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

Akkurt, M.; Yıldırım, S. Ö.; Shikhaliyev, N.Q.; Mammadova, N.A.; Niyazova, A.A.; Khrustalev, V.N.; Bhattarai, A.

doi:10.1107/S205698902200620X

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ISSN: 2056-9890

Volume 78| Part 7| July 2022| Pages 732-736

https://doi.org/10.1107/S205698902200620X

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

Mehmet Akkurt,^a Sema Öztürk Yıldırım,^b,^a Namiq Q. Shikhaliyev,^c Naila A. Mammadova,^c Ayten A. Niyazova,^c,^d Victor N. Khrustalev ^e,^f and Ajaya Bhattarai ^g ^*

^aDepartment of Physics, Faculty of Science, Erciyes University, 38039 Kayseri, Turkey, ^bDepartment of Physics, Faculty of Science, Eskisehir Technical University, Yunus Emre Campus 26470 Eskisehir, Turkey, ^cOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan, ^dAzerbaijan State University of Economics (UNEC), Istiglaliyyat str., Baku, Azerbaijan, ^ePeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation, ^fN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow, 119991, Russian Federation, and ^gDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 26 May 2022; accepted 13 June 2022; online 16 June 2022)

The molecule of the title compound, C₁₄H₈Br₃N₃O₂, consists of three almost planar groups: the central dibromoethenyldiazene fragment and two attached aromatic rings. The mean planes of these rings form dihedral angles with the plane of the central fragment of 26.35 (15) and 72.57 (14)° for bromine- and nitro-substituted rings, respectively. In the crystal, C—H⋯Br interactions connect molecules, generating zigzag C(8) chains along the [100] direction. These chains are linked by C—Br⋯π interactions into layers parallel to (001). van der Waals interactions between the layers aid in the cohesion of the crystal packing. The most substantial contributions to crystal packing, according to a Hirshfeld surface analysis, are from Br⋯H/H⋯Br (20.9%), C⋯H/H⋯C (15.2%), O⋯H/H⋯O (12.6%) and H⋯H (11.7%) contacts.

Keywords: crystal structure; non-covalent interactions; C—H⋯Br interactions; C(8) chains; Hirshfeld surface analysis.

CCDC reference: 2178832

1. Chemical context

Azo dyes constitute the largest production volume (ca 70%) of the dye industry today, and their relative importance may increase further in the future (Lipskikh et al., 2018 ). They play a crucial role in the printing market, the design of functional materials attributed to smart hydrogen bonding, photo-triggered structural switching, self-assembled layers, ionophores, liquid crystals, semiconductors, indicators, spectrophotometric reagents for determination of metal ions, photoluminescent materials, catalysts, antimicrobial agents, optical recording media, spin-coating films, etc (Zollinger, 1994 , 1995 ; Gurbanov et al., 2020a ,b ; Mahmudov et al., 2010 , 2013 ). Depending on the attached substituents, the functional properties of azo compounds and their metal complexes can be improved/controlled (Ma et al., 2020 , 2021 ). Both E/Z isomerism and azo–hydrazo tautomerism properties of azo dyes are key phenomena in the synthesis and development of new functional materials (Shixaliyev et al., 2018 , 2019 ). The attachment of non-covalent bond acceptor or donor centres to the azo dyes can be used as a synthetic strategy for the improvement of the functional properties of their metal complexes (Mahmudov et al., 2020 , 2021 , 2022 ). Thus, we have attached bromine atoms and a nitro group together with aryl rings to the –N=N– linkage leading to a new azo compound, (E)-2-(4-bromophenyl)-1-[2,2-dibromo-1-(4-nitrophenyl)ethenyl]diazene, which can provide intermolecular halogen and hydrogen bonds as well as π-interactions.

2. Structural commentary

The molecule of the title compound (Fig. 1) consists of three almost planar groups: the central dibromoethenyldiazene fragment [largest deviation from the l.s. plane is 0.039 (3) Å for N2] and two attached aromatic rings. The mean planes of these rings form dihedral angles with the plane of the central fragment of 26.35 (15) and 72.57 (14)° for the bromine- and nitro-substituted rings, respectively. The nitro group is twisted by 8.1 (2)° with respect to the C3–C8 aromatic ring. The C2—N2 bond distance of 1.406 (4) Å indicates π-conjugation between ethene and diazo groups. All other bond lengths and angles in the title compound are similar to those reported for the related azo compounds discussed in the Database survey section.

