Crystal structure and Hirshfeld surface analysis of 3-[2-(3,5-di­methyl­phen­yl)hydrazinyl­idene]benzo­furan-2(3H)-one

Atioğlu, Z.; Akkurt, M.; Shikhaliyev, N.Q.; Askerova, U.F.; Mukhtarova, S.H.; Askerov, R.K.; Bhattarai, A.

doi:10.1107/S2056989021011749

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1280-1284

https://doi.org/10.1107/S2056989021011749

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Crystal structure and Hirshfeld surface analysis of 3-[2-(3,5-dimethylphenyl)hydrazinylidene]benzofuran-2(3H)-one

Zeliha Atioğlu,^a Mehmet Akkurt,^b Namiq Q. Shikhaliyev,^c Ulviyya F. Askerova,^c Sevinc H. Mukhtarova,^c Rizvan K. Askerov ^c and Ajaya Bhattarai ^d ^*

^aDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az, 1148 Baku, Azerbaijan, and ^dDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: bkajaya@yahoo.com

Edited by H. Ishida, Okayama University, Japan (Received 20 October 2021; accepted 5 November 2021; online 12 November 2021)

In the title compound, C₁₆H₁₄N₂O₂, the 2,3-dihydro-1-benzofuran ring system is essentially planar and makes a dihedral angle of 3.69 (7)° with the dimethylphenyl ring. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond with an S(6) ring motif. In the crystal, molecules are connected by C—H⋯π and π–π stacking interactions, forming a layer lying parallel to the (11 $[\overline{1}]$ ) plane. One methyl group is disordered over two orientations, with occupancies of 0.67 (4) and 0.33 (4). Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (51.2%), O⋯H/H⋯O (17.9%), C⋯H/H⋯C (15.2%) and C⋯C (8.1%) contacts.

Keywords: crystal structure; intramolecular N—H⋯O interactions; C—H⋯π interactions; Hirshfeld surface analysis.

CCDC reference: 1983650

1. Chemical context

Hydrazones have many applications in diverse areas, such as in optical data storage, as molecular switches and antimicrobial agents, in non-linear optics, molecular recognition, dye-sensitized solar cells, color-changing materials, catalysis, liquid crystals, etc., mainly because of the azo-to-hydrazo tautomerism/isomerism and the optical properties of –N=N– unit (Maharramov et al., 2018 ; Ma et al., 2020 , 2021 ; Viswanathan et al., 2019 ). Not only E/Z isomerization, but also azo-hydrazone tautomerism is important in organic and the coordination chemistry of hydrazone dyes (Ma et al., 2017a ,b ; Mahmoudi et al., 2017 , 2018 ). The design of hydrazone dyes with electron donor or acceptor substituents has led to multidentante ligands, the corresponding coordination compounds of which have been applied effectively as catalysts in oxidation and C—C coupling reactions (Mahmudov et al., 2013 ; Mizar et al., 2012 ). Moreover, the functional properties of hydrazones or their metal complexes can be regulated by attaching functional groups to the =N—NH— unit (Gurbanov et al., 2020a ,b ; Kopylovich et al., 2011 ; Mahmudov et al., 2020 ; Shixaliyev et al., 2014 ). Thus, we have attached C=O groups and furan and aryl rings to the =N—NH— moiety, leading to a new hydrazone compound, (Z)-3-[2-(3,5-dimethylphenyl)hydrazinylidene]benzofuran-2(3H)-one, which can form intermolecular interactions.

2. Structural commentary

The molecular conformation of the title compound is stabilized by an intramolecular N—H⋯O hydrogen bond (N2—H2⋯O2; Table 1) with an S(6) ring motif (Fig. 1). The 2,3-dihydro-1-benzofuran ring system (O1/C1–C8) of the title compound is essentially planar [maximum deviations = −0.031 (2) Å for C3 and 0.026 (2) Å for C6] and makes a dihedral angle of 3.69 (7)° with the dimethylphenyl C9–C14 ring. In the molecule, the aromatic C9–C14 ring and the C=N—NH– unit are almost coplanar with a dihedral angle of 4.8 (8)° between them.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the C3–C8 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.93 (2)	2.12 (2)	2.840 (2)	133.8 (16)
C15—H15A⋯Cg3ⁱ	0.96	2.90	3.591 (3)	130
C16—H16F⋯Cg2ⁱⁱ	0.96	2.92	3.715 (3)	141
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ ; (ii) .

Figure 1
The molecular structure of the title compound with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level.

