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

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

doi:10.1107/S2056989019000707

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 237-241

https://doi.org/10.1107/S2056989019000707

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

Zeliha Atioğlu,^a Mehmet Akkurt,^b Namiq Q. Shikhaliyev,^c Gulnar T. Suleymanova,^c Khanim N. Bagirova ^c and Flavien A. A. Toze ^d ^*

^aİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cOrganic Chemistry Department, Baku State University, Z. Xalilov str. 23, Az, 1148 Baku, Azerbaijan, and ^dDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of Cameroon
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 21 November 2018; accepted 15 January 2019; online 18 January 2019)

In the title compound, C₁₄H₈Cl₂FN₃O₂, the 4-fluorophenyl ring and the nitro-substituted benzene ring form a dihedral angle of 63.29 (8)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds into chains running parallel to the c axis. The crystal packing is further stabilized by C—Cl⋯π, C—F⋯π and N—O⋯π interactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯O/O⋯H (15.5%), H⋯H (15.3%), Cl⋯H/H⋯Cl (13.8%), C⋯H/H⋯C (9.5%) and F⋯H/H⋯F (8.2%) interactions.

Keywords: crystal structure; 4-fluorophenyl ring; nitro-substituted benzene ring; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1876976

1. Chemical context

Non-covalent 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 structures of the molecule, its stabilization and particular properties (Akbari Afkhami et al., 2017 ; Desiraju, 1995 ; Gurbanov et al., 2018 ; Hazra et al., 2018 ; Jlassi et al., 2014 ; Kvyatkovskaya et al., 2017 ; Legon, 2017 , Maharramov et al., 2009 , 2018 ; Mahmoudi et al., 2018a ,b ,c ; Mahmudov et al., 2014 , 2017 ; Mahmudov & Pombeiro, 2016 ; Scheiner 2013 ; Shikhaliyev et al., 2013 , 2018 ). On the other hand, azo dyes and related hydrazone ligands and their complexes have attracted attention over the past decades because of their potential biological, pharmacological and analytical applications (Borisova et al., 2018 ; Gadzhieva et al., 2006 ; Gurbanov et al., 2017 ; Shetnev & Zubkov, 2017 ). Herein we report the structure and non-covalent interactions of the title compound.

2. Structural commentary

The molecular conformation of the title compound (Fig. 1) is not planar, the 4-fluorophenyl ring and the nitro-substituted benzene ring forming a dihedral angle of 63.29 (8)°. The C2—C1—N1—N2, C1—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 are −1.1 (2), 178.86 (13), 174.62 (14), −176.19 (11), 2.9 (2), 5.1 (2) and 63.4 (2)°, respectively. Bond lengths (Allen et al., 1987 ) and angles are within normal ranges and are comparable to those observed in related structures, viz: (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 displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, molecules are linked by C—H⋯O hydrogen bonds into chains parallel to the c axis (Table 1; Fig. 2). The crystal packing is further stabilized by weak C—Cl⋯π [Cl⋯Cg2(x, $[5\over2]$ − y, $[1\over2]$ + z) = 3.6792 (8) Å], C—F⋯π [F⋯Cg1(1 − x, 2 − y, 2 − z) = 3.5408 (16) Å] and N—O⋯π interactions [O⋯Cg1(x, $[3\over2]$ − y, − $[1\over2]$ + z) = 3.9815 (16) Å] where Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1ⁱ	0.93	2.52	3.369 (2)	152
Symmetry code: (i) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Crystal packing of the title compound, viewed down the a axis, showing the formation of chains parallel to the c axis through C—H⋯O hydrogen bonds (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. 3. 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.

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

Contact	Distance	Symmetry operation
(C8) Cl1⋯C8 (Cl1)	3.6040 (16)	2 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
(C13) H13⋯Cl1 (C8)	3.08	2 − x, 2 − y, 1 − z
(C8) Cl2⋯Cl2 (C8)	3.6506 (7)	2 − x, 2 − y, 2 − z
(C10) H10⋯O1 (N3)	2.52	x, $[{5\over 2}]$ − y, $[{1\over 2}]$ + z
(C4) F1⋯H11 (C11)	2.60	1 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
(C4) F1⋯H6 (C6)	2.56	x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z
(N3) O1⋯H3 (C3)	2.67	x, y, −1 + z
(C5) H5⋯O1 (N3)	2.74	1 − x, 2 − y, 1 − z
(N3) O1⋯H10 (C10)	2.52	x, $[{5\over 2}]$ − y, − $[{1\over 2}]$ + z
(F1) C4⋯C4 (F1)	3.541 (3)	1 − x, 2 − y, 2 − z

Figure 3
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1603 to 1.2420 a.u.