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

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, C—H⋯Br interactions connect the molecules, generating zigzag C(8) chains (Bernstein et al., 1995 ) along the [100] direction (Table 1, Figs. 2 and 3). These chains are linked by C—Br⋯π interactions [C1—Br1⋯Cg1ⁱⁱ; C1—Br1 = 1.864 (3) Å, Br1⋯Cg1ⁱⁱ = 3.5803 (16) Å, C1⋯Cg1ⁱⁱ = 4.722 (3) Å, C1—Br1⋯Cg1ⁱⁱ = 116.77 (9)°; Cg1 is the centroid of the C3–C8 ring; symmetry code (ii): x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z] into layers parallel to (001) (Fig. 4). van der Waals interactions between the layers help to keep the crystal packing together.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Br1ⁱ	0.95	2.89	3.530 (4)	126
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Figure 2
View down the a-axis of the title compound showing the C—H⋯Br interactions.

Figure 3
View down the b-axis of the title compound, showing the C—Br⋯π interactions.

Figure 4
View down the c axis of the title compound, showing the C—Br⋯π interactions.

Crystal Explorer 17.5 (Turner et al., 2017 ) was used to perform a Hirshfeld surface analysis and to generate the corresponding two-dimensional fingerprint plots, with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed color scale of −0.1401 (red) to 1.1158 (blue) a.u. (Fig. 5). The red patches represent short contacts and negative d_norm values on the surface, which correspond to the C—H⋯Br hydrogen bonds discussed above (Table 1). The C10—H10⋯Br1 interactions, which are important for molecular packing of the title compound, are responsible for the red patch that appears around Br1.

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1401 to 1.1158 a.u.

The overall two-dimensional fingerprint plot for the title compound and those delineated into Br⋯H / H⋯Br (20.9%), C⋯H/H⋯C (15.2%), O⋯H/H⋯O (12.6%) and H⋯H (11.7%) contacts are shown in Fig. 6, while numerical details for short intermolecular contacts are given in Table 2. Br⋯C/C⋯Br (8.8%), Br⋯Br (6.7%), N⋯H/H⋯N (6.5%), Br⋯O/O⋯Br (5.6%), O⋯C/C⋯O (4.1%), Br⋯N/N⋯Br (3.9%), C⋯C (2.5%), O⋯N/N⋯O (1.3%) and N⋯C/C⋯N (0.1%) contacts have little directional influence on the molecular packing.

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

Br1⋯H10	2.89	$[{1\over 2}]$ + x, $[{3\over 2}]$ − y, z
H14⋯H5	2.40	$[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, − $[{1\over 2}]$ + z
Br2⋯Br3	3.44	$[{1\over 2}]$ + x, $[{1\over 2}]$ − y, z
H10⋯C13	3.02	−x, 1 − y, $[{1\over 2}]$ + z
O1⋯H13	2.75	x, 1 + y, z
H7⋯N2	2.65	$[{1\over 2}]$ − x, $[{1\over 2}]$ + y, − $[{1\over 2}]$ + z

Figure 6
The full two-dimensional fingerprint plots for the title compound, showing all interactions (a) and delineated into (b) Br⋯H/H⋯Br, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O, and (e) H⋯H interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) for similar structures with the (E)-1-(2,2-dibromo-1-phenylethenyl)-2-phenyldiazene fragment showed that the nine closest are those of CSD refcodes TAZDIL [(I); Atioğlu et al., 2022 ], PAXDOL [(II); Çelikesir et al., 2022 ], GUPHIL [(III); Özkaraca et al., 2020b ], HONBUK [(IV); Akkurt et al., 2019 ], HONBOE [(V); Akkurt et al., 2019], HODQAV [(VI); Shikhaliyev et al., 2019], XIZREG [(VII); Atioğlu et al., 2019 ], LEQXOX [(VIII); Shikhaliyev et al., 2018] and LEQXIR [(IX); Shikhaliyev et al., 2018].

