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

Özkaraca, K.; Akkurt, M.; Shikhaliyev, N.Q.; Askerova, U.F.; Suleymanova, G.T.; Shikhaliyeva, I.M.; Bhattarai, A.

doi:10.1107/S2056989020006106

research communications

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ISSN: 2056-9890

Volume 76| Part 6| June 2020| Pages 811-815

https://doi.org/10.1107/S2056989020006106

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

Kadriye Özkaraca,^a Mehmet Akkurt,^b Namiq Q. Shikhaliyev,^c Ulviyya F. Askerova,^c Gulnar T. Suleymanova,^c Irada M. Shikhaliyeva ^c and Ajaya Bhattarai ^d ^*

^aInstitute of Natural and Applied Science, Erciyes University, 38039 Kayseri, 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 ^dDepartment 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 28 April 2020; accepted 5 May 2020; online 6 May 2020)

In the title compound, C₁₆H₁₄Cl₂FN₃, the dihedral angle between the two aromatic rings is 64.12 (14)°. The crystal structure is stabilized by a short Cl⋯H contact, C—Cl⋯π and van der Waals interactions. The Hirshfeld surface analysis and two-dimensional fingerprint plots show that H⋯H (33.3%), Cl⋯H/H⋯Cl (22.9%) and C⋯H/H⋯C (15.5%) interactions are the most important contributors towards the crystal packing.

Keywords: crystal structure; C—Cl⋯π interactions; van der Waals interactions; Hirshfeld surface analysis.

CCDC reference: 2001173

1. Chemical context

Both inter- and intramolecular weak interactions play a crucial role in determining the properties of organic compounds and controlling their molecular organization in solution and in the solid state, which is sensitive to their chemical environment, solvent polarity, temperature, etc. (Asadov et al., 2016 ; Maharramov et al., 2009 , 2010 ; Mahmudov et al., 2013 , 2014a ,b , 2015 , 2017a ,b , 2019 ; Shixaliyev et al., 2013 , 2014 ). For example, in catalysis monomeric, oligomeric or polymeric compounds can promote various organic transformations not only by coordination bonds but also through non-covalent interactions, such as hydrogen, halogen, chalcogen, pnictogen, tetrel and triel bonds, as well as metal–metal, cation–π, anion–π, lone pair–π, π–π stacking, agostic, pseudo-agostic, anagostic, dispersion-driven, lipophilic, etc, or their cooperation (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 ). On the other hand, we and other researchers have attached various types of non-covalent-bond donor synthons to dye molecules, which results in interesting analytical and solvatochromic properties (Maharramov et al., 2018 ; Mahmudov et al., 2010 , 2011 ; Mahmudov & Pombeiro, 2016 ).

In order to continue our work in this direction, we have functionalized a new azo dye, 4-{2,2-dichloro-1-[(E)-(4-fluorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline, which provides C—H⋯F and C—Cl⋯F types of intermolecular weak interactions.

2. Structural commentary

In the title compound (Fig. 1), the dihedral angle between the benzene rings (C1–C6 and C8–C13) of the 4-fluorophenyl and N,N-dimethylaniline groups is 64.12 (14)°. The amine N atom as well as the directly adjacent arene C atom are bent a little out of the plane of the other five aromatic C atoms, with deviations of 0.007 (3) Å for C11 and 0.027 (2) Å for N3. The N1—N2—C7—C14, N2—C7—C14—Cl1, N2—C7—C14—Cl2 and C8—C7—C14—Cl2 torsion angles are −172.0 (2), 2.1 (3), −177.0 (2) and 0.6 (4)°, respectively.

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, the molecules are connected by a short Cl2⋯H13A contact (2.96 Å) and C—Cl⋯π interactions, which contribute to the overall packing energy stabilization, into infinite columns along the a-axis direction (Table 1; Fig. 2).

Table 1
C—Cl⋯π interaction geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—Cl1⋯Cg1ⁱ	1.72 (1)	3.93 (1)	3.882 (3)	76 (1)
Symmetry code: (i) x-1, y, z.

Figure 2
A partial packing diagram of the title compound showing chain formation along the a-axis direction. Symmetry operators: (a) −1 + x, y, z; (b) 1 + x, y, z. Cg1 is the centroid of the C1–C6 ring.