3. Supramolecular features

In the crystal, molecules are connected by C—H⋯π interactions [C15—H15A⋯Cg3ⁱ and C16—H16F⋯Cg2ⁱⁱ; symmetry codes as given in Table 1; Fig. 2] and π–π stacking interactions [Cg1⋯Cg2^îii = 3.6227 (11) Å, slippage = 1.226 Å; Cg1⋯Cg3^îi = 3.7128 (10) Å, slippage = 1.339 Å; Symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) −x + 2, −y + 1, −z + 2], where Cg1 and Cg2 are the centroids of the oxolane O1/C1–C3/C8 and benzene C3–C8 rings, respectively, of the 2,3-dihydro-1-benzofuran ring system while Cg3 is the centroid of the dimethylphenyl C9–C14 ring (Fig. 3). These interactions link the molecules into a layer structure lying parallel to the (11 $[\overline{1}]$ ) plane (Fig. 4).

Figure 2
A partial packing view of the title compound, showing the C—H⋯π interactions (dashed lines). Only H atoms involved in the interactions and N-bound H atoms are shown for clarity [Symmetry codes: (i) x, −y − $[{1\over 2}]$ , z − $[{3\over 2}]$ ; (ii) −x + 1, −y + 1, −z + 1.]

Figure 3
A partial packing view of the title compound, showing the π–π stacking interactions (dashed lines). Only N-bound H atoms are shown for clarity [Symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) 2 − x, 1 − y, 2 − z.]

Figure 4
A packing diagram of the title compound viewed along the a-axis, showing C—H⋯π interactions (dashed lines). Only H atoms involved in the interactions and N-bound H atoms are shown for clarity.

4. Hirshfeld surface analysis

Crystal Explorer17 (Turner et al., 2017 ) was used to perform a Hirshfeld surface analysis and generate the associated two-dimensional fingerprint plots, with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed color scale of −0.0001 (red) to 1.5993 (blue) a.u. (Fig. 5a). All of the disordered H atoms of the C16 methyl group were taken into account together. The shape-index of the Hirshfeld surface is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5b clearly indicates that there are π–π interactions in the title compound.

Figure 5
Hirshfeld surfaces of the title molecule, (a) mapped with d_norm in the range −0.0001 to 1.5993 a.u. and (b) plotted over shape-index.

Two-dimensional fingerprint plots for the H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯C contacts are presented in Fig. 6. H⋯H interactions, which are located in the middle region of the fingerprint plot, contribute the most to overall crystal packing, with 51.2% (Fig. 6b). The O⋯H/H⋯O contacts contribute 17.9% (Fig. 6c) to the Hirshfeld surface, while the C⋯H/H⋯C contacts contribute 15.2% (Fig. 6d), resulting in a pair of distinctive wings. The C⋯C interactions account for 8.1% of the Hirshfeld surface. The percentage contributions to the Hirshfeld surface including other minor ones are summarized in Table 2.

Table 2
Percentage contributions of interatomic contacts to the Hirshfeld surface of the title compound

Contact	Percentage contribution
H⋯H	51.2
O⋯H/H⋯O	17.9
C⋯H/H⋯C	15.2
C⋯C	8.1
N⋯C/C⋯N	4.2
N⋯H/H⋯N	1.9
O⋯C/C⋯O	0.9
N⋯N	0.6
O⋯O	0.1

Figure 6
Fingerprint plots showing (a) all intermolecular interactions and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C and (e) C⋯C contacts.

