Crystal structure and Hirshfeld surface analysis of a new polymorph of (E)-2-(4-bromo-phen-yl)-1-[2,2-di-bromo-1-(3-nitro-phen-yl)ethen-yl]diazene.

A new polymorph of the title compound, C14H8Br3N3O2, (form-2) was obtained in the same manner as the previously reported form-1 [Akkurt et al. (2022 ▸). Acta Cryst. E78, 732-736]. The structure of the new polymorph is stabilized by a C-H⋯O hydrogen bond that links mol-ecules into chains. These chains are linked by face-to-face π-π stacking inter-actions, resulting in a layered structure. Short inter-mol-ecular Br⋯O contacts and van der Waals inter-actions between the layers aid in the cohesion of the crystal packing. In the previously reported form-1, C-H⋯Br inter-actions connect mol-ecules into zigzag chains, which are linked by C-Br⋯π inter-actions into layers, whereas the van der Waals inter-actions between the layers stabilize the crystal packing of form-2. Hirshfeld mol-ecular surface analysis was used to compare the inter-molecular inter-actions of the polymorphs. © Atioğlu et al. 2022.

Chemical context

Aromatic azo compounds provide ubiquitous motifs in organic chemistry and are widely used as indicators, organic dyes, pigments, radical reaction initiators, food additives, therapeutic agents, etc. (Zollinger 1994 ▸, 1995 ▸; Gurbanov et al., 2020a ▸,b ▸). Moreover, in azo dyes the ligands play a crucial role in coordination chemistry and in the construction of functional materials, such as ionophores, self-assembled layers, catalysts, anti­microbial agents, liquid crystals and semiconductors (Ma et al., 2020 ▸, 2021 ▸; Mahmudov et al., 2010 ▸, 2013 ▸). Depending on the attached functional groups, the chemical and physical properties of azo dyes and their transition-metal complexes can be improved. The azo-to-hydrazo tautomerization as well as E/Z isomerization of azo dyes are key phenomena in the synthesis and design of new functional materials (Shixaliyev et al., 2013 ▸, 2014 ▸). Moreover, an attachment of donor or acceptor centres of non-covalent bonds to the azo compounds can be applied as a synthetic strategy in the improvement of functional properties of their metal complexes (Mahmudov et al., 2020 ▸, 2021 ▸, 2022 ▸). Thus, we have attached bromine and nitro substituents to the aryl rings leading to a new azo dye, (E)-1-(2,2-di­bromo-1-(3-nitro­phen­yl)vin­yl)-2-(4-bromo­phen­yl)di­azene, which can participate in inter­molecular halogen and hydrogen bonds as well as in π-inter­actions.

Structural commentary

A view of the mol­ecule of the new polymorph (henceforth referred to as form-2) is shown in Fig. 1 ▸. The central fragment of the mol­ecule, C1/C2/N2/N3/C3/C9/Br1/Br2, is almost planar with the largest deviation from mean plane being 0.101 (1) Å for Br1. This plane forms dihedral angles of 13.51 (7) and 61.26 (7)° with the planes of the bromine- and nitro-substituted aromatic rings, respectively. In the previously reported polymorph (form-1), the corresponding angles were 26.35 (15) and 72.57 (14)° (Akkurt et al., 2022 ▸). All bond lengths and angles in the title compound are in agreement with 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.