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out using CrystalExplorer17.5 (Turner et al., 2017 ). Three-dimensional molecular Hirshfeld surfaces were generated using a `high standard' surface resolution colour-mapped over the normalized contact distance. The red, white and blue regions visible on the d_norm surfaces indicate contacts with distances shorter, longer and equal to the van der Waals radii (Fig. 3).

Figure 3
Front and back sides of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range 0.0350 to 0.8404 a.u.

The bright-red spots near atoms Cl2 and C13 in Fig.3a refer to the short Cl2⋯H13A contact, and near the atoms F1 and C10 in Fig. 3b to the F1⋯H10A contact. 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. 4 clearly suggests that there are no π–π interactions in the crystal structure.

Figure 4
Hirshfeld surface of the title compound plotted over shape-index.

The overall two-dimensional fingerprint plot, Fig. 5a, and those delineated into H⋯H, Cl⋯H/H⋯Cl, C⋯H/H⋯C, F⋯H/H⋯F, N⋯H/H⋯N, C⋯C and Cl⋯C/C⋯Cl contacts (McKinnon et al., 2007 ) are illustrated in Fig. 5b–h, together with their relative contributions to the Hirshfeld surface while details of the various contacts are given in Table 2. The most important interaction is H⋯H, contributing 33.3% to the overall crystal packing, which is reflected in Fig. 5b as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at d_e = d_i = 1.10 Å. The reciprocal Cl⋯H/H⋯Cl interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.80 Å and contribute 22.9% to the Hirshfeld surface (Fig. 5c). The pair of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts (Fig. 5d; 15.5% contribution to the Hirshfeld surface), have the tips at d_e + d_i ≃ 2.95 Å. The fingerprint plot for F⋯H/H⋯F contacts (9.0% contribution), Fig. 5e, has a pair of spikes with the tips at d_e + d_i = 2.55 Å. The remaining contributions from the other different interatomic contacts to the Hirshfeld surfaces are listed in Table 3. The small contribution of the other weak intermolecular N⋯H/H⋯N, C⋯C, Cl⋯C/C⋯Cl, N⋯C/C⋯N, Cl⋯N/N⋯Cl, Cl⋯F/F⋯Cl, C⋯F/F⋯C and F⋯N/N⋯F contacts has a negligible effect on the packing.

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

A⋯B	Distance	Symmetry operation for B
H15B⋯H16B	2.45	−1 + x, y, z
Cl1⋯N3	3.409 (3)	− $[{1\over 2}]$ − x, 1 − y, $[{1\over 2}]$ + z
C12⋯H6A	2.97	$[{1\over 2}]$ − x, 1 − y, − $[{1\over 2}]$ + z
Cl2⋯H13A	2.96	−1 + x, y, z
F1⋯H10A	2.66	$[{3\over 2}]$ + x, $[{3\over 2}]$ − y, 1 − z
H3A⋯H2A	2.53	$[{1\over 2}]$ + x, $[{3\over 2}]$ − y, 1 − z

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

Contact	Percentage contribution
H⋯H	33.3
Cl⋯H/H⋯Cl	22.9
C⋯H/H⋯C	15.5
F⋯H/H⋯F	9.0
N⋯H/H⋯N	4.9
C⋯C	4.7
Cl⋯C/C⋯Cl	2.7
N⋯C/C⋯N	2.0
Cl⋯N/N⋯Cl	2.0
Cl⋯F/F⋯Cl	1.9
C⋯F/F⋯C	0.8
F⋯N/N⋯F	0.3

Figure 5
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) Cl⋯H/H⋯Cl, (d) C⋯H/H⋯C, (e) F⋯H/H⋯F, (f) N⋯H/H⋯N, (g) C⋯C and (h) 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.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, Cl⋯H/H⋯Cl and C⋯H/H⋯C interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.41, update of November 2019; Groom et al., 2016 ) for structures having an (E)-1-(2,2-dichloro-1-phenylvinyl)-2-phenyldiazene unit gave 25 hits. Six compounds closely resemble the title compound, viz. 1-(4-bromophenyl)-2-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene (CSD refcode HONBOE; Akkurt et al., 2019 ), 1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene (HONBUK; Akkurt et al., 2019), 1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-fluorophenyl)ethenyl]diazene (HODQAV; Shikhaliyev et al., 2019 ), 1-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]-2-(4-fluorophenyl)diazene (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 ), 1,1-[methylenebis(4,1-phenylene)]bis{[2,2-dichloro-1-(4-chlorophenyl) ethenyl]diazene} (LEQXOX; Shikhaliyev et al., 2018).

