Skip to main content
NCBI home page
Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2022 Apr 28;78(Pt 5):530–535. doi: 10.1107/S2056989022004388

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

Zeliha Atioğlu a, Mehmet Akkurt b, Namiq Q Shikhaliyev c, Naila A Mammadova c, Gulnara V Babayeva c,d, Victor N Khrustalev e,f, Ajaya Bhattarai g,*
PMCID: PMC9069519  PMID: 35547788

C—H⋯O and C—H⋯F hydrogen bonds link mol­ecules in the crystal into layers parallel to (011). The crystal packing is consolidated through C—Br⋯π and C—F⋯π inter­actions, as well as π–π stacking inter­actions.

Keywords: crystal structure, C—H⋯O hydrogen bonds, C—H⋯F hydrogen bonds, C—Br⋯π inter­actions, C—F⋯π inter­actions, π–π stacking inter­actions, Hirshfeld surface analysis

Abstract

In the title compound, C14H8Br2FN3O2, the 4-fluoro­phenyl ring and the nitro-substituted phenyl ring form a dihedral angle of 64.37 (10)°. Mol­ecules in the crystal 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 inter­actions, as well as by π–π stacking inter­actions. According to a Hirshfeld surface analysis of the crystal structure, the most significant contributions to the crystal packing are from O⋯H/H⋯O (15.0%), H⋯H (14.3%), Br⋯H/H⋯Br (14.2%), C⋯H/H⋯C (10.1%), F⋯H/H⋯F (7.9%), Br⋯Br (7.2%) and Br⋯C/C⋯Br (5.8%) contacts.

1. Chemical context

Azo dyes are characterized by one or more azo groups R—N=N—R′, where R and R′ can be either alkyl, aryl or heterocyclic functional groups. Depending on the attached substituents, azo compounds have attracted attention because of their high synthetic potential for organic and inorganic chemistry and numerous useful properties. For example, azo dyes find applications in the design of functional materials attributed to smart hydrogen bonding, as self-assembled layers, photo-triggered structural switching, liquid crystals, ionophors, indicators, semiconductors, spectrophotometric reagents for determination of metal ions, catalysts, photoluminescent materials, optical recording media, spin-coating films and anti­microbial agents (Kopylovich et al., 2012 ▸; Ma et al., 2020 ▸, 2021 ▸; Mac Leod et al., 2012 ▸; Viswanathan et al., 2019 ▸). The azo-to-hydrazo tautomerism and E/Z isomerization properties of azo compounds are both crucial phenomena in the synthesis and design of new functional materials (Mahmudov et al., 2012 ▸, 2013 ▸, 2020 ▸; Mizar et al., 2012 ▸). Moreover, attachment of functional groups to the azo compounds acting as non-covalent donors or acceptors can be applied as a synthetic strategy for the improvement of the functional properties of this class of organic compounds (Gurbanov et al., 2020a ▸,b ▸; Mahmoudi et al., 2017 ▸, 2018 ▸; Shixaliyev et al., 2013 ▸, 2014 ▸).

In the above context, we have attached F, Br and NO2 groups and aryl rings to the –N=N– moiety leading to a new azo compound, (E)-1-[2,2-di­bromo-1-(4-nitro­phen­yl)ethen­yl]-2-(4-fluoro­phen­yl)diazene, the mol­ecular and crystal structure of which along with a Hirshfeld surface analysis are reported here. 1.

2. Structural commentary

The mol­ecular conformation of the title compound is not planar, as seen in Fig. 1 ▸, with the 4-fluoro­phenyl ring and the nitro-substituted phenyl ring subtending a dihedral angle of 64.37 (10)°. The C1=C2 double bond has a small twist, with the dihedral angle between atoms C1/Br1/Br2 and C2/C3/N2 being 3.99 (10)°, possibly to minimize steric repulsion between Br2 and H. The N3/N2/C2/C1/Br1/Br2 moiety subtends dihedral angles of 63.70 (8) and 1.39 (8)° with the C3–C8 and C9–C14 rings, respectively. The aromatic ring and olefin synthon in the mol­ecule are trans-configured with regard to the N=N double bond and are practically coplanar as revealed by the C2—N2=N3—C9 torsion angle of −178.63 (16)°. All of the bond lengths and angles in the title compound are similar to those for the related azo compounds reported in the Database survey section.

Figure 1.

