# Crystal structure and Hirshfeld surface analysis of 4-allyl-6-bromo-2-(4-chlorophenyl)-4H-imidazo[4,5-b]pyridine

Selma Bourichi, Youssef Kandri Rodi, Tuncer Hökelek, Amal Haoudi, Catherine Renard, Frederic Capet

► To cite this version:

Selma Bourichi, Youssef Kandri Rodi, Tuncer Hökelek, Amal Haoudi, Catherine Renard, et al. Crystal structure and Hirshfeld surface analysis of 4-allyl-6-bromo-2-(4-chlorophenyl)-4H-imidazo[4,5-b]pyridine. Acta crystallographica Section E: Crystallographic communications [2015-..], 2019, 75, pp.43-48. 10.1107/S2056989018017322. hal-03038104

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Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 21 November 2018

Accepted 6 December 2018

Edited by H. Ishida, Okayama University, Japan

**Keywords:** crystal structure; imidazo[4,5-**b**]pyridine; Hirshfeld surface.

CCDC reference: 1883384

**Supporting information:** this article has
supporting information at journals.iucr.org/e

# Crystal structure and Hirshfeld surface analysis of 4-allyl-6-bromo-2-(4-chlorophenyl)-4H-imidazo-[4,5-**b**]pyridine

Selma Bourichi,ª Youssef Kandri Rodi,ª Tuncer Hökelek,ᵇ Amal Haoudi,ª* Catherine Renardc and Frédéric Capetc

The title compound, C₁₅H₁₁BrClN₃, is built up from a planar imidazo[4,5-**b**]-pyridine unit linked to phenyl and allyl substituents. The allyl substituent is rotated significantly out of the imidazo[4,5-**b**]pyridine plane, while the benzene ring is inclined by 3.84 (6)° to the ring system. In the crystal, molecules are linked *via* a pair of weak intermolecular C—H···N hydrogen bonds, forming an inversion dimer with an R₂(20) ring motif. The dimers are further connected by π–π stacking interactions between the imidazo[4,5-**b**]pyridine ring systems [centroid–centroid distances = 3.7161 (13) and 3.8478 (13) Å]. The important contributions to the Hirshfeld surface are H···H (35.9%), H···Cl/Cl···H (15.0%), H···C/C···H (12.4%), H···Br/Br···H (10.8%), H···N/N···H (7.5%), C···Br/Br···C (5.9%), C···C (5.5%) and C···N/N···C (4.0%) contacts.

## 1. Chemical context

Heterocyclic ring systems having an imidazo[4,5-**b**]pyridine unit can be considered as structural analogues of purines and have shown diverse biological activity depending on the substituents of the heterocyclic ring. Their activities include anticancer (Zhiqiang *et al.*, 2005), tuberculostatic (Bukowski & Janowiec, 1989) and antimitotic (Parthiban *et al.*, 2006) actions. Some imidazo[4,5-**b**]pyridine derivatives have also been reported as corrosion inhibitors for steel in acidic medium (Bouayad *et al.*, 2018; Sikine *et al.*, 2016), and some of them can be used to treat peptic ulcers, diabetes and mental illness (Scribner *et al.*, 2007; Liang *et al.*, 2007).

<figure><img src="image_3.png" /></figure>

As a continuation of our research work devoted to the development of substituted imidazo[4,5-**b**]pyridine derivatives (Bourichi *et al.*, 2016; Ouzidan *et al.*, 2010a,b,c), we report herein the synthesis, the molecular and crystal structures along with the Hirshfeld surface analysis of the title compound, a new imidazo[4,5-**b**]pyridine derivative, which was obtained by the reaction of allyl bromide with 6-bromo-2-(4-chlorophen-

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<footnote>ªLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'immouzzer, BP 2202, Fez, Morocco, ᵇDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and ᶜUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Université Lille 1, 59650 Villeneuve d'Ascq Cedex, France. *Correspondence e-mail: amalhaoudi2017@gmail.com</footnote>
<figure><img src="image_6.png" /><figcaption>Figure 1</figcaption></figure>

The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

yl)-4H-imidazo[4,5-b]pyridine in the presence of a catalytic quantity of tetra-n-butylammonium bromide under mild conditions.

