Crystal structure and Hirshfeld surface analysis of 4-azido-2-(3,5-di­methyl­phen­yl)-5-(4-nitro­phen­yl)-2H-1,2,3-triazole

Maharramov, A.; Shikhaliyev, N.Q.; Abdullayeva, A.; Atakishiyeva, G.T.; Niyazova, A.; Khrustalev, V.N.; Gahramanova, S.I.; Atioğlu, Z.; Akkurt, M.; Bhattarai, A.

doi:10.1107/S2056989023007855

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 10| October 2023| Pages 905-909

https://doi.org/10.1107/S2056989023007855

Open

access

Crystal structure and Hirshfeld surface analysis of 4-azido-2-(3,5-dimethylphenyl)-5-(4-nitrophenyl)-2H-1,2,3-triazole

^aOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan, ^bDepartment of Engineering and Applied Sciences, Azerbaijan State University of Economics, M. Mukhtarov 194, Baku AZ1001, Azerbaijan, ^cPeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation, ^dN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow, 119991, Russian Federation, ^eInstitute of Catalysis and Inorganic Chemistry , 113 H. Javid Ave., AZ1143 Baku, Azerbaijan, ^fDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Türkiye, ^gDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, and ^hDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: akkurt@erciyes.edu.tr,, ajaya.bhattarai@mmamc.tu.edu.np

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 7 July 2023; accepted 8 September 2023; online 14 September 2023)

In the title compound, C₁₆H₁₃N₇O₂, the 3,5-dimethylphenyl and 4-nitrophenyl rings are inclined to the central 2H-1,2,3-triazole ring by 1.80 (7) and 1.79 (7)°, respectively, and to one another by 2.16 (7)°. In the crystal, the molecules are linked by C—H⋯N hydrogen bonds and π–π stacking interactions [centroid-to-centroid distances = 3.7295 (9) and 3.7971 (9) Å], forming ribbons along the b-axis direction. These ribbons are connected to each other by weak van der Waals interactions and the stability of the crystal structure is ensured. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (31.5%), N⋯H/H⋯N (19.2%), O⋯H/H⋯O (14.5%), N⋯C/C⋯C (10.9%) and C⋯H/H⋯C (10.2%) contacts.

Keywords: crystal structure; hydrogen bonds; azido group; 2H-1,2,3-triazole; Hirshfeld surface analysis.

CCDC reference: 2293836

1. Chemical context

Triazoles are used as biological agents for their anti-inflammatory, anti-thrombotic and anti-viral activities (Blass et al., 2006 ; Caliendo et al., 1999 ; Phillips et al., 2009 ). At the same time, 2H-1,2,3-triazoles are effective catalysts (Zhao et al., 2008 ; Yan et al., 2006 ; Chandrasekhar et al., 2010 ) and are used as ionic liquids (Yoshida et al., 2012 ) in organic synthesis. It should be noted that many methods for their preparation are quite complicated, which limits the possibilities of studying the biological activity of these compounds and also their use in other fields of science and technology. In general, the development of new synthesis methods for 2H-1,2,3-triazole derivatives has been a constant in the field of organic synthesis. Since the 1,2,3-triazole ring is an integral part of many medicinal preparations, research on their synthesis (Kamijo et al., 2002 ; Liu et al., 2008 ; Ghozlan et al., 2006 ; Kalisiak et al., 2008 ; Koszytkowska-Stawińska et al., 2012 ) and biological activities is constantly increasing (Ferreira et al., 2013 ; Tan et al., 2002 ; Prusiner & Sundaralingam, 1973 ; Toniolo et al., 2017 ; Caliendo et al., 1999; Blass et al., 2006; von Mutius et al., 2012 ; Ferreira et al., 2013). In particular, we can mention the synthesis of new 1,2,3-triazole-based drugs against tuberculosis (Sanna et al., 2000 ). In this regard, the synthesis of 4-azido-2H-1,2,3-triazole derivatives (Tsyrenova et al., 2021 ) from the reaction of dichlorodiazadienes with NaN₃ is a relevant issue. In the following scheme (Fig. 1), on the basis of the synthesis of (E)-1-(2,2-dichloro-1-(4-nitrophenyl)vinyl)-2-(3,5-dimethylphenyl) diazene obtained from the reaction of N-substituted hydrazone (Maharramov et al., 2018 ; Nenajdenko et al., 2020 ; Shikhaliyev et al., 2018 , 2019a ,b , 2021a ,b ) and CCl₄ with NaN₃, 4-azido-2-(3,5-dimethylphenyl)-5-(4-nitrophenyl)-2H-1,2,3-triazole was synthesized and its structure was confirmed by single-crystal X-ray analysis.