5. Database survey

A search of the Cambridge Crystallographic Database (CSD version 5.42, updated September 2021; Groom et al., 2016 ) for the 1-benzofuran-2(3H)-one unit gave 220 hits. Of these, the compound most similar to the title compound is 7-methoxy-3-(2-phenylhydrazinylidene)-1-benzofuran-2(3H)-one, I (CSD refcode IBADIC; Atioğlu et al., 2021 ). Four compounds reported by Oliveira et al. (2019 ) are closely related to the title compound, viz. 2-(4-nitro-1H-imidazol-1-yl)-N′-[1-(pyridin-2-yl)ethylidene]acetohydrazide, II (TODMEH), 2-(2-nitro-1H-imidazol-1-yl)-N′-[1-(pyridin-2-yl)ethylidene]acetohydrazide, III (TODMIL), 2-(4-nitro-1H-imidazol-1-yl)-N′-[phenyl(pyridin-2-yl)methylidene]acetohydrazide, IV (TODMOR) and 2-(4-nitro-1H-imidazol-1-yl)-N′-[phenyl(pyridin-2-yl)methylidene]acetohydrazide, V (TODMUX). Compound I crystallizes in the monoclinic space group C2/c with Z = 8. In the crystal of I, pairs of molecules are linked into dimers by N—H⋯O hydrogen bonds, forming an R₂²(12) ring motif, with the dimers stacked along the a-axis direction. These dimers are connected through π–π stacking interactions between the centroids of the benzene and furan rings of their 2,3-dihydro-1-benzofuran ring systems. Furthermore, there exists a C—H⋯π interaction that consolidates the crystal packing. Compounds II and IV crystallize in the monoclinic space group P2₁/c with Z = 4. Compound III crystallizes in the monoclinic space group I2/a with Z = 8 and V crystallizes in the triclinic space group P $[\overline{1}]$ with Z = 2. Compound VI crystallizes in the monoclinic space group P2₁/c with Z = 4. The E conformation in II, III and V is stabilized by a strong intermolecular N—H⋯O interaction. These interactions lead to the formation of dimeric structural arrangements. In the crystal of IV, an intermolecular N—H⋯N hydrogen bond results in a helical chain structure along the b-axis direction. Non-classical intermolecular C—H⋯N and C—H⋯O interactions are also observed in the crystals of II, III, IV and V.

6. Synthesis and crystallization

(Z)-3-[2-(3,5-Dimethylphenyl)hydrazinylidene]benzofuran-2(3H)-one was synthesized according to the reported method (Shikhaliyev et al., 2018 , 2019 ). A 20 mL screw-neck vial was charged with DMSO (10 mL), (E)-2-{[2-(3,5-dimethylphenyl)hydrazinylidene]methyl}phenol (240 mg, 1 mmol), tetramethylethylenediamine (TMEDA) (295 mg, 2.5 mmol), CuCl (2 mg, 0.02 mmol) and CCl₄ (20 mmol, 10 equiv). After 1–3 h (until TLC analysis showed complete consumption of the corresponding Schiff base), 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 × 20 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 (3/1–1/1). Then the substance was refluxed in methanol for 30 min, and left for evaporation. After three days, single crystals of the title compound suitable for X-ray analysis were obtained. Colorless solid (65%); m.p. 475 K. Analysis calculated for C₁₆H₁₄N₂O₂ (M = 266.30): C 72.17, H 5.30, N 10.52; found: C 72.13, H 5.26, N 10.48%. ¹H NMR (300 MHz, CDCl₃) δ 12.04 (1H, NH), 6.79–7.69 (7H, Ar), 2.37 (6H, 2CH₃). ¹³C NMR (75 MHz, CDCl₃) δ 160.47, 157.77, 134.91, 125.14, 124.12, 121.77, 121.56, 119.86, 118.21, 114.55, 108.16, 106.59, 16.85 and 16.52. ESI–MS: m/z: 267.23 [M + H]⁺.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The amine H atom was located in a difference-Fourier map and refined freely [N2—H2 = 0.93 (2) Å]. All C-bound H atoms were placed at calculated positions using a riding model, with C—H = 0.93 or 0.96 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C). The methyl group with the C16 atom attached to the atom C13 is disordered over two orientations, with occupancies of 0.67 (4) and 0.33 (4). Owing to poor agreement, nine reflections ( $[\overline{5}]$ 14 10, 7 13 0, $[\overline{11}]$ 6 5, $[\overline{10}]$ 12 4, 11 1 0, $[\overline{11}]$ 1 1, $[\overline{8}]$ 19 6, $[\overline{8}]$ 0 8 and $[\overline{10}]$ 17 4) were omitted during the final refinement cycle.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₂O₂
M_r	266.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.8644 (4), 19.9222 (8), 8.1736 (3)
β (°)	107.240 (1)
V (Å³)	1378.59 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.21 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.684, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22343, 4176, 2332
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.146, 1.04
No. of reflections	4176
No. of parameters	188
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14
Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 1983650

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011749/is5559sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011749/is5559Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021011749/is5559Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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).

