Crystal structure and Hirshfeld surface analysis of (E)-1-(2,6-di­chloro­phen­yl)-2-(2-nitro­benzyl­idene)hydrazine

Çelikesir, S.T.; Akkurt, M.; Shikhaliyev, N.Q.; Suleymanova, G.T.; Babayeva, G.V.; Gurbanova, N.V.; Mammadova, G.Z.; Bhattarai, A.

doi:10.1107/S2056989020008567

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Volume 76| Part 8| August 2020| Pages 1173-1178

https://doi.org/10.1107/S2056989020008567

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Crystal structure and Hirshfeld surface analysis of (E)-1-(2,6-dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine

Sevim Türktekin Çelikesir,^a Mehmet Akkurt,^a Namiq Q. Shikhaliyev,^b Gulnar T. Suleymanova,^b Gulnare V. Babayeva,^b Nurana V. Gurbanova,^b Gunay Z. Mammadova ^b and Ajaya Bhattarai ^c ^*

^aDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^bOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ, 1148 Baku, Azerbaijan, and ^cDepartment of Chemistry, M.M.A.M.C (Tribhuvan University), Biratnagar, Nepal
^*Correspondence e-mail: bkajaya@yahoo.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 22 June 2020; accepted 25 June 2020; online 3 July 2020)

In the title compound, C₁₃H₉Cl₂N₃O₂, the 2,6-dichlorophenyl ring and the nitro-substituted benzene ring form a dihedral angle of 21.16 (14)°. In the crystal, face-to-face π–π stacking interactions occur along the a-axis direction between the centroids of the 2,6-dichlorophenyl ring and the nitro-substituted benzene ring. Furthermore, these molecules show intramolecular N—H⋯Cl and C—H⋯O contacts and are linked by intermolecular N—H⋯O and C—H⋯Cl hydrogen bonds, forming pairs of hydrogen-bonded molecular layers parallel to (20 $[\overline{2}]$ ). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (23.0%), O⋯H/H⋯O (20.1%), Cl⋯H/H⋯Cl (19.0%), C⋯C (11.2%) and H⋯C/C⋯H (8.0%) interactions.

Keywords: crystal structure; face-to-face π–π stacking interactions; 2,6-dichlorophenyl ring; nitro-substituted benzene ring; Hirshfeld surface analysis.

CCDC reference: 2012294

1. Chemical context

Arylhydrazones and their complexes have attracted much attention because of their high synthetic potential for organic and inorganic chemistry and diverse useful properties (Maharramov et al., 2009 , 2010 , 2018 ; Mahmudov et al., 2010 , 2011 , 2014a ). The analytical and catalytic properties of this class of compounds are strongly dependent on the attached groups to the hydrazone moiety (Mahmudov et al., 2013 ; Shixaliyev et al., 2018 , 2019 ). On the other hand, intermolecular interactions organize the molecular architectures, which play a critical role in synthesis, catalysis, micellization, etc. (Akbari Afkhami et al., 2017 ; Gurbanov et al., 2017 , 2018 ; Kopylovich et al., 2011a ,b ; Ma et al., 2017a ,b ; Mahmoudi et al., 2016 , 2017a ,b ,c , 2018a ,b ). New types of non-covalent bonds such as halogen, chalcogen, pnictogen and tetrel bonds or their cooperation with hydrogen bonds are able to contribute to the synthesis and catalysis, giving materials with improved properties (Mahmudov et al., 2013, 2014b , 2015 , 2017a ,b , 2019 ; Mizar et al., 2012 ; Shixaliyev et al., 2013 , 2014 ). For that, the main skeleton of the hydrazone ligand should be decorated by non-covalent bond donor centre(s). In a continuation of our work in this regard, we have functionalized a new azo dye, (E)-1-(2,6-dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine, which provides intermolecular non-covalent interactions.

