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

Akkurt, M.; Shikhaliyev, N.Q.; Askerova, U.F.; Mukhtarova, S.H.; Mammadova, G.Z.; Toze, F.A.A.

doi:10.1107/S2056989019009642

research communications

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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1190-1194

https://doi.org/10.1107/S2056989019009642

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

Mehmet Akkurt,^a Namiq Q. Shikhaliyev,^b Ulviyya F. Askerova,^b Sevinc H. Mukhtarova,^b Gunay Z. Mammadova ^b and Flavien A. A. Toze ^c ^*

^aDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^bOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az, 1148 Baku, Azerbaijan, and ^cDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of Cameroon
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by A. J. Lough, University of Toronto, Canada (Received 27 May 2019; accepted 5 July 2019; online 16 July 2019)

In the title compound, C₁₆H₁₁Cl₂N₃O, the 4-methoxy-substituted benzene ring makes a dihedral angle of 41.86 (9)° with the benzene ring of the benzonitrile group. In the crystal, molecules are linked into layers parallel to (020) by C—H⋯O contacts and face-to-face π–π stacking interactions [centroid–centroid distances = 3.9116 (14) and 3.9118 (14) Å] between symmetry-related aromatic rings along the a-axis direction. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from Cl⋯H/H⋯Cl (22.8%), H⋯H (21.4%), N⋯H/H⋯N (16.1%), C⋯H/H⋯C (14.7%) and C⋯C (9.1%) interactions.

Keywords: crystal structure; 4-methoxyphenyl ring; benzonitrile; face-to-face π–π stacking interactions; Hirshfeld surface analysis.

CCDC reference: 1938782

1. Chemical context

Weak interactions, such as hydrogen, aerogen, halogen, chalcogen, pnicogen, tetrel and icosagen bonds, as well as n–π*, π–π stacking, π–cation, π–anion and hydrophobic interactions, can control or organize the conformation, aggregation, tertiary and quaternary structure of the molecule, its reactivity, stabilization and other properties (Asadov et al., 2016 ; Maharramov et al., 2010 ; Mahmudov et al., 2013 , 2014a ,b , 2015 , 2017a ,b , 2019 ; Shixaliyev et al., 2013 , 2014 ). The functionalization of azo/hydrazone ligands with non-covalent bond-donor or acceptor sites greatly affects their coordination ability and the catalytic activity of the corresponding coordination compounds (Akbari et al., 2017 ; Gurbanov et al., 2018 ; Karmakar et al., 2016 ; Kopylovich et al., 2011a ,b ; Ma et al., 2017a ,b ; Mahmoudi et al., 2016 , 2017a ,b ,c , 2018a ,b ,c ). In our previous work, we have attached chloro atoms to dye molecules, which lead to halogen bonding (Atioğlu et al., 2019 ; Maharramov et al., 2018 ; Shixaliyev et al., 2018 , 2019 ). In a continuation of this work, we have functionalized a new azo dye, (E)-4-{[2,2-dichloro-1-(4-methoxyphenyl)ethenyl]diazenyl}benzonitrile, which provides weak C—H⋯O intermolecular hydrogen bonds.

2. Structural commentary

In the title compound, (Fig. 1), the dihedral angle between the 4-methoxy-substituted benzene ring and the benzene ring of the benzonitrile moiety is 41.86 (9)°. The C1—C6—N1—N2, C6—N1—N2—C7, N1—N2—C7—C8, N2—C7—C8—Cl1, N2—C7—C8—Cl2, Cl1—C8—C7—C9 and C8—C7—C9—C14 torsion angles of 24.8 (2), −178.37 (15), −176.77 (17), −2.2 (2), 178.27 (14), −176.26 (14) and −52.1 (3)°, respectively, describe the essentially planar conformation of the dichloro-vinyldiazenyl moiety. Bond lengths and angles are within normal ranges and are comparable to those observed in related structures such as (E)-1-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]-2-(4-fluorophenyl)diazene (Atioğlu et al., 2019), (2E)-1-(2-hydroxy-5-methylphenyl)-3-(4-methoxyphenyl)prop-2-en-1-one (Fun et al., 2011a ), (2E)-3-(3-benzyloxyphenyl)-1-(2-hydroxy-5-methylphenyl)prop-2-en-1-one (Fun et al., 2011b ), (2E)-3-[3-(benzyloxy)phenyl]-1-(2-hydroxyphenyl)prop-2-en-1-one (Fun et al., 2011c ), (2E)-1-(2,5-dimethoxyphenyl)-3-(3-nitrophenyl)prop-2-en-1-one (Fun et al., 2011d ) and (2E)-3-(3-nitrophenyl)-1-[4-(piperidin-1-yl)phenyl]prop-2-en-1-one (Fun et al., 2012 ).