## 2. Structural commentary

The title compound is built up from an imidazo[4,5-b]pyridine unit linked to phenyl and allyl substituents (Fig. 1). The imidazo[4,5-b]pyridine ring system is planar, with a maximum deviation of 0.016 (2) Å for atom C12. The ring system is inclined by 3.84 (6)° to the benzene C1–C6 ring, with the N2–C7–C6–C1 torsion angle being 3.3 (3)°. The allyl substituent is nearly perpendicular to the imidazo[4,5-b]pyridine plane, as indicated by the C8–N3–C13–C14 torsion angle of −97.3 (2)°. Atoms C6 and C13 are 0.038 (2) and 0.014 (2) Å, respectively, away from the imidazo[4,5-b]pyridine plane.

<figure><img src="image_7.png" /><figcaption>Figure 2</figcaption></figure>

A part of the packing diagram of the title compound, viewed down [010]. The weak intermolecular C–H···N hydrogen bonds are shown as dashed lines. H atoms not involved in the hydrogen bonding have been omitted for clarity.

<caption>Table 1</caption>

Hydrogen-bond geometry (Å, °).

<table><thead><tr><th>D–H···A</th><th>D–H</th><th>H···A</th><th>D···A</th><th>D–H···A</th></tr></thead><tbody><tr><td>C15–H15A···N1<sup>i</sup></td><td>0.93</td><td>2.59</td><td>3.454 (4)</td><td>155</td></tr></tbody></table>

Symmetry code: (i) $-x, -y + 1, -z + 1$.

## 3. Supramolecular features

In the crystal, molecules are linked via a pair of weak intermolecular C–H···N hydrogen bonds [C15–H15A···N1¹; symmetry code: (i) $-x, -y + 1, -z + 1$; Table 1], forming an inversion dimer with an $R_2^2(20)$ ring motif (Fig. 2). The dimers are further connected by $\pi$–$\pi$ stacking interactions between the imidazo[4,5-b]pyridine ring systems. The centroid–centroid distances, $Cg1···Cg1^{ii}$ and $Cg1···Cg2^i$ [symmetry code: (ii) $-x + 1, -y + 1, -z + 1$], are 3.7161 (13) and 3.8478 (13) Å, respectively, where $Cg1$ and $Cg2$ are the centroids of the N1/N2/C7–C9 and N3/C8–C12 rings, respectively.

## 4. Database survey

A non-para-substituted analogue, namely 4-allyl-6-bromo-2-phenyl-4H-imidazo[4,5-b]pyridine monohydrate, has been reported (Ouzidan et al., 2010c), and three similar structures,

<figure><img src="image_8.png" /><figcaption>Figure 3</figcaption></figure>

View of the three-dimensional Hirshfeld surface of the title compound plotted over $d_{norm}$ in the range −0.1373 to 1.1294 Å.

<figure><img src="image_9.png" /><figcaption>Figure 4</figcaption></figure>

Hirshfeld surface of the title compound plotted over shape index.
4-benzyl-6-bromo-2-phenyl-4H-imidazo[4,5-b]pyridine (Ouzidan et al., 2010b), 4-benzyl-6-bromo-2-methoxyphenyl-4H-imidazo-[4,5-b]pyridine monohydrate (Ouzidan et al., 2010a) and 4-benzyl-6-bromo-2-(4-chlorophenyl)-4H-imidazo[4,5-b]pyridine (Bourichi et al., 2017), have been also reported.

5. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the
crystal of the title compound, a Hirshfeld surface (HS)
analysis (Spackman & Jayatilaka, 2009) was carried out using

CrystalExplorer17.5 (Turner et al., 2017). In the HS plotted over dnorm (Fig. 3), the white surface indicates contacts with distances equal to the sum of the van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the sum of the van der Waals radii, respectively (Venkatesan et al., 2016). The bright-red spots appearing near atoms N1 and H15A indicate their roles as the respective donors and/or acceptors in the dominant C—H···N hydrogen bond (Table 1). The shape index (Fig. 4) clearly suggests that there are π–π interactions, which are shown as adjacent red and blue triangles. The

<figure><img src="image_10.png" /><figcaption>Figure 5</figcaption></figure>

The full two-dimensional fingerprint plots for the title compound, showing (a) all contacts, and delineated into (b) H···H, (c) H···Cl/Cl···H, (d) H···C/ C···H, (e) H···Br/Br···H, (f) H···N/N···H, (g) C···Br/Br···C, (h) C···C, (i) C···N/N···C, (j) C···Cl/Cl···C, (k) N···Br/Br···N and (l) N···N contacts. The *d*<sub>i</sub> and *d*<sub>c</sub> values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.
<figure><img src="image_11.png" /><figcaption>Figure 6</figcaption></figure>

The Hirshfeld surface representations with the function $d_{norm}$ plotted onto the surface for (a) H···H, (b) H···Cl/Cl···H, (c) H···C/C···H, (d) H···Br/Br···H, (e) H···N/N···H, (f) C···Br/Br···C, (g) C···C and (h) C···N/N···C contacts.

overall two-dimensional fingerprint plot and those delineated into H···H, H···Cl/Cl···H, H···C/C···H, H···Br/Br···H, H···N/N···H, C···Br/Br···C, C···C, C···N/N···C, C···Cl/Cl···C, N···Br/Br···N and N···N contacts (McKinnon *et al.*, 2007) are illustrated in Figs. 5(a)–(l), together with their relative contributions to the Hirshfeld surface. The contributions are 35.9, 15.0, 12.4, 10.8, 7.5, 5.9, 5.5, 4.0, 1.5, 1.2 and 0.2%, respectively, for H···H, H···Cl/Cl···H, H···C/C···H, H···Br/Br···H, H···N/N···H, C···Br/Br···C, C···C, C···N/

N···C, C···Cl/Cl···C, N···Br/Br···N and N···N contacts. The most important interaction is H···H (35.9%), which is reflected as widely scattered points of high density due to the large hydrogen content of the molecule [Fig. 5(b)]. The spike with the tip at $d_e = d_i = 1.16$ Å is due to the short interatomic H···H contacts. The H···Cl/Cl···H contacts (15.0%) have a nearly symmetrical distribution of points and a pair of spikes with tips at $d_e + d_i = 2.67$ Å [Fig. 5(c)]. In the absence of C—H···π interactions, the H···C/C···H contacts (12.4%) also
<table><caption>**Table 2**
Experimental details.</caption><tbody><tr><td colspan="2">Crystal data</td></tr><tr><td>Chemical formula</td><td>C<sub>15</sub>H<sub>11</sub>BrClN<sub>3</sub></td></tr><tr><td>M<sub>r</sub></td><td>348.63</td></tr><tr><td>Crystal system, space group</td><td>Triclinic, <i>P</i>&#773;<sup>1</sup></td></tr><tr><td>Temperature (K)</td><td>296</td></tr><tr><td>a, b, c (Å)</td><td>7.6218 (5), 8.5238 (5), 11.1093 (7)</td></tr><tr><td>α, β, γ (°)</td><td>95.739 (3), 98.880 (3), 94.979 (3)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>705.66 (8)</td></tr><tr><td>Z</td><td>2</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>3.09</td></tr><tr><td>Crystal size (mm)</td><td>0.3 × 0.23 × 0.06</td></tr><tr><td colspan="2">Data collection</td></tr><tr><td>Diffractometer</td><td>Bruker APEXII CCD</td></tr><tr><td>Absorption correction</td><td>Multi-scan (<i>SADABS</i>; Bruker, 2014)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.591, 0.746</td></tr><tr><td>No. of measured, independent and observed [<i>I</i> > 2σ(<i>I</i>)] reflections</td><td>31084, 4288, 3226</td></tr><tr><td>R<sub>int</sub></td><td>0.033</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.715</td></tr><tr><td colspan="2">Refinement</td></tr><tr><td>R[F<sup>2</sup> > 2σ(F<sup>2</sup>)], wR(F<sup>2</sup>), S</td><td>0.035, 0.089, 1.03</td></tr><tr><td>No. of reflections</td><td>4288</td></tr><tr><td>No. of parameters</td><td>181</td></tr><tr><td>H-atom treatment</td><td>H-atom parameters constrained</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.57, -0.47</td></tr></tbody></table>