Figure 1

Open in a new tab

The title mol­ecule with the labelling scheme and displacement ellipsoids drawn at the 50% probability level.

3. Supra­molecular features

In the crystal, mol­ecules are linked by C—H⋯O and C—H⋯F hydrogen bonds into layers extending parallel to (011) (Table 1 ▸; Figs. 2 ▸–4 ▸ ▸). The crystal packing is consolidated by C—Br⋯π [Br1⋯Cg1 (x, Inline graphic  − y, − Inline graphic  + z) = 3.6016 (9) Å, C1—Br1⋯Cg1 = 104.24 (7)°] and C—F⋯π [F1⋯Cg2 (1 − x, 1 − y, −z) = 3.5032 (17) Å, C12—F1⋯Cg2 = 92.53 (11)°] inter­actions, and weak π–π stacking [Cg1⋯Cg2 (x, Inline graphic  − y, Inline graphic  + z) = 4.0788 (12) Å, slippage = 1.776 Å], where Cg1 and Cg2 are the centroids of the C3–C8 and C9–C14 rings, respectively, (Figs. 5 ▸–7 ▸ ▸)].

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C4—H4⋯O2i 0.95 2.47 3.331 (3) 151
C5—H5⋯F1ii 0.95 2.54 3.150 (3) 122
C11—H11⋯O2iii 0.95 2.58 3.367 (3) 140
C14—H14⋯F1iv 0.95 2.49 3.427 (3) 169
Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) Inline graphic ; (iii) Inline graphic ; (iv) Inline graphic .

Figure 2.

Figure 2

Open in a new tab

View down [100] of the C—H⋯O and C—H⋯F inter­actions (dashed lines) in the title compound.

Figure 3.

Figure 3

Open in a new tab

View down [010] of the C—H⋯O and C—H⋯F inter­actions (dashed lines) in the title compound.

Figure 4.

Figure 4

Open in a new tab

View down [001] of the C—H⋯O and C—H⋯F inter­actions (dashed lines) in the title compound.

Figure 5.

Figure 5

Open in a new tab

View down [100] of the title compound, showing the mol­ecular packing including C—Br⋯π and C—F⋯π inter­actions, as well as π–π inter­actions.

Figure 6.

Figure 6

Open in a new tab

View down [010] of the title compound, showing the mol­ecular packing including C—Br⋯π and C—F⋯π inter­actions, as well as π–π inter­actions.

Figure 7.

Figure 7

Open in a new tab

View down [001] of the title compound, showing the mol­ecular packing including C—Br⋯π and C—F⋯π inter­actions, as well as π–π inter­actions.

4. Hirshfeld surface analysis

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 −0.1845 (red) to 1.1463 (blue) a.u. (Fig. 8 ▸). The red spots symbolize short contacts and negative d norm values on the surface corresponding to the C—H⋯O and C—H⋯F hydrogen bonds described above (Table 1 ▸). The C4—H4⋯O2 and C11—H11⋯O2 inter­actions, which play a key role in the mol­ecular packing of the title compound, are responsible for the red spot that occurs around O2. The bright-red spots appearing near O2 and hydrogen atoms H4 and H11 indicate their roles as donor and/or acceptor groups in hydrogen bonding; they also appear as blue and red regions corres­ponding to positive and negative potentials on the Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ▸) shown in Fig. 9 ▸.

Figure 8.

Figure 8

Open in a new tab

View of the three-dimensional Hirshfeld surface of the title compound plotted over d norm in the range −0.1845 to 1.1463 a.u.

Figure 9.

Figure 9

Open in a new tab

View of the three-dimensional Hirshfeld surface of the title complex 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. The hydrogen-bond donor and acceptor groups are viewed as blue and red regions, respectively around the atoms, corresponding to positive and negative potentials.

The overall two-dimensional fingerprint plot for the title compound is given in Fig. 10 ▸ a, and those delineated into O⋯H/H⋯O, H⋯H, Br⋯H/H⋯Br, C⋯H/H⋯C, F⋯H/H⋯F, Br⋯Br and Br⋯C/C⋯Br contacts are shown in Fig.10b–h, while numerical details of the different contacts are given in Table 2 ▸. The percentage contributions to the Hirshfeld surfaces from the various inter­atomic contacts are compiled in Table 3 ▸. N⋯H/H⋯N, C⋯C, O⋯C/C⋯O, F⋯C/C⋯F, Br.·O/O⋯Br, N⋯C/C⋯N, N⋯O/O⋯N, N⋯N and F⋯F contacts contribute less than 5.7% to the Hirshfeld surface mapping and have little directional influence on the mol­ecular packing (Table 3 ▸).

