(E)-1-(2,6-Di­chloro­phen­yl)-2-(3-nitro­benzyl­idene)hydrazine: crystal structure and Hirshfeld surface analysis

Atioğlu, Z.; Akkurt, M.; Shikhaliyev, N.Q.; Suleymanova, G.T.; Babayeva, G.V.; Gurbanova, N.V.; Mammadova, G.Z.; Mlowe, S.

doi:10.1107/S2056989020009433

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ISSN: 2056-9890

Volume 76| Part 8| August 2020| Pages 1291-1295

https://doi.org/10.1107/S2056989020009433

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(E)-1-(2,6-Dichlorophenyl)-2-(3-nitrobenzylidene)hydrazine: crystal structure and Hirshfeld surface analysis

Zeliha Atioğlu,^a Mehmet Akkurt,^b Namiq Q. Shikhaliyev,^c Gulnar T. Suleymanova,^c Gulnare V. Babayeva,^c Nurana V. Gurbanova,^c Gunay Z. Mammadova ^c and Sixberth Mlowe ^d ^*

^aİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cOrganic Chemistry Department, Baku State University, Z. Khalilov 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 L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 4 July 2020; accepted 10 July 2020; online 17 July 2020)

The stabilized conformation of the title compound, C₁₃H₉Cl₂N₃O₂, is similar to that of the isomeric compound (E)-1-(2,6-dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine. The 2,6-dichlorophenyl ring and the nitro-substituted benzene ring form a dihedral angle of 26.25 (16)°. In the crystal, face-to-face π-π stacking interactions along the a-axis direction occur between the centroids of the 2,6-dichlorophenyl ring and the nitro-substituted benzene ring. The molecules are further linked by C—H⋯O contacts and N—H⋯O and C—H⋯Cl hydrogen bonds, forming pairs of hydrogen-bonded molecular layers parallel to (100). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (22.1%), Cl⋯H/H⋯Cl (20.5%), O⋯H/H⋯O (19.7%), C⋯C (11.1%) and C⋯H/H⋯C (8.3%) interactions.

Keywords: crystal structure; isomer; 2,6-dichlorophenyl ring; 3-nitrobenzylidene ring; Hirshfeld surface analysis.

CCDC reference: 2015528

1. Chemical context

Schiff bases as well as hydrazone ligands and their complexes have attracted much attention because of their high synthetic potential for organic and inorganic chemistry and their diverse useful properties (Maharramov et al., 2018 ; Mahmudov et al., 2014 ). The analytical and catalytic properties of this class of compounds are strongly dependent on the groups attached to the hydrazone moiety (Shixaliyev et al., 2019 ). On the other hand, intermolecular interactions organize molecular architectures, which play a critical role in synthesis, catalysis, micellization, etc (Akbari et al., 2017 ; Gurbanov et al., 2018 ; Mahmoudi et al., 2018 and references cited therein). New types of weak interactions such as halogen, chalcogen, pnictogen and tetrel bonds or their cooperation with hydrogen bonds are able to drive the synthesis and catalysis, as well as improve properties of materials (Mizar et al., 2012 ; Mahmudov et al., 2019 and references cited therein). For that, the main skeleton of the arylhydrazone ligand should be extended with weak bond-donor centre(s). In order to continue our work in this perspective, we have functionalized a new azo dye, (E)-1-(2,6-dichlorophenyl)-2-(3-nitrobenzylidene)hydrazine, (I), 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 26.25 (16)°, while the nitro group is skewed out of the attached benzene ring plane by 6.3 (2)°. The conformation is stabilized by an intramolecular N1—H1N⋯Cl1 interaction, which forms an S(6) graph-set motif (Table 1). The conformation of the title compound can be compared with that of the isomeric compound (E)-1-(2,6-dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine (CSD refcode KUWGOB; Çelikesir et al., 2020 ). Fig. 2 shows the overlay of the two isomers. The r.m.s. deviation of the overlay between the two isomers is 0.003 Å. In the 2-nitro isomer, the dihedral angles are 21.16 (14) (between the phenyl rings) and 27.06 (18)° (between between the nitro group and the phenyl ring). The difference in angles may be due to the steric interaction resulting from the position of the nitro group on the benzene ring to which it is attached. 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, N2—C7—C8—C9, C8—C13—C12—N3, C13—C12—N3—O1 and C13—C12—N3—O2 torsion angles are −0.1 (4), 3.4 (4), −147.1 (3), 177.3 (3), 178.2 (2), 165.5 (3), −15.6 (4), 178.8 (3), 6.2 (4) and −174.4 (3) °, respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1	0.95	2.54	2.940 (2)	106
N1—H1N⋯O1ⁱ	0.95	2.31	3.243 (3)	168
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+2]$ .