In the crystal structures of HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9 (2) and 64.1 (2)°, respectively. Molecules are linked through weak X⋯Cl contacts (X = Br for HONBOE and Cl for HONBUK) and C—H⋯Cl and C—Cl⋯π interactions into sheets parallel to the ab plane. Additional van der Waals interactions consolidate the three-dimensional packing. In the crystal of HODQAV, 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 XIZREG, 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. 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 are observed.

5. Synthesis and crystallization

The title compound was synthesized according to the reported method (Shixaliyev et al., 2018). A 20 mL screw-neck vial was charged with DMSO (10mL), (E)-4-{[2-(4-fluorophenyl)hydrazono]methyl}-N,N-dimethylaniline (257 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), brine (30 mL), dried over anhydrous Na₂SO₄ and concentrated in vacuo using a 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. Orange solid (78%); m.p. 418 K. Analysis calculated for C₁₆H₁₄Cl₂FN₃ (M = 338.21): C 56.82, H 4.17, N 12.42; found: C 56.78, H 4.11, N 12.34%. ¹H NMR (300 MHz, CDCl₃) δ (ppm) 3.05 (6H, NMe₂), 6.79–7.86 (8H, Ar). ¹³C NMR (75 MHz, CDCl₃) δ (ppm) 134.71, 131.08, 130.42, 128.97, 128.85, 125.34, 125.22, 124.68, 124.57, 119.46, 116.13, 115.83, 115.47, 115.17, 115.12, 111.49, 110.83, 43.94, 40.31. ESI–MS: m/z: 338.12 [M+H]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All C-bound H atoms were refined using a riding model with d(C—H) = 0.93 Å, U_iso(H) = 1.2U_eq(C) for aromatic and 0.96 Å, U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Cl₂FN₃
M_r	338.20
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.0730 (3), 15.9782 (9), 16.3860 (7)
V (Å³)	1590.03 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.42
Crystal size (mm)	0.27 × 0.24 × 0.17

Data collection
Diffractometer	Bruker APEXII PHOTON 100 detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.887, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	12082, 3215, 2696
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.084, 1.05
No. of reflections	3215
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.22
Absolute structure	Flack x determined using 1002 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	−0.02 (2)
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: 2001173

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006106/vm2232sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006106/vm2232Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020006106/vm2232Isup3.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).

4-{2,2-Dichloro-1-[(E)-(4-fluorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline top

Crystal data top

C₁₆H₁₄Cl₂FN₃	D_x = 1.413 Mg m⁻³
M_r = 338.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6056 reflections
a = 6.0730 (3) Å	θ = 2.8–26.4°
b = 15.9782 (9) Å	µ = 0.42 mm⁻¹
c = 16.3860 (7) Å	T = 296 K
V = 1590.03 (14) Å³	Block, orange
Z = 4	0.27 × 0.24 × 0.17 mm
F(000) = 696

Data collection top

Bruker APEXII PHOTON 100 detector diffractometer	2696 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.4°, θ_min = 2.5°
T_min = 0.887, T_max = 0.944	h = −7→7
12082 measured reflections	k = −19→19
3215 independent reflections	l = −20→20

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0431P)² + 0.1514P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.13 e Å⁻³
3215 reflections	Δρ_min = −0.22 e Å⁻³
201 parameters	Absolute structure: Flack x determined using 1002 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
0 restraints	Absolute structure parameter: −0.02 (2)

