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

Shikhaliyev, N.Q.; Özkaraca, K.; Akkurt, M.; Bagirova, X.N.; Suleymanova, G.T.; Abdulov, M.S.; Mlowe, S.

doi:10.1107/S2056989021010756

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 11| November 2021| Pages 1158-1163

https://doi.org/10.1107/S2056989021010756

Open

access

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

Namiq Q. Shikhaliyev,^a Kadiriye Özkaraca,^b Mehmet Akkurt,^c Xanim N. Bagirova,^a Gulnar T. Suleymanova,^a Mirjalil S. Abdulov ^a and Sixberth Mlowe ^d ^*

^aOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan, ^bInstitute of Natural and Applied Science, Erciyes University, 38039 Kayseri, 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 8 October 2021; accepted 18 October 2021; online 26 October 2021)

In the title compound, C₁₄H₇Cl₄FN₂, the dihedral angle between the 4-fluorophenyl ring and the 2,4-dichlorophenyl ring is 46.03 (19)°. In the crystal, the molecules are linked by C—H⋯N interactions along the a-axis direction, forming a C(6) chain. The molecules are further connected by C—Cl⋯π interactions and face-to-face π–π stacking interactions, forming ribbons along the a-axis direction. Hirshfeld surface analysis indicates that the greatest contributions to the crystal packing are from Cl⋯H/H⋯Cl (35.1%), H⋯H (10.6%), C⋯C (9.7%), Cl⋯Cl (9.4%) and C⋯H/H⋯C (9.2%) interactions.

Keywords: crystal structure; short inter HL⋯HL contact; C—Cl⋯π interactions; face-to-face π–π stacking interactions; Hirshfeld surface analysis.

CCDC reference: 2116300

1. Chemical context

Azo dyes find numerous applications in a diversity of areas, including as antimicrobial agents, in molecular recognition, optical data storage, molecular switches, non-linear optics, liquid crystals, dye-sensitized solar cells, color-changing materials, etc., mainly due to the possibility of the cis-to-trans isomerization and the chromophoric properties of the –N=N– synthon (Maharramov et al., 2018 ; Viswanathan et al., 2019 ). Not only azo-hydrazone tautomerisim, but also E/Z isomerization are important phenomena in the synthetic chemistry of azo dyes (Ma et al., 2017a ,b ; Mahmoudi et al., 2018a ,b ). The design of azo dyes with functional groups led to multifunctional ligands, the corresponding transition-metal complexes of which have been used effectively as catalysts in C—C coupling and oxidation reactions (Ma et al., 2020 , 2021 ; Mahmudov et al., 2013 ; Mizar et al., 2012 ). Moreover, the functional properties of azo dyes can be improved by attaching substituents with non-covalent bond donor or acceptor site(s) 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 attached halogen-bond donor centres to the –N=N– moiety, leading to a new azo dye, (E)-1-[2,2-dichloro-1-(4-fluorophenyl)ethenyl]-2-(2,4-dichlorophenyl)diazene, which provides multiple intermolecular non-covalent interactions.

2. Structural commentary

In the title compound, (Fig. 1), the dihedral angle between the 4-fluorophenyl ring C3–C8 and the 2,4-dichlorophenyl ring C9–C14 is 46.0 (2)°. The N2/N1/C1/C2/Cl1/Cl2 moiety is approximately planar, with a maximum deviation of 0.029 (1) Å for Cl1, and makes dihedral angles of 50.53 (18) and 11.75 (18)° with the C3–C8 and C9–C14 rings, respectively. In the molecule, the aromatic ring and olefin synthon adopt a trans-configuration with respect to the N=N double bond and are almost coplanar with a C1—N1=N2—C9 torsion angle of 179.1 (4)°.