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

Figure 2
Overlay of the title compound and the isomer (E)-1-(2,6-dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine (Çelikesir et al., 2020

3. Supramolecular features

In the crystal, face-to-face π–π stacking interactions [Cg1⋯Cg2(−x, − $[{1\over 2}]$ + y, 1 − z) = 3.753 (2) Å with slippage of 1.380 Å and Cgl⋯Cg2(1 − x, − $[{1\over 2}]$ + y, 1 − z) = 3.761 (2) Å with slippage of 1.423 Å, where Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively] occur between the 2,6-dichlorophenyl ring and the nitro-substituted benzene ring of the title molecule along the a-axis direction (Fig. 3). The molecules are further linked by C—H⋯O contacts and N—H⋯O and C—H⋯Cl hydrogen bonds, forming pairs of hydrogen-bonded molecular layers parallel to (100) (Tables 1 and 2; Figs. 4 and 5). In the crystal, a C—Cl⋯π interaction is also observed [C2—Cl1⋯Cg2 (−x, − $[{1\over 2}]$ + y, 1 − z) = 3.9373 (18) Å, C2—Cl1⋯Cg2 = 62.59 (10)°, where Cg2 is the centroid of the C8–C13 ring]. The large Cl⋯Cg2 distance and acute C–Cl⋯Cg2 angle, however, indicate that this interaction is only weak.

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

Contact	Distance	Symmetry operation
Cl1⋯H11A	3.13	x, − 1 + y, z
H1N⋯O1	2.31	1 − x, − $[{1\over 2}]$ + y, 2 − z
H7A⋯O2	2.77	1 − x, − $[{1\over 2}]$ + y, 2 − z
C1⋯C11	3.405	−x, − $[{1\over 2}]$ + y, 1 − z
Cl2⋯H13A	2.95	x, y, −1 + z
O2⋯H4A	2.66	x, 1 + y, 1 + z
C2⋯C8	3.426	1 − x, − $[{1\over 2}]$ + y, 1 − z
H5A⋯H10A	2.55	−x, − $[{1\over 2}]$ + y, −z

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

Figure 4
A general view of the crystal packing of the title compound along the a axis with hydrogen bonds and contacts shown as dashed lines.

Figure 5
A general view of the crystal packing of the title compound along the b axis showing the pairs of hydrogen-bonded molecular layers parallel to (100).

4. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon, et al., 2007 ) were performed with Crystal Explorer17 (Turner et al., 2017 ) to investigate the intermolecular interactions and surface morphology. The Hirshfeld surface mapped over d_norm in the range −0.2694 to 1.2224 a.u. and corresponding colours from red (shorter distance than the sum of van der Waals radii) over white to blue (longer distance than the sum of van der Waals radii) is shown in Fig. 6. The red points, which represent closer contacts and negative d_norm values on the surface, correspond to the N—H⋯O, C—H⋯O and C—H⋯Cl interactions (Table 2). 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. The plot of the Hirshfeld surface mapped over shape-index shown in Fig. 7 clearly suggests that there are π–π interactions in the title compound.

Figure 6
A view of the Hirshfeld surface mapped over d_norm in the range −0.2694 to 1.2224 arbitrary units showing C—H⋯O, N—H⋯O hydrogen bonds and H⋯H interactions (van der Waals interactions). Applied colours for atoms: grey = C, white = H, blue = N, red = O and green = Cl.

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

In the crystal there are four major types of interaction (H⋯H = 22.1%, Cl⋯H = 20.5%, O⋯H = 19.7%, C⋯C = 11.1%) on the d_norm surface. The two-dimensional fingerprint plots are shown in Fig. 8. The interaction sequence of d_norm on the two-dimensional fingerprint plot (H⋯H) > (Cl⋯H) > (O⋯H) > (C⋯C) represents the nature of the packing in the crystal structure. The contribution of these major interactions governs the overall packing of crystal structure. The percentage contributions of other weak interactions are: C⋯H/H⋯C (8.3%), N⋯H/H⋯N (4.9%), Cl⋯C/C⋯Cl (3.3%), N⋯C/C⋯N (2.9%), Cl⋯O/O⋯Cl (2.6%), Cl⋯N/N⋯Cl (1.8%), C⋯O/O⋯C (1.7%) and Cl⋯Cl (1.2%).

