Skip to main content
NCBI home page
Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2022 Jul 14;78(Pt 8):804–808. doi: 10.1107/S2056989022007113

Crystal structure and Hirshfeld surface analysis of a new polymorph of (E)-2-(4-bromo­phen­yl)-1-[2,2-di­bromo-1-(3-nitro­phen­yl)ethen­yl]diazene

Zeliha Atioğlu a, Mehmet Akkurt b, Namiq Q Shikhaliyev c, Naila A Mammadova c, Gülnara V Babayeva c,d, Victor N Khrustalev e, Ajaya Bhattarai f,*
Editor: A V Yatsenkog
PMCID: PMC9361372  PMID: 35974833

The a new polymorph of the title compound is reported in which the C—H⋯O hydrogen bonds and π-π stacking inter­actions link mol­ecules into the layers in the crystal.

Keywords: crystal structure, azo compounds, polymorphism, C—H⋯O inter­actions, Hirshfeld surface analysis

Abstract

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 mol­ecules into chains. These chains are linked by face-to-face π–π stacking inter­actions, resulting in a layered structure. Short inter-mol­ecular Br⋯O contacts and van der Waals inter­actions between the layers aid in the cohesion of the crystal packing. In the previously reported form-1, C—H⋯Br inter­actions connect mol­ecules into zigzag chains, which are linked by C—Br⋯π inter­actions into layers, whereas the van der Waals inter­actions between the layers stabilize the crystal packing of form-2. Hirshfeld mol­ecular surface analysis was used to compare the inter­molecular inter­actions of the polymorphs.

1. 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. 1.

2. 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.

Figure 1

Open in a new tab

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

3. 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(− Inline graphic  + x, y, Inline graphic  − z) = 3.7305 (11) Å, slippage: 2.057 Å; Cg1⋯Cg1( Inline graphic  + x, y, Inline graphic  − 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
Open in a new tab

Symmetry code: (i) Inline graphic .

Figure 2.

Figure 2

Open in a new tab

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

Figure 3.

Figure 3

Open in a new tab

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

Figure 4.

Figure 4

Open in a new tab

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, − Inline graphic  + y, Inline graphic  − z
H7⋯N3 2.78 − Inline graphic  + x, y, Inline graphic  − z
Br1⋯O2 3.137 (2) − Inline graphic  − x, − Inline graphic  + y, z
Br1⋯H14 2.98 Inline graphic  − x, − Inline graphic  + y, z
Br2⋯H13 3.15 Inline graphic  − x, − Inline graphic  + y, z
Br3⋯H10 3.02 Inline graphic  + x, Inline graphic  − y, 1 − z
C13⋯Br3 3.569 (2) 2 − x, 1 − y, 1 − z
Open in a new tab

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.

Figure 5

Open in a new tab

(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.

Figure 6

Open in a new tab

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.

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)-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.

5. 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]+.

6. 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
Open in a new tab

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

Supplementary Material

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

e-78-00804-sup1.cif (2.3MB, cif)

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

e-78-00804-Isup2.hkl (440.9KB, hkl)
Click here for additional data file. (5.2KB, cml)

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

CCDC reference: 2189348

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

Acknowledgments

The author’s contributions are as follows. Conceptualization, NQS, MA and AB; synthesis, NAM and GVB; X-ray analysis, ZA, VNK and MA; writing (review and editing of the manuscript) ZA, MA and AB; funding acquisition, NQS, NAM and GVB; supervision, NQS, MA and AB.

supplementary crystallographic information

Crystal data

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
Open in a new tab

Data collection

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
Open in a new tab

Refinement

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
Open in a new tab

Special details

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.
Open in a new tab

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

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*
Open in a new tab

Atomic displacement parameters (Å2)

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)
Open in a new tab

Geometric parameters (Å, º)

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)
Open in a new tab

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
C8—H8···O1i 0.95 2.56 3.394 (2) 146
Open in a new tab

Symmetry code: (i) −x, y−1/2, −z+1/2.