2. Structural commentary

The title molecule (Fig. 1) has an E configuration about the C=N bond. The 2,6-dichlorophenyl ring and the nitro-substituted benzene ring of the title compound are inclined at 21.16 (14)°, while the nitro group is skewed out of the attached benzene ring plane by 27.06 (18)°. The Cl1—C2—C1—N1, Cl2—C6—C1—N1, C2—C1—N1—N2, C1—N1—N2—C7, N1—N2—C7—C8, N2—C7—C8—C13, C7—C8—C13—N3, C8—C13—N3—O1 and C8—C13—N3—O2 torsion angles are 0.1 (3), 4.7 (4), −145.8 (2), 176.7 (2), 175.4 (2), 164.3 (3), −7.7 (4), −26.9 (4) and 155.7 (3)°, respectively. Two intramolecular N—H⋯Cl and C—H⋯O contacts are present (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1	0.95	2.48	2.939 (2)	110
N1—H1N⋯O2ⁱ	0.95	2.40	3.327 (3)	166
C7—H7A⋯O1	0.93	2.34	2.774 (4)	108
C12—H12A⋯Cl2ⁱⁱ	0.93	2.80	3.679 (3)	157
C2—Cl1⋯Cg2ⁱⁱⁱ	1.73 (1)	3.90 (1)	3.511 (3)	64 (1)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, face-to-face π–π stacking interactions [Cg1⋯Cg2( $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) = 3.7605 (17) Å with slippage of 1.352 Å, Cg1⋯Cg2( $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) = 3.8010 (17) Å with slippage of 1.457 Å, where Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively] occur between the centroids of the 2,6-dichlorophenyl ring and the nitro-substituted benzene ring of the title molecule along the a-axis direction (Figs. 2 and 3). Furthermore, these molecules are linked by intermolecular N—H⋯O and C—H⋯Cl hydrogen bonds, forming pairs of hydrogen-bonded molecular layers parallel to (20 $[\overline{2}]$ ) (Tables 1 and 2; Figs. 4 and 5). There is also a C—Cl⋯Cg interaction [Cl1⋯Cg2( $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) = 3.9026 (14) Å; C2—Cl1⋯Cg2 = 64.12 (10)°]. As a result of the large Cl ⋯ Cg2 distance and acute C—Cl⋯Cg2 angle, this interaction is only weak.

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

Contact	Distance	Symmetry operation
Cl1⋯H11A	3.06	x, 1 + y, z
C2⋯C8	3.464 (4)	$[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
H1N⋯O2	2.40	1 − x, 1 − y, 1 − z
O1⋯H4A	2.68	$[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
Cl2⋯H12A	2.80	− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
N3⋯C4	3.447 (4)	$[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z

Figure 2
A view of π–π stacking interactions of in the crystal packing of the title compound. Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 benzene rings, respectively. [Symmetry codes: (a) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (b) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (c) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (d) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z].

Figure 3
A partial view of π–π stacking interactions in the crystal packing of the title compound viewed along the b axis.

Figure 4
A general view of the crystal packing along the a axis of the title compound. Dashed lines indicate the intramolecular N—H⋯Cl, C—H⋯O, intermolecular N—H⋯O, C—H⋯Cl interactions and Cl⋯H, O⋯H contacts. [Symmetry codes: (a) x, 1 + y, z; (b) − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z; (c) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z; (d) x, −1 + y, z; (e) $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (f) 1 − x, 1 − y, 1 − z; (g) $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z; (h) 1 − x, −y, 1 − z].

Figure 5
A general view of the crystal packing with the hydrogen bonds and contacts along the b axis of the title compound, forming pairs of hydrogen-bonded molecular layers parallel to (20 $[\overline{2}]$ ).

Hirshfeld surface analysis was used to analyse the various intermolecular interactions in the title compound, through mapping the normalized contact distance (d_norm) using CrystalExplorer (Turner et al., 2017 ; Spackman & Jayatilaka, 2009 ). The Hirshfeld surface mapped over d_norm using a standard surface resolution with a fixed colour scale of −0.1980 (red) to 1.3500 (blue) a.u. is shown in Fig. 6. The white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distant contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The dark-red spots on the d_norm surface arise as a result of short interatomic contacts (Table 2), while the other weaker intermolecular interactions appear as light-red spots. The red points, which represent closer contacts and negative d_norm values on the surface, correspond to the C—H⋯O and C—H⋯Cl interactions. The shape-index of the Hirshfeld surface is a tool for visualizing the π–π stacking by the presence of adjacent red and blue triangles; if there are no such triangles, then there are no π–π interactions. The plot of the Hirshfeld surface mapped over shape-index shown in Fig. 7 clearly suggests that there are π–π interactions in the crystal packing of the title compound.

Figure 6
A view of the Hirshfeld surface mapped for the title compound over d_norm in the range −0.1980 to 1.3500 arbitrary units.

