Crystal structure and Hirshfeld surface analysis of (3Z)-7-meth­oxy-3-(2-phenyl­hydrazinyl­idene)-1-benzo­furan-2(3H)-one

Atioğlu, Z.; Akkurt, M.; Askerova, U.F.; Mukhtarova, S.H.; Askerov, R.K.; Mlowe, S.

doi:10.1107/S2056989021007891

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 9| September 2021| Pages 907-911

https://doi.org/10.1107/S2056989021007891

Open

access

Crystal structure and Hirshfeld surface analysis of (3Z)-7-methoxy-3-(2-phenylhydrazinylidene)-1-benzofuran-2(3H)-one

Zeliha Atioğlu,^a Mehmet Akkurt,^b Ulviyya F. Askerova,^c Sevinc H. Mukhtarova,^c Rizvan K. Askerov ^c and Sixberth Mlowe ^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 ^dUniversity of Dar es Salaam, Dar es Salaam University College of Education, Department of Chemistry, PO Box 2329, Dar es Salaam, Tanzania
^*Correspondence e-mail: sixberth.mlowe@duce.ac.tz

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 June 2021; accepted 2 August 2021; online 6 August 2021)

In the title compound, C₁₅H₁₂N₂O₃, 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. 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. A Hirshfeld surface analysis indicates that the most important contacts are H⋯H (40.7%), O⋯H/H⋯O (24.7%), C⋯H/H⋯C (16.1%) and C⋯C (8.8%).

Keywords: crystal structure; 2,3-dihydro-1-benzofuran ring system; dimers; hydrogen bonds; Hirshfeld surface analysis.

CCDC reference: 1984938

1. Chemical context

Hydrazones are a versatile class of organic ligands that have extensive applications in synthetic transformations, the synthesis of bioactive compounds, the design of materials and in coordination chemistry (Ma et al., 2017a ,b ; Viswanathan et al., 2019 ). Moreover, metal complexes of hydrazone ligands have been successfully applied as catalysts in organic synthesis (Gurbanov et al., 2018 ). The properties of metal-hydrazonates can be regulated by the design of ligands through the involvement of non-covalent-bond donor or acceptor substituents (Ma et al., 2020 , 2021 ; Mahmudov et al., 2013 ). Supramolecular networks of all dimensions in the crystal structures of hydrazone compounds or metal-hydrazonates, resulting from extensive hydrogen-bonding and other types of intermolecular interactions, have been reported (Gurbanov et al., 2020a ; Kopylovich et al., 2011 ). Thus, the attachment of suitable substituents or synthons to hydrazone ligands can improve their functional properties and the catalytic or biological activity of the corresponding coordination compounds (Mizar et al., 2012 ; Gurbanov et al., 2020a,b ; Khalilov et al., 2018a ,b ; Maharramov et al., 2018 ; Shihkaliyev et al., 2019 ; Shixaliyev et al., 2014 ).

In a continuation of our work in this context (Atioğlu et al., 2020 , 2021 ), we have synthesized a new hydrazone compound, (3Z)-7-methoxy-3-(2-phenylhydrazinylidene)-1-benzofuran-2(3H)-one, which shows multiple intermolecular non-covalent interactions.

2. Structural commentary

In the title compound, the molecular conformation is stabilized by an intramolecular N2—H1⋯O2 hydrogen bond, forming an S(6) ring motif (Table 1, Fig. 1; Bernstein et al., 1995 ). The 2,3-dihydro-1-benzofuran ring system (O1/C1–C8) is essentially planar [maximum deviation of 0.016 (2) Å for O1] and subtends a dihedral angle of 5.32 (14)° with the phenyl ring (C10–C15).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C10–C15 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O2	0.92 (4)	2.14 (3)	2.843 (3)	133 (3)
N2—H1⋯O2ⁱ	0.92 (4)	2.44 (4)	3.181 (4)	138 (3)
C9—H9C⋯Cg3ⁱⁱ	0.96	2.70	3.555 (4)	149
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) .

Figure 1
The title molecule with the labelling scheme and displacement ellipsoids drawn at the 30% probability level. The intramolecular N—H⋯O hydrogen bond is shown as a dashed line.