Figure 10.

Figure 10

Open in a new tab

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) Br⋯H / H⋯Br, (e) C⋯H / H⋯C, (f) F⋯H / H⋯F, (g) Br⋯Br and (h) Br⋯C / C⋯Br inter­actions. The d i and d e values are the closest inter­nal and external distances (in Å) from given points on the Hirshfeld surface.

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

Contact Distance Symmetry operation
C1⋯Br2 3.6060 −x, Inline graphic  + y, Inline graphic  − z
Br1⋯Br1 3.7247 −x, 1 − y, −z
H4⋯O2 2.47 x, Inline graphic  − y, − Inline graphic  + z
H7⋯Br2 3.08 −x, 1 − y, 1 − z
F1⋯H5 2.54 1 − x, Inline graphic  + y, Inline graphic  − z
C12⋯F1 3.3310 1 − x, 2 − y, −z
H14⋯F1 2.49 x, Inline graphic  − y, Inline graphic  + z
O2⋯H11 2.58 x, y, 1 + z
H13⋯O2 2.69 1 − x, 1 − y, 1 − z
C12⋯C12 3.5050 1 − x, 1 − y, −z
Open in a new tab

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

Contact Percentage contribution
O⋯H/H⋯O 15.0
H⋯H 14.3
Br⋯H/H⋯Br 14.2
C⋯H/H⋯C 10.1
F⋯H/H⋯F 7.9
Br⋯Br 7.2
Br.·C/C⋯Br 5.8
N⋯H/H⋯N 5.7
C⋯C 4.2
O⋯C/C⋯O 4.0
F⋯C/C⋯F 3.1
Br.·O/O⋯Br 2.7
N⋯C/C⋯N 2.1
N⋯O/O⋯N 2.0
N⋯N 1.0
F⋯F 0.8
Open in a new tab

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ▸) for the (E)-1-(2,2-di­chloro-1-phenyl­ethen­yl)-2-phenyl­diazene moiety resulted in 27 hits. Eight compounds are closely related to the title compound, viz. those with CSD refcodes GUPHIL (I) (Özkaraca et al., 2020 ▸), HONBUK (II) (Akkurt et al., 2019 ▸), HONBOE (III) (Akkurt et al., 2019 ▸), HODQAV (IV) (Shikhaliyev et al., 2019a ▸), XIZREG (V) (Atioğlu et al., 2019 ▸), LEQXOX (VI) (Shikhaliyev et al., 2018a ▸), LEQXIR (VII) (Shikhaliyev et al., 2018b ▸) and PAXDOL (VIII) (Çelikesir et al., 2022 ▸).

In the crystal of (I), 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 (II) and (III), mol­ecules are linked through weak X⋯Cl contacts [X = Cl for (II) and Br for (III)], C—H⋯Cl and C—Cl⋯π inter­actions into sheets lying parallel to (001). In the crystal of (IV), 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 (V), 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 (VI), C—H⋯N and short Cl⋯Cl contacts are observed, and in (VII), C—H⋯N and C—H⋯O hydrogen bonds and short Cl⋯O contacts occur. In the crystal of (VIII), mol­ecules are linked into chains running parallel to [001] by C—H⋯O hydrogen bonds. The crystal packing is consolidated by C—F⋯π inter­actions and π–π stacking inter­actions, and short Br⋯O [2.9828 (13) Å] contacts are also observed.

