Crystal structure and Hirshfeld surface analysis of (E)-1-(4-chloro­phen­yl)-2-[2,2-di­chloro-1-(4-fluoro­phen­yl)ethen­yl]diazene

Shikhaliyev, N.Q.; Çelikesir, S.T.; Akkurt, M.; Bagirova, K.N.; Suleymanova, G.T.; Toze, F.A.A.

doi:10.1107/S2056989019003657

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ISSN: 2056-9890

Volume 75| Part 4| April 2019| Pages 465-469

https://doi.org/10.1107/S2056989019003657

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Crystal structure and Hirshfeld surface analysis of (E)-1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-fluorophenyl)ethenyl]diazene

Namiq Q. Shikhaliyev,^a Sevim Türktekin Çelikesir,^b Mehmet Akkurt,^b Khanim N. Bagirova,^a Gulnar T. Suleymanova ^a and Flavien A. A. Toze ^c ^*

^aOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az, 1148 Baku, Azerbaijan, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, 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 H. Ishida, Okayama University, Japan (Received 4 March 2019; accepted 15 March 2019; online 26 March 2019)

In the title compound, C₁₄H₈Cl₃FN₂, the planes of the 4-fluorophenyl ring and the 4-chlorophenyl ring make a dihedral angle of 56.13 (13)°. In the crystal, molecules are stacked in a column along the a axis via a weak C—H⋯Cl hydrogen bond and face-to-face π–π stacking interactions [centroid–centroid distances = 3.8615 (18) and 3.8619 (18) Å]. The crystal packing is further stabilized by short Cl⋯Cl contacts. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from Cl⋯H/H⋯Cl (31.2%), H⋯H (14.8%), C⋯H/H⋯C (14.0%), F⋯H/H⋯F (12.8%), C⋯C (9.0%) and Cl⋯Cl (6.7%) interactions.

Keywords: crystal structure; 4-chlorophenyl; 4-fluorophenyl; face-to-face π-π stacking interaction; Hirshfeld surface analysis.

CCDC reference: 1882554

1. Chemical context

Azo compounds provide ubiquitous motifs in synthetic chemistry and are widely used as organic dyes, indicators, molecular switches, pigments, ligands, food additives, radical reaction initiators, therapeutic agents etc. (Gurbanov et al., 2017 ; Maharramov et al., 2018 ; Mahmudov et al., 2019 ). Azo dyes are also convenient model compounds to study both E/Z isomerization and noncovalent interactions (Mahmudov et al., 2015 ; Shixaliyev et al., 2018 ). Thus, decorating the structure of dyes with tailored functionalities (noncovalent bond donor centres) can be a pivotal strategy for controlling and tuning their functional properties (Mahmudov et al., 2017 ; Zubkov et al., 2018 ). Herein we report the molecular structure and noncovalent interactions in the title compound.

2. Structural commentary

The molecular conformation of the title compound is not planar (Fig. 1); the planes of the 4-fluorophenyl ring and the 4-chlorophenyl ring form a dihedral angle of 56.13 (13)°. The C4—C3—C1—N1, C8—C3—C1—C2, C3—C1—C2—Cl1, C3—C1—C2—Cl2, N1—C1—C2—Cl1, N1—C1—C2—Cl2, C1—N1—N2—C9 and N1—N2—C9—C14 torsion angles are 48.4 (4), 49.2 (4), −1.9 (4), 177.94 (19), 177.14 (18), −3.0 (3), 179.2 (2) and 175.9 (2)°, respectively.

Figure 1
The molecular structure of the title compound, with the atom-labelling scheme and 50% probability displacement ellipsoids.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, molecules are linked by a weak C—H⋯Cl hydrogen bond (Table 1), forming a column along the a axis (Figs. 2 and 3). The column is further stabilized by face-to-face π–π stacking interactions; the centroid–centroid distances between the adjacent C3–C8 rings and between the adjacent C9–C14 rings are 3.8615 (18) and 3.8619 (18) Å, respectively. Moreover, the columns are linked by intermolecular Cl⋯Cl short contacts, with distances of 3.3756 (11) and 3.3841 (11) Å (Table 2), forming a layer parallel to the bc plane (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cl1ⁱ	0.95	2.81	3.634 (3)	146
Symmetry code: (i) x-1, y, z.