Supra­molecular features and Hirshfeld surface analysis

The crystal packing of the new polymorph is stabilized by a C—H⋯O hydrogen bond that links mol­ecules into chains along the b-axis direction (Table 1 ▸, Figs. 2 ▸–4 ▸ ▸). These chains are joined by zigzag face-to-face π–π stacking inter­actions along the [100] direction [Cg1⋯Cg1(−  + x, y,  − z) = 3.7305 (11) Å, slippage: 2.057 Å; Cg1⋯Cg1(  + x, y,  − z) = 3.7305 (11) Å, slippage: 0.9775 Å; where Cg1 is the centroid of the nitro­phenyl ring], resulting in the layers parallel to (001) (Fig. 4 ▸). Short inter-mol­ecular Br1⋯O2 contacts (Table 2 ▸) and van der Waals inter­actions between the layers help to keep the crystal packing together. In the previously reported form-1 of the title compound (Akkurt et al., 2022 ▸), C—H⋯Br inter­actions connect mol­ecules, generating zigzag C(8) chains along the [100] direction, which are linked by C—Br⋯π inter­actions into layers parallel to (001), and van der Waals inter­actions between layers contribute to the crystal cohesion.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1i	0.95	2.56	3.394 (2)	146

Symmetry code: (i) .

Figure 2

View down the a-axis of the C—H⋯O and π–π inter­actions (dashed lines) in the title compound.

Figure 3

View down the b-axis of the C—H⋯O and π–π inter­actions (dashed lines) in the title compound.

Figure 4

View down the c-axis of the C—H⋯O and π–π inter­actions (dashed lines) in the title compound.

Table 2

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

H4⋯C13	2.67	−1 + x, y, z
H8⋯O1	2.56	−x, −  + y,  − z
H7⋯N3	2.78	−  + x, y,  − z
Br1⋯O2	3.137 (2)	−  − x, −  + y, z
Br1⋯H14	2.98	− x, −  + y, z
Br2⋯H13	3.15	− x, −  + y, z
Br3⋯H10	3.02	+ x,  − y, 1 − z
C13⋯Br3	3.569 (2)	2 − x, 1 − y, 1 − z

Crystal Explorer 17.5 (Turner et al., 2017 ▸) was used to perform a Hirshfeld surface analysis of form-2 and to generate the related two-dimensional fingerprint plots, with a standard resolution of the three-dimensional d norm surfaces plotted over a fixed colour scale of −0.1471 (red) to +1.1715 (blue) a.u. (Fig. 5 ▸). The red areas on the surface present short contacts and negative d norm values, which correspond to the C—H⋯O hydrogen bonds mentioned above (Table 1 ▸). The red patch that appears around O1 is due to the C8—H8⋯O1 inter­action, which is critical for the mol­ecular packing of the title compound. In form-1, the C—H⋯Br inter­actions are also prominent (Akkurt et al., 2022 ▸).

Figure 5

(a) Front and (b) back views of the three-dimensional Hirshfeld surface of the title compound plotted over d norm in the range −0.1471 to 1.1715 a.u.

The overall two-dimensional fingerprint plot for form-2 is given in Fig. 6 ▸ a, and those delineated into Br⋯H/H⋯Br (26.5%), H⋯H (12.8%), C⋯H/H⋯C (11.5%) and O⋯H/H⋯O (10.6%) contacts are shown in Fig. 6 ▸ b–e, while the numerical details for the shortest contacts are given in Table 2 ▸. Other contacts, such as Br⋯C/C⋯Br (7.7%), C⋯C (6.0%), Br⋯Br (5.8%), Br⋯O/O⋯Br (5.3%), N⋯H/H⋯N (5.3%), O⋯C/C⋯O (2.5%), Br⋯N/N⋯Br (2.3%), O⋯N/N⋯O (1.7%), O⋯O (1.3%) and N⋯C/C⋯N (0.8%), have little influence on the mol­ecular packing. For form-1, the set includes only four types of inter­actions, viz. Br⋯H/H⋯Br, H⋯H, C⋯H/H⋯C and O⋯H/H⋯O contacts (Akkurt et al., 2022 ▸). The predominant inter­actions in both cases are Br⋯H/H⋯Br and H⋯H, constituting 26.5% and 12.8%, respectively, in form-2 vs 20.9% and 15.2% in form-1.