3. Supramolecular features

In the crystal, pairs of molecules are linked into dimers by intermolecular N—H⋯O hydrogen bonds, forming an $[R_{2}^{2}]$ (12) ring motif (Table 1). These dimers are stacked along the a axis and connected by π–π stacking interactions between the centroids of the benzene and furan rings of their 2,3-dihydro-1-benzofuran ring systems [Cg1⋯Cg2(1 − x, − y, 1 − z) = 3.5316 (19) Å, slippage = 0.352 Å, where Cg1 and Cg2 are the centroids of the benzene (C3–C8) and furan (O1/C1–C3/C8) rings, respectively] (Figs. 2, 3 and 4). Furthermore, there exists a C—H⋯π interaction between the H9C atom of the methyl group C9 and the centroid of the phenyl ring (C10–C15).

Figure 2
Intermolecular N—H⋯O hydrogen bonds, C—H⋯π interactions and π–π stacking interactions (shown as dashed lines) in the title compound. [Symmetry codes: (a) 1 − x, −y, 1 − z; (b) 1 − x, 1 − y, 1 − z; (c) $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z].

Figure 3
A view of the molecular packing of the title compound along the a-axis direction. Intermolecular interactions are depicted as in Fig. 2

Figure 4
A view of the molecular packing of the title compound along the b-axis direction. Intermolecular interactions are depicted as in Fig. 2

4. Hirshfeld surface analysis

Crystal Explorer 17.5 (Turner et al., 2017 ) was used to calculate the Hirshfeld surfaces and generate the two-dimensional fingerprint plots. Hirshfeld surfaces allow for the display of intermolecular interactions by using distinct colours and intensities to indicate short and long contacts, as well as the relative strength of the interactions. The three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1718 to 1.3843 a.u. is shown in Fig. 5. The N2—H1⋯O2 interactions, which play a key role in the molecular packing of the title compound, are responsible for the red spot that occurs around O2. The bright-red spots appearing near O2 and hydrogen atom H1 indicate their roles as donors and/or acceptors in hydrogen-bonding; they also appear as blue and red regions corresponding to positive and negative potentials on the Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) shown in Fig. 6. Here the blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors).

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1718 to 1.3843 a.u. The two N—H⋯O hydrogen bonds forming the dimer are depicted as dashed lines.

Figure 6
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. The hydrogen-bond donors and acceptors are viewed as blue and red regions, respectively, around atoms, corresponding to positive and negative potentials.

The overall two-dimensional fingerprint plot for the title compound is given in Fig. 7a, and those delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯C contacts are shown in Fig. 7b–e, while numerical details of the different contacts are given in Table 2. The percentage contributions to the Hirshfeld surfaces from the various interatomic contacts are as follows: H⋯H (Fig. 7b; 40.7%), O⋯H/H⋯O (Fig. 7c; 24.7%), C⋯H/H⋯C (Fig. 7d; 16.1%) and C⋯C (Fig. 7e; 8.8%). Other minor contributions to the Hirshfeld surface are from N⋯C/C⋯N (3.8%), N⋯H/H⋯N (3.5%), O⋯C/C⋯O (1.9%), O⋯N/N⋯O (0.4%) and O⋯O (0.2%) contacts.

Table 2
Interatomic contacts of the title compound (Å)

Contact	Distance	Symmetry operation
H1⋯O2	2.44	$[{1\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z
H9B⋯N2	2.91	1 − x, −y, 1 − z
H9C⋯C11	2.93	1 − x, 1 − y, 1 − z
H5A⋯H15A	2.51	$[{1\over 2}]$ + x, − $[{1\over 2}]$ + y, z
C9⋯H14A	2.85	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
H11A⋯H11A	2.31	1 − x, y, $[{3\over 2}]$ − z
C15⋯H13A	3.07	$[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z

Figure 7
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C and (e) C⋯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 contacts.

5. Database survey

A search of the Cambridge Crystallographic Database (CSD version 5.40, update of September 2019; Groom et al., 2016 ) gave 763 hits for structures with a hydrazone moiety. Five structures that are closely related to the title compound are: 2-(4-nitro-1H-imidazol-1-yl)-N′-[1-(pyridin-2-yl)ethylidene]acetohydrazide (TODMEH; Oliveira et al., 2019 ); 2-(2-nitro-1H-imidazol-1-yl)-N′-[1-(pyridin-2-yl)ethylidene]acetohydrazide (TODMIL; Oliveira et al., 2019); 2-(4-nitro-1H-imidazol-1-yl)-N′-[phenyl(pyridin-2-yl)methylidene]acetohydrazide (TODMOR; Oliveira et al., 2019); 2-(4-nitro-1H-imidazol-1-yl)-N′-[phenyl(pyridin-2-yl)methylidene]acetohydrazide (TODMUX; Oliveira et al., 2019) and 1,1′-[1,3-phenylenebis(2,2-dichloroethene-1,1-diyl)]bis(phenyldiazene) (EXIWOA; Shikhaliyev et al., 2021 ).