Computer programs: *APEX2* and *SAINT* (Bruker, 2015), *SHELXT* (Sheldrick, 2015a), *SHELXL* (Sheldrick, 2015b), *ORTEP-3 for Windows* and *WinGX* (Farrugia, 2012) and *PLATON* (Spek, 2015).

have a nearly symmetrical distribution of points with tips at $d_e + d_i = 2.79$ Å [Fig. 5(d)]. The H···Br/Br···H contacts (10.8%) have a symmetrical distribution of points and a pair of spikes with tips at $d_e + d_i = 3.00$ Å [Fig. 5(e)]. A pair of spikes with tips at $d_e + d_i = 2.42$ Å (Fig. 5f) in the H···N/N···H contacts (7.5%) arises from the C—H···N hydrogen bond (Table 1). The C···Br/Br···C contacts (5.9%) have a pair of wings with tips at $d_e + d_i \sim 3.62$ Å [Fig. 5(g)]. The C···C contacts (5.5%) have an arrow-shaped distribution of points with the tip at $d_e = d_i = 1.75$ Å [Fig. 5(h)]. The C···N/N···C contacts (4.0%) have wide spikes with tips at $d_e + d_i = 3.44$ Å [Fig. 5(i)]. The HS representations with the function $d_{norm}$ plotted onto the surface are shown for the H···H, H···Cl/Cl···H, H···C/ C···H, H···Br/Br···H, H···N/N···H, C···Br/Br···C, C···C and C···N/N···C contacts [Figs. 6(a)–(h)].

## 5. Synthesis and crystallization

A mixture of 6-bromo-2-(4-chlorophenyl)-4H-imidazo[4,5-b]- pyridine (0.2 g, 0.65 mmol) dissolved in 25 ml of N,N-dimethylformamide (DMF) and potassium carbonate (0.13 g, 0.92 mmol) was stirred for 5 min, and then to a mixture of tetra-n-butylammonium bromide (0.032 g, 0.1 mmol) and allyl bromide (0.094 g, 0.77 mmol) was added. Stirring was continued for 6 h at room temperature. After removing the salts by filtration, DMF was evaporated under reduced pressure, and the solid obtained was dissolved in dichloromethane. The residue was extracted with distilled water and the

resulting mixture was chromatographed on a silica-gel column (eluent = ethyl acetate–hexane, 1:3 v/v). Brown single crystals suitable for X-ray diffraction were obtained by evaporation of an ethyl acetate–hexane (1:3 v/v) solution.

## 6. Refinement

Crystal data, data collection and refinement details are summarized in Table 2. All H atoms were positioned geometrically, with C—H = 0.93 or 0.97 Å, and constrained to ride on their parent C atoms, with $U_{iso}(H) = 1.2U_{eq}(C)$.

## Acknowledgements

The support of Tulane University for the Tulane Crystallography Laboratory is gratefully acknowledged.

## Funding information

Funding for this research was provided by: NSF-MRI (grant No. 1228232, for the purchase of the diffractometer); Hacetepe University Scientific Research Project Unit (grant No. 013 D04 602 004, to TH).

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Bourichi, S., Kandri Rodi, Y., Jasinski, J. P., Kaur, M., Ouzidan, Y. & Essassi, E. M. (2017). *IUCrData*, **2**, x170899.

Bourichi, S., Kandri Rodi, Y., Ouzidan, Y., Mague, J. T., Essassi, E. M. & Zouihri, H. (2016). *IUCrData*, **1**, x160763.

Bruker (2014). *SADABS*. Bruker AXS Inc., Madison, Wisconsin, USA.