Figure 6

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

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)-2-(4-bromo­phen­yl)diazene unit showed that the ten closest are those of CSD refcodes HEHKEO (I) (Akkurt et al., 2022 ▸), TAZDIL (II) (Atioğlu et al., 2022 ▸), PAXDOL (III) (Çelikesir et al., 2022 ▸), GUPHIL (IV) (Özkaraca et al., 2020b ▸), HONBUK (V) (Akkurt et al., 2019 ▸), HONBOE (VI) (Akkurt et al., 2019 ▸), HODQAV (VII) (Shikhaliyev et al., 2019 ▸), XIZREG (VIII) (Atioğlu et al., 2019 ▸), LEQXOX (IX) (Shikhaliyev et al., 2018 ▸) and LEQXIR (X) (Shikhaliyev et al., 2018 ▸).

C—H⋯Br inter­actions connect the mol­ecules in the crystal of the form-1 polymorph of the title compound, (I), resulting in zigzag C(8) chains along the [100] direction. These chains are connected by C—Br⋯π inter­actions into layers parallel to (001). van der Waals inter­actions between the layers contribute to the crystal cohesion.

The mol­ecules in (II) are joined into layers parallel to (011) by C—H⋯O and C—H⋯F hydrogen bonds. C—Br⋯π and C—F⋯π contacts, as well as π–π stacking inter­actions, strengthen the crystal packing

The mol­ecules in the crystal of (III) are connected into chains running parallel to [001] by C—H⋯O hydrogen bonds. C—F⋯π contacts and π–π stacking inter­actions help to consolidate the crystal packing, and short Br⋯O [2.9828 (13) Å] distances are also observed.

In the crystal of (IV), 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 radii 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 (V) and (VI), the 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 lying parallel to (001).

In the crystal of (VII), the mol­ecules are stacked in columns along [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 (VIII), 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 (IX), C—H⋯N and short Cl⋯Cl contacts are observed, and in (X), C—H⋯N and C—H⋯O hydrogen bonds and short Cl⋯O contacts occur.

Synthesis and crystallization

This dye was synthesized according to the reported method (Akkurt 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-(3-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 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 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 (62%); m.p. 391 K. Analysis calculated for C14H8Br3N3O2 (M = 489.95): C 34.32, H 1.65, N 8.58; found: C 34.29, H 1.66, N 8.55%. 1H NMR (300 MHz, CDCl3) δ 7.90–7.44 (8H, Ar–H). 13C NMR (75MHz, CDCl3) δ 150.88, 148.57, 148.12, 132.81, 132.47, 132.25, 130.04, 126.40, 125.30, 124.53, 123.57, 94.10. ESI-MS: m/z: 490.91 [M + H]+.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were positioned geometrically and allowed to ride on their parent atoms (C—H = 0.95 Å) with U iso(H) = 1.2U eq(C).

Table 3

Experimental details

Crystal data
Chemical formula	C14H8Br3N3O2
M r	489.96
Crystal system, space group	Orthorhombic, P b c a
Temperature (K)	100
a, b, c (Å)	6.6579 (1), 15.7683 (3), 29.0301 (6)
V (Å3)	3047.69 (10)
Z	8
Radiation type	Mo Kα
μ (mm−1)	7.95
Crystal size (mm)	0.34 × 0.06 × 0.05
Data collection
Diffractometer	Bruker AXS D8 QUEST, Photon III detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸).
T min, T max	0.020, 0.058
No. of measured, independent and observed [I > 2σ(I)] reflections	67179, 5538, 4620
R int	0.033
(sin θ/λ)max (Å−1)	0.758
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.024, 0.064, 1.05
No. of reflections	5538
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.68, −0.52

Computer programs: APEX3 and SAINT (Bruker, 2018 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2018 (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2020 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007113/yk2172sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022007113/yk2172Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022007113/yk2172Isup3.cml