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

In the crystal, the molecules are linked by C—H⋯N interactions along the a-axis direction, forming a C(6) chain (Table 1; Fig. 2; Bernstein et al., 1995 ). Furthermore, molecules are connected by C—Cl⋯Cg2 interactions (Table 1) and face-to-face π-π stacking interactions [Cg1⋯Cg1ⁱ = 3.873 (3) Å, slippage = 1.831 Å; Cg2⋯Cg2ⁱ = 3.872 (3) Å, slippage = 1.554 Å; symmetry codes: (i) x − 1, y, z;; (ii) x + 1, y, z; where Cg1 and Cg2 are the centroids of the 4-fluorophenyl (C3–C8) and 2,4-dichlorophenyl ring (C9–C14) rings, respectively], forming ribbons along the a-axis direction (Figs. 2, 3 and 4).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the 2,4-dichlorophenyl ring (C9–C14).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N2ⁱ	0.95	2.53	3.265 (5)	134
C12—Cl4⋯Cg2ⁱⁱ	1.735 (5)	3.920 (3)	3.569 (6)	66.51 (18)
Symmetry codes: (i) ; (ii) x+1, y, z.

Figure 2
A general view of the intermolecular C—H⋯N and C—Cl⋯π interactions and π–π stacking interactions, shown as dashed lines. Symmetry codes: (a) − 1 + x, y, z; (b) 1 + x, y, z.

Figure 3
The crystal packing of the title compound viewed along the b axis with intermolecular C—H⋯N and C—Cl⋯π interactions and π–π stacking interactions shown as dashed lines.

Figure 4
The crystal packing of the title compound viewed along the c axis with intermolecular C—H⋯N and C—Cl⋯π interactions and π-π stacking interactions shown as dashed lines.

4. Hirshfeld surface analysis

Crystal Explorer (Turner et al., 2017 ) was used to perform a Hirshfeld surface analysis and generate the associated two-dimensional fingerprint plots, with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed colour scale of −0.1450 (red) to 1.1580 (blue) a.u (Fig. 5). In the Hirshfeld surface mapped over d_norm (Fig. 5), the bright-red spots near atoms Cl1, Cl3, H4, N2 and F1 indicate the short C—H⋯N, C—H⋯Cl and Cl⋯F contacts (Table 2). Other contacts are equal to or longer than the sum of van der Waals radii. The Hirshfeld surface of the title compound mapped over the electrostatic potential (Spackman et al., 2008 ) is shown in Fig. 6. The positive electrostatic potential (blue regions) over the surface indicates hydrogen-donor potential, whereas the hydrogen-bond acceptors are represented by negative electrostatic potential (red regions).

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

Contact	Distance	Symmetry operation
Cl1⋯H11	3.06	−1 + x, 1 + y, z
H4⋯N2	2.53	−1 + x, y, z
Cl1⋯F1	3.016 (3)	−1 − x, $[{1\over 2}]$ + y, 1 − z
H5⋯H7	2.55	−x, − $[{1\over 2}]$ + y, 1 − z
Cl4⋯H13	2.95	2 − x, − $[{1\over 2}]$ + y, 2 − z
Cl4⋯H14	2.93	1 − x, − $[{1\over 2}]$ + y, 2 − z
Cl3⋯F1	3.116 (3)	−x, − $[{1\over 2}]$ + y, 1 − z

Figure 5
(a) Front and (b) back sides of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1450 to 1.1580 a.u.

Figure 6
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.

The overall two-dimensional fingerprint plot and those delineated into Cl⋯H/H⋯Cl, H⋯H, C⋯C, Cl⋯Cl and C⋯H/H⋯C contacts in the title molecule are illustrated in Fig. 7. The most important interaction is Cl⋯H/H⋯Cl, contributing 35.1% to the overall crystal packing (Fig. 7b). The secondary important H⋯H and C⋯C interactions contribute 10.6% (Fig. 7c) and 9.7% (Fig. 7d), respectively, to the Hirshfeld surface. The remaining contributions for the title compound are from Cl⋯Cl, C⋯H/H⋯C, Cl⋯F/F⋯Cl, Cl⋯C/C⋯Cl, F⋯H/H⋯F, N⋯H/H⋯N, N⋯N and F⋯C/ C⋯F contacts, which are less than 9.7% and have a negligible effect on the packing. The percentage contributions of all interactions are listed in Table 3.