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, the molecules are linked into layers parallel to the (020) plane by C—H⋯O contacts and face-to-face π–π stacking interactions [centroid-centroid distances = 3.9116 (14) and 3.9118 (14) Å] along the a-axis between the same aromatic rings (Table 1; Figs. 2 and 3). These molecular layers are held together by weak van der Waals forces.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.47	3.391 (2)	165
C16—H16C⋯O1ⁱⁱ	0.98	2.59	3.516 (3)	158
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Figure 2
A view of the crystal packing of the title compound. The weak C—H⋯O interactions are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
A packing diagram of the title compound, viewed along the a axis. The C—H⋯O interactions are shown as dashed lines.

Hirshfeld surfaces and fingerprint plots were generated for the title compound using CrystalExplorer (McKinnon et al., 2007 ) to quantify and visualize the intermolecular interactions and to explain the observed crystal packing. The Hirshfeld surface mapped over d_norm using a standard surface resolution with a fixed colour scale of −0.1603 (red) to 1.2420 (blue) a.u. is shown in Fig. 4. 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 interactions. The Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) is shown in Fig. 5. The red regions indicate atoms with the potential to be hydrogen-bond acceptors (negative electrostatic potential), while blue regions indicate atoms with positive electrostatic potential, i.e. hydrogen-bond donors. The shape-index of the Hirshfeld surface is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 6 clearly suggest that there are π–π interactions in the title compound.

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

Contact	Distance	Symmetry operation
Cl1⋯H5	3.05	1 + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
Cl1⋯H10	2.98	x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
O1⋯H16C	2.59	1 + x, y, z
Cl2⋯N3	3.462	1 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H16B⋯C13	2.90	2 − x, 2 − y, 1 − z
O1⋯H2	2.47	1 + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z
H4⋯N3	2.78	−x, 1 − y, 1 − z
H4⋯N3	2.82	1 − x, 1 − y, 1 − z
H13⋯H13	2.52	1 − x, 2 − y, 1 − z

Figure 4
A view of the three-dimensional Hirshfeld surface of the title compound mapped over d_norm showing the C—H⋯O interactions (dashed lines).

Figure 5
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 around the atoms, corresponding to positive and negative potentials, respectively.

Figure 6
Hirshfeld surface of the title compound plotted over shape-index.

The percentage contributions of the various contacts to the total Hirshfeld surface are shown in the two dimensional fingerprint plots in Table 3. The reciprocal Cl⋯H/H⋯Cl interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.8 Å and contribute 22.8% to the Hirshfeld surface (Fig. 7b). The H⋯H interactions appear in the middle of the scattered points in the two dimensional fingerprint plots, with an overall contribution to the Hirshfeld surface of 21.4% (Fig. 7c). The N⋯H/H⋯N and C⋯H/H⋯C interactions also appear as two symmetrical broad wings with d_e + d_i ≃ 2.6 and 2.8 Å, respectively, and contribute 16.1 and 14.7%, respectively, to the Hirshfeld surface (Fig. 7d,e). The C⋯C interactions appear in the middle of the scattered points in the two-dimensional fingerprint plots with an overall contribution to the Hirshfeld surface of 9.1% (Fig. 7f). The small percentage contributions from the other different interatomic contacts to the Hirshfeld surfaces are listed in Table 3. The large number of Cl⋯H/H⋯Cl, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C and C⋯C interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface

Contact	Percentage contribution
Cl⋯H/H⋯Cl	22.8
H⋯H	21.4
N⋯H/H⋯N	16.1
C⋯H/H⋯C	14.7
C⋯C	9.1
O⋯H/H⋯O	5.3
N⋯C/C⋯N	4.2
Cl⋯N/N⋯Cl	2.6
Cl⋯C/C⋯Cl	1.7
Cl⋯Cl	1.6
C⋯O/O⋯C	0.4
N⋯N	0.2

Figure 7
The Hirshfeld surface representations and two-dimensional fingerprint plots of the title compound showing all interactions, and the most significant individual types of interactions.

4. Synthesis and crystallization

The title compound was synthesized according to the reported method (Atioğlu et al., 2019; Maharramov et al., 2018; Shikhaliyev et al., 2018, 2019). A 20 mL screw-neck vial was charged with DMSO (10 mL), (E)-4-[2-(4-methoxybenzylidene)hydrazineyl]benzonitrile (251 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 (after TLC analysis showed complete consumption of the corresponding Schiff base), the reaction mixture was poured into an 0.01 M solution of HCl (100 mL, pH = 2–3) and extracted with dichloromethane (3x20 mL). The combined organic phase was washed with water (3x50 mL), brine (30 mL), dried over anhydrous Na₂SO₄ and concentrated in vacuo of the rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3/1–1/1), giving an orange solid (63%); m.p. 471 K. Analysis calculated for C₁₆H₁₁Cl₂N₃O (M = 332.18): C 57.85, H 3.34, N 12.65; found: C 57.78, H 3.29, N 12.58%. ¹H NMR (300 MHz, CDCl₃) δ 3.83–3.93 (3H, OCH₃), 6.89–7.70 (8H, Ar). ¹³C NMR (75 MHz, CDCl₃) δ 153.89, 133.85, 133.14, 130.54, 130.37, 130.34, 115.49, 115.00, 113.80, 55.51, 29.72, 14.15. ESI–MS: m/z: 333.17 [M + H]⁺.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The H atoms of aromatic and methyl groups were placed in calculated positions (C—H = 0.95 and 0.98 Å, respectively) and refined using a riding model with U_iso= 1.2U_eq(C-aromatic) and 1.5U_eq(C-methyl).

Table 4
Experimental details

Crystal data
Chemical formula	C₁₆H₁₁Cl₂N₃O
M_r	332.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.9117 (8), 25.109 (5), 14.968 (3)
β (°)	97.07 (3)
V (Å³)	1459.0 (5)
Z	4
Radiation type	Synchrotron, λ = 0.80246 Å
μ (mm⁻¹)	0.63
Crystal size (mm)	0.25 × 0.05 × 0.03

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.850, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	22750, 3144, 2978
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.07
No. of reflections	3144
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.46
Computer programs: Marccd (Doyle, 2011 ), iMosflm (Battye et al., 2011 ), SHELXLS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1938782

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009642/lh5909sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009642/lh5909Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009642/lh5909Isup3.cml

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: SHELXLS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

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

Crystal data top

C₁₆H₁₁Cl₂N₃O	F(000) = 680
M_r = 332.18	D_x = 1.512 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.80246 Å
a = 3.9117 (8) Å	Cell parameters from 600 reflections
b = 25.109 (5) Å	θ = 1.8–30.0°
c = 14.968 (3) Å	µ = 0.63 mm⁻¹
β = 97.07 (3)°	T = 100 K
V = 1459.0 (5) Å³	Needle, orange
Z = 4	0.25 × 0.05 × 0.03 mm

Data collection top

Rayonix SX165 CCD diffractometer	2978 reflections with I > 2σ(I)
/f scan	R_int = 0.068
Absorption correction: multi-scan (Scala; Evans, 2006)	θ_max = 30.9°, θ_min = 1.8°
T_min = 0.850, T_max = 0.975	h = −4→4
22750 measured reflections	k = −32→32
3144 independent reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.066P)² + 0.9448P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.30 e Å⁻³
3144 reflections	Δρ_min = −0.46 e Å⁻³
201 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.049 (5)