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

Contact	Distance	Symmetry operation
H4⋯N2	2.67	1 + x, y, z
Cl1⋯Cl3	3.3756 (11)	−x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
Cl1⋯Cl3	3.3841 (11)	1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
Cl2⋯H14	3.03	1 + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
H11⋯F1	2.81	x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z
H7⋯F1	2.67	1 − x, −y, 1 − z
F1⋯H11	2.84	1 + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z

Figure 2
A packing diagram of the title compound, viewed along the a axis, showing the C—H⋯Cl interactions (dashed lines).

Figure 3
A packing diagram of the title compound, viewed along the b axis, showing the C—H⋯Cl interactions (dashed lines).

Hirshfeld surfaces and fingerprint plots were generated for the title compound using CrystalExplorer (McKinnon et al., 2007 ). The Hirshfeld surface mapped over d_norm using a standard surface resolution with a fixed colour scale of −0.0941 (red) to 1.4174 a.u. (blue) is shown in Fig. 4. This plot was generated to quantify and visualize the intermolecular interactions and to explain the observed crystal packing. The dark-red spots on the d_norm surface arise as a result of the C—H⋯Cl interaction and short interatomic contacts (Tables 1 and 2), while the other weaker intermolecular interactions appear as light-red spots. 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. 5 clearly suggests that there are π–π interactions in the title compound.

Figure 4
View of the Hirshfeld surface of the title compound plotted over d_norm in the range from −0.0941 to 1.4174 a.u.

Figure 5
View of the 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 2D fingerprint plots in Fig. 6. The reciprocal Cl⋯H/H⋯Cl interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.7 Å and contribute 31.2% to the Hirshfeld surface (Fig. 6b). The H⋯H interactions appear in the middle of the scattered points in the 2D fingerprint plots, with an overall contribution to the Hirshfeld surface of 14.8% (Fig. 6c). The C⋯H/H⋯C interactions, with a 14.0% contribution, are present as bump symmetrical spikes at diagonal axes (Fig. 6d). The F⋯H/H⋯F interactions, with a 12.8% contribution, are present as sharp symmetrical spikes at diagonal axes d_e + d_i ≃ 2.55 Å (Fig. 6e). The C⋯C interactions appear in the middle of the scattered points in the 2D fingerprint plots with an overall contribution to the Hirshfeld surface of 9.0% (Fig. 6f). The small percentage contributions from the other different interatomic contacts to the Hirshfeld surfaces are as follows: Cl⋯Cl (6.7%) (Fig. 6g), N⋯H/H⋯N (3.4%) (Fig. 6h), Cl⋯C/C⋯Cl (3.1%) (Fig. 6i), N⋯C/C⋯N (2.8%), N⋯N (1.0%), Cl⋯N/N⋯Cl (0.8%), F⋯F (0.4%) and F⋯C/C⋯F (0.1%). Hirshfeld surface representations with the function d_norm plotted onto the surface for Cl⋯H/H⋯Cl, H⋯H, C⋯H/H⋯C, F⋯H/H⋯F, C⋯C, Cl⋯Cl, N⋯H/H⋯N and Cl⋯C/C⋯Cl interactions are shown in Fig. 7. The large number of Cl⋯H/H⋯Cl, H⋯H, C⋯H/H⋯C, F⋯H/H⋯F 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 ).