TODMEH and TODMOR crystallize in the monoclinic space group P2₁/c with Z = 4. TODMIL crystallizes in the monoclinic space group I2/a with Z = 8 and TODMUX crystallizes in the triclinic space group P $[\overline{1}]$ with Z = 2. EXIWOA crystallizes in the monoclinic space group P2₁/c with Z = 4. The E conformation in TODMEH, TODMIL and TODMUX is stabilized by a strong intermolecular N—H⋯O interaction. These interactions lead to the formation of dimeric structural arrangements. In the crystal packing of TODMOR, an intermolecular N—H⋯N interaction results in a zigzag structural arrangement, with the formation of chains along the crystallographic b axis. Non-classical intermolecular C—H⋯N and C—H⋯O interactions are also observed in the crystal structures of TODMEH, TODMIL, TODMOR and TODMUX. In EXIWOA, molecules are linked by C—H⋯π, C—Cl⋯π, Cl⋯Cl and Cl⋯H interactions, forming a three-dimensional supramolecular network.

6. Synthesis and crystallization

A 20 ml screw-neck vial was charged with dimethyl sulfoxide (DMSO; 10 ml), (E)-2-{[2-(3,5-dimethylphenyl)hydrazineylidene]methyl}phenol (240 mg, 1 mmol), tetramethylethyl-enediamine (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 × 50 ml), brine (30 ml), dried over anhydrous Na₂SO₄ and concentrated in vacuo in 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). Colourless solid (yield 65%); m.p. 475 K. Analysis calculated for C₁₅H₁₂N₂O₃ (M = 268.27): C 67.16, H 4.51, N 10.44; found: C 67.11, H 4.47, N 10.35%. ¹H NMR (300 MHz, CDCl₃) δ 12.13 (s, 1H, NH), 6.91–7.43 (8H, Ar), 3.99 (s, 3H, OCH₃). ¹³C NMR (75 MHz,CDCl₃) δ 186.20, 161.87, 150.65, 141.76, 129.60, 125.09, 124.44, 123.87, 114.90, 112.74, 111.44, 108.76, 56.46. ESI–MS: m/z: 269.26 [M + H]⁺. Crystals suitable for X-ray analysis were obtained by slow evaporation of a dichloromethane solution.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atom of the NH group was located in a difference-Fourier map and refined freely [N2—H1 = 0.92 (4) Å]. H atoms bonded to C atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 or 0.96 Å, and with U_iso(H) = 1.2U_eq(C) for aromatic or 1.5U_eq(C) for methyl H atoms. Owing to poor agreement between observed and calculated intensities, seven outliers, ( $[\overline{13}]$ 7 1), ( $[\overline{8}]$ 6 13), (13 7 0), ( $[\overline{9}]$ 5 19), ( $[\overline{7}]$ 5 20), ( $[\overline{15}]$ 5 12) and (0 6 16), were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₂O₃
M_r	268.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	17.436 (2), 7.2485 (7), 20.595 (2)
β (°)	99.181 (4)
V (Å³)	2569.6 (5)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.49 × 0.15 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.629, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	12800, 2427, 1463
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.152, 1.01
No. of reflections	2427
No. of parameters	187
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 1984938

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021007891/wm5614sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021007891/wm5614Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021007891/wm5614Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

(3Z)-7-Methoxy-3-(2-phenylhydrazinylidene)-1-benzofuran-2(3H)-one top

Crystal data top

C₁₅H₁₂N₂O₃	F(000) = 1120
M_r = 268.27	D_x = 1.387 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.436 (2) Å	Cell parameters from 2240 reflections
b = 7.2485 (7) Å	θ = 2.4–26.3°
c = 20.595 (2) Å	µ = 0.10 mm⁻¹
β = 99.181 (4)°	T = 296 K
V = 2569.6 (5) Å³	Prism, colourless
Z = 8	0.49 × 0.15 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	1463 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.085
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.0°, θ_min = 2.0°
T_min = 0.629, T_max = 0.745	h = −21→21
12800 measured reflections	k = −8→8
2427 independent reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.0517P)² + 2.9831P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2427 reflections	Δρ_max = 0.18 e Å⁻³
187 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL2016/6 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.0015 (4)