In (I), the molecules are connected by C—H⋯O and C—H⋯F hydrogen bonds into layers parallel to (011). The crystal packing is consolidated by C—Br⋯π and C—F⋯π contacts, as well as by π–π stacking interactions. In the crystal of (II), the molecules are linked into chains running parallel to [001] by C—H⋯O hydrogen bonds. The crystal packing is consolidated by C—F⋯π contacts and π–π stacking interactions, and short Br⋯O [2.9828 (13) Å] distances are also observed. In the crystal of (III), the molecules are linked into inversion dimers via short halogen–halogen contacts [Cl1⋯Cl1 = 3.3763 (9) Å, C16—Cl1⋯Cl1 = 141.47 (7)°] compared to the van der Waals radius sum of 3.50 Å for two chlorine atoms. No other directional contacts could be identified, and the shortest aromatic ring centroid separation is greater than 5.25 Å. In the crystals of (IV) and (V), the molecules are linked through weak X⋯Cl contacts [X = Cl for (IV) and Br for (V)], C—H⋯Cl and C—Cl⋯π interactions into sheets lying parallel to (001). In the crystal of (VI), the molecules are stacked in columns parallel to [100] 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 (VII), molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running parallel to [001]. The crystal packing also features C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In (VIII), C—H⋯N and short Cl⋯Cl contacts are observed, and in (IX), C—H⋯N and C—H⋯O hydrogen bonds and short Cl⋯O contacts occur.

5. Synthesis and crystallization

This dye was synthesized according to the reported method (Akkurt et al., 2019; Atioğlu et al., 2019; Maharramov et al., 2018 ; Özkaraca et al., 2020a ,b). A 20 mL screw neck vial was charged with DMSO (10 mL), (E)-1-(4-bromophenyl)-2-(4-nitrobenzylidene)hydrazine (1 mmol), tetramethylethylenediamine (TMEDA; 295 mg, 2.5 mmol), CuCl (2 mg, 0.02 mmol) and CBr₄ (4.5 mmol). After 1-3 h (until TLC analysis showed complete consumption of 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. Red solid (58%); m.p. 398 K. Analysis calculated for C₁₄H₈Br₃N₃O₂ (M = 489.95): C 34.32, H 1.65, N 8.58; found: C 34.27, H 1.70, N 8.56%. ¹H NMR (300 MHz, CDCl₃) δ 8.16–7.41 (8H, Ar–H). ¹³C NMR (75MHz, CDCl₃) δ 150.89, 149.62, 148.26, 136.43, 132.25, 127.77, 125.57, 124.53, 123.57, 93.24. ESI–MS: m/z: 490.96 [M + H]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and constrained to ride on their parent atoms (C—H = 0.95 Å) with U_iso(H) = 1.2U_eq(C). One reflection (110), affected by the beam stop, was omitted in the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₄H₈Br₃N₃O₂
M_r	489.96
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	13.8678 (5), 13.5442 (5), 8.3017 (3)
V (Å³)	1559.29 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.77
Crystal size (mm)	0.31 × 0.14 × 0.08

Data collection
Diffractometer	Bruker D8 QUEST, Photon III detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.044, 0.110
No. of measured, independent and observed [I > 2σ(I)] reflections	75835, 7370, 5962
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.826

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.02
No. of reflections	7370
No. of parameters	199
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.41, −0.97
Absolute structure	Flack parameter determined using 2437 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	0.003 (5)
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2178832

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902200620X/yk2170sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902200620X/yk2170Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902200620X/yk2170Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

(E)-2-(4-Bromophenyl)-1-[2,2-dibromo-1-(4-nitrophenyl)ethenyl]diazene top

Crystal data top

C₁₄H₈Br₃N₃O₂	D_x = 2.087 Mg m⁻³
M_r = 489.96	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 9976 reflections
a = 13.8678 (5) Å	θ = 2.9–34.8°
b = 13.5442 (5) Å	µ = 7.77 mm⁻¹
c = 8.3017 (3) Å	T = 100 K
V = 1559.29 (10) Å³	Block, red
Z = 4	0.31 × 0.14 × 0.08 mm
F(000) = 936