The percentage contributions of various contacts to the total Hirshfeld surface are shown in the two-dimensional fingerprint plots in Fig. 4. The reciprocal O⋯H/H⋯O interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.2 Å and contribute 15.5% to the Hirshfeld surface (Fig. 5b). The reciprocal Cl⋯H/H⋯Cl, C⋯H/H⋯C and F⋯H/H⋯F interactions (13.8, 9.5 and 8.2% contributions, respectively) are present as sharp symmetrical spikes at diagonal axes d_e + d_i ≃ 2.9, 3.0 and 2.4 Å, respectively (Fig. 5d–f). The small percentage contributions to the Hirshfeld surfaces from the various other interatomic contacts are listed in Table 3. Hirshfeld surface representations with the function d_norm plotted onto the surface for all interactions are shown in Fig. 5. The large number of O⋯H/H⋯O, H⋯H, Cl⋯H/H⋯Cl, C⋯H/H⋯C, F⋯H/H⋯F, Cl⋯Cl, N⋯H/H⋯N and Cl⋯C/C⋯Cl interactions suggest that van der Waals interactions and hydrogen bonding play a major role in the crystal packing (Hathwar et al., 2015 ). The shape-index of the Hirshfeld surface is a tool for visualizing the π–π stacking by the presence of adjacent red and blue triangles; if there are no such triangles, then there are no π–π interactions. The plot of the Hirshfeld surface mapped over shape-index shown in Fig. 6 clearly suggests that there are no π–π interactions in the title compound.

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

Contact	Percentage contribution
O⋯H/H⋯O	15.5
H⋯H	15.3
Cl⋯H/H⋯Cl	13.8
C⋯H/H⋯C	9.5
F⋯H/H⋯F	8.2
Cl⋯Cl	6.4
N⋯H/H⋯N	5.6
Cl⋯C/C⋯Cl	5.5
C⋯C	4.1
O⋯C/C⋯O	3.7
Cl⋯O/O⋯Cl	3.1
F⋯C/C⋯F	3.1
N⋯C/C⋯N	2.2
O⋯N/N⋯O	2.1
F⋯F	0.9
N⋯N	0.8

Figure 4
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) Cl⋯H/H⋯Cl, (e) C⋯H/H⋯C, (f) F⋯H/H⋯F, (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.

Figure 5
Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) all interactions, (b) O⋯H/H⋯O, (c) H⋯H, (d) Cl⋯H/H⋯Cl, (e) C⋯H/H⋯C, (f) F⋯H/H⋯F, (g) Cl⋯Cl, (h) N⋯H/H⋯N and (i) Cl⋯C/C⋯Cl interactions.

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

4. Synthesis and crystallization

The title compound was synthesized according to the method reported by Shikhaliyev et al. (2018). A 20 mL screw-neck vial was charged with DMSO (10 mL), (E)-1-(4-fluorophenyl)-2-(4-nitrobenzylidene)hydrazine (259 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 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 by 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). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Yield (62%); m.p. 421 K. Analysis calculated for C₁₄H₈Cl₂FN₃O₂ (M = 340.14): C, 49.44; H, 2.37; N, 12.35; found: C, 49.38; H, 2.40; N, 12.24%. ¹H NMR (300 MHz, CDCl₃) δ 8.32–8.29 (d, 2H, J = 9.21Hz), 7.81–7.77 (m 2H), 7.40–7.37 (d, 2H, J = 9.02Hz), 7.17–7.12 (t, 2H, J = 9.22Hz).¹³C NMR (75 MHz, CDCl₃) δ 166.69, 163.32, 150.43, 149.17, 147.95, 139.40, 131.26, 125.51, 125.39, 123.41, 116.42, 116.11. ESI–MS: m/z: 341.06 [M + H]⁺.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. C-bound H atoms were constrained to an ideal geometry with C—H = 0.93 Å and refined as riding with U_iso(H) = 1.2U_eq(C). Three outliers (100, 110, 200) were omitted in the last cycles of refinement.