Figure 8
(a) The full two-dimensional fingerprint plot for the title compound and (b)–(f) those delineated into H⋯H (22.1%), Cl⋯H/H⋯Cl (20.5%), O⋯H/H⋯O (19.7%), C⋯C (11.1%) and C⋯H/H⋯C (8.3%) contacts, respectively.

5. Database survey

A search of the Cambridge Structural Database (CSD version 5.40, update of September 2019; Groom et al., 2016 ) gave only seven entries closely resembling the title compound. Our recently published compound (E)-1-(2,6-dichlorophenyl)-2-(2-nitrobenzylidene)hydrazine (KUWGOB: Çelikesir et al., 2020) is an isomer of the title compound. The other six compounds are 1-(2,4-dinitrophenyl)-2-[(E)-(3,4,5-trimethoxybenzylidene)hydrazine] (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 and these related compounds are comparable and within normal ranges.

6. Synthesis and crystallization

The title compound was synthesized according to the reported method (Atioğlu et al., 2019 ; Maharramov et al., 2018). A mixture of 3-nitrobenzaldehyde (10 mmol), CH₃COONa (0.82 g), ethanol (50 mL) and (2,6-dichlorophenyl)hydrazine (10.2 mmol) was refluxed at 353 K with 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 of rotary evaporator. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution; yellow solid; yield 95%; m.p. 423 K. Analysis calculated for C₁₃H₉Cl₂N₃O₂ (M = 310.13): C 50.35, H 2.93, N 13.55; found: C 50.32, H 2.90, N 13.47%. ¹H NMR (300 MHz, DMSO-d₆): δ 9.95 (1H, –NH), 8.40 (1H, –CH), 7.00–8.20 (7H, aromatic). ¹³C NMR (75 MHz, DMSO-d₆): δ 149.00, 138.01, 137.50, 136.05, 132.11, 130.50, 129.04, 128.23, 126.24, 123.16, 119.90. ESI-MS: m/z: 311.14 [M+H]⁺.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. 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 3
Experimental details

Crystal data
Chemical formula	C₁₃H₉Cl₂N₃O₂
M_r	310.13
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	7.1212 (14), 12.711 (3), 7.6991 (16)
β (°)	105.940 (7)
V (Å³)	670.1 (2)
Z	2
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	0.873, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	22230, 2744, 2392
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.064, 1.11
No. of reflections	2744
No. of parameters	181
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16
Absolute structure	Flack x determined using 1032 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.04 (3)
Computer programs: APEX3 (Bruker, 2007 ), SAINT (Bruker, 2007), SHELXT2016/6 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and OLEX2 (Dolomanov et al., 2009 ), PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2015528

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009433/vm2237sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009433/vm2237Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020009433/vm2237Isup3.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) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: PLATON (Spek, 2020).