Data collection top

Bruker D8 QUEST, Photon III detector diffractometer	7370 independent reflections
Radiation source: fine-focus sealed X-Ray tube	5962 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 7.31 pixels mm^-1	θ_max = 36.0°, θ_min = 2.9°
φ and ω shutterless scans	h = −22→22
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −22→22
T_min = 0.044, T_max = 0.110	l = −13→13
75835 measured reflections

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0438P)² + 0.8309P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
7370 reflections	Δρ_max = 1.41 e Å⁻³
199 parameters	Δρ_min = −0.97 e Å⁻³
1 restraint	Absolute structure: Flack parameter determined using 2437 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.003 (5)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.49964 (2)	0.72932 (3)	0.49158 (6)	0.02765 (8)
Br2	0.44572 (2)	0.50470 (2)	0.51189 (7)	0.02906 (8)
Br3	−0.10955 (3)	0.24165 (3)	0.55241 (7)	0.03182 (9)
O1	0.1810 (2)	1.1045 (2)	0.3729 (4)	0.0333 (6)
O2	0.1662 (3)	1.1002 (2)	0.6323 (4)	0.0326 (6)
N1	0.18506 (19)	1.0613 (2)	0.5020 (5)	0.0231 (5)
N2	0.24431 (19)	0.57755 (19)	0.5188 (4)	0.0207 (5)
N3	0.15599 (19)	0.5982 (2)	0.5376 (4)	0.0228 (6)
C1	0.4020 (2)	0.6350 (2)	0.5012 (6)	0.0222 (6)
C2	0.3073 (2)	0.6586 (2)	0.5080 (5)	0.0205 (5)
C3	0.2727 (2)	0.7629 (2)	0.5040 (5)	0.0196 (5)
C4	0.2373 (3)	0.8055 (3)	0.6449 (5)	0.0221 (6)
H4	0.233234	0.767615	0.741062	0.027*
C5	0.2076 (3)	0.9043 (3)	0.6441 (5)	0.0222 (6)
H5	0.184039	0.934772	0.739348	0.027*
C6	0.2136 (2)	0.9563 (2)	0.5016 (5)	0.0212 (5)
C7	0.2468 (3)	0.9148 (3)	0.3596 (5)	0.0249 (7)
H7	0.248972	0.952162	0.262834	0.030*
C8	0.2769 (3)	0.8171 (3)	0.3629 (5)	0.0235 (6)
H8	0.300598	0.787169	0.267351	0.028*
C9	0.0971 (2)	0.5110 (2)	0.5422 (5)	0.0208 (6)
C10	0.0066 (3)	0.5207 (3)	0.6113 (5)	0.0251 (7)
H10	−0.013356	0.582330	0.654399	0.030*
C11	−0.0553 (3)	0.4391 (3)	0.6172 (5)	0.0262 (7)
H11	−0.117165	0.444374	0.665505	0.031*