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supporting information

Acta Cryst. (2019). E75, 43-48 [https://doi.org/10.1107/S2056989018017322]

# Crystal structure and Hirshfeld surface analysis of 4-allyl-6-bromo-2-(4-chlorophenyl)-4H-imidazo[4,5-b]pyridine

Selma Bourichi, Youssef Kandri Rodi, Tuncer Hökelek, Amal Haoudi, Catherine Renard and Frédéric Capet

## Computing details

Data collection: *APEX2* (Bruker, 2015); cell refinement: *SAINT* (Bruker, 2015); data reduction: *APEX2* (Bruker, 2015); program(s) used to solve structure: *SHELXT* (Sheldrick, 2015a); program(s) used to refine structure: *SHELXL* (Sheldrick, 2015b); molecular graphics: *ORTEP-3 for Windows* (Farrugia, 2012); software used to prepare material for publication: *WinGX* (Farrugia, 2012) and *PLATON* (Spek, 2015).

## 4-Allyl-6-bromo-2-(4-chlorophenyl)-4H-imidazo[4,5-b]pyridine

### Crystal data

$C_{15}H_{11}BrClN_3$

$M_r = 348.63$

Triclinic, $P\bar{1}$

$a = 7.6218 (5) Å$

$b = 8.5238 (5) Å$

$c = 11.1093 (7) Å$

$\alpha = 95.739 (3)°$

$\beta = 98.880 (3)°$

$\gamma = 94.979 (3)°$

$V = 705.66 (8) Å³$

$Z = 2$

$F(000) = 348$

$D_x = 1.641 Mg m⁻³$

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 9961 reflections

$\theta = 2.4–25.8°$

$\mu = 3.09 mm⁻¹$

$T = 296 K$

Plate, colourless

0.3 × 0.23 × 0.06 mm

### Data collection

Bruker APEX-II CCD
diffractometer

$\varphi$ and $\omega$ scans

Absorption correction: multi-scan
(SADABS; Bruker, 2014)

$T_{min} = 0.591, T_{max} = 0.746$

31084 measured reflections

4288 independent reflections

3226 reflections with $I > 2\sigma(I)$

$R_{int} = 0.033$

$\theta_{max} = 30.5°, \theta_{min} = 1.9°$

$h = -10 \rightarrow 10$

$k = -12 \rightarrow 12$

$l = -15 \rightarrow 15$

### Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.035$

$wR(F^2) = 0.089$

$S = 1.02$

4288 reflections

181 parameters

0 restraints

Hydrogen site location: inferred from
neighbouring sites

H-atom parameters constrained

$w = 1/[\sigma^2(F_o^2) + (0.0395P)^2 + 0.2342P]$ where $P = (F_o^2 + 2F_c^2)/3$

($\Delta/\sigma)_{max} = 0.002$

$\Delta\rho_{max} = 0.57 e Å^{-3}$

$\Delta\rho_{min} = -0.47 e Å^{-3}$
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.