Figure 1
Reaction scheme for the synthesis of the title compound.

2. Structural commentary

The molecule of the title compound, (Fig. 2), except for the methyl H atoms, can be described as essentially planar [maximum deviations = 0.060 (1) Å for C15 and −0.076 (1) Å for N6] with the substituents rotated slightly around the triazole centre. The planar 3,5-dimethylphenyl (C6–C11) and 4-nitrophenyl (C14–C19) rings are inclined to the central 2H-1,2,3-triazole ring (N1–N3/C4/C5) by 1.80 (7) and 1.79 (7)°, respectively, and to one another by 2.16 (7)°. The nitro group is co-planar with the benzene ring (C14–C19) to which it is connected [torsion angles O1—N7—C17—C16 = 0.4 (2)° and O2—N7—C17—C16 = −179.18 (12)°]. The azido group (–N3=N4⁺=N5⁻) is almost co-planar with the central 2H-1,2,3-triazole ring to which it is connected [N6—N5—N4 = 171.56 (14)° and torsion angles N5—N4—C4—N3 = −1.69 (19)° and N5—N4—C4—C5 = 177.54 (13)°].

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 and Hirshfeld surface analysis

In the crystal, the molecules are linked by C—H⋯N hydrogen bonds and π–π stacking interactions [Cg1⋯Cg2ⁱ = 3.7295 (9) Å; slippage = 1.489 Å and Cg2⋯Cg3ⁱⁱ = 3.7971 (9) Å; slippage = 1.783 Å; symmetry codes: (i) −x + 1, −y, −z + 1, (ii) −x + 1, −y + 1, −z + 1; Cg1, Cg2 and Cg3 are the centroids of the 2H-1,2,3-triazole (N1–N3/C4/C5), 3,5-dimethylphenyl (C6–C11) and 4-nitrophenyl (C14–C19) rings, respectively], forming ribbons along the b-axis direction (Tables 1 and 2; Fig. 3). These ribbons are connected to each other by weak van der Waals interactions and the stability of the crystal structure is ensured.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯N6ⁱ	0.98	2.61	3.570 (2)	166
Symmetry code: (i) .

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

O1⋯C12	3.36	x, 1 + y, 1 + z
N5⋯O1	2.98	1 − x, 1 − y, 2 − z
H13A⋯O2	2.90	1 − x, 1 − y, 1 − z
H7⋯H13A	2.59	−1 + x, y, z
H19⋯H18	2.37	−x, 1 − y, 1 − z
H12A⋯N6	2.61	1 − x, −y, 1 − z
H13C⋯H11	2.51	2 − x, −y, 1 − z
H15⋯N6	2.75	2 − x, 1 − y, 2 − z
H12A⋯C12	2.93	−x, −y, −z

Figure 3
The crystal packing of the title compound viewed along the a-axis with intermolecular C—H⋯N contacts and π–π stacking interactions shown as dashed lines.

In order to investigate the intermolecular interactions in a visual manner, a Hirshfeld surface analysis was performed using CrystalExplorer 17.5 (Spackman et al., 2021 ). The bright-red spots on the Hirshfeld surface mapped over d_norm (Fig. 4) indicate the presence of C—H⋯N interactions. The fingerprint plots (Fig. 5) are given for all contacts, and those delineated into H⋯H (31.5%), N⋯H/H⋯N (19.2%), O⋯H/H⋯O (14.5%), N⋯C/C⋯N (10.9%), C⋯H/H⋯C (10.2%), C⋯C (5.2%), O⋯N/N⋯O (4.0%), O⋯C/C⋯O (2.4%) and N⋯N (2.1%). The most important contributions to the crystal packing are H⋯H and N⋯H/H⋯N contacts.

Figure 4
(a) Front and (b) back views of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm.

Figure 5
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) N⋯H/H⋯N, (d) O⋯H/H⋯O, (e) N⋯C/C⋯N and (e) C⋯H/H⋯C 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

The ten most similar compounds found in a search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) for the 2H-1,2,3-triazole group are JADSEP (Canseco-González et al., 2015 ), JELTEC (Zukerman-Schpector et al., 2017 ), HUYTEC (Haslinger et al., 2015 ), FEVLIE, FEVLOK, FEVLUQ, FEVMAX, FEVMEB and FEVMOL (Farrán et al., 2018 ) and SECQUO (Altimari et al., 2012 ).