Table 4
Experimental details

Crystal data
Chemical formula	C₁₄H₈Cl₂FN₃O₂
M_r	340.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	15.8644 (5), 7.2242 (2), 12.7595 (4)
β (°)	97.038 (2)
V (Å³)	1451.32 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.47
Crystal size (mm)	0.34 × 0.23 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.861, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	11383, 2851, 2359
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.05
No. of reflections	2851
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21
Computer programs: APEX3 and SAINT (Bruker, 2007 ), SHELXT2016 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1876976

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019000707/rz5248sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019000707/rz5248Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019000707/rz5248Isup3.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 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

(E)-1-[2,2-Dichloro-1-(4-nitrophenyl)ethenyl]-2-(4-fluorophenyl)diazene top

Crystal data top

C₁₄H₈Cl₂FN₃O₂	F(000) = 688
M_r = 340.13	D_x = 1.557 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.8644 (5) Å	Cell parameters from 4877 reflections
b = 7.2242 (2) Å	θ = 3.1–25.9°
c = 12.7595 (4) Å	µ = 0.47 mm⁻¹
β = 97.038 (2)°	T = 296 K
V = 1451.32 (8) Å³	Block, orange
Z = 4	0.34 × 0.23 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2359 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.019
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.0°, θ_min = 3.2°
T_min = 0.861, T_max = 0.925	h = −14→19
11383 measured reflections	k = −8→8
2851 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0427P)² + 0.3915P] where P = (F_o² + 2F_c²)/3
2851 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻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	0.97386 (3)	1.20992 (9)	0.70124 (4)	0.07088 (18)
Cl2	0.92856 (3)	1.13756 (8)	0.90771 (4)	0.06189 (17)
F1	0.47733 (7)	0.7105 (2)	1.03511 (10)	0.0765 (4)
O1	0.68767 (10)	1.0573 (2)	0.24070 (11)	0.0720 (4)
O2	0.80699 (11)	0.9169 (2)	0.23689 (11)	0.0788 (5)
N1	0.69628 (8)	0.95452 (19)	0.76270 (10)	0.0402 (3)
N2	0.76871 (8)	1.00408 (18)	0.80363 (10)	0.0390 (3)
N3	0.75395 (11)	0.9908 (2)	0.28420 (12)	0.0521 (4)
C1	0.64239 (9)	0.8985 (2)	0.83834 (12)	0.0365 (3)
C2	0.66658 (10)	0.8947 (2)	0.94654 (12)	0.0406 (4)
H2	0.720428	0.934987	0.974163	0.049*
C3	0.61096 (11)	0.8315 (3)	1.01287 (13)	0.0481 (4)