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
C1	0.4566 (5)	0.66476 (7)	0.67302 (12)	0.0215 (4)
H1	0.463381	0.687885	0.723440	0.026*
C2	0.3294 (5)	0.61359 (7)	0.67752 (13)	0.0221 (4)
H2	0.244963	0.601450	0.730780	0.026*
C3	0.3261 (5)	0.57981 (7)	0.60312 (13)	0.0215 (4)
C4	0.4409 (5)	0.59720 (7)	0.52351 (12)	0.0228 (4)
H4	0.436434	0.574023	0.473208	0.027*
C5	0.5621 (5)	0.64912 (7)	0.51906 (12)	0.0214 (4)
H5	0.636172	0.661965	0.464913	0.026*
C6	0.5748 (5)	0.68213 (7)	0.59378 (12)	0.0197 (4)
C7	0.9517 (5)	0.80678 (7)	0.65882 (12)	0.0199 (4)
C8	1.0851 (5)	0.82299 (7)	0.74254 (13)	0.0218 (4)
C9	0.9344 (5)	0.84019 (7)	0.57700 (12)	0.0199 (4)
C10	1.0545 (5)	0.82125 (7)	0.49838 (13)	0.0210 (4)
H10	1.155098	0.786823	0.498109	0.025*
C11	1.0283 (5)	0.85197 (7)	0.42152 (12)	0.0213 (4)
H11	1.108147	0.838403	0.368576	0.026*
C12	0.8849 (5)	0.90295 (7)	0.42105 (12)	0.0198 (4)
C13	0.7626 (5)	0.92238 (7)	0.49813 (13)	0.0208 (4)
H13	0.662374	0.956840	0.498230	0.025*
C14	0.7886 (5)	0.89082 (7)	0.57518 (13)	0.0210 (4)
H14	0.704725	0.904154	0.627752	0.025*
C15	0.1992 (5)	0.52632 (8)	0.61044 (13)	0.0249 (4)
C16	0.7123 (5)	0.98149 (7)	0.33590 (13)	0.0246 (4)
H16A	0.731494	0.997143	0.276745	0.037*
H16B	0.823240	1.005003	0.383095	0.037*
H16C	0.468596	0.977180	0.343527	0.037*
N1	0.7074 (4)	0.73473 (6)	0.58427 (10)	0.0207 (3)
N2	0.8218 (4)	0.75417 (6)	0.65946 (10)	0.0212 (3)
N3	0.1007 (5)	0.48385 (7)	0.61986 (13)	0.0345 (4)
O1	0.8781 (4)	0.93062 (5)	0.34222 (9)	0.0233 (3)
Cl1	1.07739 (13)	0.78390 (2)	0.83659 (3)	0.02703 (18)
Cl2	1.27416 (13)	0.88356 (2)	0.76669 (3)	0.02496 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0237 (9)	0.0195 (9)	0.0207 (9)	0.0005 (7)	−0.0001 (7)	0.0001 (7)
C2	0.0246 (9)	0.0192 (9)	0.0220 (9)	0.0002 (7)	0.0009 (7)	0.0028 (7)
C3	0.0234 (9)	0.0166 (8)	0.0234 (9)	−0.0005 (7)	−0.0012 (7)	0.0016 (7)
C4	0.0285 (10)	0.0197 (9)	0.0193 (9)	−0.0018 (7)	−0.0009 (7)	−0.0006 (7)
C5	0.0242 (9)	0.0195 (8)	0.0193 (8)	−0.0005 (7)	−0.0021 (7)	0.0024 (7)
C6	0.0207 (9)	0.0154 (8)	0.0218 (9)	0.0007 (7)	−0.0020 (7)	0.0027 (6)
C7	0.0223 (9)	0.0159 (8)	0.0211 (9)	0.0008 (7)	0.0016 (7)	−0.0007 (6)
C8	0.0257 (9)	0.0173 (8)	0.0223 (9)	0.0005 (7)	0.0025 (7)	−0.0010 (7)
C9	0.0215 (9)	0.0167 (8)	0.0207 (9)	−0.0021 (7)	−0.0003 (7)	−0.0006 (6)
C10	0.0244 (9)	0.0159 (8)	0.0221 (9)	0.0002 (7)	0.0000 (7)	−0.0026 (7)
C11	0.0244 (9)	0.0181 (8)	0.0211 (9)	−0.0005 (7)	0.0016 (7)	−0.0021 (7)
C12	0.0221 (9)	0.0186 (8)	0.0179 (8)	−0.0029 (7)	−0.0007 (7)	0.0012 (6)
C13	0.0237 (9)	0.0150 (8)	0.0231 (9)	−0.0004 (7)	0.0006 (7)	−0.0003 (7)
C14	0.0247 (9)	0.0178 (8)	0.0201 (9)	−0.0004 (7)	0.0017 (7)	−0.0018 (6)
C15	0.0294 (10)	0.0231 (10)	0.0217 (9)	−0.0028 (8)	0.0011 (7)	−0.0002 (7)
C16	0.0290 (10)	0.0182 (9)	0.0254 (10)	0.0013 (7)	−0.0015 (7)	0.0030 (7)
N1	0.0225 (8)	0.0161 (7)	0.0227 (8)	0.0004 (6)	−0.0004 (6)	0.0013 (6)
N2	0.0251 (8)	0.0164 (7)	0.0212 (8)	−0.0003 (6)	−0.0007 (6)	−0.0006 (6)
N3	0.0490 (12)	0.0242 (9)	0.0304 (9)	−0.0092 (8)	0.0046 (8)	−0.0008 (7)
O1	0.0307 (7)	0.0186 (6)	0.0203 (7)	0.0020 (5)	0.0018 (5)	0.0023 (5)
Cl1	0.0386 (3)	0.0223 (3)	0.0191 (3)	−0.00365 (18)	−0.00068 (19)	0.00226 (16)
Cl2	0.0343 (3)	0.0185 (3)	0.0213 (3)	−0.00454 (17)	0.00074 (18)	−0.00278 (15)