In the crystal of JADSEP, molecules are linked via C—H⋯I hydrogen bonds, forming slabs parallel to the ab plane. Within the slabs there are weak π–π interactions present involving the mesityl and phenyl rings. In the crystal of JELTEC, the three-dimensional packing is stabilized by a combination of methylene-C—H⋯O, methylene-C—H⋯π, C—H⋯π and nitro-O⋯π (nitrobenzene) interactions, along with weak π (triazolyl)–π (nitrobenzene) contacts. In the crystal of HUYTEC, the water molecules are connected into [010] chains by O—H⋯O hydrogen bonds, while O—H⋯N hydrogen bonds connect the water molecules to the organic molecules, generating corrugated (100) sheets. In the crystals of FEVLIE, FEVLOK, FEVLUQ, FEVMAX, FEVMEB and FEVMOL, there are no C_ar—H⋯F—C intramolecular contacts. If the aryl groups were coplanar with the triazole ring, the C—F and the C—H atoms would be too close. Thus, the steric effect is more efficient than the weak hydrogen bond. Only compound FEVMOL clearly shows a hydrogen bond (O—H⋯N). In the crystal of SECQUO, the molecules pack in a head-to-tail arrangement along the a-axis direction with closest inter-centroid distances between the triazole rings of 3.7372 (12) Å.

5. Synthesis and crystallization

The title compound was synthesized according to a literature protocol (Tsyrenova et al., 2021). A 20 ml screw-neck vial was charged with DMSO (20 ml), (E)-1-[2,2-dichloro-1-(4-nitrophenyl)vinyl]-2-(3,5-dimethylphenyl)diazene (350 mg, 1 mmol) and sodium azide (NaN₃; 390 mq; 3 mmol). After 1–3 h (until TLC analysis showed complete consumption of the corresponding triazole), the reaction mixture was poured into a 0.01 M solution of HCl (100 ml, pH = 2–3), and extracted with dichloromethane (3 × 20 ml). The combined organic phase was washed with water (3 × 50 ml), brine (30 ml), dried over anhydrous Na₂SO₄ and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (v/v: 3/1–1/1). Red solid (yield 75%); m.p. 375 K. Analysis calculated for C₁₆H₁₃N₇O₂ (M = 335.33): ¹H NMR (300 MHz, chloroform-d) δ 8.84 (s, 1H), 8.40–8.27 (m, 1H), 8.20 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.62 (t, J = 8.0 Hz, 1H), 7.02 (s, 1H), 2.44 (s, 6H). ¹³C NMR (75 MHz, CDCl₃) δ 143.9, 134.7, 134.4, 130.1, 127.3, 126.1, 125.0, 118.3, 116.5, 111.4, 16.8. The compound was dissolved in dichloromethane and then left at room temperature for slow evaporation; red crystal of the title compound suitable for X-rays started to form after ca 2 d.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and allowed to ride on their parent atoms (C—H = 0.95–0.98 Å) with U_iso(H) = 1.2 or 1.5U_eq(C). Owing to poor agreement between observed and calculated intensities, sixteen outliers (6 $[\overline{10}]$ 1, $[\overline{5}]$ 12 0, $[\overline{7}]$ 11 0, $[\overline{6}]$ 12 1, 6 $[\overline{12}]$ 1, 7 $[\overline{11}]$ 1, 5 $[\overline{10}]$ 1, $[\overline{2}]$ 2 6, 2 $[\overline{1}]$ 1, 1 1 4, $[\overline{2}]$ 4 1, $[\overline{1}]$ 1 1, 0 2 0, $[\overline{2}]$ 1 2, $[\overline{1}]$ 4 4, 2 0 5) were omitted during the final refinement cycle.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₁₃N₇O₂
M_r	335.33
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.4400 (8), 9.920 (1), 11.5200 (13)
α, β, γ (°)	93.071 (9), 105.349 (10), 108.879 (11)
V (Å³)	766.71 (16)
Z	2
Radiation type	Synchrotron, λ = 0.79313 Å
μ (mm⁻¹)	0.13
Crystal size (mm)	0.09 × 0.05 × 0.03

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.969, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	13293, 3466, 2976
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.133, 1.08
No. of reflections	3466
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.22
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: 2293836

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007855/zn2031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023007855/zn2031Isup2.hkl

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).