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

Contact	Percentage contribution
Cl⋯H/H⋯Cl	35.1
H⋯H	10.6
C⋯C	9.7
Cl⋯Cl	9.4
C⋯H/H⋯C	9.2
Cl⋯F/F⋯Cl	6.7
Cl⋯C/C⋯Cl	5.0
F⋯H/H⋯F	5.0
N⋯H/H⋯N	4.4
N⋯C/C⋯N	3.5
F⋯F	0.9
N⋯N	0.3
F⋯C/C⋯F	0.1

Figure 7
The full two-dimensional fingerprint plot for the title compound and those delineated into (b) Cl⋯H/H⋯Cl (35.1%), (c) H⋯H (10.6%), (d) C⋯C (9.7%), (e) Cl⋯Cl (9.4%) and (f) C⋯H/H⋯C (9.2%) interactions.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.41, update of November 2019; Groom et al., 2016 ) for the (E)-1-(2,2-dichloro-1-phenylethenyl)-2-phenyldiazene unit resulted in 28 hits. Nine compounds are closely related to the title compound, viz. LEQXOX (I; Shikhaliyev et al., 2018 ), LEQXIR (II; Shikhaliyev et al., 2018), XIZREG (III; Atioğlu et al., 2019 ), HODQAV (IV; Shikhaliyev et al., 2019 ), HONBUK (V; Akkurt et al., 2019 ), HONBOE (VI; Akkurt et al., 2019), DULTAI (VII; Özkaraca et al., 2020b ), GUPHIL (VIII; Özkaraca et al., 2020a ) and EBUCUD (IX; Shikhaliyev et al., 2021 ).

In the crystals of I and II, the dihedral angles between the aromatic rings are 56.18 (12) and 60.31 (14)°, respectively. In I, C—H⋯N and short Cl⋯Cl contacts are observed and in II, C—H⋯N and C—H⋯O hydrogen bonds and short C—Cl⋯O contacts occur. In III, the benzene rings form a dihedral angle of 63.29 (8)° and the molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In IV, the benzene rings make a dihedral angle of 56.13 (13)°. Molecules are stacked in columns along the a-axis direction via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further consolidated by short Cl⋯Cl contacts. In V and VI, the aromatic rings form dihedral angles of 60.9 (2) and 64.1 (2)°, respectively. In the crystals, molecules are linked through weak X⋯Cl contacts (X = Cl for V and Br for VI), 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 VII, the dihedral angle between the two aromatic rings is 64.12 (14)°. The crystal structure is stabilized by a short C—H⋯Cl contact, C—Cl⋯π and van der Waals interactions. In VIII, the benzene rings subtend a dihedral angle of 77.07 (10)°. In the crystal, molecules are associated into inversion dimers via short Cl⋯Cl contacts [3.3763 (9) Å]. In IX, the asymmetric unit comprises two similar molecules, in which the dihedral angles between the two aromatic rings are 70.1 (3) and 73.2 (2)°. The crystal structure features short C—H⋯Cl and C—H⋯O contacts and C—H⋯π and van der Waals interactions.

