C19	120.12 (14)
C6—C7—C8	118.34 (13)	C21—C20—H20	119.9
C6—C7—C16	121.23 (13)	C19—C20—H20	119.9
C8—C7—C16	120.43 (13)	C20—C21—C16	119.98 (13)
C8A—C8—C7	117.77 (13)	C20—C21—H21	120.0
C8A—C8—C22	116.44 (12)	C16—C21—H21	120.0
C7—C8—C22	125.79 (13)	N22—C22—C8	173.67 (15)
N1—C8A—N4	106.01 (12)	O2—S1—C24	105.38 (7)
N1—C8A—C8	131.52 (13)	O2—S1—C23	105.07 (7)
N4—C8A—C8	122.47 (13)	C24—S1—C23	99.29 (8)
C10—C9—C14	120.41 (13)	S1—C23—H23A	109.5
C10—C9—N2	123.15 (13)	S1—C23—H23B	109.5
C14—C9—N2	116.43 (13)	H23A—C23—H23B	109.5
C9—C10—C11	118.88 (14)	S1—C23—H23C	109.5
C9—C10—H10	120.6	H23A—C23—H23C	109.5
C11—C10—H10	120.6	H23B—C23—H23C	109.5
C12—C11—C10	121.06 (14)	S1—C24—H24A	109.5
C12—C11—H11	119.5	S1—C24—H24B	109.5
C10—C11—H11	119.5	H24A—C24—H24B	109.5
C11—C12—C13	119.36 (14)	S1—C24—H24C	109.5
C11—C12—H12	120.3	H24A—C24—H24C	109.5
C13—C12—H12	120.3	H24B—C24—H24C	109.5
C14—C13—C12	120.29 (14)

C8A—N1—C2—N3	−1.59 (16)	N3—N4—C8A—C8	179.38 (12)
C8A—N1—C2—N2	178.85 (12)	C5—N4—C8A—C8	−4.9 (2)
N3—C2—N2—C9	1.7 (2)	C7—C8—C8A—N1	−178.46 (13)
N1—C2—N2—C9	−178.83 (13)	C22—C8—C8A—N1	2.0 (2)
N2—C2—N3—N4	−179.43 (14)	C7—C8—C8A—N4	1.4 (2)
N1—C2—N3—N4	1.07 (15)	C22—C8—C8A—N4	−178.22 (13)
C2—N3—N4—C8A	−0.17 (14)	C2—N2—C9—C10	14.8 (2)
C2—N3—N4—C5	−175.92 (12)	C2—N2—C9—C14	−166.01 (14)
C8A—N4—C5—O1	−174.55 (13)	C14—C9—C10—C11	1.3 (2)
N3—N4—C5—O1	0.7 (2)	N2—C9—C10—C11	−179.53 (14)
C8A—N4—C5—C6	6.19 (19)	C9—C10—C11—C12	0.4 (2)
N3—N4—C5—C6	−178.59 (11)	C10—C11—C12—C13	−1.4 (3)
O1—C5—C6—C7	176.10 (14)	C11—C12—C13—C14	0.8 (2)
N4—C5—C6—C7	−4.69 (19)	C12—C13—C14—C9	0.8 (2)
O1—C5—C6—C15	−7.8 (2)	C10—C9—C14—C13	−1.9 (2)
N4—C5—C6—C15	171.43 (11)	N2—C9—C14—C13	178.89 (13)
C15—C6—C7—C8	−173.97 (12)	C6—C7—C16—C17	−134.34 (14)
C5—C6—C7—C8	1.8 (2)	C8—C7—C16—C17	46.20 (19)
C15—C6—C7—C16	6.6 (2)	C6—C7—C16—C21	47.42 (19)
C5—C6—C7—C16	−177.65 (12)	C8—C7—C16—C21	−132.04 (14)
C6—C7—C8—C8A	0.09 (19)	C21—C16—C17—C18	0.1 (2)
C16—C7—C8—C8A	179.57 (12)	C7—C16—C17—C18	−178.18 (13)
C6—C7—C8—C22	179.62 (13)	C16—C17—C18—C19	−0.2 (2)
C16—C7—C8—C22	−0.9 (2)	C17—C18—C19—C20	−0.1 (2)
C2—N1—C8A—N4	1.35 (14)	C18—C19—C20—C21	0.5 (2)
C2—N1—C8A—C8	−178.81 (14)	C19—C20—C21—C16	−0.6 (2)
N3—N4—C8A—N1	−0.77 (15)	C17—C16—C21—C20	0.3 (2)
C5—N4—C8A—N1	174.93 (12)	C7—C16—C21—C20	178.61 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.88 (2)	1.84 (2)	2.6249 (16)	146.9 (17)
N2—H2···O2	0.90 (2)	2.07 (2)	2.8680 (16)	147.7 (17)
C10—H10···N3	0.95	2.39	2.9956 (19)	121
C23—H23B···O1ⁱ	0.98	2.44	3.166 (2)	131
C24—H24B···N22	0.98	2.53	3.474 (2)	162

Symmetry code: (i) x+1, y+1, z.