(E)-1-(2,6-Dichlorophenyl)-2-(3-nitrobenzylidene)hydrazine top

Crystal data top

C₁₃H₉Cl₂N₃O₂	F(000) = 316
M_r = 310.13	D_x = 1.537 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.1212 (14) Å	Cell parameters from 9800 reflections
b = 12.711 (3) Å	θ = 2.8–26.3°
c = 7.6991 (16) Å	µ = 0.49 mm⁻¹
β = 105.940 (7)°	T = 296 K
V = 670.1 (2) Å³	Plate, orange
Z = 2	0.26 × 0.22 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	2392 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.062
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.4°, θ_min = 2.8°
T_min = 0.873, T_max = 0.902	h = −8→8
22230 measured reflections	k = −15→15
2744 independent reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0217P)² + 0.0759P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2744 reflections	Δρ_max = 0.15 e Å⁻³
181 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1032 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (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	0.28649 (13)	0.12020 (5)	0.58310 (10)	0.0583 (2)
Cl2	0.28511 (15)	0.43809 (7)	0.10800 (12)	0.0666 (3)
O1	0.3919 (5)	0.7625 (2)	1.1215 (3)	0.0799 (8)
O2	0.2541 (5)	0.9024 (2)	0.9937 (4)	0.0848 (9)
N1	0.3362 (4)	0.34075 (17)	0.4897 (3)	0.0465 (6)
H1N	0.401372	0.310054	0.602708	0.056*
N2	0.2806 (3)	0.44380 (18)	0.4863 (3)	0.0397 (5)
N3	0.3101 (4)	0.8121 (2)	0.9871 (4)	0.0531 (7)
C1	0.2672 (4)	0.2769 (2)	0.3396 (4)	0.0365 (6)
C2	0.2365 (4)	0.1696 (2)	0.3645 (4)	0.0411 (7)
C3	0.1710 (5)	0.1009 (2)	0.2220 (4)	0.0543 (8)
H3A	0.152757	0.030205	0.243822	0.065*
C4	0.1330 (5)	0.1370 (3)	0.0483 (5)	0.0588 (9)
H4A	0.086569	0.091344	−0.048297	0.071*
C5	0.1641 (5)	0.2419 (3)	0.0174 (4)	0.0558 (8)
H5A	0.139312	0.266660	−0.100398	0.067*
C6	0.2322 (4)	0.3105 (2)	0.1614 (4)	0.0426 (7)
C7	0.3439 (5)	0.4963 (2)	0.6318 (4)	0.0413 (7)
H7A	0.421014	0.463484	0.734710	0.050*
C8	0.2957 (4)	0.6082 (2)	0.6376 (3)	0.0359 (6)
C9	0.2219 (5)	0.6675 (2)	0.4811 (4)	0.0433 (7)
H9A	0.201931	0.635668	0.368765	0.052*
C10	0.1784 (5)	0.7724 (2)	0.4908 (4)	0.0512 (8)
H10A	0.131772	0.810787	0.384850	0.061*
C11	0.2029 (5)	0.8214 (2)	0.6557 (4)	0.0475 (7)
H11A	0.169393	0.891678	0.662994	0.057*
C12	0.2790 (4)	0.7623 (2)	0.8092 (4)	0.0387 (6)
C13	0.3274 (4)	0.6576 (2)	0.8048 (4)	0.0375 (6)
H13A	0.380225	0.620594	0.911236	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0720 (6)	0.0433 (4)	0.0608 (5)	0.0025 (4)	0.0200 (4)	0.0100 (4)
Cl2	0.0988 (8)	0.0470 (4)	0.0610 (5)	0.0050 (5)	0.0339 (5)	0.0121 (4)
O1	0.122 (2)	0.0705 (17)	0.0406 (13)	0.0047 (16)	0.0118 (14)	−0.0139 (12)
O2	0.106 (2)	0.0565 (16)	0.0844 (19)	0.0181 (15)	0.0135 (16)	−0.0350 (14)
N1	0.0622 (17)	0.0308 (12)	0.0418 (13)	0.0081 (10)	0.0060 (11)	−0.0040 (9)
N2	0.0457 (13)	0.0285 (10)	0.0451 (12)	0.0019 (11)	0.0128 (10)	−0.0042 (10)
N3	0.0580 (18)	0.0489 (15)	0.0529 (16)	−0.0065 (13)	0.0163 (14)	−0.0188 (13)
C1	0.0341 (15)	0.0321 (12)	0.0434 (14)	0.0045 (11)	0.0110 (12)	−0.0048 (10)
C2	0.0420 (17)	0.0315 (13)	0.0513 (17)	0.0049 (12)	0.0153 (13)	−0.0011 (11)
C3	0.0538 (19)	0.0350 (16)	0.073 (2)	0.0013 (14)	0.0155 (16)	−0.0127 (15)
C4	0.059 (2)	0.055 (2)	0.0569 (19)	0.0011 (16)	0.0081 (15)	−0.0228 (15)
C5	0.058 (2)	0.066 (2)	0.0420 (17)	0.0124 (17)	0.0099 (15)	−0.0063 (14)
C6	0.0452 (18)	0.0368 (14)	0.0477 (16)	0.0057 (13)	0.0158 (14)	−0.0013 (13)
C7	0.0522 (19)	0.0326 (14)	0.0385 (15)	0.0020 (12)	0.0116 (13)	−0.0017 (11)
C8	0.0366 (14)	0.0336 (13)	0.0379 (13)	−0.0044 (12)	0.0108 (11)	−0.0043 (12)
C9	0.0506 (19)	0.0418 (16)	0.0354 (15)	−0.0022 (13)	0.0080 (13)	−0.0064 (11)
C10	0.059 (2)	0.0423 (16)	0.0455 (18)	0.0014 (15)	0.0033 (15)	0.0060 (13)
C11	0.0504 (19)	0.0295 (13)	0.0594 (19)	0.0028 (13)	0.0097 (15)	−0.0045 (13)
C12	0.0380 (15)	0.0361 (14)	0.0417 (16)	−0.0054 (12)	0.0104 (12)	−0.0109 (11)
C13	0.0422 (16)	0.0355 (13)	0.0355 (14)	−0.0025 (11)	0.0119 (12)	−0.0009 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.739 (3)	C4—H4A	0.9300
Cl2—C6	1.740 (3)	C5—C6	1.389 (4)
O1—N3	1.215 (4)	C5—H5A	0.9300
O2—N3	1.220 (4)	C7—C8	1.467 (4)
N1—N2	1.367 (3)	C7—H7A	0.9300
N1—C1	1.387 (3)	C8—C13	1.393 (3)
N1—H1N	0.9500	C8—C9	1.396 (4)
N2—C7	1.275 (3)	C9—C10	1.375 (4)
N3—C12	1.469 (3)	C9—H9A	0.9300
C1—C6	1.392 (4)	C10—C11	1.382 (4)
C1—C2	1.404 (4)	C10—H10A	0.9300
C2—C3	1.379 (4)	C11—C12	1.379 (4)
C3—C4	1.369 (5)	C11—H11A	0.9300
C3—H3A	0.9300	C12—C13	1.378 (4)
C4—C5	1.383 (5)	C13—H13A	0.9300