CCDC reference: 2189348

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H8Br3N3O2	Dx = 2.136 Mg m−3
Mr = 489.96	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9783 reflections
a = 6.6579 (1) Å	θ = 2.7–34.8°
b = 15.7683 (3) Å	µ = 7.95 mm−1
c = 29.0301 (6) Å	T = 100 K
V = 3047.69 (10) Å3	Needle, red
Z = 8	0.34 × 0.06 × 0.05 mm
F(000) = 1872

Bruker AXS D8 QUEST, Photon III detector diffractometer	5538 independent reflections
Radiation source: fine-focus sealed X-Ray tube	4620 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 7.31 pixels mm-1	θmax = 32.6°, θmin = 2.6°
φ and ω shutterless scans	h = −10→10
Absorption correction: multi-scan (SADABS; Krause et al., 2015).	k = −23→23
Tmin = 0.020, Tmax = 0.058	l = −43→43
67179 measured reflections

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0318P)2 + 2.0035P] where P = (Fo2 + 2Fc2)/3
5538 reflections	(Δ/σ)max = 0.002
199 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.52 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	−0.15339 (3)	0.13530 (2)	0.34586 (2)	0.02722 (5)
Br2	0.15481 (3)	0.10023 (2)	0.42549 (2)	0.02936 (5)
Br3	1.20530 (3)	0.41027 (2)	0.48664 (2)	0.02853 (5)
O1	−0.0475 (3)	0.54340 (9)	0.25282 (6)	0.0379 (3)
O2	0.0602 (3)	0.54406 (9)	0.32311 (5)	0.0353 (3)
N1	0.0276 (2)	0.50824 (10)	0.28639 (6)	0.0272 (3)
N2	0.3641 (2)	0.25393 (10)	0.38915 (6)	0.0238 (3)
N3	0.4595 (2)	0.31953 (10)	0.37700 (5)	0.0237 (3)
C1	0.0855 (3)	0.16829 (11)	0.37477 (6)	0.0238 (3)
C2	0.1967 (3)	0.23522 (11)	0.36103 (6)	0.0226 (3)
C3	0.1509 (2)	0.28572 (11)	0.31884 (6)	0.0215 (3)
C4	0.1146 (3)	0.37242 (11)	0.32230 (6)	0.0221 (3)
H4	0.115991	0.400016	0.351386	0.027*
C5	0.0763 (3)	0.41751 (11)	0.28225 (6)	0.0224 (3)
C6	0.0770 (3)	0.38058 (12)	0.23897 (6)	0.0236 (3)
H6	0.050338	0.413167	0.212131	0.028*
C7	0.1178 (3)	0.29485 (13)	0.23606 (6)	0.0250 (3)
H7	0.121139	0.268071	0.206755	0.030*
C8	0.1540 (3)	0.24729 (11)	0.27555 (6)	0.0228 (3)
H8	0.180911	0.188307	0.273038	0.027*
C9	0.6294 (3)	0.33715 (12)	0.40511 (6)	0.0233 (3)
C10	0.7117 (3)	0.27990 (12)	0.43672 (7)	0.0254 (3)
H10	0.650813	0.226090	0.441376	0.030*
C11	0.8820 (3)	0.30204 (12)	0.46115 (7)	0.0267 (3)
H11	0.940184	0.263540	0.482488	0.032*
C12	0.9671 (3)	0.38174 (12)	0.45398 (6)	0.0239 (3)
C13	0.8856 (3)	0.43973 (12)	0.42367 (6)	0.0257 (3)
H13	0.944333	0.494183	0.419849	0.031*
C14	0.7154 (3)	0.41659 (12)	0.39883 (6)	0.0248 (3)
H14	0.657723	0.455267	0.377500	0.030*