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	0.42001 (12)	0.2382 (3)	0.41831 (10)	0.0546 (6)
O2	0.31175 (13)	0.3077 (4)	0.45997 (10)	0.0648 (7)
O3	0.53382 (14)	0.1359 (4)	0.34426 (11)	0.0728 (8)
N1	0.42389 (15)	0.3396 (4)	0.58811 (12)	0.0477 (7)
N2	0.35184 (16)	0.3699 (4)	0.59750 (13)	0.0500 (7)
C1	0.38107 (19)	0.2841 (5)	0.46932 (14)	0.0483 (8)
C2	0.43742 (17)	0.2955 (4)	0.52959 (13)	0.0434 (8)
C3	0.51208 (17)	0.2536 (4)	0.51198 (14)	0.0450 (8)
C4	0.58718 (18)	0.2419 (5)	0.54600 (16)	0.0591 (10)
H4A	0.598100	0.265759	0.590895	0.071*
C5	0.64493 (19)	0.1937 (5)	0.51096 (18)	0.0653 (10)
H5A	0.695811	0.185900	0.532762	0.078*
C6	0.6297 (2)	0.1564 (5)	0.44427 (17)	0.0615 (10)
H6A	0.670362	0.122386	0.422508	0.074*
C7	0.55574 (19)	0.1688 (5)	0.40953 (15)	0.0521 (9)
C8	0.49847 (17)	0.2183 (4)	0.44538 (14)	0.0466 (8)
C9	0.5936 (2)	0.0804 (6)	0.30818 (17)	0.0778 (12)
H9A	0.571774	0.063916	0.262729	0.117*
H9B	0.615969	−0.033713	0.325700	0.117*
H9C	0.633113	0.173711	0.311913	0.117*
C10	0.33773 (18)	0.4270 (4)	0.65966 (14)	0.0467 (8)
C11	0.3957 (2)	0.4326 (5)	0.71354 (14)	0.0594 (10)
H11A	0.445790	0.395598	0.709579	0.071*
C12	0.3796 (2)	0.4926 (5)	0.77285 (16)	0.0671 (11)
H12A	0.419310	0.497293	0.808808	0.081*
C13	0.3062 (2)	0.5458 (5)	0.78029 (16)	0.0640 (10)
H13A	0.295701	0.585028	0.820967	0.077*
C14	0.2482 (2)	0.5402 (5)	0.72659 (16)	0.0604 (10)
H14A	0.198194	0.577300	0.730814	0.073*
C15	0.26373 (19)	0.4799 (5)	0.66640 (15)	0.0538 (9)
H15A	0.224071	0.475136	0.630425	0.065*
H1	0.313 (2)	0.352 (5)	0.5627 (17)	0.082 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0484 (13)	0.0750 (18)	0.0406 (11)	−0.0036 (12)	0.0072 (10)	−0.0031 (11)
O2	0.0484 (15)	0.092 (2)	0.0533 (14)	−0.0061 (13)	0.0049 (11)	−0.0059 (12)
O3	0.0659 (16)	0.103 (2)	0.0527 (14)	0.0041 (14)	0.0200 (12)	−0.0074 (14)
N1	0.0488 (16)	0.0505 (18)	0.0441 (14)	−0.0068 (13)	0.0082 (12)	0.0010 (12)
N2	0.0471 (17)	0.060 (2)	0.0427 (15)	−0.0017 (14)	0.0062 (13)	−0.0044 (13)
C1	0.049 (2)	0.054 (2)	0.0428 (17)	−0.0112 (17)	0.0118 (15)	0.0010 (15)
C2	0.0476 (18)	0.044 (2)	0.0375 (16)	−0.0077 (15)	0.0050 (14)	0.0020 (14)
C3	0.0498 (19)	0.042 (2)	0.0431 (16)	−0.0085 (15)	0.0082 (14)	0.0052 (14)
C4	0.053 (2)	0.073 (3)	0.0489 (18)	−0.0091 (18)	0.0014 (16)	0.0038 (17)
C5	0.044 (2)	0.083 (3)	0.068 (2)	−0.0021 (18)	0.0070 (18)	0.012 (2)
C6	0.054 (2)	0.067 (3)	0.067 (2)	−0.0014 (18)	0.0194 (18)	0.0100 (19)
C7	0.058 (2)	0.051 (2)	0.0499 (19)	−0.0049 (17)	0.0159 (17)	0.0025 (16)
C8	0.0481 (19)	0.047 (2)	0.0447 (17)	−0.0073 (15)	0.0070 (15)	0.0063 (15)
C9	0.092 (3)	0.084 (3)	0.066 (2)	0.011 (2)	0.038 (2)	−0.006 (2)
C10	0.052 (2)	0.047 (2)	0.0404 (16)	−0.0068 (15)	0.0080 (15)	−0.0010 (15)
C11	0.055 (2)	0.076 (3)	0.0456 (18)	0.0031 (18)	0.0016 (16)	−0.0101 (17)
C12	0.074 (3)	0.080 (3)	0.0446 (19)	0.003 (2)	0.0019 (18)	−0.0106 (18)
C13	0.078 (3)	0.069 (3)	0.047 (2)	−0.002 (2)	0.0174 (19)	−0.0081 (17)
C14	0.060 (2)	0.061 (3)	0.065 (2)	0.0041 (18)	0.0248 (19)	0.0021 (18)
C15	0.050 (2)	0.060 (2)	0.0511 (19)	−0.0028 (17)	0.0061 (16)	0.0037 (16)