4-Azido-2-(3,5-dimethylphenyl)-5-(4-nitrophenyl)-2H-1,2,3-triazole top

Crystal data top

C₁₆H₁₃N₇O₂	Z = 2
M_r = 335.33	F(000) = 348
Triclinic, P1	D_x = 1.452 Mg m⁻³
a = 7.4400 (8) Å	Synchrotron radiation, λ = 0.79313 Å
b = 9.920 (1) Å	Cell parameters from 1000 reflections
c = 11.5200 (13) Å	θ = 2.1–28.0°
α = 93.071 (9)°	µ = 0.13 mm⁻¹
β = 105.349 (10)°	T = 100 K
γ = 108.879 (11)°	Prism, red
V = 766.71 (16) Å³	0.09 × 0.05 × 0.03 mm

Data collection top

Rayonix SX165 CCD diffractometer	2976 reflections with I > 2σ(I)
/f scan	R_int = 0.025
Absorption correction: multi-scan (SCALA; Evans, 2006)	θ_max = 31.0°, θ_min = 2.1°
T_min = 0.969, T_max = 0.990	h = −9→9
13293 measured reflections	k = −12→12
3466 independent reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0764P)² + 0.1976P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3466 reflections	Δρ_max = 0.27 e Å⁻³
229 parameters	Δρ_min = −0.22 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: 0.074 (7)

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	0.18207 (18)	0.76197 (12)	0.92289 (10)	0.0446 (3)
O2	−0.03369 (17)	0.69879 (12)	0.74319 (11)	0.0423 (3)
N1	0.47322 (16)	0.30620 (12)	0.54670 (10)	0.0295 (3)
N2	0.59776 (16)	0.23870 (12)	0.53829 (10)	0.0280 (3)
N3	0.74669 (16)	0.25675 (12)	0.64053 (10)	0.0295 (3)
N4	0.83239 (17)	0.38805 (13)	0.84246 (10)	0.0326 (3)
N5	0.96905 (17)	0.34031 (13)	0.87091 (10)	0.0332 (3)
N6	1.10029 (19)	0.30585 (14)	0.91074 (12)	0.0387 (3)
N7	0.11839 (19)	0.69804 (13)	0.81792 (11)	0.0343 (3)
C4	0.71164 (19)	0.34137 (14)	0.71900 (12)	0.0291 (3)
C5	0.54163 (19)	0.37371 (14)	0.66201 (12)	0.0282 (3)
C6	0.57495 (19)	0.15443 (14)	0.42750 (12)	0.0279 (3)
C7	0.41649 (19)	0.14311 (14)	0.32646 (12)	0.0284 (3)
H7	0.3240	0.1885	0.3323	0.034*
C8	0.3946 (2)	0.06480 (14)	0.21667 (12)	0.0305 (3)
C9	0.5333 (2)	−0.00175 (14)	0.21177 (13)	0.0325 (3)
H9	0.5185	−0.0562	0.1373	0.039*
C10	0.6915 (2)	0.00999 (15)	0.31301 (13)	0.0331 (3)
C11	0.7126 (2)	0.08921 (15)	0.42256 (13)	0.0323 (3)
H11	0.8196	0.0984	0.4929	0.039*
C12	0.2269 (2)	0.05374 (16)	0.10597 (13)	0.0361 (3)
H12A	0.1186	−0.0385	0.0952	0.054*
H12B	0.2744	0.0595	0.0341	0.054*
H12C	0.1783	0.1330	0.1163	0.054*
C13	0.8416 (2)	−0.05959 (18)	0.30537 (15)	0.0420 (4)
H13A	0.9732	0.0151	0.3219	0.063*
H13B	0.8026	−0.1137	0.2236	0.063*
H13C	0.8465	−0.1254	0.3657	0.063*
C14	0.43732 (19)	0.45871 (14)	0.70518 (12)	0.0280 (3)
C15	0.5043 (2)	0.53230 (15)	0.82427 (12)	0.0319 (3)
H15	0.6221	0.5286	0.8796	0.038*
C16	0.4004 (2)	0.61052 (15)	0.86228 (12)	0.0330 (3)
H16	0.4453	0.6600	0.9433	0.040*
C17	0.2301 (2)	0.61509 (14)	0.77992 (12)	0.0303 (3)
C18	0.1596 (2)	0.54308 (15)	0.66123 (13)	0.0326 (3)
H18	0.0421	0.5477	0.6063	0.039*
C19	0.2631 (2)	0.46465 (15)	0.62443 (12)	0.0317 (3)
H19	0.2160	0.4142	0.5437	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0571 (7)	0.0466 (6)	0.0388 (6)	0.0239 (5)	0.0224 (5)	0.0007 (5)
O2	0.0407 (6)	0.0442 (6)	0.0509 (6)	0.0247 (5)	0.0162 (5)	0.0061 (5)
N1	0.0288 (5)	0.0328 (6)	0.0295 (6)	0.0152 (5)	0.0077 (4)	0.0019 (4)
N2	0.0263 (5)	0.0323 (6)	0.0273 (5)	0.0144 (4)	0.0065 (4)	0.0030 (4)
N3	0.0273 (5)	0.0334 (6)	0.0283 (6)	0.0133 (4)	0.0059 (4)	0.0041 (4)
N4	0.0292 (6)	0.0376 (6)	0.0305 (6)	0.0154 (5)	0.0050 (5)	−0.0014 (5)
N5	0.0331 (6)	0.0367 (6)	0.0288 (6)	0.0134 (5)	0.0065 (5)	0.0032 (5)
N6	0.0351 (6)	0.0455 (7)	0.0364 (6)	0.0196 (5)	0.0057 (5)	0.0058 (5)
N7	0.0402 (6)	0.0317 (6)	0.0383 (6)	0.0160 (5)	0.0193 (5)	0.0052 (5)
C4	0.0276 (6)	0.0317 (6)	0.0286 (6)	0.0123 (5)	0.0069 (5)	0.0046 (5)
C5	0.0278 (6)	0.0304 (6)	0.0272 (6)	0.0116 (5)	0.0077 (5)	0.0035 (5)
C6	0.0290 (6)	0.0288 (6)	0.0290 (6)	0.0127 (5)	0.0106 (5)	0.0035 (5)
C7	0.0268 (6)	0.0289 (6)	0.0311 (7)	0.0117 (5)	0.0091 (5)	0.0027 (5)
C8	0.0298 (6)	0.0294 (6)	0.0320 (7)	0.0104 (5)	0.0093 (5)	0.0026 (5)
C9	0.0360 (7)	0.0306 (6)	0.0344 (7)	0.0139 (5)	0.0143 (6)	0.0014 (5)
C10	0.0342 (7)	0.0332 (7)	0.0379 (7)	0.0167 (6)	0.0146 (6)	0.0052 (5)
C11	0.0306 (6)	0.0369 (7)	0.0334 (7)	0.0174 (6)	0.0093 (5)	0.0058 (5)
C12	0.0359 (7)	0.0384 (7)	0.0314 (7)	0.0152 (6)	0.0049 (6)	−0.0029 (5)
C13	0.0411 (8)	0.0484 (8)	0.0449 (8)	0.0268 (7)	0.0136 (6)	0.0019 (7)
C14	0.0279 (6)	0.0292 (6)	0.0273 (6)	0.0110 (5)	0.0080 (5)	0.0031 (5)
C15	0.0312 (6)	0.0357 (7)	0.0279 (6)	0.0133 (5)	0.0056 (5)	0.0021 (5)
C16	0.0366 (7)	0.0344 (7)	0.0278 (6)	0.0131 (6)	0.0091 (5)	0.0004 (5)
C17	0.0329 (7)	0.0301 (6)	0.0324 (7)	0.0136 (5)	0.0139 (5)	0.0038 (5)
C18	0.0310 (6)	0.0366 (7)	0.0320 (7)	0.0160 (5)	0.0075 (5)	0.0028 (5)
C19	0.0319 (7)	0.0361 (7)	0.0275 (6)	0.0159 (6)	0.0055 (5)	−0.0002 (5)