6. Synthesis and crystallization

The title dye was synthesized according to the reported method (Shikhaliyev et al., 2018, 2019 ). A 20 mL screw-neck vial was charged with DMSO (10 mL), (E)-1-(2,4-dichlorophenyl)-2-(4-fluorobenzylidene)hydrazine (283 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 (44%); m.p. 345 K. Analysis calculated for C₁₄H₇Cl₄FN₂ (M = 364.02): C 46.19, H 1.94, N 7.70; found: C 46.11, H 1.98, N 7.67%. ¹H NMR (300 MHz, CDCl₃) δ 7.31–7.83 (7H, Ar). ¹³C NMR (75 MHz, CDCl₃) δ 114.89, 115.12, 115.41, 115.74, 115.97, 118.33, 127.73, 128.08, 128.67, 129.17, 130.48, 132.04, 132.15 and 136.83. ESI–MS: m/z: 365.11 [M + H]⁺.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 4. The Moscow synchrotron radiation source was used for the data collection. H atoms were positioned geometrically and treated as riding atoms where C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C). Five outliers $[\overline{3}]$ 2 2, $[\overline{3}]$ $[\overline{2}]$ 2, $[\overline{2}]$ 11 3, $[\overline{2}]$ 2 1 and $[\overline{2}]$ $[\overline{2}]$ 1 were omitted during the final refinement cycle because of large differences between observed and calculated intensities.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₄H₇Cl₄FN₂
M_r	364.02
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	3.8720 (8), 10.434 (2), 18.138 (4)
β (°)	95.03 (3)
V (Å³)	730.0 (3)
Z	2
Radiation type	Synchrotron, λ = 0.79475 Å
μ (mm⁻¹)	1.10
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.800, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	8595, 3120, 2972
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.106, 1.09
No. of reflections	3120
No. of parameters	191
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.30
Absolute structure	Flack x determined using 1318 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.04 (2)
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: 2116300

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021010756/vm2255sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021010756/vm2255Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021010756/vm2255Isup3.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: 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)-1-[2,2-Dichloro-1-(4-fluorophenyl)ethenyl]-2-(2,4-dichlorophenyl)diazene top

Crystal data top

C₁₄H₇Cl₄FN₂	F(000) = 364
M_r = 364.02	D_x = 1.656 Mg m⁻³
Monoclinic, P2₁	Synchrotron radiation, λ = 0.79475 Å
a = 3.8720 (8) Å	Cell parameters from 600 reflections
b = 10.434 (2) Å	θ = 2.8–28.0°
c = 18.138 (4) Å	µ = 1.12 mm⁻¹
β = 95.03 (3)°	T = 100 K
V = 730.0 (3) Å³	Prism, colourless
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection top

Rayonix SX165 CCD diffractometer	2972 reflections with I > 2σ(I)
/f scan	R_int = 0.027
Absorption correction: multi-scan (Scala; Evans, 2006)	θ_max = 31.0°, θ_min = 2.5°
T_min = 0.800, T_max = 0.880	h = −5→5
8595 measured reflections	k = −12→13
3120 independent reflections	l = −23→23