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	0.4252 (4)	0.61833 (16)	0.56623 (16)	0.0443 (6)
C2	0.5620 (5)	0.68715 (18)	0.55987 (18)	0.0509 (7)
H2A	0.540332	0.725536	0.517976	0.061*
C3	0.7298 (5)	0.6994 (2)	0.61488 (17)	0.0573 (8)
H3A	0.823241	0.745307	0.610610	0.069*
C4	0.7553 (5)	0.6416 (2)	0.67653 (18)	0.0594 (8)
C5	0.6205 (6)	0.5739 (2)	0.6855 (2)	0.0673 (9)
H5A	0.641740	0.536178	0.728082	0.081*
C6	0.4535 (5)	0.56267 (19)	0.63053 (18)	0.0574 (8)
H6A	0.358152	0.517491	0.636245	0.069*
C7	−0.0179 (4)	0.53364 (16)	0.45205 (16)	0.0439 (6)
C8	−0.0207 (4)	0.58320 (16)	0.37493 (15)	0.0421 (6)
C9	−0.1979 (4)	0.63333 (18)	0.35356 (16)	0.0465 (6)
H9A	−0.319781	0.635689	0.387856	0.056*
C10	−0.1976 (4)	0.67976 (18)	0.28261 (16)	0.0470 (7)
H10A	−0.319254	0.712725	0.270104	0.056*
C11	−0.0185 (4)	0.67833 (17)	0.22914 (15)	0.0419 (6)
C12	0.1597 (5)	0.62650 (17)	0.25034 (16)	0.0463 (6)
H12A	0.280540	0.622891	0.215669	0.056*
C13	0.1577 (5)	0.58098 (17)	0.32175 (17)	0.0473 (6)
H13A	0.278742	0.547916	0.334730	0.057*
C14	−0.1613 (5)	0.47174 (16)	0.46824 (16)	0.0469 (6)
C15	−0.1744 (6)	0.7909 (2)	0.14541 (19)	0.0624 (8)
H15A	−0.174793	0.828007	0.191458	0.094*
H15B	−0.318008	0.766689	0.138916	0.094*
H15C	−0.136230	0.821563	0.097069	0.094*
C16	0.1532 (6)	0.7139 (2)	0.09817 (19)	0.0666 (8)
H16A	0.162051	0.655738	0.083877	0.100*
H16B	0.292048	0.732038	0.119880	0.100*
H16C	0.118356	0.746158	0.050458	0.100*
Cl1	−0.16032 (15)	0.41361 (5)	0.55620 (5)	0.0677 (3)
Cl2	−0.36345 (14)	0.44180 (5)	0.40139 (5)	0.0680 (3)
F1	0.9220 (4)	0.65309 (16)	0.73030 (13)	0.0957 (8)
N1	0.2619 (4)	0.60931 (14)	0.50431 (14)	0.0477 (5)
N2	0.1433 (4)	0.54576 (14)	0.51363 (13)	0.0469 (5)
N3	−0.0159 (4)	0.72557 (16)	0.15854 (14)	0.0554 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0531 (15)	0.0378 (14)	0.0420 (13)	0.0006 (11)	−0.0011 (12)	−0.0018 (11)
C2	0.0671 (18)	0.0421 (15)	0.0436 (14)	−0.0075 (13)	0.0032 (14)	0.0000 (12)
C3	0.0676 (19)	0.0562 (17)	0.0480 (16)	−0.0201 (15)	0.0029 (15)	−0.0036 (14)
C4	0.0617 (18)	0.070 (2)	0.0468 (15)	−0.0164 (16)	−0.0090 (15)	0.0004 (15)
C5	0.079 (2)	0.065 (2)	0.0583 (18)	−0.0209 (17)	−0.0234 (17)	0.0185 (15)
C6	0.0655 (18)	0.0480 (17)	0.0588 (17)	−0.0192 (15)	−0.0148 (15)	0.0152 (14)
C7	0.0430 (13)	0.0427 (14)	0.0461 (14)	0.0082 (11)	−0.0043 (12)	−0.0006 (11)
C8	0.0433 (13)	0.0398 (14)	0.0433 (13)	0.0034 (11)	−0.0052 (12)	−0.0006 (11)
C9	0.0409 (14)	0.0550 (16)	0.0436 (14)	0.0078 (12)	0.0017 (12)	−0.0020 (12)
C10	0.0421 (14)	0.0513 (15)	0.0474 (15)	0.0121 (12)	−0.0034 (13)	0.0028 (12)
C11	0.0416 (14)	0.0435 (15)	0.0406 (14)	0.0010 (11)	−0.0047 (12)	−0.0043 (11)
C12	0.0384 (13)	0.0517 (15)	0.0486 (14)	0.0059 (12)	0.0035 (13)	−0.0033 (12)
C13	0.0392 (13)	0.0478 (14)	0.0547 (15)	0.0077 (12)	−0.0061 (13)	−0.0012 (12)
C14	0.0453 (14)	0.0438 (14)	0.0515 (14)	0.0037 (12)	−0.0048 (13)	−0.0001 (11)
C15	0.0624 (19)	0.0655 (19)	0.0591 (18)	0.0090 (16)	−0.0018 (17)	0.0153 (15)
C16	0.0647 (19)	0.075 (2)	0.0595 (18)	0.0020 (18)	0.0144 (18)	0.0095 (16)
Cl1	0.0720 (5)	0.0627 (5)	0.0683 (5)	−0.0060 (4)	0.0004 (5)	0.0197 (4)
Cl2	0.0576 (4)	0.0620 (5)	0.0845 (5)	−0.0089 (4)	−0.0209 (4)	0.0044 (4)
F1	0.0914 (16)	0.1181 (18)	0.0777 (13)	−0.0488 (14)	−0.0399 (12)	0.0172 (13)
N1	0.0566 (14)	0.0415 (12)	0.0450 (12)	−0.0009 (11)	−0.0058 (11)	0.0018 (10)
N2	0.0506 (12)	0.0449 (12)	0.0454 (11)	−0.0031 (11)	−0.0081 (11)	0.0016 (10)
N3	0.0568 (15)	0.0634 (16)	0.0461 (12)	0.0129 (12)	0.0076 (12)	0.0089 (11)