	U11	U22	U33	U12	U13	U23
Br1	0.02466 (8)	0.02296 (8)	0.03404 (10)	−0.00303 (6)	−0.00384 (7)	0.00397 (7)
Br2	0.02669 (9)	0.02915 (9)	0.03225 (10)	0.00022 (7)	−0.00123 (7)	0.01012 (7)
Br3	0.02656 (9)	0.02931 (9)	0.02972 (9)	−0.00397 (7)	−0.00470 (7)	0.00276 (7)
O1	0.0417 (9)	0.0284 (7)	0.0437 (9)	0.0056 (6)	−0.0074 (7)	0.0110 (7)
O2	0.0422 (8)	0.0260 (7)	0.0378 (8)	0.0048 (6)	0.0005 (7)	−0.0047 (6)
N1	0.0234 (7)	0.0231 (7)	0.0352 (8)	0.0012 (6)	0.0018 (6)	0.0035 (6)
N2	0.0218 (6)	0.0251 (7)	0.0246 (7)	−0.0002 (5)	0.0002 (6)	0.0006 (6)
N3	0.0220 (6)	0.0243 (7)	0.0248 (7)	0.0003 (5)	−0.0002 (5)	0.0003 (6)
C1	0.0222 (7)	0.0227 (7)	0.0264 (8)	0.0017 (6)	−0.0009 (6)	0.0028 (6)
C2	0.0223 (7)	0.0222 (7)	0.0232 (8)	0.0019 (6)	−0.0003 (6)	0.0003 (6)
C3	0.0188 (7)	0.0219 (7)	0.0237 (8)	0.0000 (6)	0.0000 (6)	0.0010 (6)
C4	0.0212 (7)	0.0215 (7)	0.0237 (8)	0.0007 (6)	0.0006 (6)	0.0006 (6)
C5	0.0185 (7)	0.0214 (7)	0.0274 (8)	0.0001 (6)	0.0003 (6)	0.0016 (6)
C6	0.0177 (7)	0.0290 (8)	0.0242 (8)	−0.0007 (6)	0.0004 (6)	0.0036 (6)
C7	0.0210 (7)	0.0307 (9)	0.0232 (8)	−0.0013 (6)	0.0006 (6)	−0.0031 (7)
C8	0.0200 (7)	0.0223 (7)	0.0262 (8)	−0.0001 (6)	−0.0013 (6)	−0.0026 (6)
C9	0.0235 (7)	0.0235 (8)	0.0230 (8)	0.0007 (6)	0.0002 (6)	−0.0008 (6)
C10	0.0245 (8)	0.0241 (8)	0.0275 (8)	−0.0015 (6)	−0.0015 (7)	0.0032 (7)
C11	0.0274 (8)	0.0252 (8)	0.0275 (9)	0.0002 (7)	−0.0035 (7)	0.0030 (7)
C12	0.0225 (7)	0.0263 (8)	0.0227 (8)	−0.0011 (6)	−0.0006 (6)	−0.0012 (6)
C13	0.0281 (8)	0.0232 (8)	0.0259 (8)	−0.0024 (7)	−0.0004 (7)	0.0004 (6)
C14	0.0266 (8)	0.0235 (8)	0.0244 (8)	0.0014 (6)	−0.0004 (6)	0.0028 (6)