Geometric parameters (Å, º) top

C1—C2	1.382 (3)	C9—C14	1.392 (2)
C1—C6	1.395 (3)	C9—C10	1.403 (3)
C1—H1	0.9500	C10—C11	1.378 (3)
C2—C3	1.399 (3)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.397 (3)
C3—C4	1.394 (3)	C11—H11	0.9500
C3—C15	1.441 (3)	C12—O1	1.367 (2)
C4—C5	1.392 (3)	C12—C13	1.391 (3)
C4—H4	0.9500	C13—C14	1.393 (3)
C5—C6	1.388 (3)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500
C6—N1	1.433 (2)	C15—N3	1.149 (3)
C7—C8	1.359 (3)	C16—O1	1.430 (2)
C7—N2	1.416 (2)	C16—H16A	0.9800
C7—C9	1.479 (2)	C16—H16B	0.9800
C8—Cl2	1.7103 (19)	C16—H16C	0.9800
C8—Cl1	1.7196 (19)	N1—N2	1.257 (2)

C2—C1—C6	119.40 (17)	C10—C9—C7	121.08 (16)
C2—C1—H1	120.3	C11—C10—C9	120.81 (17)
C6—C1—H1	120.3	C11—C10—H10	119.6
C1—C2—C3	119.55 (18)	C9—C10—H10	119.6
C1—C2—H2	120.2	C10—C11—C12	120.36 (17)
C3—C2—H2	120.2	C10—C11—H11	119.8
C4—C3—C2	121.20 (17)	C12—C11—H11	119.8
C4—C3—C15	120.48 (17)	O1—C12—C13	124.46 (17)
C2—C3—C15	118.32 (17)	O1—C12—C11	115.79 (16)
C5—C4—C3	118.80 (17)	C13—C12—C11	119.74 (17)
C5—C4—H4	120.6	C12—C13—C14	119.34 (17)
C3—C4—H4	120.6	C12—C13—H13	120.3
C6—C5—C4	119.96 (17)	C14—C13—H13	120.3
C6—C5—H5	120.0	C9—C14—C13	121.59 (17)
C4—C5—H5	120.0	C9—C14—H14	119.2
C5—C6—C1	121.04 (17)	C13—C14—H14	119.2
C5—C6—N1	116.61 (16)	N3—C15—C3	177.3 (2)
C1—C6—N1	122.33 (16)	O1—C16—H16A	109.5
C8—C7—N2	111.75 (16)	O1—C16—H16B	109.5
C8—C7—C9	124.52 (17)	H16A—C16—H16B	109.5
N2—C7—C9	123.71 (15)	O1—C16—H16C	109.5
C7—C8—Cl2	124.62 (15)	H16A—C16—H16C	109.5
C7—C8—Cl1	122.71 (15)	H16B—C16—H16C	109.5
Cl2—C8—Cl1	112.66 (11)	N2—N1—C6	111.24 (15)
C14—C9—C10	118.16 (17)	N1—N2—C7	116.40 (15)
C14—C9—C7	120.73 (17)	C12—O1—C16	118.13 (15)