C12	−0.0249 (3)	0.3509 (2)	0.5516 (5)	0.0243 (6)
C13	0.0662 (2)	0.3397 (2)	0.4837 (5)	0.0246 (7)
H13	0.085933	0.277960	0.440465	0.030*
C14	0.1275 (2)	0.4203 (2)	0.4803 (5)	0.0236 (6)
H14	0.190380	0.413915	0.435972	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01833 (12)	0.02119 (13)	0.0434 (2)	−0.00217 (10)	0.00069 (14)	0.00037 (16)
Br2	0.02025 (12)	0.01897 (13)	0.0480 (2)	0.00223 (10)	−0.00256 (15)	−0.00061 (14)
Br3	0.02917 (16)	0.02402 (15)	0.0423 (2)	−0.00937 (12)	−0.00254 (18)	0.00189 (17)
O1	0.0460 (17)	0.0222 (13)	0.0317 (15)	0.0060 (12)	0.0009 (13)	0.0062 (11)
O2	0.0450 (16)	0.0217 (13)	0.0310 (16)	0.0042 (12)	0.0006 (13)	−0.0038 (11)
N1	0.0211 (10)	0.0185 (11)	0.0296 (15)	0.0000 (8)	0.0007 (13)	−0.0001 (12)
N2	0.0179 (10)	0.0190 (10)	0.0251 (15)	−0.0007 (8)	−0.0006 (10)	0.0012 (11)
N3	0.0184 (11)	0.0192 (11)	0.0306 (17)	−0.0012 (8)	0.0016 (10)	0.0014 (11)
C1	0.0181 (11)	0.0170 (11)	0.0315 (16)	0.0001 (9)	−0.0020 (13)	−0.0003 (13)
C2	0.0182 (11)	0.0171 (11)	0.0263 (15)	0.0002 (9)	−0.0010 (12)	0.0015 (12)
C3	0.0164 (10)	0.0167 (11)	0.0257 (15)	−0.0004 (8)	−0.0012 (13)	0.0022 (12)
C4	0.0237 (14)	0.0183 (13)	0.0243 (16)	0.0015 (11)	0.0002 (12)	0.0010 (12)
C5	0.0215 (14)	0.0211 (14)	0.0241 (16)	0.0024 (11)	0.0005 (12)	−0.0010 (12)
C6	0.0194 (11)	0.0166 (11)	0.0275 (15)	0.0000 (9)	−0.0004 (13)	−0.0007 (13)
C7	0.0262 (15)	0.0209 (14)	0.0276 (18)	0.0018 (12)	0.0018 (13)	0.0031 (12)
C8	0.0238 (14)	0.0202 (14)	0.0265 (17)	0.0003 (11)	0.0022 (13)	0.0003 (12)
C9	0.0189 (12)	0.0167 (11)	0.0269 (17)	−0.0010 (9)	−0.0007 (11)	0.0000 (12)
C10	0.0230 (14)	0.0182 (13)	0.0342 (19)	0.0003 (11)	0.0021 (13)	−0.0015 (13)
C11	0.0203 (13)	0.0209 (14)	0.037 (2)	−0.0021 (11)	0.0034 (13)	−0.0005 (13)
C12	0.0238 (13)	0.0185 (12)	0.0305 (17)	−0.0061 (10)	−0.0016 (13)	0.0016 (14)
C13	0.0246 (13)	0.0182 (12)	0.0312 (19)	−0.0007 (10)	0.0009 (14)	−0.0027 (13)
C14	0.0205 (12)	0.0208 (13)	0.0295 (19)	−0.0005 (10)	0.0035 (13)	−0.0024 (13)