Br1—C1	1.8723 (18)	C6—C7	1.381 (3)
Br2—C1	1.8796 (18)	C6—H6	0.9500
Br3—C12	1.9016 (18)	C7—C8	1.391 (3)
O1—N1	1.227 (2)	C7—H7	0.9500
O2—N1	1.226 (2)	C8—H8	0.9500
N1—C5	1.472 (2)	C9—C14	1.389 (3)
N2—N3	1.264 (2)	C9—C10	1.399 (3)
N2—C2	1.413 (2)	C10—C11	1.382 (3)
N3—C9	1.422 (2)	C10—H10	0.9500
C1—C2	1.349 (2)	C11—C12	1.394 (3)
C2—C3	1.493 (2)	C11—H11	0.9500
C3—C4	1.392 (2)	C12—C13	1.380 (3)
C3—C8	1.395 (3)	C13—C14	1.392 (3)
C4—C5	1.386 (2)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.385 (3)
O2—N1—O1	123.67 (17)	C6—C7—H7	119.6
O2—N1—C5	118.68 (16)	C8—C7—H7	119.6
O1—N1—C5	117.64 (17)	C7—C8—C3	120.37 (17)
N3—N2—C2	113.96 (15)	C7—C8—H8	119.8
N2—N3—C9	113.53 (15)	C3—C8—H8	119.8
C2—C1—Br1	123.43 (14)	C14—C9—C10	120.46 (17)
C2—C1—Br2	122.92 (14)	C14—C9—N3	115.35 (16)
Br1—C1—Br2	113.64 (9)	C10—C9—N3	124.18 (17)
C1—C2—N2	115.18 (16)	C11—C10—C9	119.65 (17)
C1—C2—C3	123.21 (16)	C11—C10—H10	120.2
N2—C2—C3	121.60 (15)	C9—C10—H10	120.2
C4—C3—C8	119.61 (16)	C10—C11—C12	118.98 (17)
C4—C3—C2	120.02 (16)	C10—C11—H11	120.5
C8—C3—C2	120.30 (16)	C12—C11—H11	120.5
C5—C4—C3	118.36 (17)	C13—C12—C11	122.18 (17)
C5—C4—H4	120.8	C13—C12—Br3	119.28 (14)
C3—C4—H4	120.8	C11—C12—Br3	118.53 (14)
C6—C5—C4	122.99 (17)	C12—C13—C14	118.48 (17)
C6—C5—N1	118.92 (16)	C12—C13—H13	120.8
C4—C5—N1	118.07 (16)	C14—C13—H13	120.8
C7—C6—C5	117.88 (17)	C9—C14—C13	120.23 (17)
C7—C6—H6	121.1	C9—C14—H14	119.9
C5—C6—H6	121.1	C13—C14—H14	119.9
C6—C7—C8	120.75 (17)
C2—N2—N3—C9	−179.14 (15)	C4—C5—C6—C7	0.1 (3)
Br1—C1—C2—N2	175.57 (13)	N1—C5—C6—C7	−178.28 (16)
Br2—C1—C2—N2	−3.5 (2)	C5—C6—C7—C8	0.9 (3)
Br1—C1—C2—C3	−5.5 (3)	C6—C7—C8—C3	−0.4 (3)
Br2—C1—C2—C3	175.44 (13)	C4—C3—C8—C7	−1.0 (3)
N3—N2—C2—C1	−176.40 (16)	C2—C3—C8—C7	−177.89 (16)
N3—N2—C2—C3	4.6 (2)	N2—N3—C9—C14	−168.04 (16)
C1—C2—C3—C4	121.4 (2)	N2—N3—C9—C10	13.1 (3)
N2—C2—C3—C4	−59.7 (2)	C14—C9—C10—C11	−1.3 (3)
C1—C2—C3—C8	−61.7 (2)	N3—C9—C10—C11	177.51 (18)
N2—C2—C3—C8	117.13 (19)	C9—C10—C11—C12	0.6 (3)
C8—C3—C4—C5	1.9 (2)	C10—C11—C12—C13	0.8 (3)
C2—C3—C4—C5	178.81 (16)	C10—C11—C12—Br3	−178.42 (15)
C3—C4—C5—C6	−1.5 (3)	C11—C12—C13—C14	−1.5 (3)
C3—C4—C5—N1	176.87 (15)	Br3—C12—C13—C14	177.71 (14)
O2—N1—C5—C6	−167.63 (17)	C10—C9—C14—C13	0.6 (3)
O1—N1—C5—C6	13.8 (2)	N3—C9—C14—C13	−178.32 (17)
O2—N1—C5—C4	13.9 (2)	C12—C13—C14—C9	0.8 (3)
O1—N1—C5—C4	−164.68 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1i	0.95	2.56	3.394 (2)	146