Crystal structure and Hirshfeld surface analysis of (E)-4-({2,2-di­chloro-1-[4-(di­methyl­amino)­phen­yl]ethenyl}diazen­yl)benzo­nitrile

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

doi:10.1107/S2056989021009154

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 77| Part 10| October 2021| Pages 994-998

https://doi.org/10.1107/S2056989021009154

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Crystal structure and Hirshfeld surface analysis of (E)-4-({2,2-dichloro-1-[4-(dimethylamino)phenyl]ethenyl}diazenyl)benzonitrile

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

^aOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan, ^bDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Turkey, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, 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 23 August 2021; accepted 3 September 2021; online 7 September 2021)

In the title compound, C₁₇H₁₄Cl₂N₄, the dihedral angle between the aromatic rings is 50.09 (9)°. The central –N=N– unit shows an E configuration. In the crystal, C—H⋯N interactions, C—Cl⋯π and π–π stacking interactions [centroid-to-centroid distance = 3.7719 (14) Å] link the molecules, forming molecular layers approximately parallel to the (002) plane. Additional weak van der Waals interactions between the layers consolidate the three-dimensional packing. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (33.6%), N⋯H/ H⋯N (17.2%), Cl⋯H/H⋯Cl (14.1%) and C⋯H/H⋯C (14.1%) contacts.

Keywords: crystal structure; C—H⋯N interactions; C—Cl⋯π interactions; π–π stacking interactions; Hirshfeld surface analysis.

CCDC reference: 2107472

1. Chemical context

Azo dyes find numerous applications in a diversity of areas, including in molecular recognition, optical data storage, non-linear optics and as molecular switches, antimicrobial agents, colour-changing materials, liquid crystals, dye-sensitized solar cells, mainly because of the ability for cis-to-trans isomerization and the chromophoric properties of the –N=N– synthon (Maharramov et al., 2018 ; Viswanathan et al., 2019 ). Not only isomerization, but azo-hydrazone tautomerisim is also an important phenomenon in the coordination chemistry of azo dyes (Mahmoudi et al., 2018a ,b ). Modification of azo dyes with functional groups leads to multifunctional ligands, of which the corresponding metal complexes are effective catalysts in oxidation and in C—C coupling reactions (Ma et al., 2020 , 2021 ; Mahmudov et al., 2013 ; Mizar et al., 2012 ). Moreover, the functional properties of azo dyes are dependent on non-covalent bond-donor or -acceptor site(s) attached to the –N=N– synthon (Gurbanov et al., 2020a ,b ; Kopylovich et al., 2011 ; Mahmudov et al., 2020 ; Shixaliyev et al., 2014 ). Thus, we have introduced halogen-bond-donor centres to the –N=N– moiety, leading to a new azo dye, (E)-4-({2,2-dichloro-1-[4-(dimethylamino)phenyl]ethenyl}diazenyl)benzonitrile, which provides multiple intermolecular non-covalent interactions.

2. Structural commentary

The aromatic rings C3–C8 and C11–C16 of the title compound (Fig. 1) form a dihedral angle of 50.09 (9)°. In the dimethylamino group, the sum of bond angles about N3 is 357.02° and the nitrogen atom has a flattened trigonal–pyramidal conformation. The atoms of the dimethylamino group and those of its attached benzene ring (C3–C8) are nearly coplanar, with maximum deviations of −0.058 (2), 0.179 (2), and 0.087 (2) Å for N3, C9 and C10, respectively. The title molecule adopts an E configuration with respect to the N1=N2 bond. The N1/N2/C1–C3/Cl1/Cl2 unit is approximately planar with a maximum deviation of 0.102 (2) Å, and makes dihedral angles of 55.44 (9) and 5.36 (9)°, respectively, with the C3–C8 and C11–C16 benzene rings.