3-[2-(3,5-Dimethylphenyl)hydrazinylidene]benzofuran-2(3H)-one top

Crystal data top

C₁₆H₁₄N₂O₂	F(000) = 560
M_r = 266.29	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.8644 (4) Å	Cell parameters from 3738 reflections
b = 19.9222 (8) Å	θ = 2.4–30.5°
c = 8.1736 (3) Å	µ = 0.09 mm⁻¹
β = 107.240 (1)°	T = 296 K
V = 1378.59 (10) Å³	Prism, colourless
Z = 4	0.40 × 0.21 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	2332 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.058
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 30.5°, θ_min = 2.4°
T_min = 0.684, T_max = 0.746	h = −12→12
22343 measured reflections	k = −28→28
4176 independent reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0465P)² + 0.2174P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4176 reflections	Δρ_max = 0.15 e Å⁻³
188 parameters	Δρ_min = −0.14 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	Occ. (<1)
C1	0.7095 (2)	0.56971 (8)	0.9270 (2)	0.0519 (4)
C2	0.76884 (18)	0.52981 (8)	0.8095 (2)	0.0482 (4)
C3	0.92693 (18)	0.55352 (8)	0.8274 (2)	0.0493 (4)
C4	1.0448 (2)	0.53565 (9)	0.7563 (3)	0.0624 (5)
H4	1.028478	0.502040	0.673914	0.075*
C5	1.1879 (2)	0.56929 (11)	0.8114 (3)	0.0728 (6)
H5	1.268324	0.558312	0.764500	0.087*
C6	1.2129 (2)	0.61884 (11)	0.9347 (3)	0.0749 (6)
H6	1.310276	0.640405	0.969456	0.090*
C7	1.0974 (2)	0.63715 (10)	1.0075 (3)	0.0673 (5)
H7	1.114142	0.670299	1.091089	0.081*
C8	0.95594 (19)	0.60361 (8)	0.9495 (2)	0.0538 (4)
C9	0.4768 (2)	0.40926 (8)	0.6127 (2)	0.0530 (4)
C10	0.5476 (2)	0.37321 (9)	0.5108 (2)	0.0603 (5)
H10	0.648784	0.384407	0.508401	0.072*
C11	0.4678 (3)	0.32049 (9)	0.4125 (2)	0.0702 (6)
C12	0.3181 (3)	0.30497 (10)	0.4188 (3)	0.0779 (6)
H12	0.263853	0.269826	0.351887	0.093*
C13	0.2457 (2)	0.33984 (10)	0.5213 (3)	0.0693 (6)
C14	0.3266 (2)	0.39267 (9)	0.6189 (2)	0.0598 (5)
H14	0.280284	0.416993	0.688386	0.072*
C15	0.5458 (3)	0.28029 (12)	0.3040 (3)	0.1039 (9)
H15A	0.513973	0.234174	0.302284	0.156*
H15B	0.658448	0.283384	0.351251	0.156*
H15C	0.514651	0.297710	0.189347	0.156*
C16	0.0820 (3)	0.32121 (12)	0.5296 (3)	0.0972 (8)
H16D	0.052299	0.350758	0.607547	0.146*	0.67 (4)
H16E	0.082700	0.275746	0.568674	0.146*	0.67 (4)
H16F	0.007489	0.325362	0.417644	0.146*	0.67 (4)
H16A	0.013993	0.359673	0.500891	0.146*	0.33 (4)
H16B	0.088531	0.306500	0.643291	0.146*	0.33 (4)
H16C	0.039964	0.285692	0.449682	0.146*	0.33 (4)
N1	0.69683 (16)	0.48115 (7)	0.70999 (18)	0.0508 (3)
N2	0.55439 (17)	0.46316 (7)	0.7133 (2)	0.0545 (4)
H2	0.513 (2)	0.4843 (10)	0.792 (3)	0.077 (6)*
O1	0.82605 (14)	0.61480 (6)	1.00954 (16)	0.0609 (3)
O2	0.58433 (14)	0.56775 (7)	0.95705 (17)	0.0666 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0428 (9)	0.0531 (9)	0.0561 (10)	−0.0041 (7)	0.0089 (8)	−0.0012 (8)
C2	0.0422 (9)	0.0501 (9)	0.0482 (9)	−0.0004 (7)	0.0073 (7)	0.0016 (7)
C3	0.0403 (8)	0.0503 (9)	0.0546 (10)	0.0026 (7)	0.0100 (7)	0.0083 (7)
C4	0.0525 (11)	0.0673 (11)	0.0680 (12)	0.0056 (9)	0.0186 (9)	0.0090 (9)
C5	0.0459 (11)	0.0842 (14)	0.0898 (16)	0.0066 (10)	0.0223 (11)	0.0224 (12)
C6	0.0445 (11)	0.0770 (13)	0.0958 (16)	−0.0094 (9)	0.0092 (11)	0.0179 (12)
C7	0.0512 (11)	0.0607 (11)	0.0808 (14)	−0.0092 (9)	0.0053 (10)	0.0015 (10)
C8	0.0409 (9)	0.0531 (9)	0.0630 (11)	−0.0004 (7)	0.0088 (8)	0.0055 (8)
C9	0.0536 (10)	0.0501 (9)	0.0461 (9)	−0.0056 (8)	0.0005 (8)	0.0030 (7)
C10	0.0700 (12)	0.0553 (10)	0.0511 (10)	−0.0063 (9)	0.0109 (9)	0.0003 (8)
C11	0.0950 (16)	0.0537 (11)	0.0542 (11)	−0.0090 (10)	0.0102 (11)	−0.0011 (9)
C12	0.0988 (17)	0.0575 (12)	0.0572 (12)	−0.0205 (11)	−0.0078 (12)	−0.0005 (10)
C13	0.0649 (12)	0.0635 (12)	0.0621 (12)	−0.0153 (9)	−0.0080 (10)	0.0156 (10)
C14	0.0534 (10)	0.0616 (11)	0.0553 (10)	−0.0066 (8)	0.0020 (8)	0.0065 (8)
C15	0.150 (2)	0.0746 (15)	0.0865 (17)	−0.0083 (15)	0.0348 (17)	−0.0243 (13)
C16	0.0724 (15)	0.0949 (17)	0.1019 (18)	−0.0327 (12)	−0.0085 (13)	0.0192 (14)
N1	0.0466 (8)	0.0525 (8)	0.0497 (8)	−0.0017 (6)	0.0086 (6)	0.0028 (6)
N2	0.0475 (8)	0.0574 (9)	0.0553 (9)	−0.0059 (7)	0.0100 (7)	−0.0065 (7)
O1	0.0496 (7)	0.0610 (7)	0.0690 (8)	−0.0061 (6)	0.0127 (6)	−0.0130 (6)
O2	0.0473 (7)	0.0790 (9)	0.0757 (9)	−0.0041 (6)	0.0213 (6)	−0.0101 (7)