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0549P)² + 0.7552P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.036	(Δ/σ)_max < 0.001
wR(F²) = 0.106	Δρ_max = 0.61 e Å⁻³
S = 1.09	Δρ_min = −0.30 e Å⁻³
3120 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
191 parameters	Extinction coefficient: 0.044 (8)
1 restraint	Absolute structure: Flack x determined using 1318 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Hydrogen site location: inferred from neighbouring sites	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	−0.3214 (3)	0.89506 (12)	0.70389 (6)	0.0309 (3)
Cl2	−0.0221 (4)	0.81658 (13)	0.84672 (7)	0.0392 (3)
Cl3	0.2392 (3)	0.19949 (12)	0.70702 (6)	0.0334 (3)
Cl4	0.8795 (3)	0.10530 (13)	0.97679 (6)	0.0340 (3)
F1	−0.2885 (9)	0.5192 (3)	0.42861 (16)	0.0383 (7)
N1	0.1181 (11)	0.5745 (4)	0.7820 (2)	0.0281 (9)
N2	0.1962 (11)	0.4658 (4)	0.7569 (2)	0.0273 (8)
C1	−0.0396 (12)	0.6583 (5)	0.7275 (3)	0.0274 (9)
C2	−0.1180 (12)	0.7756 (5)	0.7555 (3)	0.0293 (10)
C3	−0.1089 (12)	0.6232 (5)	0.6480 (2)	0.0255 (9)
C4	−0.2763 (12)	0.5073 (5)	0.6280 (3)	0.0267 (9)
H4	−0.347529	0.452035	0.665430	0.032*
C5	−0.3391 (13)	0.4726 (5)	0.5540 (3)	0.0288 (10)
H5	−0.455606	0.394787	0.540530	0.035*
C6	−0.2292 (13)	0.5531 (5)	0.5008 (3)	0.0295 (10)
C7	−0.0634 (12)	0.6678 (5)	0.5181 (3)	0.0289 (10)
H7	0.006934	0.722093	0.480114	0.035*
C8	−0.0016 (12)	0.7022 (5)	0.5920 (3)	0.0281 (9)
H8	0.114818	0.780287	0.604727	0.034*
C9	0.3594 (11)	0.3839 (5)	0.8125 (2)	0.0261 (9)
C10	0.3960 (12)	0.2556 (5)	0.7935 (3)	0.0265 (9)
C11	0.5577 (13)	0.1679 (5)	0.8440 (3)	0.0275 (9)
H11	0.581566	0.080365	0.830976	0.033*
C12	0.6813 (13)	0.2120 (5)	0.9131 (3)	0.0291 (10)
C13	0.6495 (12)	0.3405 (5)	0.9334 (3)	0.0289 (10)
H13	0.736480	0.368972	0.981195	0.035*
C14	0.4893 (13)	0.4255 (5)	0.8827 (3)	0.0300 (10)
H14	0.467401	0.513039	0.895888	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0349 (6)	0.0218 (6)	0.0353 (6)	0.0044 (5)	−0.0005 (4)	−0.0001 (4)
Cl2	0.0528 (8)	0.0325 (7)	0.0312 (6)	0.0116 (6)	−0.0029 (5)	−0.0065 (5)
Cl3	0.0426 (6)	0.0263 (6)	0.0301 (6)	0.0037 (5)	−0.0030 (4)	−0.0036 (4)
Cl4	0.0385 (6)	0.0315 (7)	0.0318 (5)	0.0058 (5)	0.0018 (4)	0.0071 (5)
F1	0.0507 (18)	0.0339 (18)	0.0296 (15)	0.0000 (14)	0.0002 (12)	−0.0029 (12)
N1	0.031 (2)	0.022 (2)	0.032 (2)	0.0034 (16)	0.0042 (15)	−0.0011 (15)
N2	0.028 (2)	0.025 (2)	0.0291 (19)	0.0041 (15)	0.0052 (15)	0.0005 (15)
C1	0.027 (2)	0.023 (2)	0.033 (2)	0.0038 (17)	0.0032 (17)	0.0004 (18)
C2	0.027 (2)	0.027 (3)	0.034 (2)	0.0060 (18)	0.0015 (18)	−0.0031 (19)
C3	0.027 (2)	0.020 (2)	0.029 (2)	0.0037 (17)	0.0026 (16)	0.0005 (17)
C4	0.028 (2)	0.019 (2)	0.034 (2)	0.0029 (17)	0.0062 (17)	0.0004 (17)
C5	0.029 (2)	0.022 (2)	0.036 (2)	0.0031 (17)	0.0024 (18)	0.0000 (18)
C6	0.030 (2)	0.030 (3)	0.028 (2)	0.0053 (18)	0.0009 (17)	−0.0018 (17)
C7	0.028 (2)	0.025 (3)	0.033 (2)	0.0024 (17)	0.0034 (17)	0.0035 (18)
C8	0.028 (2)	0.023 (2)	0.033 (2)	0.0029 (19)	0.0019 (16)	0.0018 (19)
C9	0.024 (2)	0.026 (2)	0.029 (2)	0.0012 (18)	0.0052 (15)	0.0031 (18)
C10	0.029 (2)	0.024 (2)	0.027 (2)	0.0040 (18)	0.0044 (17)	−0.0001 (17)
C11	0.029 (2)	0.024 (3)	0.030 (2)	0.0045 (17)	0.0046 (16)	0.0013 (17)
C12	0.029 (2)	0.027 (3)	0.032 (2)	0.0030 (19)	0.0055 (17)	0.0057 (19)
C13	0.031 (2)	0.029 (3)	0.026 (2)	−0.0010 (19)	0.0017 (17)	−0.0041 (18)
C14	0.035 (2)	0.024 (3)	0.031 (2)	0.0021 (18)	0.0043 (18)	0.0002 (18)