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, molecules are linked by C—H⋯N interactions (Table 1), C—H⋯π [Cl2⋯Cg2ⁱⁱ = 3.3910 (12) Å, C2⋯Cg2ⁱⁱ = 3.858 (2) Å, C2—Cl2⋯Cg2ⁱⁱ = 92.07 (7)°; symmetry code: (ii) x, 1 + y, z; where Cg2 is the centroid of the C11–C16 benzene ring] and π–π stacking interactions [Cg2⋯Cg1ⁱⁱⁱ = 3.7719 (14) Å, slippage = 1.741 Å; Cg1⋯Cg2^iv = 3.7719 (14) Å, slippage = 1.336 Å; symmetry codes: (iii) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iv) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; where Cg1 and Cg2 are the centroids of the C3—C8 and C11–C16 benzene rings, respectively], forming molecular layers approximately parallel to the (002) plane with the molecules having a bellows-like shape when viewed along the a axis (Figs. 2 and 3). Weak van der Waals interactions between these layers increase the stability of the crystal structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯N4ⁱ	0.95	2.48	3.428 (3)	175
Symmetry code: (i) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A general view of the C—H⋯N contacts, C—Cl⋯π interactions and π–π stacking interactions in the crystal packing of the title compound [symmetry codes: (a) −1 + x, y, z; (b) −1 + x, 1 + y, z; (c) x, 1 + y, z; (d) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (e) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (f) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (g) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z].

Figure 3
The crystal packing of the title compound, viewed along the a axis, showing the C—Cl⋯π interactions and π–π stacking interactions as dashed lines.

To visualize the intermolecular interactions in the title molecule, CrystalExplorer17 (Turner et al., 2017 ) was used to compute Hirshfeld surfaces (McKinnon et al., 2007 ) and their corresponding two-dimensional fingerprint plots (Spackman & McKinnon, 2002 ). The Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) is shown in Fig. 4. The positive electrostatic potential (blue region) over the surface indicates hydrogen-bond donors, whereas the hydrogen-bond acceptors are represented by a negative electrostatic potential (red region). In the Hirshfeld surface mapped over d_norm (Fig. 5), the bright-red spots near atoms H7, H13, N4 and Cl1 indicate the short C—H⋯N and C—H⋯Cl contacts (Table 2). Other contacts are equal to or longer than the sum of van der Waals radii. The most important interaction is H⋯H, contributing 33.6% to the overall crystal packing, which is reflected in Fig. 6b as widely scattered points of high density due to the large hydrogen content of the molecule, with the tip at d_e = d_i = 1.15 Å. The reciprocal N⋯H/H⋯N interactions appear as two symmetrical broad wings with d_e + d_i = 2.3 Å and contribute 17.2% to the Hirshfeld surface (Fig. 6c). The reciprocal Cl⋯H/H⋯Cl interactions (14.1% contribution) are present as two symmetrical broad wings with d_e + d_i = 2.7 (Fig. 6d). The pair of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts (Fig. 6e; 14.1% contribution) have the tips at d_e + d_i = 2.8 Å. The smaller percentage contributions to the Hirshfeld surface from the various other interatomic contact are comparatively listed in Table 3.

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

Contact	Distance	Symmetry operation
Cl1⋯H4	2.86	x, 1 + y, z
Cl2⋯Cl1	3.60	2 − x, 3 − y, 1 − z
H9C⋯C7	2.95	1 − x, 2 − y, 1 − z
Cl2⋯H10B	3.01	1 + x, y, z
C2⋯C2	3.47	2 − x, 2 − y, 1 − z
N4⋯H13	2.48	$[{5\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
N4⋯H7	2.70	$[{3\over 2}]$ − x, − $[{3\over 2}]$ + y, $[{1\over 2}]$ − z

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

Contact	Percentage contribution
H⋯H	33.6
N⋯H/H⋯N	17.2
Cl⋯H/H⋯Cl	14.1
C⋯H/H⋯C	14.1
C⋯C	6.7
Cl⋯C/C⋯Cl	6.3
Cl⋯Cl	3.5
Cl⋯N/N⋯Cl	2.5
N⋯C/C⋯N	1.9
N⋯N	0.1

Figure 4
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. Hydrogen-bond donors and acceptors are shown as blue and red regions, respectively, around the atoms, corresponding to positive and negative potentials.

Figure 5
Hirshfeld surface mapped over d_norm highlighting the regions of C—H⋯Cl and C—H⋯N intermolecular contacts.

Figure 6
(a) The full two-dimensional fingerprint plot for the title compound and those delineated into (b) H⋯H (33.6%), (c) N⋯H/H⋯N (17.2%), (d) Cl⋯H/H⋯Cl (14.1%) and (e) C⋯H/H⋯C (14.1%) contacts.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, update November 2018; Groom et al., 2016 ) for structures having an (E)-1-(2,2-dichloro-1-phenylethenyl)-2-phenyldiazene unit gave 25 hits. Six compounds closely resemble the title compound, viz. 4-{2,2-dichloro-1-[(E)-2-(4-methylphenyl)diazen-1-yl]ethenyl}-N,N-dimethylaniline [(I); Özkaraca et al., 2020 ], 4-{2,2-dichloro-1-[(E)-(4-fluorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline [(II); Özkaraca et al., 2020], 1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-fluorophenyl)ethenyl]diazene [(III); Shikhaliyev et al., 2019 ], 1-(4-bromophenyl)-2-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene [(IV); Akkurt et al., 2019 ], 1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene [(V); Akkurt et al., 2019] and 1-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]-2-(4-fluorophenyl)diazene [(VI); Atioğlu et al., 2019 ].