H3	0.626481	0.828004	1.085535	0.058*
C4	0.53205 (11)	0.7736 (3)	0.96946 (14)	0.0488 (4)
C5	0.50562 (11)	0.7772 (3)	0.86378 (15)	0.0539 (5)
H5	0.451398	0.737848	0.837092	0.065*
C6	0.56182 (10)	0.8409 (3)	0.79752 (13)	0.0485 (4)
H6	0.545439	0.845134	0.725037	0.058*
C7	0.82440 (9)	1.0572 (2)	0.73073 (12)	0.0379 (3)
C8	0.89916 (10)	1.1249 (2)	0.77426 (13)	0.0440 (4)
C9	0.80338 (9)	1.0366 (2)	0.61456 (12)	0.0364 (3)
C10	0.73747 (10)	1.1361 (2)	0.55905 (13)	0.0426 (4)
H10	0.704682	1.214863	0.595145	0.051*
C11	0.72030 (10)	1.1192 (2)	0.45128 (13)	0.0433 (4)
H11	0.675811	1.184705	0.414101	0.052*
C12	0.77022 (10)	1.0035 (2)	0.39955 (12)	0.0392 (4)
C13	0.83517 (11)	0.9005 (2)	0.45209 (13)	0.0456 (4)
H13	0.867698	0.822187	0.415369	0.055*
C14	0.85078 (10)	0.9161 (2)	0.55996 (13)	0.0433 (4)
H14	0.893493	0.845300	0.596958	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0507 (3)	0.0932 (4)	0.0709 (3)	−0.0250 (3)	0.0163 (2)	−0.0040 (3)
Cl2	0.0511 (3)	0.0837 (4)	0.0477 (3)	0.0004 (2)	−0.0067 (2)	−0.0095 (2)
F1	0.0605 (7)	0.1118 (10)	0.0615 (7)	−0.0204 (7)	0.0249 (6)	0.0118 (7)
O1	0.0832 (10)	0.0843 (10)	0.0443 (7)	−0.0050 (9)	−0.0089 (7)	0.0071 (7)
O2	0.1061 (12)	0.0883 (11)	0.0464 (8)	0.0037 (9)	0.0273 (8)	−0.0124 (7)
N1	0.0380 (7)	0.0491 (8)	0.0341 (7)	0.0013 (6)	0.0068 (5)	−0.0010 (6)
N2	0.0381 (7)	0.0441 (7)	0.0352 (7)	0.0023 (6)	0.0062 (5)	0.0007 (6)
N3	0.0712 (10)	0.0461 (8)	0.0395 (8)	−0.0162 (8)	0.0090 (8)	0.0005 (7)
C1	0.0369 (8)	0.0395 (8)	0.0337 (7)	0.0030 (6)	0.0077 (6)	−0.0024 (6)
C2	0.0386 (8)	0.0453 (9)	0.0374 (8)	−0.0011 (7)	0.0031 (6)	−0.0021 (7)
C3	0.0510 (10)	0.0597 (11)	0.0342 (8)	−0.0030 (8)	0.0076 (7)	0.0020 (8)
C4	0.0464 (9)	0.0572 (11)	0.0458 (9)	−0.0041 (8)	0.0180 (8)	0.0021 (8)
C5	0.0372 (9)	0.0727 (12)	0.0517 (10)	−0.0091 (8)	0.0056 (8)	−0.0067 (9)
C6	0.0428 (9)	0.0670 (12)	0.0353 (8)	−0.0010 (8)	0.0031 (7)	−0.0046 (8)
C7	0.0361 (8)	0.0395 (8)	0.0384 (8)	0.0044 (6)	0.0065 (6)	0.0013 (7)
C8	0.0382 (8)	0.0491 (9)	0.0446 (9)	0.0023 (7)	0.0048 (7)	−0.0012 (8)
C9	0.0331 (7)	0.0395 (8)	0.0376 (8)	−0.0017 (6)	0.0079 (6)	0.0027 (7)
C10	0.0416 (8)	0.0463 (9)	0.0414 (9)	0.0092 (7)	0.0116 (7)	0.0022 (7)
C11	0.0400 (8)	0.0475 (9)	0.0422 (9)	0.0032 (7)	0.0046 (7)	0.0087 (7)
C12	0.0457 (9)	0.0389 (8)	0.0343 (8)	−0.0099 (7)	0.0093 (7)	0.0016 (7)
C13	0.0455 (9)	0.0467 (9)	0.0469 (9)	0.0038 (8)	0.0154 (7)	−0.0044 (8)
C14	0.0384 (8)	0.0473 (9)	0.0447 (9)	0.0086 (7)	0.0069 (7)	0.0031 (7)