Geometric parameters (Å, º) top

O1—N7	1.2284 (16)	C9—H9	0.9500
O2—N7	1.2296 (17)	C10—C11	1.3944 (19)
N1—N2	1.3261 (15)	C10—C13	1.5085 (19)
N1—C5	1.3410 (16)	C11—H11	0.9500
N2—N3	1.3435 (15)	C12—H12A	0.9800
N2—C6	1.4268 (17)	C12—H12B	0.9800
N3—C4	1.3323 (17)	C12—H12C	0.9800
N4—N5	1.2317 (16)	C13—H13A	0.9800
N4—C4	1.4242 (17)	C13—H13B	0.9800
N5—N6	1.1299 (17)	C13—H13C	0.9800
N7—C17	1.4681 (17)	C14—C15	1.3996 (18)
C4—C5	1.4069 (18)	C14—C19	1.4020 (18)
C5—C14	1.4640 (18)	C15—C16	1.3866 (19)
C6—C11	1.3876 (18)	C15—H15	0.9500
C6—C7	1.3897 (18)	C16—C17	1.383 (2)
C7—C8	1.3905 (18)	C16—H16	0.9500
C7—H7	0.9500	C17—C18	1.3886 (19)
C8—C9	1.4043 (19)	C18—C19	1.3798 (19)
C8—C12	1.4995 (19)	C18—H18	0.9500
C9—C10	1.389 (2)	C19—H19	0.9500