Figure 6
The full 2D fingerprint plots for the title compound, showing (a) all interactions, and those delineated into (b) Cl⋯H/H⋯Cl, (c) H⋯H, (d) C⋯H/H⋯C, (e) F⋯H/H⋯F, (f) C⋯C, (g) Cl⋯Cl, (h) N⋯H/H⋯N and (i) Cl⋯C/C⋯Cl interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

Figure 7
Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) all interactions, (b) Cl⋯H/H⋯Cl, (c) H⋯H, (d) C⋯H/H⋯C, (e) F⋯H/H⋯F, (f) C⋯C, (g) Cl⋯Cl, (h) N⋯H/H⋯N and (i) Cl⋯C/C⋯Cl interactions.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, November 2018; Groom et al., 2016 ) for structures having an (E)-1-(2,2-dichloro-1-phenylvinyl)-2-phenyldiazene unit gave 18 hits. Three compounds closely resemble the title compound, viz. 1-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]-2-(4-fluorophenyl)diazene (CSD refcode XIZREG; Atioğlu et al., 2019 ), 1,1′-[methylenebis(4,1-phenylene)]bis[(2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene (LEQXIR; Shixaliyev et al., 2018) and 1,1′-[methylenebis(4,1-phenylene)]bis{[2,2-dichloro-1-(4-chlorophenyl)ethenyl]diazene} (LEQXOX; Shixaliyev et al., 2018). In XIZREG (Atioğlu et al., 2019), molecules are linked by a C—H⋯O hydrogen bond into a zigzag chain running along the c axis. The crystal packing is further stabilized by C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In the crystal of LEQXIR, C—H⋯N and C—H⋯O hydrogen bonds and Cl⋯O contacts were found, and in LEQXOX, C—H⋯N and Cl⋯Cl contacts were observed.

5. Synthesis and crystallization

This dye was synthesized according to a reported method (Shixaliyev et al., 2018). A 20 ml screw-necked vial was charged with dimethyl sulfoxide (10 ml), (E)-1-(4-chlorophenyl)-2-(4-fluorobenzylidene)hydrazine (248 mg, 1 mmol), tetramethylethylenediamine (295 mg, 2.5 mmol), CuCl (2 mg, 0.02 mmol) and CCl₄ (20 mmol, 10 equiv.). After 1–3 h (until thin-layer chromatography analysis showed complete consumption of the corresponding Schiff base), the reaction mixture was poured into a ∼0.01 M solution of HCl (100 ml, ∼pH = 2–3) and extracted with dichloromethane (3 × 20 ml). The combined organic phase was washed with water (3 × 50 ml), brine (30 ml), dried over anhydrous Na₂SO₄ and concentrated in vacuo with a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3:1–1:1 v/v).

Red solid (yield 46%); m.p. 340–338 K. Analysis calculated (%) for C₁₄H₈Cl₃FN₂: C 51.02, H 2.45, N 8.50; found: C 49.95, H 2.43, N 8.47. ¹H NMR (300 MHz, CDCl₃): δ 7.15-7.17 (m, 4H), 7.42–7.45 (d, 2H, J = 9.21 Hz), 7.73–7.75 (d, 2H, J = 6.04 Hz). ¹³C NMR (75 MHz, CDCl₃): δ 115.29, 115.58, 124.49, 127.46, 129.37, 130.43, 131.88, 131.99, 137.73, 151.13. ESI-MS: m/z: 330.44 [M + H]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were constrained to an ideal geometry, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). Nine outliers ( $[\overline{4}]$ ,2,12; $[\overline{4}]$ ,1,12; $[\overline{3}]$ ,18,11; 2,21,1; $[\overline{4}]$ ,3,12; $[\overline{3}]$ ,19,10; 0,13,17; $[\overline{4}]$ ,4,10; 2,20,0) were omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₄H₈Cl₃FN₂
M_r	329.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.8617 (8), 24.249 (5), 14.724 (3)
β (°)	94.30 (3)
V (Å³)	1374.9 (5)
Z	4
Radiation type	Synchrotron, λ = 0.80246 Å
μ (mm⁻¹)	0.93
Crystal size (mm)	0.20 × 0.10 × 0.02

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.840, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	20761, 2984, 2719
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.142, 1.05
No. of reflections	2984
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.72
Computer programs: Marccd (Doyle, 2011 ), iMosflm (Battye et al., 2011 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1882554