In the crystal of (I), molecules are linked by pairs of C—Cl⋯π interactions, forming inversion dimers. A short intermolecular Cl⋯Cl contact [3.2555 (9) Å] links the dimers, forming a ribbon along the c-axis direction. The crystal structure of (II) is stabilized by C—Cl⋯π and van der Waals interactions. In (III), molecules are stacked in columns along the a axis via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further stabilized by short Cl⋯Cl contacts. In the crystals of (IV) and (V), molecules are linked through weak X⋯Cl contacts [X = Br for (IV) and Cl for (V)] and C—H⋯Cl and C—Cl⋯π interactions into sheets parallel to the ab plane. In (VI), molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing is further stabilized by C—Cl⋯π, C—F⋯π and N—O⋯π interactions.

5. Synthesis and crystallization

The title compound was synthesized according to a reported method (Shikhaliyev et al., 2018 , 2019 ). A 20 mL screw-neck vial was charged with DMSO (10 mL), (Z)-4-{2-[4-(dimethylamino)benzylidene]hydrazinyl}benzonitrile (264 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 ∼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) and brine (30 mL), dried over anhydrous Na₂SO₄ and concentrated using a vacuum rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3/1–1/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Colourless solid (69%); m.p. 395 K. Analysis calculated for C₁₇H₁₄Cl₂N₄: C 59.15, H 4.09, N 16.23%; found: C 59.05, H 4.02, N 16.19%. ¹H NMR (300 MHz, CDCl₃) δ 3.04 (6H, NMe₂), 6.75–7.89 (8H, Ar). ¹³C NMR (75 MHz, CDCl₃) δ 162.08, 154.31, 152.59, 146.76, 135.98, 132.50, 131.25, 128.75, 120.90, 117.76, 115.52 and 38.42. ESI–MS: m/z: 346.18 [M + H]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The C-bound H atoms were positioned geometrically and treated as riding atoms, C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C) for aromatic H atoms and C—H = 0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₇H₁₄Cl₂N₄
M_r	345.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.396 (3), 6.5280 (7), 20.758 (3)
β (°)	104.39 (2)
V (Å³)	1627.1 (5)
Z	4
Radiation type	Synchrotron, λ = 0.79475 Å
μ (mm⁻¹)	0.54
Crystal size (mm)	0.10 × 0.08 × 0.05

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.939, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	21540, 3712, 2913
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.06
No. of reflections	3712
No. of parameters	211
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36
Computer programs: Marccd(Doyle, 2011 ), iMosflm (Battye et al., 2011 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2107472

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021009154/vm2253sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021009154/vm2253Isup2.hkl

checkCIF report

Computing details top

Data collection: Marccd(Doyle, 2011); cell refinement: iMosflm (Battye et al., 2011); data reduction: iMosflm (Battye et al., 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

(E)-4-({2,2-Dichloro-1-[4-(dimethylamino)phenyl]ethenyl}diazenyl)benzonitrile top

Crystal data top

C₁₇H₁₄Cl₂N₄	F(000) = 712
M_r = 345.22	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.79475 Å
a = 12.396 (3) Å	Cell parameters from 600 reflections
b = 6.5280 (7) Å	θ = 2.0–28.0°
c = 20.758 (3) Å	µ = 0.54 mm⁻¹
β = 104.39 (2)°	T = 100 K
V = 1627.1 (5) Å³	Prism, colourless
Z = 4	0.10 × 0.08 × 0.05 mm

Data collection top

Rayonix SX165 CCD diffractometer	2913 reflections with I > 2σ(I)
/f scan	R_int = 0.066
Absorption correction: multi-scan (SCALA; Evans, 2006)	θ_max = 31.0°, θ_min = 2.0°
T_min = 0.939, T_max = 0.966	h = −16→16
21540 measured reflections	k = −8→8
3712 independent reflections	l = −25→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0535P)² + 0.5596P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3712 reflections	Δρ_max = 0.34 e Å⁻³
211 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.0082 (8)