6. Synthesis and crystallization

The title compound was synthesized according to a reported method (Akkurt et al., 2019 ▸; Atioğlu et al., 2019 ▸; Maharramov et al., 2018 ▸; Özkaraca et al., 2020 ▸; Shikhaliyev et al., 2018a ▸,b ▸, 2019a ▸,b ▸). A 20 ml screw-neck vial was charged with dimethyl sulfoxide (10 ml), (E)-1-(4-fluoro­phen­yl)-2-(4-nitro­benzyl­idene)hydrazine (1 mmol), tetra­methyl­ethylenedi­amine (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 the corresponding Schiff base), the reaction mixture was poured into a 0.01 M HCl solution (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 (v/v 3/1–1/1). Light-orange solid (yield 52%); m.p. 377 K. Analysis calculated for C14H8Br2FN3O2 (M = 429.04): C 39.19, H 1.88, N 9.79; found: C 39.17, H 1.85, N 9.76%. 1H NMR (300MHz, CDCl3) δ 7.36–7.14 (8H, Ar–H). 13C NMR (75MHz, CDCl3) δ 164.35, 153.13, 152.46, 133.69, 133.24, 131.74, 127.98, 127.89, 127.75, 127.42, 119.07, 89.02. ESI–MS: m/z: 430.06 [M + H]+. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. All H atoms were positioned geometrically [C—H = 0.95 Å] and refined using a riding model with U iso(H) = 1.2U eq(C). The maximum electron density in the final difference map is located 0.75 Å from atom Br1, while the minimum electron density is located 0.72 Å from Br2.

Table 4. Experimental details.

Crystal data
Chemical formula C14H8Br2FN3O2
M r 429.05
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 16.0658 (2), 7.0329 (1), 12.7934 (2)
β (°) 96.8470 (6)
V (Å3) 1435.21 (4)
Z 4
Radiation type Mo Kα
μ (mm−1) 5.67
Crystal size (mm) 0.37 × 0.21 × 0.08
 
Data collection
Diffractometer Bruker AXS D8 QUEST, Photon III detector
Absorption correction Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max 0.415, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections 44165, 4177, 3809
R int 0.102
(sin θ/λ)max (Å−1) 0.703
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.034, 0.096, 1.05
No. of reflections 4177
No. of parameters 199
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 2.00, −1.04
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/S2056989022004388/wm5642sup1.cif

e-78-00530-sup1.cif (1.6MB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004388/wm5642Isup2.hkl

e-78-00530-Isup2.hkl (332.9KB, hkl)

CCDC reference: 2168678

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

Acknowledgments

The authors’ 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

C14H8Br2FN3O2 F(000) = 832
Mr = 429.05 Dx = 1.986 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å
a = 16.0658 (2) Å Cell parameters from 9926 reflections
b = 7.0329 (1) Å θ = 3.2–33.2°
c = 12.7934 (2) Å µ = 5.67 mm−1
β = 96.8470 (6)° T = 100 K
V = 1435.21 (4) Å3 Plate, light red
Z = 4 0.37 × 0.21 × 0.08 mm
Open in a new tab

Data collection

Bruker AXS D8 QUEST, Photon III detector diffractometer 4177 independent reflections
Radiation source: fine-focus sealed X-Ray tube 3809 reflections with I > 2σ(I)
Graphite monochromator Rint = 0.102
Detector resolution: 7.31 pixels mm-1 θmax = 30.0°, θmin = 2.6°
φ and ω shutterless scans h = −22→22
Absorption correction: multi-scan (SADABS; Krause et al., 2015) k = −9→9
Tmin = 0.415, Tmax = 0.747 l = −17→17
44165 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)] = 0.034 Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096 H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0647P)2 + 0.5442P] where P = (Fo2 + 2Fc2)/3
4177 reflections (Δ/σ)max < 0.001
199 parameters Δρmax = 2.00 e Å−3
0 restraints Δρmin = −1.04 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 0.07857 (2) 0.35922 (3) 0.08663 (2) 0.01718 (8)
Br2 0.02778 (2) 0.28084 (3) 0.31239 (2) 0.02246 (8)
C1 0.10911 (13) 0.3752 (3) 0.23267 (15) 0.0143 (3)
C2 0.18336 (12) 0.4450 (3) 0.27612 (15) 0.0135 (3)
C3 0.20411 (12) 0.4693 (3) 0.39184 (15) 0.0131 (3)
C4 0.26892 (13) 0.3653 (3) 0.44734 (16) 0.0151 (4)
H4 0.301935 0.282209 0.410651 0.018*
C5 0.28537 (13) 0.3827 (3) 0.55606 (16) 0.0148 (3)
H5 0.329792 0.313645 0.594394 0.018*
C6 0.23537 (13) 0.5033 (3) 0.60701 (15) 0.0141 (3)
C7 0.17169 (13) 0.6115 (3) 0.55419 (16) 0.0158 (4)
H7 0.139047 0.694455 0.591491 0.019*
C8 0.15669 (12) 0.5958 (3) 0.44533 (15) 0.0143 (3)
H8 0.114268 0.670850 0.407127 0.017*
N1 0.24975 (12) 0.5135 (2) 0.72236 (14) 0.0178 (3)
O1 0.19544 (12) 0.5861 (2) 0.76893 (13) 0.0259 (3)
O2 0.31534 (11) 0.4454 (2) 0.76654 (12) 0.0245 (3)
N2 0.23866 (11) 0.4967 (2) 0.20300 (13) 0.0153 (3)
N3 0.31074 (11) 0.5492 (3) 0.24360 (14) 0.0165 (3)
C9 0.36346 (12) 0.6039 (3) 0.16716 (15) 0.0144 (3)
C10 0.33917 (13) 0.6020 (3) 0.05795 (16) 0.0158 (4)
H10 0.285307 0.556049 0.030764 0.019*
C11 0.39360 (14) 0.6669 (3) −0.00982 (16) 0.0177 (4)
H11 0.377788 0.667540 −0.083780 0.021*
C12 0.47214 (14) 0.7314 (3) 0.03294 (17) 0.0185 (4)
C13 0.49862 (14) 0.7325 (3) 0.13950 (18) 0.0203 (4)
H13 0.553030 0.776322 0.165862 0.024*
C14 0.44330 (14) 0.6675 (3) 0.20716 (17) 0.0186 (4)
H14 0.459864 0.666418 0.280965 0.022*
F1 0.52527 (9) 0.7950 (2) −0.03383 (11) 0.0261 (3)
Open in a new tab