Figure 7
View of the three-dimensional Hirshfeld surface of the title compound plotted over shape-index.

The percentage contributions of various contacts to the total Hirshfeld surface are listed in Table 3 and shown in the two-dimensional fingerprint plots in Fig. 8. As revealed by the two-dimensional fingerprint plots (Fig. 8), the crystal packing is dominated by H⋯H contacts, representing van der Waals interactions (23.0% contribution to the overall surface), followed by O⋯H and Cl⋯H interactions, which contribute 20.1% and 19.0%, respectively.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
H⋯H	23.0
O⋯H/H⋯O	20.1
Cl⋯H/H⋯Cl	19.0
C⋯C	11.2
H⋯C/C⋯H	8.0
N⋯H/H⋯N	5.5
Cl⋯Cl	3.3
N⋯C/C⋯N	3.1
Cl⋯C/C⋯Cl	3.0
O⋯C/C⋯O	1.4
Cl⋯O/O⋯Cl	1.3
Cl⋯N/N⋯Cl	0.8
O⋯O	0.2
O⋯N/N⋯O	0.1

Figure 8
(a) The full two-dimensional fingerprint plot for the title compound and (b)–(f) those delineated into H⋯H, O⋯H/H⋯O, Cl⋯H/H⋯Cl, C⋯C and C⋯H/H⋯C contacts, respectively.

4. Database survey

Six compounds closely resemble the title compound, viz. 1-(2,4-dinitrophenyl)-2-[(E)-(3,4,5-trimethoxybenzylidene)hydrazine] (CSD refcode GISJAV; Chantrapromma et al., 2014 ), (E)-1-(2,4-dinitrophenyl)-2-[1-(3-methoxyphenyl)ethylidene]hydrazine (XEBCEO; Fun et al., 2012 ), 1-(2,4-dinitrophenyl)-2-[(E)-2,4,5-trimethoxybenzylidene]hydrazine (AFUSEB; Fun et al., 2013 ), (E)-1-(2,4-dinitrophenyl)-2-(1-(2-methoxyphenyl)ethylidene)hydrazine (OBUJAY; Fun et al., 2011 ), (E)-1-(2,4-dinitrophenyl)-2-[1-(3-fluorophenyl)ethylidene]hydrazine (PAVKAA; Chantrapromma et al., 2012 ) and (E)-1-(2,4-dinitrophenyl)-2-[1-(2-nitrophenyl)ethylidene]hydrazine (YAHRUW; Nilwanna et al., 2011 ). All bond lengths (Allen et al., 1987 ) and angles for the title compound are within normal ranges and are comparable to those observed in these structures. In each one, the configuration of the imine C=N bond is E.

5. Synthesis and crystallization

The title compound was synthesized according to the reported method (Atioğlu et al., 2019 ; Maharramov et al., 2018; Shixaliyev et al., 2018, 2019). A mixture of 2-nitrobenzaldehyde (10 mmol), CH₃COONa (0.82 g), ethanol (50 mL) and (2,6-dichlorophenyl)hydrazine (10.2 mmol) was refluxed at 353 K under stirring for 2 h. The reaction mixture was cooled to room temperature and water (50 mL) was added to give a precipitate of the crude product, which was filtered off, washed with diluted ethanol (1:1 with water) and dried in vacuo using a rotary evaporator. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Title compound: orange solid (90%); m.p. 398 K. Analysis calculated for C₁₃H₉Cl₂N₃O₂ (M = 310.13): C 50.35, H 2.93, N 13.55; found: C 50.27, H 2.86, N 13.54%. ¹H NMR (300 MHz, DMSO-d₆): δ 10.20 (1H, –NH), 8.41 (1H, –CH), 7.13–8.08 (7H, aromatic). ¹³C NMR (75 MHz, DMSO-d₆): δ 147.47, 137.80, 133.76, 133.32, 130.17, 129.85, 129.16, 128.00, 127.08, 125.86, 124.96. ESI–MS: m/z: 311.08 [M+H]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All H atoms were refined using a riding model with d(C—H) = 0.93 Å, d(N—H) = 0.95 Å and U_iso = 1.2U_eq(N,C).