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	0.88106 (4)	1.32286 (7)	0.48668 (2)	0.03392 (14)
Cl2	1.05932 (4)	1.18867 (7)	0.43125 (2)	0.03201 (14)
N1	0.91524 (13)	0.8624 (3)	0.37007 (8)	0.0292 (3)
N2	0.85729 (13)	0.7167 (3)	0.33932 (8)	0.0300 (3)
N3	0.40040 (13)	0.8913 (3)	0.40216 (9)	0.0380 (4)
N4	1.13398 (14)	−0.0162 (3)	0.21331 (9)	0.0398 (4)
C1	0.85825 (15)	0.9987 (3)	0.40327 (9)	0.0284 (4)
C2	0.92392 (15)	1.1508 (3)	0.43572 (9)	0.0295 (4)
C3	0.73981 (15)	0.9728 (3)	0.40425 (9)	0.0291 (4)
C4	0.70143 (15)	0.7904 (3)	0.42580 (9)	0.0310 (4)
H4	0.7525	0.6816	0.4404	0.037*
C5	0.59082 (16)	0.7638 (3)	0.42649 (10)	0.0330 (4)
H5	0.5678	0.6384	0.4421	0.040*
C6	0.51174 (15)	0.9206 (3)	0.40439 (9)	0.0310 (4)
C7	0.55024 (15)	1.1054 (3)	0.38262 (9)	0.0312 (4)
H7	0.4994	1.2145	0.3678	0.037*
C8	0.66197 (15)	1.1295 (3)	0.38267 (9)	0.0294 (4)
H8	0.6859	1.2551	0.3677	0.035*
C9	0.36642 (18)	0.7158 (4)	0.43561 (12)	0.0434 (5)
H9A	0.3835	0.5892	0.4148	0.065*
H9B	0.2862	0.7231	0.4319	0.065*
H9C	0.4067	0.7169	0.4826	0.065*
C10	0.32281 (16)	1.0620 (4)	0.38642 (11)	0.0410 (5)
H10A	0.3390	1.1609	0.4231	0.061*
H10B	0.2465	1.0113	0.3800	0.061*
H10C	0.3307	1.1290	0.3456	0.061*
C11	0.92081 (15)	0.5780 (3)	0.30993 (9)	0.0291 (4)
C12	1.03445 (15)	0.6030 (3)	0.31285 (9)	0.0315 (4)
H12	1.0731	0.7214	0.3330	0.038*
C13	1.08971 (15)	0.4540 (3)	0.28610 (9)	0.0318 (4)
H13	1.1666	0.4692	0.2878	0.038*
C14	1.03148 (15)	0.2803 (3)	0.25645 (9)	0.0297 (4)
C15	0.91773 (15)	0.2583 (3)	0.25146 (9)	0.0308 (4)
H15	0.8784	0.1423	0.2299	0.037*
C16	0.86290 (15)	0.4084 (3)	0.27846 (9)	0.0308 (4)
H16	0.7855	0.3952	0.2754	0.037*
C17	1.08914 (15)	0.1179 (3)	0.23155 (10)	0.0329 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0306 (2)	0.0350 (3)	0.0359 (3)	0.00155 (18)	0.00763 (19)	−0.00490 (19)
Cl2	0.0255 (2)	0.0375 (3)	0.0326 (2)	−0.00150 (18)	0.00657 (17)	0.00029 (19)
N1	0.0276 (7)	0.0326 (9)	0.0261 (8)	0.0018 (6)	0.0045 (6)	0.0004 (6)
N2	0.0254 (7)	0.0358 (9)	0.0275 (8)	0.0029 (6)	0.0043 (6)	−0.0011 (7)
N3	0.0275 (8)	0.0428 (10)	0.0457 (10)	0.0004 (7)	0.0126 (7)	0.0039 (8)
N4	0.0316 (8)	0.0444 (11)	0.0441 (10)	0.0004 (8)	0.0109 (7)	−0.0063 (8)
C1	0.0270 (9)	0.0323 (10)	0.0254 (9)	0.0026 (7)	0.0055 (7)	0.0026 (7)
C2	0.0257 (9)	0.0348 (10)	0.0272 (9)	0.0036 (7)	0.0052 (7)	0.0033 (7)
C3	0.0271 (9)	0.0333 (10)	0.0261 (9)	0.0017 (7)	0.0051 (7)	−0.0007 (7)
C4	0.0284 (9)	0.0334 (11)	0.0300 (9)	0.0034 (7)	0.0049 (7)	0.0010 (8)
C5	0.0313 (9)	0.0375 (11)	0.0304 (10)	−0.0013 (8)	0.0081 (8)	0.0007 (8)
C6	0.0258 (9)	0.0384 (11)	0.0289 (9)	−0.0008 (8)	0.0071 (7)	−0.0017 (8)
C7	0.0276 (9)	0.0352 (10)	0.0301 (9)	0.0048 (8)	0.0062 (7)	−0.0010 (8)
C8	0.0269 (9)	0.0326 (10)	0.0277 (9)	0.0013 (7)	0.0053 (7)	0.0000 (8)
C9	0.0360 (11)	0.0539 (14)	0.0430 (12)	−0.0065 (10)	0.0153 (9)	0.0035 (10)
C10	0.0251 (9)	0.0503 (13)	0.0475 (12)	0.0022 (9)	0.0089 (8)	−0.0047 (10)
C11	0.0258 (9)	0.0345 (11)	0.0264 (9)	0.0030 (7)	0.0052 (7)	0.0024 (8)
C12	0.0266 (9)	0.0347 (10)	0.0326 (10)	−0.0018 (8)	0.0064 (7)	0.0001 (8)
C13	0.0255 (9)	0.0388 (11)	0.0317 (10)	−0.0001 (8)	0.0085 (7)	0.0016 (8)
C14	0.0271 (9)	0.0364 (11)	0.0258 (9)	0.0020 (7)	0.0069 (7)	0.0010 (8)
C15	0.0274 (9)	0.0355 (10)	0.0287 (9)	−0.0008 (8)	0.0057 (7)	0.0000 (8)
C16	0.0231 (8)	0.0403 (11)	0.0283 (9)	−0.0002 (8)	0.0052 (7)	−0.0014 (8)
C17	0.0267 (9)	0.0405 (11)	0.0311 (9)	−0.0009 (8)	0.0064 (7)	−0.0002 (9)