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Br1 0.01901 (12) 0.01931 (12) 0.01257 (11) 0.00170 (7) −0.00084 (8) −0.00163 (6)
Br2 0.02126 (13) 0.02844 (14) 0.01798 (12) −0.00940 (8) 0.00360 (8) 0.00113 (8)
C1 0.0179 (9) 0.0133 (8) 0.0121 (8) −0.0006 (7) 0.0030 (7) 0.0007 (6)
C2 0.0173 (8) 0.0111 (8) 0.0124 (8) 0.0016 (6) 0.0022 (6) 0.0007 (6)
C3 0.0144 (8) 0.0131 (8) 0.0118 (8) −0.0003 (6) 0.0022 (6) 0.0005 (6)
C4 0.0176 (9) 0.0159 (9) 0.0124 (8) 0.0025 (7) 0.0038 (7) 0.0002 (6)
C5 0.0165 (8) 0.0144 (8) 0.0134 (8) 0.0000 (7) 0.0013 (7) 0.0020 (7)
C6 0.0196 (9) 0.0124 (8) 0.0105 (8) −0.0044 (7) 0.0027 (7) −0.0002 (6)
C7 0.0197 (9) 0.0124 (8) 0.0159 (9) 0.0001 (7) 0.0052 (7) −0.0017 (7)
C8 0.0156 (8) 0.0133 (8) 0.0142 (8) 0.0016 (7) 0.0023 (7) 0.0000 (7)
N1 0.0269 (9) 0.0122 (7) 0.0147 (8) −0.0054 (6) 0.0037 (6) −0.0008 (6)
O1 0.0394 (9) 0.0243 (8) 0.0159 (7) 0.0010 (7) 0.0107 (7) −0.0038 (6)
O2 0.0325 (9) 0.0245 (8) 0.0150 (7) −0.0041 (7) −0.0029 (6) 0.0020 (6)
N2 0.0182 (8) 0.0141 (7) 0.0139 (7) 0.0018 (6) 0.0026 (6) 0.0002 (6)
N3 0.0192 (8) 0.0158 (8) 0.0148 (7) 0.0010 (6) 0.0034 (6) 0.0005 (6)
C9 0.0172 (9) 0.0133 (8) 0.0128 (8) 0.0019 (7) 0.0026 (7) −0.0002 (7)
C10 0.0179 (9) 0.0154 (8) 0.0140 (8) 0.0004 (7) 0.0012 (7) −0.0010 (7)
C11 0.0212 (9) 0.0184 (9) 0.0132 (8) −0.0013 (8) 0.0015 (7) −0.0007 (7)
C12 0.0194 (9) 0.0183 (9) 0.0188 (9) −0.0006 (7) 0.0062 (8) 0.0009 (7)
C13 0.0168 (9) 0.0232 (10) 0.0205 (10) −0.0025 (8) 0.0012 (8) −0.0018 (8)
C14 0.0198 (9) 0.0217 (9) 0.0140 (9) −0.0006 (8) 0.0004 (7) −0.0017 (7)
F1 0.0239 (7) 0.0354 (8) 0.0202 (6) −0.0064 (6) 0.0081 (5) 0.0037 (6)
Open in a new tab