Table 4
Experimental details

Crystal data
Chemical formula	C₁₃H₉Cl₂N₃O₂
M_r	310.13
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.1138 (4), 12.6827 (6), 15.1613 (8)
β (°)	100.571 (2)
V (Å³)	1344.67 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.49
Crystal size (mm)	0.26 × 0.22 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.868, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	22007, 2521, 2184
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.118, 1.07
No. of reflections	2521
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.40
Computer programs: APEX3 and SAINT (Bruker, 2007 ), SHELXT2016/6 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2012294

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020008567/vm2235sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020008567/vm2235Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020008567/vm2235Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXT2016/6 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

(E)-1-(2,6-Dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine top

Crystal data top

C₁₃H₉Cl₂N₃O₂	F(000) = 632
M_r = 310.13	D_x = 1.532 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.1138 (4) Å	Cell parameters from 9979 reflections
b = 12.6827 (6) Å	θ = 2.7–27.9°
c = 15.1613 (8) Å	µ = 0.49 mm⁻¹
β = 100.571 (2)°	T = 296 K
V = 1344.67 (12) Å³	Plate, orange
Z = 4	0.26 × 0.22 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	2184 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.057
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.0°, θ_min = 2.7°
T_min = 0.868, T_max = 0.906	h = −8→8
22007 measured reflections	k = −15→15
2521 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: mixed
wR(F²) = 0.118	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.026P)² + 1.7039P] where P = (F_o² + 2F_c²)/3
2521 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.40 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
Cl1	0.48623 (11)	0.84495 (6)	0.29065 (5)	0.0562 (2)
Cl2	0.26473 (16)	0.52094 (7)	0.06054 (6)	0.0807 (3)
O1	0.7013 (4)	0.44141 (18)	0.49042 (15)	0.0702 (7)
O2	0.6516 (4)	0.2943 (2)	0.55110 (15)	0.0863 (8)
N1	0.4068 (4)	0.62149 (17)	0.24789 (15)	0.0473 (6)
H1N	0.396165	0.657432	0.301808	0.057*
N2	0.4727 (3)	0.52096 (16)	0.24606 (15)	0.0419 (5)
N3	0.6564 (3)	0.3486 (2)	0.48539 (15)	0.0509 (6)
C1	0.3930 (4)	0.6850 (2)	0.17229 (17)	0.0405 (6)
C2	0.4275 (4)	0.7938 (2)	0.18315 (18)	0.0410 (6)
C3	0.4131 (4)	0.8620 (2)	0.1116 (2)	0.0530 (7)
H3A	0.435083	0.933692	0.121363	0.064*
C4	0.3661 (5)	0.8234 (3)	0.0258 (2)	0.0623 (9)
H4A	0.359130	0.868645	−0.023006	0.075*
C5	0.3296 (4)	0.7177 (3)	0.0122 (2)	0.0594 (8)
H5A	0.298464	0.691722	−0.046044	0.071*
C6	0.3384 (4)	0.6497 (2)	0.08380 (19)	0.0487 (7)
C7	0.4904 (4)	0.4688 (2)	0.31903 (18)	0.0414 (6)
H7A	0.467933	0.500896	0.371280	0.050*
C8	0.5469 (4)	0.35755 (19)	0.31939 (17)	0.0377 (5)
C9	0.5193 (4)	0.3022 (2)	0.23815 (19)	0.0468 (6)
H9A	0.473272	0.337842	0.184977	0.056*
C10	0.5589 (4)	0.1961 (2)	0.2353 (2)	0.0565 (8)
H10A	0.541762	0.161493	0.180264	0.068*
C11	0.6239 (4)	0.1405 (2)	0.3132 (2)	0.0586 (8)
H11A	0.649659	0.068772	0.310822	0.070*
C12	0.6501 (4)	0.1916 (2)	0.3942 (2)	0.0515 (7)
H12A	0.691729	0.154697	0.447219	0.062*
C13	0.6139 (4)	0.2987 (2)	0.39640 (17)	0.0396 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0685 (5)	0.0450 (4)	0.0534 (4)	−0.0010 (3)	0.0064 (3)	−0.0065 (3)
Cl2	0.1061 (8)	0.0636 (5)	0.0648 (5)	−0.0150 (5)	−0.0046 (5)	−0.0194 (4)
O1	0.0956 (18)	0.0501 (13)	0.0590 (14)	−0.0025 (12)	−0.0014 (12)	−0.0147 (11)
O2	0.130 (2)	0.0877 (18)	0.0400 (12)	−0.0075 (17)	0.0109 (13)	0.0151 (12)
N1	0.0694 (16)	0.0337 (11)	0.0405 (12)	0.0096 (10)	0.0143 (11)	0.0029 (9)
N2	0.0482 (13)	0.0343 (11)	0.0444 (12)	0.0006 (9)	0.0112 (10)	0.0012 (9)
N3	0.0540 (14)	0.0554 (15)	0.0415 (13)	0.0043 (11)	0.0042 (11)	0.0005 (11)
C1	0.0391 (13)	0.0418 (14)	0.0398 (13)	0.0053 (11)	0.0053 (11)	0.0044 (11)
C2	0.0384 (13)	0.0408 (13)	0.0440 (14)	0.0039 (11)	0.0077 (11)	0.0041 (11)
C3	0.0544 (17)	0.0450 (16)	0.0610 (18)	0.0080 (13)	0.0140 (14)	0.0148 (14)
C4	0.064 (2)	0.071 (2)	0.0523 (18)	0.0132 (16)	0.0128 (15)	0.0224 (16)
C5	0.0589 (19)	0.079 (2)	0.0383 (15)	0.0090 (16)	0.0042 (13)	0.0023 (15)
C6	0.0492 (16)	0.0520 (16)	0.0427 (15)	0.0016 (13)	0.0023 (12)	−0.0015 (13)
C7	0.0481 (15)	0.0363 (13)	0.0414 (14)	0.0031 (11)	0.0120 (11)	−0.0008 (11)
C8	0.0381 (13)	0.0366 (13)	0.0398 (13)	−0.0018 (10)	0.0110 (10)	−0.0004 (10)
C9	0.0527 (16)	0.0465 (15)	0.0421 (14)	0.0006 (12)	0.0111 (12)	−0.0035 (12)
C10	0.0641 (19)	0.0477 (16)	0.0602 (19)	−0.0038 (14)	0.0178 (15)	−0.0190 (15)
C11	0.0602 (19)	0.0317 (14)	0.085 (2)	−0.0011 (13)	0.0175 (17)	−0.0048 (15)
C12	0.0545 (17)	0.0377 (14)	0.0615 (18)	0.0005 (12)	0.0089 (14)	0.0091 (13)
C13	0.0401 (13)	0.0374 (13)	0.0415 (14)	−0.0018 (10)	0.0078 (11)	−0.0008 (11)