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019003657/is5510sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019003657/is5510Isup2.hkl

checkCIF report

Computing details top

Data collection: Marccd (Doyle, 2011); cell refinement: iMosflm (Battye et al., 2011); data reduction: iMosflm; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

(E)-1-(4-Chlorophenyl)-2-[2,2-dichloro-1-(4-fluorophenyl)ethenyl]\ diazene top

Crystal data top

C₁₄H₈Cl₃FN₂	F(000) = 664
M_r = 329.57	D_x = 1.592 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.80246 Å
a = 3.8617 (8) Å	Cell parameters from 600 reflections
b = 24.249 (5) Å	θ = 3.3–30.0°
c = 14.724 (3) Å	µ = 0.93 mm⁻¹
β = 94.30 (3)°	T = 100 K
V = 1374.9 (5) Å³	Plate, orange
Z = 4	0.20 × 0.10 × 0.02 mm

Data collection top

Rayonix SX165 CCD diffractometer	2719 reflections with I > 2σ(I)
/f scan	R_int = 0.115
Absorption correction: multi-scan (Scala; Evans, 2006)	θ_max = 30.9°, θ_min = 3.3°
T_min = 0.840, T_max = 0.970	h = −4→4
20761 measured reflections	k = −30→31
2984 independent reflections	l = −18→18