Geometric parameters (Å, º) top

O1—C1	1.380 (3)	C6—C7	1.375 (5)
O1—C8	1.400 (3)	C6—H6A	0.9300
O2—C1	1.205 (3)	C7—C8	1.381 (4)
O3—C7	1.359 (4)	C9—H9A	0.9600
O3—C9	1.431 (4)	C9—H9B	0.9600
N1—C2	1.304 (3)	C9—H9C	0.9600
N1—N2	1.320 (3)	C10—C15	1.374 (4)
N2—C10	1.404 (4)	C10—C11	1.377 (4)
N2—H1	0.92 (4)	C11—C12	1.367 (4)
C1—C2	1.457 (4)	C11—H11A	0.9300
C2—C3	1.438 (4)	C12—C13	1.369 (5)
C3—C8	1.378 (4)	C12—H12A	0.9300
C3—C4	1.386 (4)	C13—C14	1.375 (5)
C4—C5	1.374 (4)	C13—H13A	0.9300
C4—H4A	0.9300	C14—C15	1.381 (4)
C5—C6	1.383 (5)	C14—H14A	0.9300
C5—H5A	0.9300	C15—H15A	0.9300

C1—O1—C8	106.9 (2)	C3—C8—C7	123.8 (3)
C7—O3—C9	116.7 (3)	C3—C8—O1	112.3 (3)
C2—N1—N2	119.5 (3)	C7—C8—O1	123.9 (3)
N1—N2—C10	119.5 (3)	O3—C9—H9A	109.5
N1—N2—H1	118 (2)	O3—C9—H9B	109.5
C10—N2—H1	123 (2)	H9A—C9—H9B	109.5
O2—C1—O1	121.0 (3)	O3—C9—H9C	109.5
O2—C1—C2	130.6 (3)	H9A—C9—H9C	109.5
O1—C1—C2	108.4 (3)	H9B—C9—H9C	109.5
N1—C2—C3	126.1 (3)	C15—C10—C11	119.4 (3)
N1—C2—C1	127.2 (3)	C15—C10—N2	118.6 (3)
C3—C2—C1	106.7 (2)	C11—C10—N2	122.1 (3)
C8—C3—C4	119.4 (3)	C12—C11—C10	120.1 (3)
C8—C3—C2	105.7 (3)	C12—C11—H11A	120.0
C4—C3—C2	134.9 (3)	C10—C11—H11A	120.0
C5—C4—C3	117.6 (3)	C11—C12—C13	121.2 (3)
C5—C4—H4A	121.2	C11—C12—H12A	119.4
C3—C4—H4A	121.2	C13—C12—H12A	119.4
C4—C5—C6	122.1 (3)	C12—C13—C14	118.8 (3)
C4—C5—H5A	119.0	C12—C13—H13A	120.6
C6—C5—H5A	119.0	C14—C13—H13A	120.6
C7—C6—C5	121.3 (3)	C13—C14—C15	120.5 (3)
C7—C6—H6A	119.4	C13—C14—H14A	119.8
C5—C6—H6A	119.4	C15—C14—H14A	119.8
O3—C7—C6	126.6 (3)	C10—C15—C14	120.0 (3)
O3—C7—C8	117.5 (3)	C10—C15—H15A	120.0
C6—C7—C8	115.9 (3)	C14—C15—H15A	120.0