N2—N1—C1	120.7 (2)	C5—C6—Cl2	116.6 (2)
N2—N1—H1N	118.5	C1—C6—Cl2	121.8 (2)
C1—N1—H1N	119.7	N2—C7—C8	120.4 (3)
C7—N2—N1	117.0 (2)	N2—C7—H7A	119.8
O1—N3—O2	122.6 (3)	C8—C7—H7A	119.8
O1—N3—C12	119.0 (3)	C13—C8—C9	118.7 (2)
O2—N3—C12	118.5 (3)	C13—C8—C7	119.0 (2)
N1—C1—C6	124.6 (2)	C9—C8—C7	122.2 (2)
N1—C1—C2	119.2 (3)	C10—C9—C8	120.9 (3)
C6—C1—C2	116.1 (2)	C10—C9—H9A	119.5
C3—C2—C1	122.5 (3)	C8—C9—H9A	119.5
C3—C2—Cl1	118.4 (2)	C9—C10—C11	120.9 (3)
C1—C2—Cl1	119.0 (2)	C9—C10—H10A	119.6
C4—C3—C2	119.9 (3)	C11—C10—H10A	119.6
C4—C3—H3A	120.1	C12—C11—C10	117.5 (3)
C2—C3—H3A	120.1	C12—C11—H11A	121.2
C3—C4—C5	119.6 (3)	C10—C11—H11A	121.2
C3—C4—H4A	120.2	C13—C12—C11	123.2 (2)
C5—C4—H4A	120.2	C13—C12—N3	117.7 (3)
C4—C5—C6	120.3 (3)	C11—C12—N3	119.1 (2)
C4—C5—H5A	119.8	C12—C13—C8	118.7 (2)
C6—C5—H5A	119.8	C12—C13—H13A	120.7
C5—C6—C1	121.5 (3)	C8—C13—H13A	120.7

C1—N1—N2—C7	177.3 (3)	N1—N2—C7—C8	178.2 (2)
N2—N1—C1—C6	35.6 (4)	N2—C7—C8—C13	165.5 (3)
N2—N1—C1—C2	−147.1 (3)	N2—C7—C8—C9	−15.6 (4)
N1—C1—C2—C3	−179.0 (3)	C13—C8—C9—C10	−1.0 (4)
C6—C1—C2—C3	−1.5 (4)	C7—C8—C9—C10	−179.9 (3)
N1—C1—C2—Cl1	−0.1 (4)	C8—C9—C10—C11	−1.3 (5)
C6—C1—C2—Cl1	177.4 (2)	C9—C10—C11—C12	2.3 (5)
C1—C2—C3—C4	−0.2 (5)	C10—C11—C12—C13	−1.2 (4)
Cl1—C2—C3—C4	−179.1 (3)	C10—C11—C12—N3	179.1 (3)
C2—C3—C4—C5	1.2 (5)	O1—N3—C12—C13	6.2 (4)
C3—C4—C5—C6	−0.4 (5)	O2—N3—C12—C13	−174.4 (3)
C4—C5—C6—C1	−1.4 (5)	O1—N3—C12—C11	−174.0 (3)
C4—C5—C6—Cl2	175.0 (3)	O2—N3—C12—C11	5.4 (4)
N1—C1—C6—C5	179.6 (3)	C11—C12—C13—C8	−1.0 (4)
C2—C1—C6—C5	2.3 (4)	N3—C12—C13—C8	178.8 (3)
N1—C1—C6—Cl2	3.4 (4)	C9—C8—C13—C12	2.0 (4)
C2—C1—C6—Cl2	−173.9 (2)	C7—C8—C13—C12	−179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.95	2.54	2.940 (2)	106
N1—H1N···O1ⁱ	0.95	2.31	3.243 (3)	168