Geometric parameters (Å, º) top

Cl1—C2	1.709 (5)	C5—H5	0.9500
Cl2—C2	1.718 (5)	C6—C7	1.381 (7)
Cl3—C10	1.733 (5)	C7—C8	1.388 (7)
Cl4—C12	1.735 (5)	C7—H7	0.9500
F1—C6	1.357 (6)	C8—H8	0.9500
N1—N2	1.269 (6)	C9—C10	1.393 (7)
N1—C1	1.416 (6)	C9—C14	1.398 (7)
N2—C9	1.426 (6)	C10—C11	1.403 (7)
C1—C2	1.369 (7)	C11—C12	1.380 (7)
C1—C3	1.490 (6)	C11—H11	0.9500
C3—C8	1.399 (7)	C12—C13	1.399 (7)
C3—C4	1.404 (7)	C13—C14	1.384 (7)
C4—C5	1.390 (7)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.375 (7)

N2—N1—C1	113.8 (4)	C8—C7—H7	120.7
N1—N2—C9	112.8 (4)	C7—C8—C3	120.8 (5)
C2—C1—N1	112.9 (4)	C7—C8—H8	119.6
C2—C1—C3	123.4 (4)	C3—C8—H8	119.6
N1—C1—C3	123.6 (4)	C10—C9—C14	119.2 (4)
C1—C2—Cl1	123.8 (4)	C10—C9—N2	116.7 (4)
C1—C2—Cl2	122.9 (4)	C14—C9—N2	124.1 (5)
Cl1—C2—Cl2	113.3 (3)	C9—C10—C11	121.0 (4)
C8—C3—C4	118.7 (4)	C9—C10—Cl3	120.9 (4)
C8—C3—C1	121.2 (4)	C11—C10—Cl3	118.1 (4)
C4—C3—C1	120.1 (4)	C12—C11—C10	118.4 (5)
C5—C4—C3	120.8 (4)	C12—C11—H11	120.8
C5—C4—H4	119.6	C10—C11—H11	120.8
C3—C4—H4	119.6	C11—C12—C13	121.8 (5)
C6—C5—C4	118.6 (5)	C11—C12—Cl4	119.3 (4)
C6—C5—H5	120.7	C13—C12—Cl4	118.9 (4)
C4—C5—H5	120.7	C14—C13—C12	118.9 (4)
F1—C6—C5	118.8 (5)	C14—C13—H13	120.5
F1—C6—C7	118.7 (5)	C12—C13—H13	120.5
C5—C6—C7	122.5 (5)	C13—C14—C9	120.7 (5)
C6—C7—C8	118.7 (5)	C13—C14—H14	119.6
C6—C7—H7	120.7	C9—C14—H14	119.6