Geometric parameters (Å, º) top

Cl1—C8	1.7088 (17)	C5—C6	1.381 (2)
Cl2—C8	1.7120 (17)	C5—H5	0.9300
F1—C4	1.3569 (19)	C6—H6	0.9300
O1—N3	1.225 (2)	C7—C8	1.339 (2)
O2—N3	1.217 (2)	C7—C9	1.486 (2)
N1—N2	1.2547 (18)	C9—C10	1.389 (2)
N1—C1	1.4242 (19)	C9—C14	1.392 (2)
N2—C7	1.4123 (19)	C10—C11	1.374 (2)
N3—C12	1.466 (2)	C10—H10	0.9300
C1—C6	1.384 (2)	C11—C12	1.375 (2)
C1—C2	1.387 (2)	C11—H11	0.9300
C2—C3	1.373 (2)	C12—C13	1.377 (2)
C2—H2	0.9300	C13—C14	1.373 (2)
C3—C4	1.371 (2)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.362 (3)

N2—N1—C1	113.22 (12)	C8—C7—C9	121.96 (14)
N1—N2—C7	114.73 (13)	N2—C7—C9	123.20 (13)
O2—N3—O1	123.66 (16)	C7—C8—Cl1	122.91 (13)
O2—N3—C12	118.56 (16)	C7—C8—Cl2	123.47 (13)
O1—N3—C12	117.78 (16)	Cl1—C8—Cl2	113.61 (9)
C6—C1—C2	119.92 (14)	C10—C9—C14	119.18 (14)
C6—C1—N1	115.71 (14)	C10—C9—C7	121.30 (14)
C2—C1—N1	124.35 (14)	C14—C9—C7	119.53 (14)
C3—C2—C1	119.97 (15)	C11—C10—C9	120.58 (15)
C3—C2—H2	120.0	C11—C10—H10	119.7
C1—C2—H2	120.0	C9—C10—H10	119.7
C4—C3—C2	118.44 (15)	C10—C11—C12	118.64 (15)
C4—C3—H3	120.8	C10—C11—H11	120.7
C2—C3—H3	120.8	C12—C11—H11	120.7
F1—C4—C5	118.34 (16)	C11—C12—C13	122.39 (15)
F1—C4—C3	118.34 (16)	C11—C12—N3	118.64 (15)
C5—C4—C3	123.32 (16)	C13—C12—N3	118.96 (15)
C4—C5—C6	117.96 (16)	C14—C13—C12	118.43 (15)
C4—C5—H5	121.0	C14—C13—H13	120.8
C6—C5—H5	121.0	C12—C13—H13	120.8
C5—C6—C1	120.38 (16)	C13—C14—C9	120.72 (15)
C5—C6—H6	119.8	C13—C14—H14	119.6
C1—C6—H6	119.8	C9—C14—H14	119.6
C8—C7—N2	114.83 (14)

C1—N1—N2—C7	178.86 (13)	C8—C7—C9—C10	−116.26 (18)
N2—N1—C1—C6	−179.49 (15)	N2—C7—C9—C10	65.2 (2)
N2—N1—C1—C2	−1.1 (2)	C8—C7—C9—C14	63.4 (2)
C6—C1—C2—C3	0.9 (2)	N2—C7—C9—C14	−115.15 (17)
N1—C1—C2—C3	−177.43 (16)	C14—C9—C10—C11	−1.4 (2)
C1—C2—C3—C4	−0.1 (3)	C7—C9—C10—C11	178.25 (15)
C2—C3—C4—F1	179.75 (16)	C9—C10—C11—C12	−0.7 (2)
C2—C3—C4—C5	−0.6 (3)	C10—C11—C12—C13	1.8 (2)
F1—C4—C5—C6	−179.76 (17)	C10—C11—C12—N3	−177.72 (14)
C3—C4—C5—C6	0.6 (3)	O2—N3—C12—C11	166.51 (16)
C4—C5—C6—C1	0.2 (3)	O1—N3—C12—C11	−12.8 (2)
C2—C1—C6—C5	−0.9 (3)	O2—N3—C12—C13	−13.0 (2)
N1—C1—C6—C5	177.56 (16)	O1—N3—C12—C13	167.66 (16)
N1—N2—C7—C8	174.62 (14)	C11—C12—C13—C14	−0.7 (2)
N1—N2—C7—C9	−6.7 (2)	N3—C12—C13—C14	178.84 (15)
N2—C7—C8—Cl1	−176.19 (11)	C12—C13—C14—C9	−1.6 (2)
N2—C7—C8—Cl2	2.9 (2)	C10—C9—C14—C13	2.6 (2)
C9—C7—C8—Cl2	−175.78 (12)	C7—C9—C14—C13	−177.11 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱ	0.93	2.52	3.369 (2)	152

Symmetry code: (i) x, −y+5/2, z+1/2.

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

Contact	Distance	Symmetry operation
(C8) Cl1···C8 (Cl1)	3.6040 (16)	2 - x, 1/2 + y, 3/2 - z
(C13) H13···Cl1 (C8)	3.08	2 - x, 2 - y, 1 - z
(C8) Cl2···Cl2 (C8)	3.6506 (7)	2 - x, 2 - y, 2 - z
(C10) H10···O1 (N3)	2.52	x, 5/2 - y, 1/2 + z
(C4) F1···H11 (C11)	2.60	1 - x, -1/2 + y, 3/2 - z
(C4) F1···H6 (C6)	2.56	x, 3/2 - y, 1/2 + z
(N3) O1···H3 (C3)	2.67	x, y, -1 + z
(C5) H5···O1 (N3)	2.74	1 - x, 2 - y, 1 - z
(N3) O1···H10 (C10)	2.52	x, 5/2 - y, -1/2 + z
(F1) C4···C4 (F1)	3.541 (3)	1 - x, 2 - y, 2 - z

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

Contact	Percentage contribution
O···H/H···O	15.5
H···H	15.3
Cl···H/H···Cl	13.8
C···H/H···C	9.5
F···H/H···F	8.2
Cl···Cl	6.4
N···H/H···N	5.6
Cl···C/C···Cl	5.5
C···C	4.1
O···C/C···O	3.7
Cl···O/O···Cl	3.1
F···C/C···F	3.1
N···C/C···N	2.2
O···N/N···O	2.1
F···F	0.9
N···N	0.8

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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