Geometric parameters (Å, º) top

Cl1—C2	1.732 (3)	C4—H4A	0.9300
Cl2—C6	1.731 (3)	C5—C6	1.380 (4)
O1—N3	1.218 (3)	C5—H5A	0.9300
O2—N3	1.217 (3)	C7—C8	1.467 (3)
N1—N2	1.361 (3)	C7—H7A	0.9300
N1—C1	1.390 (3)	C8—C13	1.394 (4)
N1—H1N	0.9510	C8—C9	1.400 (4)
N2—C7	1.275 (3)	C9—C10	1.377 (4)
N3—C13	1.471 (3)	C9—H9A	0.9300
C1—C6	1.400 (4)	C10—C11	1.381 (5)
C1—C2	1.406 (4)	C10—H10A	0.9300
C2—C3	1.376 (4)	C11—C12	1.371 (4)
C3—C4	1.374 (4)	C11—H11A	0.9300
C3—H3A	0.9300	C12—C13	1.384 (4)
C4—C5	1.374 (5)	C12—H12A	0.9300

N2—N1—C1	119.9 (2)	C5—C6—Cl2	117.5 (2)
N2—N1—H1N	123.3	C1—C6—Cl2	121.2 (2)
C1—N1—H1N	115.2	N2—C7—C8	119.0 (2)
C7—N2—N1	116.6 (2)	N2—C7—H7A	120.5
O2—N3—O1	122.8 (3)	C8—C7—H7A	120.5
O2—N3—C13	118.4 (3)	C13—C8—C9	116.1 (2)
O1—N3—C13	118.7 (2)	C13—C8—C7	124.7 (2)
N1—C1—C6	124.7 (2)	C9—C8—C7	119.0 (2)
N1—C1—C2	119.2 (2)	C10—C9—C8	121.4 (3)
C6—C1—C2	116.0 (2)	C10—C9—H9A	119.3
C3—C2—C1	122.6 (3)	C8—C9—H9A	119.3
C3—C2—Cl1	118.5 (2)	C9—C10—C11	120.6 (3)
C1—C2—Cl1	119.0 (2)	C9—C10—H10A	119.7
C4—C3—C2	119.6 (3)	C11—C10—H10A	119.7
C4—C3—H3A	120.2	C12—C11—C10	119.7 (3)
C2—C3—H3A	120.2	C12—C11—H11A	120.2
C5—C4—C3	119.8 (3)	C10—C11—H11A	120.2
C5—C4—H4A	120.1	C11—C12—C13	119.3 (3)
C3—C4—H4A	120.1	C11—C12—H12A	120.3
C4—C5—C6	120.8 (3)	C13—C12—H12A	120.3
C4—C5—H5A	119.6	C12—C13—C8	122.8 (3)
C6—C5—H5A	119.6	C12—C13—N3	115.9 (3)
C5—C6—C1	121.2 (3)	C8—C13—N3	121.3 (2)