N2—N1—C5	104.92 (11)	C6—C11—H11	120.4
N1—N2—N3	115.31 (11)	C10—C11—H11	120.4
N1—N2—C6	121.86 (11)	C8—C12—H12A	109.5
N3—N2—C6	122.82 (11)	C8—C12—H12B	109.5
C4—N3—N2	102.74 (11)	H12A—C12—H12B	109.5
N5—N4—C4	113.98 (11)	C8—C12—H12C	109.5
N6—N5—N4	171.56 (14)	H12A—C12—H12C	109.5
O1—N7—O2	123.90 (12)	H12B—C12—H12C	109.5
O1—N7—C17	117.93 (12)	C10—C13—H13A	109.5
O2—N7—C17	118.17 (12)	C10—C13—H13B	109.5
N3—C4—C5	110.21 (11)	H13A—C13—H13B	109.5
N3—C4—N4	122.95 (12)	C10—C13—H13C	109.5
C5—C4—N4	126.83 (12)	H13A—C13—H13C	109.5
N1—C5—C4	106.82 (11)	H13B—C13—H13C	109.5
N1—C5—C14	120.20 (12)	C15—C14—C19	119.20 (12)
C4—C5—C14	132.97 (12)	C15—C14—C5	122.24 (12)
C11—C6—C7	121.96 (12)	C19—C14—C5	118.56 (12)
C11—C6—N2	119.59 (12)	C16—C15—C14	120.60 (13)
C7—C6—N2	118.43 (11)	C16—C15—H15	119.7
C6—C7—C8	119.39 (12)	C14—C15—H15	119.7
C6—C7—H7	120.3	C17—C16—C15	118.67 (12)
C8—C7—H7	120.3	C17—C16—H16	120.7
C7—C8—C9	118.67 (13)	C15—C16—H16	120.7
C7—C8—C12	120.20 (12)	C16—C17—C18	122.11 (13)
C9—C8—C12	121.13 (12)	C16—C17—N7	119.61 (12)
C10—C9—C8	121.71 (13)	C18—C17—N7	118.28 (12)
C10—C9—H9	119.1	C19—C18—C17	118.84 (13)
C8—C9—H9	119.1	C19—C18—H18	120.6
C9—C10—C11	119.17 (13)	C17—C18—H18	120.6
C9—C10—C13	120.99 (13)	C18—C19—C14	120.58 (12)
C11—C10—C13	119.84 (13)	C18—C19—H19	119.7
C6—C11—C10	119.10 (13)	C14—C19—H19	119.7

C5—N1—N2—N3	−0.26 (15)	C8—C9—C10—C11	0.4 (2)
C5—N1—N2—C6	−179.58 (11)	C8—C9—C10—C13	−178.68 (13)
N1—N2—N3—C4	0.38 (15)	C7—C6—C11—C10	0.0 (2)
C6—N2—N3—C4	179.70 (12)	N2—C6—C11—C10	−178.46 (12)
N2—N3—C4—C5	−0.34 (14)	C9—C10—C11—C6	−0.1 (2)
N2—N3—C4—N4	179.00 (12)	C13—C10—C11—C6	178.98 (13)
N5—N4—C4—N3	−1.69 (19)	N1—C5—C14—C15	−179.28 (12)
N5—N4—C4—C5	177.54 (13)	C4—C5—C14—C15	1.9 (2)
N2—N1—C5—C4	0.03 (14)	N1—C5—C14—C19	1.52 (19)
N2—N1—C5—C14	−179.08 (11)	C4—C5—C14—C19	−177.31 (14)
N3—C4—C5—N1	0.21 (15)	C19—C14—C15—C16	−0.1 (2)
N4—C4—C5—N1	−179.10 (12)	C5—C14—C15—C16	−179.32 (12)
N3—C4—C5—C14	179.16 (13)	C14—C15—C16—C17	−0.4 (2)
N4—C4—C5—C14	−0.1 (2)	C15—C16—C17—C18	0.5 (2)
N1—N2—C6—C11	178.22 (12)	C15—C16—C17—N7	−179.59 (12)
N3—N2—C6—C11	−1.1 (2)	O1—N7—C17—C16	0.4 (2)
N1—N2—C6—C7	−0.33 (19)	O2—N7—C17—C16	−179.18 (12)
N3—N2—C6—C7	−179.60 (11)	O1—N7—C17—C18	−179.69 (12)
C11—C6—C7—C8	−0.3 (2)	O2—N7—C17—C18	0.70 (19)
N2—C6—C7—C8	178.25 (12)	C16—C17—C18—C19	−0.1 (2)
C6—C7—C8—C9	0.5 (2)	N7—C17—C18—C19	−179.95 (12)
C6—C7—C8—C12	−178.79 (12)	C17—C18—C19—C14	−0.5 (2)
C7—C8—C9—C10	−0.6 (2)	C15—C14—C19—C18	0.6 (2)
C12—C8—C9—C10	178.72 (13)	C5—C14—C19—C18	179.82 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N1	0.95	2.47	2.7900 (18)	100
C12—H12A···N6ⁱ	0.98	2.61	3.570 (2)	166
C15—H15···N4	0.95	2.51	3.174 (2)	127
C19—H19···N1	0.95	2.47	2.810 (2)	101