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)] = 0.053	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0557P)² + 1.092P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2984 reflections	Δρ_max = 0.59 e Å⁻³
182 parameters	Δρ_min = −0.72 e Å⁻³
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.026 (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	0.68912 (17)	0.12097 (2)	0.17209 (4)	0.0265 (2)
Cl2	0.48467 (18)	0.22728 (2)	0.10431 (4)	0.0283 (2)
Cl3	−0.18247 (18)	0.50802 (2)	0.35787 (5)	0.0318 (2)
F1	0.5868 (5)	0.06509 (7)	0.58998 (10)	0.0386 (4)
N1	0.3562 (6)	0.25699 (8)	0.28387 (14)	0.0246 (5)
N2	0.2435 (6)	0.27366 (8)	0.35685 (14)	0.0230 (4)
C1	0.4622 (7)	0.20110 (9)	0.28183 (16)	0.0225 (5)
C2	0.5361 (7)	0.18506 (9)	0.19760 (16)	0.0237 (5)
C3	0.4936 (7)	0.16469 (9)	0.36354 (16)	0.0232 (5)
C4	0.6716 (7)	0.18329 (10)	0.44378 (16)	0.0249 (5)
H4	0.7714	0.2191	0.4459	0.030*
C5	0.7036 (7)	0.14978 (10)	0.52038 (16)	0.0283 (6)
H5	0.8242	0.1622	0.5752	0.034*
C6	0.5558 (8)	0.09804 (10)	0.51483 (17)	0.0287 (6)
C7	0.3803 (7)	0.07791 (10)	0.43694 (17)	0.0280 (5)
H7	0.2840	0.0418	0.4352	0.034*
C8	0.3485 (7)	0.11196 (10)	0.36103 (17)	0.0243 (5)
H8	0.2264	0.0992	0.3067	0.029*
C9	0.1482 (7)	0.33066 (9)	0.35229 (16)	0.0225 (5)
C10	0.1990 (7)	0.36475 (10)	0.27784 (16)	0.0251 (5)
H10	0.3012	0.3504	0.2261	0.030*
C11	0.1000 (7)	0.41943 (10)	0.27997 (16)	0.0257 (5)
H11	0.1332	0.4430	0.2298	0.031*
C12	−0.0490 (7)	0.43956 (10)	0.35640 (17)	0.0246 (5)
C13	−0.0997 (7)	0.40658 (10)	0.43064 (17)	0.0255 (5)
H13	−0.2002	0.4212	0.4824	0.031*
C14	−0.0012 (7)	0.35157 (10)	0.42818 (16)	0.0248 (5)
H14	−0.0358	0.3282	0.4784	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0363 (4)	0.0157 (3)	0.0273 (3)	0.0018 (2)	0.0006 (2)	−0.0038 (2)
Cl2	0.0408 (4)	0.0196 (3)	0.0243 (3)	0.0022 (2)	0.0017 (2)	0.0020 (2)
Cl3	0.0384 (4)	0.0125 (3)	0.0442 (4)	0.0020 (2)	0.0011 (3)	0.0002 (2)
F1	0.0622 (12)	0.0241 (8)	0.0290 (8)	0.0040 (8)	−0.0004 (7)	0.0087 (6)
N1	0.0333 (12)	0.0135 (9)	0.0266 (10)	−0.0008 (8)	0.0000 (8)	−0.0019 (7)
N2	0.0292 (11)	0.0128 (9)	0.0269 (10)	0.0004 (8)	0.0008 (8)	−0.0015 (7)
C1	0.0273 (13)	0.0123 (10)	0.0272 (11)	−0.0027 (9)	−0.0017 (9)	−0.0010 (8)
C2	0.0286 (13)	0.0146 (10)	0.0272 (11)	−0.0032 (9)	−0.0019 (9)	−0.0014 (8)
C3	0.0301 (13)	0.0143 (11)	0.0253 (11)	0.0017 (9)	0.0013 (9)	−0.0013 (8)
C4	0.0316 (14)	0.0149 (11)	0.0279 (11)	0.0016 (9)	0.0007 (10)	−0.0005 (9)
C5	0.0361 (15)	0.0214 (12)	0.0267 (11)	0.0039 (10)	−0.0023 (10)	−0.0023 (9)
C6	0.0407 (15)	0.0175 (11)	0.0280 (11)	0.0064 (10)	0.0037 (10)	0.0060 (9)
C7	0.0376 (15)	0.0143 (11)	0.0321 (12)	0.0007 (10)	0.0037 (10)	0.0016 (9)
C8	0.0291 (13)	0.0153 (11)	0.0285 (11)	0.0000 (9)	0.0013 (10)	−0.0017 (9)
C9	0.0288 (13)	0.0112 (10)	0.0269 (11)	0.0003 (9)	−0.0025 (9)	−0.0011 (8)
C10	0.0315 (14)	0.0176 (11)	0.0259 (11)	−0.0001 (9)	−0.0004 (9)	0.0001 (9)
C11	0.0332 (14)	0.0157 (11)	0.0277 (11)	−0.0010 (9)	−0.0020 (10)	0.0022 (9)
C12	0.0286 (13)	0.0132 (11)	0.0312 (12)	−0.0020 (9)	−0.0037 (10)	−0.0005 (9)
C13	0.0302 (13)	0.0165 (11)	0.0292 (11)	−0.0012 (9)	−0.0009 (9)	−0.0037 (9)
C14	0.0319 (14)	0.0175 (11)	0.0243 (11)	−0.0007 (9)	−0.0019 (9)	0.0013 (9)

Geometric parameters (Å, º) top

Cl1—C2	1.714 (2)	C6—C7	1.377 (4)
Cl2—C2	1.713 (2)	C7—C8	1.388 (3)
Cl3—C12	1.739 (2)	C7—H7	0.9500
F1—C6	1.363 (3)	C8—H8	0.9500
N1—N2	1.256 (3)	C9—C14	1.391 (3)
N1—C1	1.417 (3)	C9—C10	1.399 (3)
N2—C9	1.431 (3)	C10—C11	1.381 (3)
C1—C2	1.351 (3)	C10—H10	0.9500
C1—C3	1.490 (3)	C11—C12	1.390 (4)
C3—C8	1.395 (3)	C11—H11	0.9500
C3—C4	1.396 (3)	C12—C13	1.380 (3)
C4—C5	1.388 (3)	C13—C14	1.389 (3)
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.378 (4)	C14—H14	0.9500
C5—H5	0.9500