C2—N1—N2—C10	−176.6 (3)	C4—C3—C8—C7	0.8 (5)
C8—O1—C1—O2	−179.2 (3)	C2—C3—C8—C7	−178.7 (3)
C8—O1—C1—C2	0.8 (3)	C4—C3—C8—O1	−179.3 (3)
N2—N1—C2—C3	−178.2 (3)	C2—C3—C8—O1	1.2 (4)
N2—N1—C2—C1	3.7 (5)	O3—C7—C8—C3	179.2 (3)
O2—C1—C2—N1	−1.8 (6)	C6—C7—C8—C3	−0.3 (5)
O1—C1—C2—N1	178.3 (3)	O3—C7—C8—O1	−0.6 (5)
O2—C1—C2—C3	179.9 (4)	C6—C7—C8—O1	179.8 (3)
O1—C1—C2—C3	−0.1 (3)	C1—O1—C8—C3	−1.3 (3)
N1—C2—C3—C8	−179.0 (3)	C1—O1—C8—C7	178.6 (3)
C1—C2—C3—C8	−0.7 (3)	N1—N2—C10—C15	172.0 (3)
N1—C2—C3—C4	1.5 (6)	N1—N2—C10—C11	−7.6 (5)
C1—C2—C3—C4	179.9 (4)	C15—C10—C11—C12	−0.8 (5)
C8—C3—C4—C5	−0.4 (5)	N2—C10—C11—C12	178.7 (3)
C2—C3—C4—C5	178.9 (4)	C10—C11—C12—C13	0.8 (6)
C3—C4—C5—C6	−0.5 (6)	C11—C12—C13—C14	−0.7 (6)
C4—C5—C6—C7	1.0 (6)	C12—C13—C14—C15	0.7 (5)
C9—O3—C7—C6	0.9 (5)	C11—C10—C15—C14	0.8 (5)
C9—O3—C7—C8	−178.5 (3)	N2—C10—C15—C14	−178.8 (3)
C5—C6—C7—O3	179.9 (3)	C13—C14—C15—C10	−0.8 (5)
C5—C6—C7—C8	−0.6 (5)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C10–C15 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O2	0.92 (4)	2.14 (3)	2.843 (3)	133 (3)
N2—H1···O2ⁱ	0.92 (4)	2.44 (4)	3.181 (4)	138 (3)
C9—H9C···Cg3ⁱⁱ	0.96	2.70	3.555 (4)	149

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

Interatomic contacts of the title compound (Å) top

Contact	Distance	Symmetry operation
H1···O2	2.44	1/2 - x, 1/2 - y, 1 - z
H9B···N2	2.91	1 - x, -y, 1 - z
H9C···C11	2.93	1 - x, 1 - y, 1 - z
H5A···H15A	2.51	1/2 + x, -1/2 + y, z
C9···H14A	2.85	1/2 + x, 1/2 - y, -1/2 + z
H11A···H11A	2.31	1 - x, y, 3/2 - z
C15···H13A	3.07	1/2 - x, -1/2 + y, 3/2 - z

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

Contact	Percentage contribution
H···H	40.7
O···H/H···O	24.7
C···H/H···C	16.1
C···C	8.8
N···C/C···N	3.8
N···H/H···N	3.5
O···C/C···O	1.9
O···N/N···O	0.4
O···O	0.2

Acknowledgements

The authors' contributions are as follows. Conceptualization, MA and UFA; methodology, ZA and SHM; investigation, SHM, RKA, and ZA; writing (original draft), MA and SM; writing (review and editing of the manuscript), MA and UFA; visualization, RKA, ZA and MA; funding acquisition, UFA, SHM and RKA; resources, RKA, ZA and SHM; supervision, MA and SM.

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).