Geometric parameters (Å, º) top

Br1—C1	1.864 (3)	C5—H5	0.9500
Br2—C1	1.868 (3)	C6—C7	1.384 (6)
Br3—C12	1.888 (3)	C7—C8	1.388 (5)
O1—N1	1.223 (5)	C7—H7	0.9500
O2—N1	1.231 (5)	C8—H8	0.9500
N1—C6	1.477 (4)	C9—C10	1.386 (5)
N2—N3	1.266 (4)	C9—C14	1.397 (5)
N2—C2	1.406 (4)	C10—C11	1.400 (5)
N3—C9	1.437 (4)	C10—H10	0.9500
C1—C2	1.352 (4)	C11—C12	1.378 (5)
C2—C3	1.492 (4)	C11—H11	0.9500
C3—C8	1.384 (5)	C12—C13	1.392 (5)
C3—C4	1.394 (5)	C13—C14	1.384 (5)
C4—C5	1.400 (5)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.379 (5)

O1—N1—O2	123.8 (3)	C6—C7—H7	121.0
O1—N1—C6	118.1 (3)	C8—C7—H7	121.0
O2—N1—C6	118.1 (3)	C3—C8—C7	120.7 (3)
N3—N2—C2	115.9 (3)	C3—C8—H8	119.6
N2—N3—C9	111.8 (3)	C7—C8—H8	119.6
C2—C1—Br1	123.1 (2)	C10—C9—C14	120.6 (3)
C2—C1—Br2	122.4 (2)	C10—C9—N3	116.6 (3)
Br1—C1—Br2	114.43 (15)	C14—C9—N3	122.8 (3)
C1—C2—N2	115.0 (3)	C9—C10—C11	119.7 (3)
C1—C2—C3	122.3 (3)	C9—C10—H10	120.2
N2—C2—C3	122.7 (3)	C11—C10—H10	120.2
C8—C3—C4	120.3 (3)	C12—C11—C10	118.9 (3)
C8—C3—C2	120.5 (3)	C12—C11—H11	120.6
C4—C3—C2	119.1 (3)	C10—C11—H11	120.6
C3—C4—C5	119.7 (3)	C11—C12—C13	122.1 (3)
C3—C4—H4	120.2	C11—C12—Br3	119.2 (3)
C5—C4—H4	120.2	C13—C12—Br3	118.7 (3)
C6—C5—C4	118.3 (3)	C14—C13—C12	118.7 (3)
C6—C5—H5	120.8	C14—C13—H13	120.7
C4—C5—H5	120.8	C12—C13—H13	120.7
C5—C6—C7	122.9 (3)	C13—C14—C9	120.0 (3)
C5—C6—N1	118.3 (3)	C13—C14—H14	120.0
C7—C6—N1	118.8 (3)	C9—C14—H14	120.0
C6—C7—C8	118.0 (3)

C2—N2—N3—C9	178.1 (3)	O2—N1—C6—C7	−171.8 (3)
Br1—C1—C2—N2	−178.4 (3)	C5—C6—C7—C8	−1.2 (5)
Br2—C1—C2—N2	−1.8 (6)	N1—C6—C7—C8	177.5 (3)
Br1—C1—C2—C3	1.6 (6)	C4—C3—C8—C7	0.6 (5)
Br2—C1—C2—C3	178.2 (3)	C2—C3—C8—C7	−178.5 (3)
N3—N2—C2—C1	174.8 (4)	C6—C7—C8—C3	0.6 (5)
N3—N2—C2—C3	−5.2 (5)	N2—N3—C9—C10	160.3 (4)
C1—C2—C3—C8	72.2 (5)	N2—N3—C9—C14	−20.0 (5)
N2—C2—C3—C8	−107.7 (4)	C14—C9—C10—C11	−0.9 (6)
C1—C2—C3—C4	−106.9 (5)	N3—C9—C10—C11	178.9 (4)
N2—C2—C3—C4	73.1 (5)	C9—C10—C11—C12	−0.9 (6)
C8—C3—C4—C5	−1.3 (5)	C10—C11—C12—C13	1.7 (7)
C2—C3—C4—C5	177.8 (3)	C10—C11—C12—Br3	−177.8 (3)
C3—C4—C5—C6	0.8 (5)	C11—C12—C13—C14	−0.8 (6)
C4—C5—C6—C7	0.5 (5)	Br3—C12—C13—C14	178.8 (3)
C4—C5—C6—N1	−178.2 (3)	C12—C13—C14—C9	−1.0 (6)
O1—N1—C6—C5	−172.7 (3)	C10—C9—C14—C13	1.8 (6)
O2—N1—C6—C5	6.9 (4)	N3—C9—C14—C13	−177.9 (4)
O1—N1—C6—C7	8.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Br1ⁱ	0.95	2.89	3.530 (4)	126

Symmetry code: (i) x−1/2, −y+3/2, z.

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

Br1···H10	2.89	1/2 + x, 3/2 - y, z
H14···H5	2.40	1/2 - x, -1/2 + y, -1/2 + z
Br2···Br3	3.44	1/2 + x, 1/2 - y, z
H10···C13	3.02	-x, 1 - y, 1/2 + z
O1···H13	2.75	x, 1 + y, z
H7···N2	2.65	1/2 - x, 1/2 + y, -1/2 + z

Acknowledgements

The authors' contributions are as follows. Conceptualization, NQS, MA and AB; synthesis, NAM and GTS; X-ray analysis, SÖY, VNK and MA; writing (review and editing of the manuscript) SÖY, MA and AB; funding acquisition, NQS, NAM and GTS; supervision, NQS, MA and AB.

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).

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