C1—N1—N2—C9	179.1 (4)	C6—C7—C8—C3	−0.8 (7)
N2—N1—C1—C2	−179.2 (4)	C4—C3—C8—C7	0.9 (7)
N2—N1—C1—C3	0.0 (7)	C1—C3—C8—C7	179.1 (4)
N1—C1—C2—Cl1	−178.0 (4)	N1—N2—C9—C10	168.4 (4)
C3—C1—C2—Cl1	2.8 (7)	N1—N2—C9—C14	−13.2 (7)
N1—C1—C2—Cl2	1.7 (6)	C14—C9—C10—C11	0.6 (7)
C3—C1—C2—Cl2	−177.6 (4)	N2—C9—C10—C11	179.1 (4)
C2—C1—C3—C8	50.4 (7)	C14—C9—C10—Cl3	180.0 (4)
N1—C1—C3—C8	−128.7 (5)	N2—C9—C10—Cl3	−1.6 (6)
C2—C1—C3—C4	−131.3 (5)	C9—C10—C11—C12	−0.2 (7)
N1—C1—C3—C4	49.5 (6)	Cl3—C10—C11—C12	−179.6 (4)
C8—C3—C4—C5	−0.9 (7)	C10—C11—C12—C13	−0.1 (7)
C1—C3—C4—C5	−179.2 (4)	C10—C11—C12—Cl4	179.5 (4)
C3—C4—C5—C6	1.0 (7)	C11—C12—C13—C14	0.1 (7)
C4—C5—C6—F1	179.7 (4)	Cl4—C12—C13—C14	−179.6 (4)
C4—C5—C6—C7	−0.9 (7)	C12—C13—C14—C9	0.3 (7)
F1—C6—C7—C8	−179.8 (4)	C10—C9—C14—C13	−0.7 (7)
C5—C6—C7—C8	0.9 (7)	N2—C9—C14—C13	−179.0 (4)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C9–C14 2,4-dichlorophenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N2ⁱ	0.95	2.53	3.265 (6)	134
C12—Cl4···Cg2ⁱⁱ	1.74 (1)	3.92 (1)	3.569 (6)	66 (1)

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

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

Contact	Distance	Symmetry operation
Cl1···H11	3.06	- 1 + x, 1 + y, z
H4···N2	2.53	- 1 + x, y, z
Cl1···F1	3.016 (3)	- 1 - x, 1/2 + y, 1 - z
H5···H7	2.55	- x, - 1/2 + y, 1 - z
Cl4···H13	2.95	2 - x, - 1/2 + y, 2 - z
Cl4···H14	2.93	1 - x, - 1/2 + y, 2 - z
Cl3···.F1	3.116 (3)	- x, - 1/2 + y, 1 - z

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

Contact	Percentage contribution
Cl···H/H···Cl	35.1
H···H	10.6
C···C	9.7
Cl···Cl	9.4
C···H/H···C	9.2
Cl···F/F···Cl	6.7
Cl···C/C···Cl	5.0
F···H/H···F	5.0
N···H/H···N	4.4
N···C/C···N	3.5
F···F	0.9
N···N	0.3
F···C/C···F	0.1

Acknowledgements

The author's contributions are as follows. Conceptualization, NQS, MA and SM; synthesis, XNB, GTS and MSA; X-ray analysis, KÖ and MA; writing (review and editing of the manuscript), funding acquisition, NQS, XNB, GTS and MSA; 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).