Geometric parameters (Å, º) top

Cl1—C2	1.715 (2)	C7—H7	0.9500
Cl2—C2	1.7217 (19)	C8—H8	0.9500
N1—N2	1.265 (2)	C9—H9A	0.9800
N1—C1	1.417 (2)	C9—H9B	0.9800
N2—C11	1.432 (2)	C9—H9C	0.9800
N3—C6	1.383 (2)	C10—H10A	0.9800
N3—C10	1.456 (3)	C10—H10B	0.9800
N3—C9	1.455 (3)	C10—H10C	0.9800
N4—C17	1.150 (3)	C11—C16	1.391 (3)
C1—C2	1.353 (3)	C11—C12	1.404 (2)
C1—C3	1.483 (2)	C12—C13	1.383 (3)
C3—C4	1.396 (3)	C12—H12	0.9500
C3—C8	1.401 (3)	C13—C14	1.402 (3)
C4—C5	1.386 (3)	C13—H13	0.9500
C4—H4	0.9500	C14—C15	1.395 (3)
C5—C6	1.412 (3)	C14—C17	1.444 (3)
C5—H5	0.9500	C15—C16	1.388 (3)
C6—C7	1.412 (3)	C15—H15	0.9500
C7—C8	1.394 (3)	C16—H16	0.9500