Funding Statement

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

  1. 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. [DOI] [PMC free article] [PubMed]
  2. Akkurt, M., Yıldırım, S. Ö., Shikhaliyev, N. Q., Mammadova, N. A., Niyazova, A. A., Khrustalev, V. N. & Bhattarai, A. (2022). Acta Cryst. E78, 732–736. [DOI] [PMC free article] [PubMed]
  3. Atioğlu, Z., Akkurt, M., Shikhaliyev, N. Q., Mammadova, N. A., Babayeva, G. V., Khrustalev, V. N. & Bhattarai, A. (2022). Acta Cryst. E78, 530–535. [DOI] [PMC free article] [PubMed]
  4. Atioğlu, Z., Akkurt, M., Shikhaliyev, N. Q., Suleymanova, G. T., Bagirova, K. N. & Toze, F. A. A. (2019). Acta Cryst. E75, 237–241. [DOI] [PMC free article] [PubMed]
  5. Bruker (2018). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  6. Çelikesir, S. T., Akkurt, M., Shikhaliyev, N. Q., Mammadova, N. A., Suleymanova, G. T., Khrustalev, V. N. & Bhattarai, A. (2022). Acta Cryst. E78, 404–408. [DOI] [PMC free article] [PubMed]
  7. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
  8. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
  9. 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.
  10. Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020b). Chem. Eur. J. 26, 14833–14837. [DOI] [PubMed]
  11. Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. [DOI] [PMC free article] [PubMed]
  12. 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.
  13. Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 423, 213482.
  14. 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.
  15. Mahmudov, K. T., Gurbanov, A. V., Aliyeva, V. A., Guedes da Silva, M. F. C., Resnati, G. & Pombeiro, A. J. L. (2022). Coord. Chem. Rev. 464, 214556.
  16. Mahmudov, K. T., Gurbanov, A. V., Aliyeva, V. A., Resnati, G. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 418, 213381.
  17. Mahmudov, K. T., Huseynov, F. E., Aliyeva, V. A., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Chem. Eur. J. 27, 14370–14389. [DOI] [PubMed]
  18. Mahmudov, K. T., Kopylovich, M. N. & Pombeiro, A. J. L. (2013). Coord. Chem. Rev. 257, 1244–1281.
  19. Mahmudov, K. T., Maharramov, A. M., Aliyeva, R. A., Aliyev, I. A., Kopylovich, M. N. & Pombeiro, A. J. L. (2010). Anal. Lett. 43, 2923–2938.
  20. 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. [DOI] [PMC free article] [PubMed]
  21. Özkaraca, K., Akkurt, M., Shikhaliyev, N. Q., Askerova, U. F., Suleymanova, G. T., Shikhaliyeva, I. M. & Bhattarai, A. (2020b). Acta Cryst. E76, 811–815. [DOI] [PMC free article] [PubMed]
  22. Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
  23. Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
  24. 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.
  25. 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.
  26. 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.
  27. Shixaliyev, N. Q., Maharramov, A. M., Gurbanov, A. V., Nenajdenko, V. G., Muzalevskiy, V. M., Mahmudov, K. T. & Kopylovich, M. N. (2013). Catal. Today, 217, 76–79.
  28. Spek, A. L. (2020). Acta Cryst. E76, 1–11. [DOI] [PMC free article] [PubMed]
  29. Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17.5. University of Western Australia.http://hirshfeldsuface.net
  30. Zollinger, H. (1994). Diazo Chemistry I: Aromatic and Heteroaromatic Compounds. New York: Wiley.
  31. Zollinger, H. (1995). Diazo Chemistry II: Aliphatic, Inorganic and Organometallic Compounds. Weinheim: VCH.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

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

e-78-00804-sup1.cif (2.3MB, cif)

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

e-78-00804-Isup2.hkl (440.9KB, hkl)
Click here for additional data file. (5.2KB, cml)

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

CCDC reference: 2189348

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

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography

RESOURCES