C1—N1—N2—C7	176.7 (2)	N2—C7—C8—C13	164.3 (3)
N2—N1—C1—C6	37.1 (4)	N2—C7—C8—C9	−20.8 (4)
N2—N1—C1—C2	−145.8 (2)	C13—C8—C9—C10	−0.8 (4)
N1—C1—C2—C3	−178.8 (2)	C7—C8—C9—C10	−176.0 (3)
C6—C1—C2—C3	−1.4 (4)	C8—C9—C10—C11	1.3 (5)
N1—C1—C2—Cl1	0.1 (3)	C9—C10—C11—C12	−0.3 (5)
C6—C1—C2—Cl1	177.4 (2)	C10—C11—C12—C13	−1.1 (5)
C1—C2—C3—C4	−1.0 (4)	C11—C12—C13—C8	1.6 (4)
Cl1—C2—C3—C4	−179.8 (2)	C11—C12—C13—N3	−176.6 (3)
C2—C3—C4—C5	1.5 (5)	C9—C8—C13—C12	−0.7 (4)
C3—C4—C5—C6	0.3 (5)	C7—C8—C13—C12	174.3 (3)
C4—C5—C6—C1	−2.9 (5)	C9—C8—C13—N3	177.4 (2)
C4—C5—C6—Cl2	173.1 (3)	C7—C8—C13—N3	−7.7 (4)
N1—C1—C6—C5	−179.5 (3)	O2—N3—C13—C12	−26.1 (4)
C2—C1—C6—C5	3.3 (4)	O1—N3—C13—C12	151.3 (3)
N1—C1—C6—Cl2	4.7 (4)	O2—N3—C13—C8	155.7 (3)
C2—C1—C6—Cl2	−172.5 (2)	O1—N3—C13—C8	−26.9 (4)
N1—N2—C7—C8	175.4 (2)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.95	2.48	2.939 (2)	110
N1—H1N···O2ⁱ	0.95	2.40	3.327 (3)	166
C7—H7A···O1	0.93	2.34	2.774 (4)	108
C12—H12A···Cl2ⁱⁱ	0.93	2.80	3.679 (3)	157
C2—Cl1···Cg2ⁱⁱⁱ	1.73 (1)	3.90 (1)	3.511 (3)	64 (1)

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

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

Contact	Distance	Symmetry operation
Cl1···H11A	3.06	x, 1 + y, z
C2···C8	3.464 (4)	1/2 - x, 1/2 + y, 1/2 - z
H1N···O2	2.40	1 - x, 1 - y, 1 - z
O1···H4A	2.68	1/2 + x, 3/2 - y, 1/2 + z
Cl2···H12A	2.80	-1/2 + x, 1/2 - y, -1/2 + z
N3···C4	3.447 (4)	3/2 - x, -1/2 + y, 1/2 - z

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

Contact	Percentage contribution
H···H	23.0
O···H/H···O	20.1
Cl···H/H···Cl	19.0
C···C	11.2
H···C/C···H	8.0
N···H/H···N	5.5
Cl···Cl	3.3
N···C/C···N	3.1
Cl···C/C···Cl	3.0
O···C/C···O	1.4
Cl···O/O···Cl	1.3
Cl···N/N···Cl	0.8
O···O	0.2
O···N/N···O	0.1

Funding information

This work was funded by Science Development Foundation under the President of the Republic of Azerbaijan, grant No. EIF/MQM/Elm-Tehsil-1–2016-1(26)–71/06/4.

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