Geometric parameters (Å, º) top

C1—C2	1.382 (4)	C10—C11	1.397 (4)
C1—C6	1.389 (4)	C10—H10A	0.9300
C1—N1	1.426 (3)	C11—N3	1.381 (3)
C2—C3	1.374 (4)	C11—C12	1.406 (4)
C2—H2A	0.9300	C12—C13	1.378 (4)
C3—C4	1.377 (4)	C12—H12A	0.9300
C3—H3A	0.9300	C13—H13A	0.9300
C4—F1	1.354 (3)	C14—Cl2	1.713 (3)
C4—C5	1.365 (4)	C14—Cl1	1.715 (3)
C5—C6	1.369 (4)	C15—N3	1.436 (4)
C5—H5A	0.9300	C15—H15A	0.9600
C6—H6A	0.9300	C15—H15B	0.9600
C7—C14	1.344 (4)	C15—H15C	0.9600
C7—N2	1.419 (3)	C16—N3	1.438 (4)
C7—C8	1.491 (4)	C16—H16A	0.9600
C8—C9	1.387 (4)	C16—H16B	0.9600
C8—C13	1.391 (4)	C16—H16C	0.9600
C9—C10	1.379 (4)	N1—N2	1.255 (3)
C9—H9A	0.9300

C2—C1—C6	119.5 (3)	N3—C11—C10	121.7 (2)
C2—C1—N1	116.4 (2)	N3—C11—C12	121.3 (2)
C6—C1—N1	124.1 (2)	C10—C11—C12	117.0 (2)
C3—C2—C1	120.6 (3)	C13—C12—C11	120.9 (3)
C3—C2—H2A	119.7	C13—C12—H12A	119.5
C1—C2—H2A	119.7	C11—C12—H12A	119.5
C2—C3—C4	118.0 (3)	C12—C13—C8	121.7 (2)
C2—C3—H3A	121.0	C12—C13—H13A	119.1
C4—C3—H3A	121.0	C8—C13—H13A	119.1
F1—C4—C5	119.0 (3)	C7—C14—Cl2	122.9 (2)
F1—C4—C3	118.1 (3)	C7—C14—Cl1	124.2 (2)
C5—C4—C3	122.9 (3)	Cl2—C14—Cl1	112.87 (16)
C4—C5—C6	118.5 (3)	N3—C15—H15A	109.5
C4—C5—H5A	120.8	N3—C15—H15B	109.5
C6—C5—H5A	120.8	H15A—C15—H15B	109.5
C5—C6—C1	120.5 (3)	N3—C15—H15C	109.5
C5—C6—H6A	119.8	H15A—C15—H15C	109.5
C1—C6—H6A	119.8	H15B—C15—H15C	109.5
C14—C7—N2	114.0 (2)	N3—C16—H16A	109.5
C14—C7—C8	123.4 (2)	N3—C16—H16B	109.5
N2—C7—C8	122.5 (2)	H16A—C16—H16B	109.5
C9—C8—C13	117.5 (2)	N3—C16—H16C	109.5
C9—C8—C7	122.0 (2)	H16A—C16—H16C	109.5
C13—C8—C7	120.6 (2)	H16B—C16—H16C	109.5
C10—C9—C8	121.5 (3)	N2—N1—C1	113.2 (2)
C10—C9—H9A	119.2	N1—N2—C7	114.8 (2)
C8—C9—H9A	119.2	C11—N3—C15	121.0 (2)
C9—C10—C11	121.4 (2)	C11—N3—C16	120.9 (2)
C9—C10—H10A	119.3	C15—N3—C16	118.0 (2)
C11—C10—H10A	119.3