C6—C1—C2—C3	0.9 (3)	C14—C9—C10—C11	0.0 (3)
C1—C2—C3—C4	−1.6 (3)	C7—C9—C10—C11	178.04 (17)
C1—C2—C3—C15	178.65 (18)	C9—C10—C11—C12	0.8 (3)
C2—C3—C4—C5	0.3 (3)	C10—C11—C12—O1	178.52 (17)
C15—C3—C4—C5	−179.91 (18)	C10—C11—C12—C13	−1.1 (3)
C3—C4—C5—C6	1.5 (3)	O1—C12—C13—C14	−178.90 (17)
C4—C5—C6—C1	−2.2 (3)	C11—C12—C13—C14	0.7 (3)
C4—C5—C6—N1	179.12 (16)	C10—C9—C14—C13	−0.4 (3)
C2—C1—C6—C5	0.9 (3)	C7—C9—C14—C13	−178.47 (17)
C2—C1—C6—N1	179.54 (17)	C12—C13—C14—C9	0.0 (3)
N2—C7—C8—Cl2	178.27 (14)	C5—C6—N1—N2	−156.50 (17)
C9—C7—C8—Cl2	−3.3 (3)	C1—C6—N1—N2	24.8 (2)
N2—C7—C8—Cl1	−2.2 (2)	C6—N1—N2—C7	−178.37 (15)
C9—C7—C8—Cl1	176.26 (14)	C8—C7—N2—N1	−176.77 (17)
C8—C7—C9—C14	−52.1 (3)	C9—C7—N2—N1	4.8 (3)
N2—C7—C9—C14	126.2 (2)	C13—C12—O1—C16	−4.7 (3)
C8—C7—C9—C10	129.9 (2)	C11—C12—O1—C16	175.67 (16)
N2—C7—C9—C10	−51.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.47	3.391 (2)	165
C16—H16C···O1ⁱⁱ	0.98	2.59	3.516 (3)	158

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

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

Contact	Distance	Symmetry operation
Cl1···H5	3.05	1 + x, 3/2 - y, 1/2 + z
Cl1···H10	2.98	x, 3/2 - y, 1/2 + z
O1···H16C	2.59	1 + x, y, z
Cl2···N3	3.462	1 - x, 1/2 + y, 3/2 - z
H16B···C13	2.90	2 - x, 2 - y, 1 - z
O1···H2	2.47	1 + x, 3/2 - y, -1/2 + z
H4···N3	2.78	-x, 1 - y, 1 - z
H4···N3	2.82	1 - x, 1 - y, 1 - z
H13···H13	2.52	1 - x, 2 - y, 1 - z

Percentage contributions of interatomic contacts to the Hirshfeld surface top

Contact	Percentage contribution
Cl···H/H···Cl	22.8
H···H	21.4
N···H/H···N	16.1
C···H/H···C	14.7
C···C	9.1
O···H/H···O	5.3
N···C/C···N	4.2
Cl···N/N···Cl	2.6
Cl···C/C···Cl	1.7
Cl···Cl	1.6
C···O/O···C	0.4
N···N	0.2

Funding information

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

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