Geometric parameters (Å, º)

Br1—C1 1.878 (2) N1—O1 1.225 (2)
Br2—C1 1.872 (2) N1—O2 1.232 (3)
C1—C2 1.347 (3) N2—N3 1.266 (2)
C2—N2 1.412 (3) N3—C9 1.421 (3)
C2—C3 1.488 (3) C9—C14 1.397 (3)
C3—C4 1.395 (3) C9—C10 1.405 (3)
C3—C8 1.402 (3) C10—C11 1.380 (3)
C4—C5 1.390 (3) C10—H10 0.9500
C4—H4 0.9500 C11—C12 1.390 (3)
C5—C6 1.384 (3) C11—H11 0.9500
C5—H5 0.9500 C12—F1 1.354 (2)
C6—C7 1.385 (3) C12—C13 1.379 (3)
C6—N1 1.468 (2) C13—C14 1.390 (3)
C7—C8 1.389 (3) C13—H13 0.9500
C7—H7 0.9500 C14—H14 0.9500
C8—H8 0.9500
C2—C1—Br2 123.06 (15) O1—N1—O2 123.97 (19)
C2—C1—Br1 123.08 (15) O1—N1—C6 118.25 (18)
Br2—C1—Br1 113.85 (10) O2—N1—C6 117.77 (17)
C1—C2—N2 114.61 (17) N3—N2—C2 114.84 (17)
C1—C2—C3 122.32 (17) N2—N3—C9 112.81 (17)
N2—C2—C3 123.05 (17) C14—C9—C10 120.10 (19)
C4—C3—C8 120.02 (18) C14—C9—N3 115.55 (18)
C4—C3—C2 120.73 (17) C10—C9—N3 124.33 (18)
C8—C3—C2 119.23 (17) C11—C10—C9 119.98 (19)
C5—C4—C3 120.28 (18) C11—C10—H10 120.0
C5—C4—H4 119.9 C9—C10—H10 120.0
C3—C4—H4 119.9 C10—C11—C12 118.29 (19)
C6—C5—C4 118.27 (18) C10—C11—H11 120.9
C6—C5—H5 120.9 C12—C11—H11 120.9
C4—C5—H5 120.9 F1—C12—C13 118.6 (2)
C5—C6—C7 122.93 (18) F1—C12—C11 118.07 (19)
C5—C6—N1 118.21 (18) C13—C12—C11 123.3 (2)
C7—C6—N1 118.85 (17) C12—C13—C14 118.0 (2)
C6—C7—C8 118.38 (18) C12—C13—H13 121.0
C6—C7—H7 120.8 C14—C13—H13 121.0
C8—C7—H7 120.8 C13—C14—C9 120.3 (2)
C7—C8—C3 120.04 (18) C13—C14—H14 119.8
C7—C8—H8 120.0 C9—C14—H14 119.8
C3—C8—H8 120.0
Br2—C1—C2—N2 175.66 (13) C7—C6—N1—O1 14.3 (3)
Br1—C1—C2—N2 −3.1 (3) C5—C6—N1—O2 14.4 (3)
Br2—C1—C2—C3 −5.6 (3) C7—C6—N1—O2 −166.82 (18)
Br1—C1—C2—C3 175.56 (14) C1—C2—N2—N3 −175.03 (18)
C1—C2—C3—C4 115.8 (2) C3—C2—N2—N3 6.3 (3)
N2—C2—C3—C4 −65.7 (3) C2—N2—N3—C9 −178.63 (16)
C1—C2—C3—C8 −63.1 (3) N2—N3—C9—C14 178.57 (18)
N2—C2—C3—C8 115.5 (2) N2—N3—C9—C10 0.4 (3)
C8—C3—C4—C5 1.7 (3) C14—C9—C10—C11 −1.4 (3)
C2—C3—C4—C5 −177.12 (18) N3—C9—C10—C11 176.7 (2)
C3—C4—C5—C6 0.8 (3) C9—C10—C11—C12 0.6 (3)
C4—C5—C6—C7 −2.1 (3) C10—C11—C12—F1 −179.95 (19)
C4—C5—C6—N1 176.62 (18) C10—C11—C12—C13 0.5 (3)
C5—C6—C7—C8 1.0 (3) F1—C12—C13—C14 179.7 (2)
N1—C6—C7—C8 −177.77 (17) C11—C12—C13—C14 −0.7 (3)
C6—C7—C8—C3 1.5 (3) C12—C13—C14—C9 −0.1 (3)
C4—C3—C8—C7 −2.9 (3) C10—C9—C14—C13 1.2 (3)
C2—C3—C8—C7 175.96 (18) N3—C9—C14—C13 −177.1 (2)
C5—C6—N1—O1 −164.51 (19)
Open in a new tab