Geometric parameters (Å, º) top

C1—O2	1.2064 (19)	C10—H10	0.9300
C1—O1	1.3842 (19)	C11—C12	1.378 (3)
C1—C2	1.459 (2)	C11—C15	1.506 (3)
C2—N1	1.304 (2)	C12—C13	1.384 (3)
C2—C3	1.445 (2)	C12—H12	0.9300
C3—C8	1.380 (2)	C13—C14	1.385 (2)
C3—C4	1.385 (2)	C13—C16	1.519 (3)
C4—C5	1.386 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.381 (3)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—C7	1.377 (3)	C16—H16D	0.9600
C6—H6	0.9300	C16—H16E	0.9600
C7—C8	1.375 (2)	C16—H16F	0.9600
C7—H7	0.9300	C16—H16A	0.9600
C8—O1	1.397 (2)	C16—H16B	0.9600
C9—C10	1.383 (2)	C16—H16C	0.9600
C9—C14	1.387 (2)	N1—N2	1.3206 (19)
C9—N2	1.402 (2)	N2—H2	0.93 (2)
C10—C11	1.383 (2)

O2—C1—O1	121.34 (16)	C11—C12—C13	122.29 (18)
O2—C1—C2	130.48 (16)	C11—C12—H12	118.9
O1—C1—C2	108.18 (14)	C13—C12—H12	118.9
N1—C2—C3	125.97 (16)	C12—C13—C14	118.4 (2)
N1—C2—C1	127.59 (15)	C12—C13—C16	121.7 (2)
C3—C2—C1	106.43 (14)	C14—C13—C16	119.9 (2)
C8—C3—C4	119.17 (16)	C13—C14—C9	119.93 (19)
C8—C3—C2	106.10 (15)	C13—C14—H14	120.0
C4—C3—C2	134.70 (17)	C9—C14—H14	120.0
C3—C4—C5	118.10 (19)	C11—C15—H15A	109.5
C3—C4—H4	121.0	C11—C15—H15B	109.5
C5—C4—H4	121.0	H15A—C15—H15B	109.5
C6—C5—C4	121.07 (19)	C11—C15—H15C	109.5
C6—C5—H5	119.5	H15A—C15—H15C	109.5
C4—C5—H5	119.5	H15B—C15—H15C	109.5
C7—C6—C5	121.71 (19)	C13—C16—H16D	109.5
C7—C6—H6	119.1	C13—C16—H16E	109.5
C5—C6—H6	119.1	H16D—C16—H16E	109.5
C8—C7—C6	116.17 (19)	C13—C16—H16F	109.5
C8—C7—H7	121.9	H16D—C16—H16F	109.5
C6—C7—H7	121.9	H16E—C16—H16F	109.5
C7—C8—C3	123.77 (18)	C13—C16—H16A	109.5
C7—C8—O1	124.32 (17)	C13—C16—H16B	109.5
C3—C8—O1	111.89 (14)	H16A—C16—H16B	109.5
C10—C9—C14	120.63 (16)	C13—C16—H16C	109.5
C10—C9—N2	121.31 (16)	H16A—C16—H16C	109.5
C14—C9—N2	118.05 (17)	H16B—C16—H16C	109.5
C11—C10—C9	119.94 (19)	C2—N1—N2	118.89 (15)
C11—C10—H10	120.0	N1—N2—C9	120.08 (15)
C9—C10—H10	120.0	N1—N2—H2	117.9 (13)
C12—C11—C10	118.8 (2)	C9—N2—H2	121.7 (13)
C12—C11—C15	121.18 (19)	C1—O1—C8	107.39 (13)
C10—C11—C15	120.0 (2)