Symmetry code: (i) −x+1, −y, −z+1.

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

O1···C12	3.36	x, 1 + y, 1 + z
N5···O1	2.98	1 - x, 1 - y, 2 - z
H13A···O2	2.90	1 - x, 1 - y, 1 - z
H7···H13A	2.59	-1 + x, y, z
H19···H18	2.37	-x, 1 - y, 1 - z
H12A···N6	2.61	1 - x, -y, 1 - z
H13C···H11	2.51	2 - x, -y, 1 - z
H15···N6	2.75	2 - x, 1 - y, 2 - z
H12A···C12	2.93	-x, -y, -z

Acknowledgements

The authors' contributions are as follows. Conceptualization, ZA, MA and AB; synthesis, AA, AN and GTA; X-ray analysis, VK, SG and MA; writing (review and editing of the manuscript) ZA, MA and AB; funding acquisition, NQS, and AM; supervision, NQS, MA and AB.

Funding information

This work was funded by the Science Development Foundation under the President of the Republic of Azerbaijan, grant No. EIF–BGM-4-RFTF-1/2017–21/13/4.

References

Altimari, J. M., Healy, P. C. & Henderson, L. C. (2012). Acta Cryst. E68, o3159. CSD CrossRef IUCr Journals 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
Blass, B. E., Coburn, K., Lee, W., Fairweather, N., Fluxe, A., Wu, S., Janusz, J. M., Murawsky, M., Fadayel, G. M., Fang, B., Hare, M., Ridgeway, J., White, R., Jackson, C., Djandjighian, L., Hedges, R., Wireko, F. C. & Ritter, A. L. (2006). Bioorg. Med. Chem. Lett. 16, 4629–4632. Web of Science CSD CrossRef PubMed CAS Google Scholar
Caliendo, G., Fiorino, F., Grieco, P., Perissutti, E., Santagada, V., Meli, R., Raso, G. M., Zanesco, A. & De Nucci, G. (1999). Eur. J. Med. Chem. 34, 1043–1051. Web of Science CrossRef CAS Google Scholar
Canseco-González, D., García, J. J. & Flores-Alamo, M. (2015). Acta Cryst. E71, o1041–o1042. CSD CrossRef IUCr Journals Google Scholar
Chandrasekhar, S., Kumar, T. P., Haribabu, K. & Reddy, C. R. (2010). Tetrahedron Asymmetry, 21, 2372–2375. Web of Science CrossRef CAS Google Scholar
Doyle, R. A. (2011). Marccd software manual. Rayonix LLC, Evanston, IL 60201, USA. Google Scholar
Evans, P. (2006). Acta Cryst. D62, 72–82. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrán, M. Á., Bonet, M. Á., Claramunt, R. M., Torralba, M. C., Alkorta, I. & Elguero, J. (2018). Acta Cryst. C74, 513–522. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ferreira, V. F., da Rocha, D. R., da Silva, F. C., Ferreira, P. G., Boechat, N. A. & Magalhães, J. L. (2013). Expert Opin. Ther. Pat. 23, 319–331. Web of Science CrossRef CAS PubMed Google Scholar
Ghozlan, S. A., Abdelhamid, I. A., Ibrahim, H. M. & Elnagdi, M. H. (2006). Arkivoc, 2006, 53–60. Web of Science CrossRef 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
Haslinger, S., Laus, G., Wurst, K. & Schottenberger, H. (2015). Acta Cryst. E71, o945–o946. CSD CrossRef IUCr Journals Google Scholar
Kalisiak, J., Sharpless, K. B. & Fokin, V. V. (2008). Org. Lett. 10, 3171–3174. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kamijo, S., Jin, T., Huo, Z. & Yamamoto, Y. (2002). Tetrahedron Lett. 43, 9707–9710. Web of Science CrossRef CAS Google Scholar
Koszytkowska-Stawińska, M., Mironiuk-Puchalska, E. & Rowicki, T. (2012). Tetrahedron, 68, 214–225. Google Scholar
Liu, Y., Yan, W., Chen, Y., Petersen, J. L. & Shi, X. (2008). Org. Lett. 10, 5389–5392. Web of Science CSD CrossRef PubMed 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. (2018). Dyes Pigments, 159, 135–141. Web of Science CrossRef CAS Google Scholar