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
C4—H4···O2i 0.95 2.47 3.331 (3) 151
C5—H5···F1ii 0.95 2.54 3.150 (3) 122
C11—H11···O2iii 0.95 2.58 3.367 (3) 140
C14—H14···F1iv 0.95 2.49 3.427 (3) 169
Open in a new tab

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x, y, z−1; (iv) x, −y+3/2, 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. 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]
  3. Bruker (2018). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  4. 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]
  5. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
  6. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
  7. 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.
  8. Gurbanov, A. V., Kuznetsov, M. L., Mahmudov, K. T., Pombeiro, A. J. L. & Resnati, G. (2020b). Chem. Eur. J. 26, 14833–14837. [DOI] [PubMed]
  9. Kopylovich, M. N., Mac Leod, T. C. O., Haukka, M., Amanullayeva, G. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2012). J. Inorg. Biochem. 115, 72–77. [DOI] [PubMed]
  10. Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. [DOI] [PMC free article] [PubMed]
  11. 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.
  12. Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 423, 213482.
  13. Mac Leod, T. C., Kopylovich, M. N., Guedes da Silva, M. F. C., Mahmudov, K. T. & Pombeiro, A. J. L. (2012). Appl. Catal. Gen. 439–440, 15–23.
  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. 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. (2018). Inorg. Chem. 57, 4395–4408. [DOI] [PubMed]
  16. Mahmoudi, G., Zaręba, J. K., Gurbanov, A. V., Bauzá, A., Zubkov, F. I., Kubicki, M., Stilinović, V., Kinzhybalo, V. & Frontera, A. (2017). Eur. J. Inorg. Chem. pp. 4763–4772.
  17. Mahmudov, K. T., Guedes da Silva, M. F. C., Glucini, M., Renzi, M., Gabriel, K. C. P., Kopylovich, M. N., Sutradhar, M., Marchetti, F., Pettinari, C., Zamponi, S. & Pombeiro, A. J. L. (2012). Inorg. Chem. Commun. 22, 187–189.
  18. Mahmudov, K. T., Gurbanov, A. V., Aliyeva, V. A., Resnati, G. & Pombeiro, A. J. L. (2020). Coord. Chem. Rev. 418, 213381.
  19. 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.
  20. 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.
  21. Özkaraca, K., Akkurt, M., Shikhaliyev, N. Q., Askerova, U. F., Suleymanova, G. T., Mammadova, G. Z. & Shadrack, D. M. (2020). Acta Cryst. E76, 1251–1254. [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. (2018a). Dyes Pigments, 150, 377–381.
  25. 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. (2018b). Dyes Pigments, 150, 377–381.
  26. 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. (2019a). CrystEngComm, 21, 5032–5038.
  27. 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. (2019b). CrystEngComm, 21, 5032–5038.
  28. 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.
  29. 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.
  30. Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388.
  31. Spek, A. L. (2020). Acta Cryst. E76, 1–11. [DOI] [PMC free article] [PubMed]
  32. 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.
  33. Viswanathan, A., Kute, D., Musa, A., Mani, S. K., Sipilä, V., Emmert-Streib, F., Zubkov, F. I., Gurbanov, A. V., Yli-Harja, O. & Kandhavelu, M. (2019). Eur. J. Med. Chem. 166, 291–303. [DOI] [PubMed]

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/S2056989022004388/wm5642sup1.cif

e-78-00530-sup1.cif (1.6MB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004388/wm5642Isup2.hkl

e-78-00530-Isup2.hkl (332.9KB, hkl)

CCDC reference: 2168678

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