References

Atioğlu, Z., Akkurt, M., Shikhaliyev, N. Q., Askerova, U. F., Niyazova, A. A. & Mlowe, S. (2021). Acta Cryst. E77, 829–833. Web of Science CSD CrossRef IUCr Journals Google Scholar
Atioğlu, Z., Akkurt, M., Shikhaliyev, N. Q., Suleymanova, G. T., Babayeva, G. V., Gurbanova, N. V., Mammadova, G. Z. & Mlowe, S. (2020). Acta Cryst. E76, 1291–1295. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2017). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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., Kuznetsov, M. L., Demukhamedova, S. D., Alieva, I. N., Godjaev, N. M., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2020a). CrystEngComm, 22, 628–633. Web of Science CSD CrossRef CAS Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020b). Chem. Eur. J. 26, 14833–14837. Web of Science CSD CrossRef CAS PubMed Google Scholar
Gurbanov, A. V., Maharramov, A. M., Zubkov, F. I., Saifutdinov, A. M. & Guseinov, F. I. (2018). Aust. J. Chem. 71, 190–194. Web of Science CrossRef CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Maharramov, A. M., Nagiyev, F. N. & Brito, I. (2018a). Z. Kristallogr. New Cryst. Struct. 233, 1019–1020. Web of Science CSD CrossRef CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Nagiyev, F. N. & Brito, I. (2018b). Z. Kristallogr. New Cryst. Struct. 233, 947–948. Web of Science CSD CrossRef CAS Google Scholar
Kopylovich, M. N., Mahmudov, K. T., Mizar, A. & Pombeiro, A. J. L. (2011). Chem. Commun. 47, 7248–7250. Web of Science CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Ma, Z., Gurbanov, A. V., Maharramov, A. M., Guseinov, F. I., Kopylovich, M. N., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2017a). J. Mol. Catal. A Chem. 426, 526–533. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Sutradhar, M., Kopylovich, M. N., Mahmudov, K. T., Maharramov, A. M., Guseinov, F. I., Zubkov, F. I. & Pombeiro, A. J. L. (2017b). Mol. Catal. 428, 17–23. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Coord. Chem. Rev. 437, 213859. Web of Science CrossRef Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 423, 213482. Web of Science CrossRef Google Scholar
Maharramov, A. M., Shikhaliyev, N. Q., Suleymanova, G. T., Gurbanov, A. V., Babayeva, G. V., Mammadova, G. Z., Zubkov, F. I., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Dyes Pigments, 159, 135–141. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Haukka, M., Mahmudova, G. S., Esmaeila, E. F., Chyragov, F. M. & Pombeiro, A. J. L. (2013). J. Mol. Struct. 1048, 108–112. Web of Science CSD CrossRef CAS Google Scholar
Mizar, A., Guedes da Silva, M. F. C., Kopylovich, M. N., Mukherjee, S., Mahmudov, K. T. & Pombeiro, A. J. L. (2012). Eur. J. Inorg. Chem. pp. 2305–2313. Web of Science CSD CrossRef Google Scholar
Oliveira, A. P. A., Ferreira, I. P., Despaigne, A. A. R., Silva, J. G. da, Vieira, A. C. S., Santos, M. S., Alexandre-Moreira, M. S., Diniz, R. & Beraldo, H. (2019). Acta Cryst. C75, 320–328. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shikhaliyev, N. Q., Atioğlu, Z., Akkurt, M., Ahmadova, N. E., Askerov, R. K. & Bhattarai, A. (2021). Acta Cryst. E77, 814–818. Web of Science CSD CrossRef IUCr Journals 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. L. (2019). CrystEngComm, 21, 5032–5038. Web of Science CSD CrossRef CAS Google Scholar
Shixaliyev, N. Q., Gurbanov, A. V., Maharramov, A. M., Mahmudov, K. T., Kopylovich, M. N., Martins, L. M. D. R. S., Muzalevskiy, V. M., Nenajdenko, V. G. & Pombeiro, A. J. L. (2014). New J. Chem. 38, 4807–4815. Web of Science CSD CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. The University of Western Australia. Google Scholar
Viswanathan, A., Kute, D., Musa, A., Mani, S. K., Sipilä, V., Emmert-Streib, F., Zubkov, F. I., Gurbanov, A. V., Yli-Harja, O. & Kandhavelu, M. (2019). Eur. J. Med. Chem. 166, 291–303. Web of Science CrossRef CAS PubMed 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.