Mutius, E. von & Drazen, J. M. (2012). N. Engl. J. Med. 366, 827–834. Web of Science PubMed Google Scholar
Nenajdenko, V. G., Shikhaliyev, N. G., Maharramov, A. M., Bagirova, K. N., Suleymanova, G. T., Novikov, A. S., Khrustalev, V. N. & Tskhovrebov, A. G. (2020). Molecules, 25, 5013. Web of Science CSD CrossRef PubMed Google Scholar
Phillips, O. A., Udo, E. E., Abdel-Hamid, M. E. & Varghese, R. (2009). Eur. J. Med. Chem. 44, 3217–3227. Web of Science CrossRef PubMed CAS Google Scholar
Prusiner, P. T. & Sundaralingam, M. (1973). Nature New Biol. 244, 116–118. CrossRef CAS PubMed Web of Science Google Scholar
Sanna, P., Carta, A. & Nikookar, M. E. (2000). Eur. J. Med. Chem. 35, 535–543. Web of Science CrossRef PubMed CAS 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
Shikhaliyev, N. G., Maharramov, A. M., Bagirova, K. N., Suleymanova, G. T., Tsyrenova, B. D., Nenajdenko, V. G., Novikov, A. S., Khrustalev, V. N. & Tskhovrebov, A. G. (2021a). Mendeleev Commun. 31, 191–193. Web of Science CSD CrossRef CAS Google Scholar
Shikhaliyev, N. G., Maharramov, A. M., Suleymanova, G. T., Babayeva, G. V., Mammadova, G. Z., Shikhaliyeva, I. M., Babazade, A. A. & Nenajdenko, V. G. (2021b). Organic Chemistry, (part iii), 67–75. Google Scholar
Shikhaliyev, N. G., Suleymanova, G. T., İsrayilova, A. A., Ganbarov, K. G., Babayeva, G. V., Garazadeh, K. A., Mammadova, G. Z. & Nenajdenko, V. G. (2019b). Organic Chemistry, (part vi), 64–73. Google Scholar
Shikhaliyev, N. Q., Ahmadova, N. E., Gurbanov, A. V., Maharramov, A. M., Mammadova, G. Z., Nenajdenko, V. G., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. (2018). Dyes Pigments, 150, 377–381. Web of Science CSD CrossRef CAS Google Scholar
Shikhaliyev, N. Q., Kuznetsov, M. L., Maharramov, A. M., Gurbanov, A. V., Ahmadova, N. E., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. (2019a). CrystEngComm, 21, 5032–5038. Web of Science CSD 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
Tan, S. L., Pause, A., Shi, Y. & Sonenberg, N. (2002). Nat. Rev. Drug Discov. 1, 867–881. Web of Science CrossRef PubMed CAS Google Scholar
Toniolo, N., Taveri, G., Hurle, K., Roether, J., Ercole, P., Dlouhy, I. & Boccaccini, A. R. (2017). Journal of Ceramic Science and Technology, 8, 411–420. Google Scholar
Tsyrenova, B. D., Khrustalev, V. N. & Nenajdenko, V. G. (2021). Org. Biomol. Chem. 19, 8140–8152. Web of Science CSD CrossRef CAS PubMed Google Scholar
Yan, Z. Y., Niu, Y. N., Wei, H. L., Wu, L. Y., Zhao, Y. B. & Liang, Y. M. (2006). Tetrahedron Asymmetry, 17, 3288–3293. Web of Science CrossRef CAS Google Scholar
Yoshida, Y., Takizawa, S. & Sasai, H. (2012). Tetrahedron Asymmetry, 23, 843–851. Web of Science CrossRef CAS Google Scholar
Zhao, Y. B., Zhang, L. W., Wu, L. Y., Zhong, X., Li, R. & Ma, J. T. (2008). Tetrahedron Asymmetry, 19, 1352–1355. Web of Science CrossRef CAS Google Scholar
Zukerman-Schpector, J., Dallasta Pedroso, S., Sousa Madureira, L., Weber Paixão, M., Ali, A. & Tiekink, E. R. T. (2017). Acta Cryst. E73, 1716–1720. CSD CrossRef IUCr Journals 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.