N2—N1—C1	116.43 (19)	C8—C7—H7	121.0
N1—N2—C9	112.0 (2)	C7—C8—C3	120.9 (2)
C2—C1—N1	112.1 (2)	C7—C8—H8	119.6
C2—C1—C3	124.1 (2)	C3—C8—H8	119.6
N1—C1—C3	123.8 (2)	C14—C9—C10	120.4 (2)
C1—C2—Cl2	122.99 (19)	C14—C9—N2	115.8 (2)
C1—C2—Cl1	124.22 (18)	C10—C9—N2	123.9 (2)
Cl2—C2—Cl1	112.79 (14)	C11—C10—C9	119.6 (2)
C8—C3—C4	119.3 (2)	C11—C10—H10	120.2
C8—C3—C1	120.9 (2)	C9—C10—H10	120.2
C4—C3—C1	119.8 (2)	C10—C11—C12	119.2 (2)
C5—C4—C3	120.4 (2)	C10—C11—H11	120.4
C5—C4—H4	119.8	C12—C11—H11	120.4
C3—C4—H4	119.8	C13—C12—C11	122.0 (2)
C6—C5—C4	118.3 (2)	C13—C12—Cl3	118.9 (2)
C6—C5—H5	120.9	C11—C12—Cl3	119.10 (18)
C4—C5—H5	120.9	C12—C13—C14	118.7 (2)
F1—C6—C7	118.4 (2)	C12—C13—H13	120.6
F1—C6—C5	118.3 (2)	C14—C13—H13	120.6
C7—C6—C5	123.2 (2)	C13—C14—C9	120.1 (2)
C6—C7—C8	117.9 (2)	C13—C14—H14	119.9
C6—C7—H7	121.0	C9—C14—H14	119.9

C1—N1—N2—C9	179.2 (2)	C5—C6—C7—C8	−0.8 (4)
N2—N1—C1—C2	171.9 (2)	C6—C7—C8—C3	0.7 (4)
N2—N1—C1—C3	−9.0 (4)	C4—C3—C8—C7	−0.3 (4)
N1—C1—C2—Cl2	−3.0 (3)	C1—C3—C8—C7	179.5 (2)
C3—C1—C2—Cl2	177.94 (19)	N1—N2—C9—C14	175.9 (2)
N1—C1—C2—Cl1	177.14 (18)	N1—N2—C9—C10	−4.5 (4)
C3—C1—C2—Cl1	−1.9 (4)	C14—C9—C10—C11	0.0 (4)
C2—C1—C3—C8	−49.2 (4)	N2—C9—C10—C11	−179.6 (2)
N1—C1—C3—C8	131.8 (3)	C9—C10—C11—C12	0.0 (4)
C2—C1—C3—C4	130.5 (3)	C10—C11—C12—C13	0.3 (4)
N1—C1—C3—C4	−48.4 (4)	C10—C11—C12—Cl3	−178.57 (19)
C8—C3—C4—C5	−0.1 (4)	C11—C12—C13—C14	−0.6 (4)
C1—C3—C4—C5	−179.9 (2)	Cl3—C12—C13—C14	178.31 (19)
C3—C4—C5—C6	0.0 (4)	C12—C13—C14—C9	0.5 (4)
C4—C5—C6—F1	−180.0 (2)	C10—C9—C14—C13	−0.2 (4)
C4—C5—C6—C7	0.4 (4)	N2—C9—C14—C13	179.4 (2)
F1—C6—C7—C8	179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cl1ⁱ	0.95	2.81	3.634 (3)	146

Symmetry code: (i) x−1, y, z.

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

Contact	Distance	Symmetry operation
H4···N2	2.67	1+x ,y, z
Cl1···Cl3	3.3756 (11)	-x, -1/2+y, 1/2-z
Cl1···Cl3	3.3841 (11)	1-x, -1/2+y, 1/2-z
Cl2···H14	3.03	1+x, 1/2-y, -1/2+z
H11···F1	2.81	x, 1/2-y, -1/2+z
H7···F1	2.67	1-x, -y, 1-z
F1···H11	2.84	1+x, 1/2-y, 1/2+z

Funding information

Funding for this research was provided by: 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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