C6—C1—C2—C3	2.2 (4)	N3—C11—C12—C13	178.6 (3)
N1—C1—C2—C3	−177.5 (2)	C10—C11—C12—C13	−1.4 (4)
C1—C2—C3—C4	−0.6 (4)	C11—C12—C13—C8	1.1 (4)
C2—C3—C4—F1	179.3 (3)	C9—C8—C13—C12	−0.1 (4)
C2—C3—C4—C5	−0.7 (5)	C7—C8—C13—C12	−179.7 (3)
F1—C4—C5—C6	−179.6 (3)	N2—C7—C14—Cl2	−177.0 (2)
C3—C4—C5—C6	0.4 (6)	C8—C7—C14—Cl2	0.6 (4)
C4—C5—C6—C1	1.2 (5)	N2—C7—C14—Cl1	2.1 (3)
C2—C1—C6—C5	−2.5 (5)	C8—C7—C14—Cl1	179.6 (2)
N1—C1—C6—C5	177.1 (3)	C2—C1—N1—N2	−179.9 (2)
C14—C7—C8—C9	63.2 (4)	C6—C1—N1—N2	0.4 (4)
N2—C7—C8—C9	−119.4 (3)	C1—N1—N2—C7	−178.6 (2)
C14—C7—C8—C13	−117.3 (3)	C14—C7—N2—N1	−172.0 (2)
N2—C7—C8—C13	60.1 (3)	C8—C7—N2—N1	10.4 (3)
C13—C8—C9—C10	−0.4 (4)	C10—C11—N3—C15	13.1 (4)
C7—C8—C9—C10	179.1 (3)	C12—C11—N3—C15	−166.9 (3)
C8—C9—C10—C11	0.0 (4)	C10—C11—N3—C16	−170.4 (3)
C9—C10—C11—N3	−179.1 (3)	C12—C11—N3—C16	9.6 (4)
C9—C10—C11—C12	0.9 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—Cl1···Cg1ⁱ	1.72 (1)	3.93 (1)	3.882 (3)	76 (1)

Symmetry code: (i) x−1, y, z.

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

A···B	Distance	Symmetry operation for B
H15B···H16B	2.45	-1 + x, y, z
Cl1···N3	3.409 (3)	-1/2 - x, 1 - y, 1/2 + z
C12···H6A	2.97	1/2 - x, 1 - y, -1/2 + z
Cl2···H13A	2.96	-1 + x, y, z
F1···H10A	2.66	3/2 + x, 3/2 - y, 1 - z
H3A···H2A	2.53	1/2 + x, 3/2 - y, 1 - z

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

Contact	Percentage contribution
H···H	33.3
Cl···H/H···Cl	22.9
C···H/H···C	15.5
F···H/H···F	9.0
N···H/H···N	4.9
C···C	4.7
Cl···C/C···Cl	2.7
N···C/C···N	2.0
Cl···N/N···Cl	2.0
Cl···F/F···Cl	1.9
C···F/F···C	0.8
F···N/N···F	0.3

Funding information

This work was funded by the Science Development Foundation under the President of the Republic of Azerbaijan, grant No. EIF– BGM-4-RFTF-1/2017–21/13/4, and RFBR grant No.18–53-06006.

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