N2—N1—C1	115.36 (15)	N3—C9—H9B	109.5
N1—N2—C11	112.77 (15)	H9A—C9—H9B	109.5
C6—N3—C10	120.00 (18)	N3—C9—H9C	109.5
C6—N3—C9	119.85 (18)	H9A—C9—H9C	109.5
C10—N3—C9	117.17 (17)	H9B—C9—H9C	109.5
C2—C1—N1	113.08 (16)	N3—C10—H10A	109.5
C2—C1—C3	123.52 (17)	N3—C10—H10B	109.5
N1—C1—C3	123.36 (17)	H10A—C10—H10B	109.5
C1—C2—Cl1	123.19 (15)	N3—C10—H10C	109.5
C1—C2—Cl2	123.55 (15)	H10A—C10—H10C	109.5
Cl1—C2—Cl2	113.26 (11)	H10B—C10—H10C	109.5
C4—C3—C8	117.53 (17)	C16—C11—C12	120.54 (17)
C4—C3—C1	121.25 (17)	C16—C11—N2	115.41 (16)
C8—C3—C1	121.21 (18)	C12—C11—N2	124.03 (17)
C5—C4—C3	121.80 (18)	C13—C12—C11	119.48 (18)
C5—C4—H4	119.1	C13—C12—H12	120.3
C3—C4—H4	119.1	C11—C12—H12	120.3
C4—C5—C6	120.97 (19)	C12—C13—C14	119.54 (17)
C4—C5—H5	119.5	C12—C13—H13	120.2
C6—C5—H5	119.5	C14—C13—H13	120.2
N3—C6—C5	121.14 (18)	C15—C14—C13	121.10 (18)
N3—C6—C7	121.41 (18)	C15—C14—C17	118.60 (18)
C5—C6—C7	117.41 (17)	C13—C14—C17	120.29 (17)
C8—C7—C6	120.71 (18)	C16—C15—C14	118.99 (18)
C8—C7—H7	119.6	C16—C15—H15	120.5
C6—C7—H7	119.6	C14—C15—H15	120.5
C7—C8—C3	121.57 (19)	C15—C16—C11	120.29 (17)
C7—C8—H8	119.2	C15—C16—H16	119.9
C3—C8—H8	119.2	C11—C16—H16	119.9
N3—C9—H9A	109.5	N4—C17—C14	177.5 (2)

C1—N1—N2—C11	−176.74 (15)	C4—C5—C6—C7	−0.9 (3)
N2—N1—C1—C2	179.58 (16)	N3—C6—C7—C8	−177.38 (18)
N2—N1—C1—C3	1.6 (3)	C5—C6—C7—C8	0.5 (3)
N1—C1—C2—Cl1	−173.44 (13)	C6—C7—C8—C3	−0.1 (3)
C3—C1—C2—Cl1	4.5 (3)	C4—C3—C8—C7	0.1 (3)
N1—C1—C2—Cl2	5.4 (2)	C1—C3—C8—C7	179.17 (17)
C3—C1—C2—Cl2	−176.62 (14)	N1—N2—C11—C16	176.66 (16)
C2—C1—C3—C4	−123.2 (2)	N1—N2—C11—C12	−1.9 (3)
N1—C1—C3—C4	54.5 (3)	C16—C11—C12—C13	−2.2 (3)
C2—C1—C3—C8	57.7 (3)	N2—C11—C12—C13	176.31 (17)
N1—C1—C3—C8	−124.5 (2)	C11—C12—C13—C14	0.0 (3)
C8—C3—C4—C5	−0.4 (3)	C12—C13—C14—C15	2.2 (3)
C1—C3—C4—C5	−179.54 (18)	C12—C13—C14—C17	−176.58 (18)
C3—C4—C5—C6	0.9 (3)	C13—C14—C15—C16	−2.2 (3)
C10—N3—C6—C5	173.06 (19)	C17—C14—C15—C16	176.56 (18)
C9—N3—C6—C5	13.1 (3)	C14—C15—C16—C11	0.0 (3)
C10—N3—C6—C7	−9.1 (3)	C12—C11—C16—C15	2.1 (3)
C9—N3—C6—C7	−169.03 (19)	N2—C11—C16—C15	−176.47 (17)
C4—C5—C6—N3	177.02 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N4ⁱ	0.95	2.48	3.428 (3)	175

Symmetry code: (i) −x+5/2, y+1/2, −z+1/2.

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

Contact	Distance	Symmetry operation
Cl1···H4	2.86	x, 1 + y, z
Cl2···Cl1	3.60	2 - x, 3 - y, 1 - z
H9C···C7	2.95	1 - x, 2 - y, 1 - z
Cl2···H10B	3.01	1 + x, y, z
C2···C2	3.47	2 - x, 2 - y, 1 - z
N4···H13	2.48	5/2 - x, -1/2 + y, 1/2 - z
N4···H7	2.70	3/2 - x, -3/2 + y, 1/2 - z

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

Contact	Percentage contribution
H···H	33.6
N···H/H···N	17.2
Cl···H/H···Cl	14.1
C···H/H···C	14.1
C···C	6.7
Cl···C/C···Cl	6.3
Cl···Cl	3.5
Cl···N/N···Cl	2.5
N···C/C···N	1.9
N···N	0.1

Acknowledgements

The authors' contributions are as follows. Conceptualization, NQS, MA and SM; synthesis, GTS and GVB; X-ray analysis, ZA and MA; writing (review and editing of the manuscript), funding acquisition, NQS, GTS and GVB; supervision, NQS, 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).

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