Symmetry code: (i) −x+1, y−1/2, −z+2.

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

Contact	Distance	Symmetry operation
Cl1···H11A	3.13	x, - 1 + y, z
H1N···O1	2.31	1 - x, -1/2 + y, 2 - z
H7A···O2	2.77	1 - x, -1/2 + y, 2 - z
C1···C11	3.405	-x, -1/2 + y, 1 - z
Cl2···H13A	2.95	x, y, -1 + z
O2···H4A	2.66	x, 1 + y, 1 + z
C2···C8	3.426	1 - x, -1/2 + y, 1 - z
H5A···H10A	2.55	-x, -1/2 + y, -z

Funding information

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

References

Akbari Afkhami, F., Mahmoudi, G., Gurbanov, A. V., Zubkov, F. I., Qu, F., Gupta, A. & Safin, D. A. (2017). Dalton Trans. 46, 14888–14896. Web of Science CSD CrossRef CAS PubMed Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Atioğlu, Z., Akkurt, M., Shikhaliyev, N. Q., Suleymanova, G. T., Bagirova, K. N. & Toze, F. A. A. (2019). Acta Cryst. E75, 237–241. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Çelikesir, S. T., Akkurt, M., Shikhaliyev, N. Q., Suleymanova, G. T., Babayeva, G. V., Gurbanova, N. V., Mammadova, G. Z. & Bhattarai, A. (2020). Acta Cryst. E76, 1173–1178. CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Nilwanna, B., Kobkeatthawin, T., Jansrisewangwong, P. & Fun, H.-K. (2012). Acta Cryst. E68, o1644–o1645. CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Ruanwas, P., Boonnak, N., Chidan Kumar, C. S. & Fun, H.-K. (2014). Acta Cryst. E70, o188–o189. CSD CrossRef IUCr Journals Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fun, H.-K., Chantrapromma, S., Nilwanna, B. & Kobkeatthawin, T. (2012). Acta Cryst. E68, o2144–o2145. CSD CrossRef CAS IUCr Journals Google Scholar
Fun, H.-K., Chantrapromma, S., Nilwanna, B., Kobkeatthawin, T. & Boonnak, N. (2013). Acta Cryst. E69, o1203–o1204. CSD CrossRef CAS IUCr Journals Google Scholar
Fun, H.-K., Nilwanna, B., Jansrisewangwong, P., Kobkeatthawin, T. & Chantrapromma, S. (2011). Acta Cryst. E67, o3202–o3203. Web of Science CSD 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., 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
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
Mahmoudi, G., Seth, S. K., Bauzá, A., Zubkov, F. I., Gurbanov, A. V., White, J., Stilinović, V., Doert, T. & Frontera, A. (2018). CrystEngComm, 20, 2812–2821. Web of Science CSD CrossRef CAS Google Scholar
Mahmudov, K. T., Gurbanov, A. V., Guseinov, F. I. & Guedes da Silva, M. F. C. (2019). Coord. Chem. Rev. 387, 32–46. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Maharramov, A. M., Kurbanova, M. M., Gurbanov, A. V. & Pombeiro, A. J. L. (2014). Coord. Chem. Rev. 265, 1–37. Web of Science CrossRef CAS Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef 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
Nilwanna, B., Chantrapromma, S., Jansrisewangwong, P. & Fun, H.-K. (2011). Acta Cryst. E67, o3084–o3085. Web of Science CSD CrossRef IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals 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. Q., Çelikesir, S. T., Akkurt, M., Bagirova, K. N., Suleymanova, G. T. & Toze, F. A. A. (2019). Acta Cryst. E75, 465–469. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef 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

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