<table><caption>Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)</caption><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th></tr></thead><tbody><tr><td>Br1</td><td>0.17874 (3)</td><td>1.01452 (2)</td><td>0.68946 (2)</td><td>0.05997 (10)</td></tr><tr><td>Cl1</td><td>0.27559 (10)</td><td>-0.20635 (8)</td><td>0.05226 (6)</td><td>0.07320 (19)</td></tr><tr><td>N1</td><td>0.1843 (2)</td><td>0.4932 (2)</td><td>0.37610 (15)</td><td>0.0451 (4)</td></tr><tr><td>N2</td><td>0.3231 (2)</td><td>0.36057 (19)</td><td>0.53108 (14)</td><td>0.0408 (3)</td></tr><tr><td>N3</td><td>0.3389 (2)</td><td>0.57048 (19)</td><td>0.69517 (14)</td><td>0.0416 (3)</td></tr><tr><td>C1</td><td>0.3258 (3)</td><td>0.0867 (2)</td><td>0.36107 (18)</td><td>0.0460 (4)</td></tr><tr><td>H1</td><td>0.3669</td><td>0.0842</td><td>0.4441</td><td>0.055*</td></tr><tr><td>C2</td><td>0.3317 (3)</td><td>-0.0449 (3)</td><td>0.27905 (19)</td><td>0.0502 (5)</td></tr><tr><td>H2</td><td>0.3753</td><td>-0.1360</td><td>0.3063</td><td>0.060*</td></tr><tr><td>C3</td><td>0.2715 (3)</td><td>-0.0391 (3)</td><td>0.15560 (19)</td><td>0.0506 (5)</td></tr><tr><td>C4</td><td>0.2054 (3)</td><td>0.0941 (3)</td><td>0.11321 (19)</td><td>0.0538 (5)</td></tr><tr><td>H4</td><td>0.1664</td><td>0.0962</td><td>0.0299</td><td>0.065*</td></tr><tr><td>C5</td><td>0.1979 (3)</td><td>0.2241 (3)</td><td>0.19575 (19)</td><td>0.0493 (5)</td></tr><tr><td>H5</td><td>0.1515</td><td>0.3137</td><td>0.1678</td><td>0.059*</td></tr><tr><td>C6</td><td>0.2590 (3)</td><td>0.2232 (2)</td><td>0.32120 (17)</td><td>0.0420 (4)</td></tr><tr><td>C7</td><td>0.2538 (2)</td><td>0.3616 (2)</td><td>0.40937 (17)</td><td>0.0400 (4)</td></tr><tr><td>C8</td><td>0.2942 (2)</td><td>0.5038 (2)</td><td>0.57750 (16)</td><td>0.0390 (4)</td></tr><tr><td>C9</td><td>0.2078 (3)</td><td>0.5896 (2)</td><td>0.48503 (17)</td><td>0.0408 (4)</td></tr><tr><td>C10</td><td>0.1670 (3)</td><td>0.7408 (2)</td><td>0.51508 (19)</td><td>0.0453 (4)</td></tr><tr><td>H10</td><td>0.1095</td><td>0.7982</td><td>0.4567</td><td>0.054*</td></tr><tr><td>C11</td><td>0.2162 (3)</td><td>0.8041 (2)</td><td>0.63802 (19)</td><td>0.0444 (4)</td></tr><tr><td>C12</td><td>0.3010 (3)</td><td>0.7204 (2)</td><td>0.72501 (18)</td><td>0.0452 (4)</td></tr><tr><td>H12</td><td>0.3328</td><td>0.7673</td><td>0.8056</td><td>0.054*</td></tr><tr><td>C13</td><td>0.4300 (3)</td><td>0.4809 (3)</td><td>0.78916 (18)</td><td>0.0489 (5)</td></tr><tr><td>H13A</td><td>0.5192</td><td>0.5528</td><td>0.8446</td><td>0.059*</td></tr><tr><td>H13B</td><td>0.4916</td><td>0.4010</td><td>0.7491</td><td>0.059*</td></tr><tr><td>C14</td><td>0.3080 (3)</td><td>0.4023 (3)</td><td>0.8615 (2)</td><td>0.0550 (5)</td></tr><tr><td>H14</td><td>0.3600</td><td>0.3461</td><td>0.9228</td><td>0.066*</td></tr><tr><td>C15</td><td>0.1374 (4)</td><td>0.4035 (3)</td><td>0.8484 (3)</td><td>0.0709 (7)</td></tr><tr><td>H15A</td><td>0.0789</td><td>0.4579</td><td>0.7884</td><td>0.085*</td></tr><tr><td>H15B</td><td>0.0727</td><td>0.3499</td><td>0.8990</td><td>0.085*</td></tr></tbody></table>