O2—C1—C2—N1	−1.0 (3)	N2—C9—C10—C11	−179.74 (16)
O1—C1—C2—N1	178.73 (15)	C9—C10—C11—C12	−0.1 (3)
O2—C1—C2—C3	−179.52 (18)	C9—C10—C11—C15	−178.83 (18)
O1—C1—C2—C3	0.23 (17)	C10—C11—C12—C13	−0.7 (3)
N1—C2—C3—C8	−178.02 (16)	C15—C11—C12—C13	178.06 (19)
C1—C2—C3—C8	0.52 (17)	C11—C12—C13—C14	0.8 (3)
N1—C2—C3—C4	−0.4 (3)	C11—C12—C13—C16	−178.75 (19)
C1—C2—C3—C4	178.17 (19)	C12—C13—C14—C9	−0.3 (3)
C8—C3—C4—C5	−0.1 (3)	C16—C13—C14—C9	179.33 (17)
C2—C3—C4—C5	−177.49 (18)	C10—C9—C14—C13	−0.5 (3)
C3—C4—C5—C6	0.5 (3)	N2—C9—C14—C13	179.91 (15)
C4—C5—C6—C7	−0.3 (3)	C3—C2—N1—N2	176.94 (15)
C5—C6—C7—C8	−0.4 (3)	C1—C2—N1—N2	−1.3 (2)
C6—C7—C8—C3	0.9 (3)	C2—N1—N2—C9	−177.48 (14)
C6—C7—C8—O1	179.25 (16)	C10—C9—N2—N1	1.1 (2)
C4—C3—C8—C7	−0.7 (3)	C14—C9—N2—N1	−179.26 (15)
C2—C3—C8—C7	177.41 (16)	O2—C1—O1—C8	178.89 (16)
C4—C3—C8—O1	−179.19 (14)	C2—C1—O1—C8	−0.88 (17)
C2—C3—C8—O1	−1.11 (19)	C7—C8—O1—C1	−177.24 (17)
C14—C9—C10—C11	0.6 (3)	C3—C8—O1—C1	1.27 (19)

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of the C3–C8 and C9–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.93 (2)	2.12 (2)	2.840 (2)	133.8 (16)
C15—H15A···Cg3ⁱ	0.96	2.90	3.591 (3)	130
C16—H16F···Cg2ⁱⁱ	0.96	2.92	3.715 (3)	141

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

Percentage contributions of interatomic contacts to the Hirshfeld surface of the title compound top

Contact	Percentage contribution
H···H	51.2
O···H/H···O	17.9
C···H/H···C	15.2
C···C	8.1
N···C/C···N	4.2
N···H/H···N	1.9
O···C/C···O	0.9
N···N	0.6
O···O	0.1

Acknowledgements

The author's contributions are as follows. Conceptualization, NQS, MA and AB; synthesis, UFA and SHM; X-ray analysis, ZA, RKA and MA; writing (review and editing of the manuscript) ZA, MA and AB; funding acquisition, NQS, UFA, SHM and RKA; supervision, NQS, MA and AB.

Funding information

This work was performed under the support of the Science Development Foundation under the President of the Republic of Azerbaijan (grant No. EIF-BGM-4-RFTF-1/2017–21/13/4).

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