References

Akkurt, M., Shikhaliyev, N. Q., Suleymanova, G. T., Babayeva, G. V., Mammadova, G. Z., Niyazova, A. A., Shikhaliyeva, I. M. & Toze, F. A. A. (2019). Acta Cryst. E75, 1199–1204. Web of Science CSD CrossRef IUCr Journals 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
Battye, T. G. G., Kontogiannis, L., Johnson, O., Powell, H. R. & Leslie, A. G. W. (2011). Acta Cryst. D67, 271–281. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Doyle, R. A. (2011). Marccd software manual. Rayonix L. L. C., Evanston, IL 60201, USA. Google Scholar
Evans, P. (2006). Acta Cryst. D62, 72–82. 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
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., Kuznetsov, M. L., Demukhamedova, S. D., Alieva, I. N., Godjaev, N. M., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2020a). CrystEngComm, 22, 628–633. Web of Science CSD CrossRef CAS Google Scholar
Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020b). Chem. Eur. J. 26, 14833–14837. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kopylovich, M. N., Mahmudov, K. T., Mizar, A. & Pombeiro, A. J. L. (2011). Chem. Commun. 47, 7248–7250. Web of Science CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Maharramov, A. M., Guseinov, F. I., Kopylovich, M. N., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2017a). J. Mol. Catal. A Chem. 426, 526–533. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Gurbanov, A. V., Sutradhar, M., Kopylovich, M. N., Mahmudov, K. T., Maharramov, A. M., Guseinov, F. I., Zubkov, F. I. & Pombeiro, A. J. L. (2017b). Mol. Catal. 428, 17–23. Web of Science CSD CrossRef CAS Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Coord. Chem. Rev. 437, 213859. Web of Science CrossRef Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 423, 213482. Web of Science CrossRef 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., Afkhami, F. A., Castiñeiras, A., García-Santos, I., Gurbanov, A., Zubkov, F. I., Mitoraj, M. P., Kukułka, M., Sagan, F., Szczepanik, D. W., Konyaeva, I. A. & Safin, D. A. (2018a). Inorg. Chem. 57, 4395–4408. Web of Science CSD CrossRef CAS PubMed Google Scholar
Mahmoudi, G., Zangrando, E., Mitoraj, M. P., Gurbanov, A. V., Zubkov, F. I., Moosavifar, M., Konyaeva, I. A., Kirillov, A. M. & Safin, D. A. (2018b). New J. Chem. 42, 4959–4971. Web of Science CSD CrossRef CAS Google Scholar
Mahmudov, K. T., Gurbanov, A. V., Aliyeva, V. A., Resnati, G. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 418, 213381. Web of Science CrossRef Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Haukka, M., Mahmudova, G. S., Esmaeila, E. F., Chyragov, F. M. & Pombeiro, A. J. L. (2013). J. Mol. Struct. 1048, 108–112. Web of Science CSD CrossRef CAS 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
Özkaraca, K., Akkurt, M., Shikhaliyev, N. Q., Askerova, U. F., Suleymanova, G. T., Mammadova, G. Z. & Shadrack, D. M. (2020a). Acta Cryst. E76, 1251–1254. Web of Science CSD CrossRef IUCr Journals Google Scholar
Özkaraca, K., Akkurt, M., Shikhaliyev, N. Q., Askerova, U. F., Suleymanova, G. T., Shikhaliyeva, I. M. & Bhattarai, A. (2020b). Acta Cryst. E76, 811–815. 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 CSD 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., Ahmadova, N. E., Gurbanov, A. V., Maharramov, A. M., Mammadova, G. Z., Nenajdenko, V. G., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Dyes Pigments, 150, 377–381. Web of Science CSD CrossRef CAS Google Scholar
Shikhaliyev, N. Q., Atioğlu, Z., Akkurt, M., Qacar, A. M., Askerov, R. K. & Bhattarai, A. (2021). Acta Cryst. E77, 965–970. CSD 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
Shikhaliyev, N. Q., Kuznetsov, M. L., Maharramov, A. M., Gurbanov, A. V., Ahmadova, N. E., Nenajdenko, V. G., Mahmudov, K. T. & Pombeiro, A. J. L. (2019). CrystEngComm, 21, 5032–5038. Web of Science CSD CrossRef CAS Google Scholar
Shixaliyev, N. Q., Gurbanov, A. V., Maharramov, A. M., Mahmudov, K. T., Kopylovich, M. N., Martins, L. M. D. R. S., Muzalevskiy, V. M., Nenajdenko, V. G. & Pombeiro, A. J. L. (2014). New J. Chem. 38, 4807–4815. Web of Science CSD CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. 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
Viswanathan, A., Kute, D., Musa, A., Konda Mani, S., Sipilä, V., Emmert-Streib, F., Zubkov, F. I., Gurbanov, A. V., Yli-Harja, O. & Kandhavelu, M. (2019). Eur. J. Med. Chem. 166, 291–303. Web of Science CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.