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

Contact	Distance	Symmetry operation
O1···H23B	2.44	-1 + x, -1 + y, z
H17···O1	2.65	-x, 1 - y, 1 - z
O1···H24A	2.63	1 - x, 1 - y, 1 - z
H1···O2	1.84	x, y, z
H14···C21	2.98	1 - x, 1 - y, 1 - z
H19···N15	2.73	-x, 1 - y, 2 - z
H18···N22	2.82	1 - x, 2 - y, 2 - z
C22···H23B	3.08	1 - x, 2 - y, 1 - z
C9···H20	3.05	x, y, -1 + z
C11···C11	3.53	-x, -y, -z
C12···H18	3.05	x, -1 + y, -1 + z
H19···H23A	2.54	x, y, 1 + z
H12···H24A	2.41	-1 + x, -1 + y, -1 + z
H12···S1	3.04	1 - x, 1 - y, -z
H23C···H23C	2.43	1 - x, 2 - y, 1 - z

Acknowledgements

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

Funding information

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

References

Aydemir, E., Kansiz, S., Gumus, M. K., Gorobets, N. Y. & Dege, N. (2018). Acta Cryst. E74, 367–370. Web of Science CSD CrossRef IUCr Journals Google Scholar
Barsy, M. A., El Rady, E. A. & El Latif, F. M. A. (2008). J. Heterocycl. Chem. 45, 773–778. CSD 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
Çelik, M. S., Çetinus, A., Yenidünya, A. F., Çetinkaya, S. & Tüzün, B. (2023). J. Mol. Struct. 1272, 134158. Google Scholar
Chalkha, M., Ameziane el Hassani, A., Nakkabi, A., Tüzün, B., Bakhouch, M., Benjelloun, A. T., Sfaira, M., Saadi, M., Ammari, L. E. & Yazidi, M. E. (2023). J. Mol. Struct. 1273, 134255. Web of Science CSD CrossRef 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
Gumus, M. K., Kansiz, S., Yuksektepe Ataol, C., Dege, N. & Fritsky, I. O. (2019). Acta Cryst. E75, 492–498. CSD CrossRef IUCr Journals Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020). Chem. Eur. J. 26, 14833–14837. Web of Science CSD CrossRef CAS PubMed Google Scholar
Jones, G. & Abarca, B. (2010). Adv. Heterocycl. Chem. 100, 195–252. CrossRef CAS Google Scholar
Kotovshchikov, Y. N., Voloshkin, V. A., Latyshev, G. V., Lukashev, N. V. & Beletskaya, I. P. (2021). Russ. J. Org. Chem. 57, 1212–1244. CrossRef CAS 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
Mohamed, S. K., Soliman, A. M., El Remaily, M. A. A. & Abdel-Ghany, H. (2013). J. Heterocycl. Chem. 50, 1425–1430. Web of Science CrossRef CAS 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
Poustforoosh, A., Hashemipour, H., Tüzün, B., Azadpour, M., Faramarz, S., Pardakhty, A., Mehrabani, M. & Nematollahi, M. H. (2022). Curr. Microbiol. 79, 241. Web of Science CrossRef PubMed Google Scholar
Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. 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
Soliman, A. M., Mohamed, S. K., El-Remaily, M. A. A. & Abdel-Ghany, H. (2014). J. Heterocycl. Chem. 51, 1202–1209. Web of Science CrossRef CAS 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
Tapera, M., Kekeçmuhammed, H., Tüzün, B., Sarıpınar, E., Koçyiğit, M., Yıldırım, E., Doğan, M. & Zorlu, Y. (2022). J. Mol. Struct. 1269, 133816. Web of Science CSD CrossRef Google Scholar
Zubkov, F. I., Mertsalov, D. F., Zaytsev, V. P., Varlamov, A. V., Gurbanov, A. V., Dorovatovskii, P. V., Timofeeva, T. V., Khrustalev, V. N. & Mahmudov, K. T. (2018). J. Mol. Liq. 249, 949–952. Web of Science CSD CrossRef CAS Google Scholar

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