<table><caption>Atomic displacement parameters (Å²)</caption><thead><tr><th></th><th>U<sup>11</sup></th><th>U<sup>22</sup></th><th>U<sup>33</sup></th><th>U<sup>12</sup></th><th>U<sup>13</sup></th><th>U<sup>23</sup></th></tr></thead><tbody><tr><td>Br1</td><td>0.05960 (16)</td><td>0.03754 (12)</td><td>0.08491 (19)</td><td>0.00970 (9)</td><td>0.01673 (12)</td><td>0.00593 (10)</td></tr><tr><td>Cl1</td><td>0.0863 (5)</td><td>0.0732 (4)</td><td>0.0594 (3)</td><td>0.0184 (3)</td><td>0.0175 (3)</td><td>-0.0136 (3)</td></tr><tr><td>N1</td><td>0.0482 (9)</td><td>0.0466 (9)</td><td>0.0414 (8)</td><td>0.0074 (7)</td><td>0.0058 (7)</td><td>0.0105 (7)</td></tr><tr><td>N2</td><td>0.0446 (9)</td><td>0.0398 (8)</td><td>0.0399 (8)</td><td>0.0079 (7)</td><td>0.0079 (7)</td><td>0.0090 (6)</td></tr></tbody></table>
<table><tr><td>N3</td><td>0.0486 (9)</td><td>0.0397 (8)</td><td>0.0383 (8)</td><td>0.0076 (7)</td><td>0.0078 (7)</td><td>0.0100 (6)</td></tr><tr><td>C1</td><td>0.0462 (11)</td><td>0.0510 (11)</td><td>0.0425 (10)</td><td>0.0094 (9)</td><td>0.0090 (8)</td><td>0.0066 (8)</td></tr><tr><td>C2</td><td>0.0508 (12)</td><td>0.0515 (12)</td><td>0.0511 (11)</td><td>0.0131 (9)</td><td>0.0133 (9)</td><td>0.0050 (9)</td></tr><tr><td>C3</td><td>0.0479 (11)</td><td>0.0554 (12)</td><td>0.0489 (11)</td><td>0.0053 (9)</td><td>0.0158 (9)</td><td>-0.0042 (9)</td></tr><tr><td>C4</td><td>0.0542 (12)</td><td>0.0648 (14)</td><td>0.0407 (10)</td><td>0.0030 (10)</td><td>0.0055 (9)</td><td>0.0041 (9)</td></tr><tr><td>C5</td><td>0.0487 (11)</td><td>0.0521 (12)</td><td>0.0464 (10)</td><td>0.0054 (9)</td><td>0.0033 (9)</td><td>0.0092 (9)</td></tr><tr><td>C6</td><td>0.0370 (9)</td><td>0.0468 (11)</td><td>0.0426 (9)</td><td>0.0016 (8)</td><td>0.0086 (8)</td><td>0.0058 (8)</td></tr><tr><td>C7</td><td>0.0369 (9)</td><td>0.0427 (10)</td><td>0.0419 (9)</td><td>0.0040 (8)</td><td>0.0082 (7)</td><td>0.0094 (8)</td></tr><tr><td>C8</td><td>0.0390 (9)</td><td>0.0395 (9)</td><td>0.0410 (9)</td><td>0.0042 (7)</td><td>0.0095 (7)</td><td>0.0117 (7)</td></tr><tr><td>C9</td><td>0.0394 (10)</td><td>0.0421 (10)</td><td>0.0441 (9)</td><td>0.0056 (8)</td><td>0.0096 (8)</td><td>0.0145 (8)</td></tr><tr><td>C10</td><td>0.0441 (10)</td><td>0.0407 (10)</td><td>0.0546 (11)</td><td>0.0079 (8)</td><td>0.0094 (9)</td><td>0.0182 (9)</td></tr><tr><td>C11</td><td>0.0436 (10)</td><td>0.0347 (9)</td><td>0.0584 (11)</td><td>0.0048 (8)</td><td>0.0161 (9)</td><td>0.0094 (8)</td></tr><tr><td>C12</td><td>0.0508 (11)</td><td>0.0403 (10)</td><td>0.0458 (10)</td><td>0.0038 (8)</td><td>0.0130 (9)</td><td>0.0054 (8)</td></tr><tr><td>C13</td><td>0.0532 (12)</td><td>0.0523 (12)</td><td>0.0416 (10)</td><td>0.0121 (9)</td><td>0.0019 (9)</td><td>0.0107 (9)</td></tr><tr><td>C14</td><td>0.0662 (15)</td><td>0.0521 (12)</td><td>0.0472 (11)</td><td>0.0093 (10)</td><td>0.0024 (10)</td><td>0.0170 (9)</td></tr><tr><td>C15</td><td>0.0673 (17)</td><td>0.0755 (18)</td><td>0.0765 (17)</td><td>0.0097 (13)</td><td>0.0144 (13)</td><td>0.0348 (14)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>Br1—C11</td><td>1.886 (2)</td><td>C6—C1</td><td>1.395 (3)</td></tr><tr><td>C11—C3</td><td>1.744 (2)</td><td>C6—C5</td><td>1.401 (3)</td></tr><tr><td>N1—C7</td><td>1.342 (3)</td><td>C7—C6</td><td>1.464 (3)</td></tr><tr><td>N1—C9</td><td>1.371 (3)</td><td>C8—C9</td><td>1.431 (3)</td></tr><tr><td>N2—C7</td><td>1.375 (2)</td><td>C9—C10</td><td>1.373 (3)</td></tr><tr><td>N2—C8</td><td>1.327 (2)</td><td>C10—H10</td><td>0.9300</td></tr><tr><td>N3—C8</td><td>1.352 (2)</td><td>C11—C10</td><td>1.399 (3)</td></tr><tr><td>N3—C12</td><td>1.355 (3)</td><td>C11—C12</td><td>1.373 (3)</td></tr><tr><td>N3—C13</td><td>1.477 (2)</td><td>C12—H12</td><td>0.9300</td></tr><tr><td>C1—H1</td><td>0.9300</td><td>C13—H13A</td><td>0.9700</td></tr><tr><td>C1—C2</td><td>1.381 (3)</td><td>C13—H13B</td><td>0.9700</td></tr><tr><td>C2—H2</td><td>0.9300</td><td>C13—C14</td><td>1.480 (3)</td></tr><tr><td>C2—C3</td><td>1.384 (3)</td><td>C14—H14</td><td>0.9300</td></tr><tr><td>C4—H4</td><td>0.9300</td><td>C14—C15</td><td>1.287 (4)</td></tr><tr><td>C4—C3</td><td>1.378 (3)</td><td>C15—H15A</td><td>0.9300</td></tr><tr><td>C5—H5</td><td>0.9300</td><td>C15—H15B</td><td>0.9300</td></tr><tr><td>C5—C4</td><td>1.377 (3)</td><td></td><td></td></tr><tr><td>Br1—C14<sup>i</sup></td><td>3.624 (2)</td><td>N3—H15A</td><td>2.5350</td></tr><tr><td>Br1—C15<sup>i</sup></td><td>3.660 (3)</td><td>C1—C11<sup>ii</sup></td><td>3.532 (3)</td></tr><tr><td>Br1—C2<sup>ii</sup></td><td>3.677 (2)</td><td>C1—C12<sup>ii</sup></td><td>3.472 (3)</td></tr><tr><td>Br1—C6<sup>iii</sup></td><td>3.729 (2)</td><td>C5—C13<sup>ii</sup></td><td>3.595 (3)</td></tr><tr><td>Br1—H10<sup>iv</sup></td><td>3.1682</td><td>C6—C12<sup>ii</sup></td><td>3.470 (3)</td></tr><tr><td>C11—H12<sup>v</sup></td><td>2.8304</td><td>C7—C8<sup>ii</sup></td><td>3.512 (3)</td></tr><tr><td>C11—H14<sup>vi</sup></td><td>3.1002</td><td>C7—C10<sup>iii</sup></td><td>3.499 (3)</td></tr><tr><td>C11—H15B<sup>vii</sup></td><td>2.9750</td><td>C8—C15</td><td>3.559 (4)</td></tr><tr><td>N3—C6<sup>ii</sup></td><td>3.437 (3)</td><td>C9—C9<sup>iii</sup></td><td>3.473 (3)</td></tr><tr><td>N1—H5</td><td>2.6087</td><td>C12—C15</td><td>3.378 (3)</td></tr><tr><td>N1—H15A<sup>iii</sup></td><td>2.5889</td><td>C5—H13A<sup>ii</sup></td><td>2.8677</td></tr></table>
<table><tbody><tr><td>N2···H13B</td><td>2.5360</td><td>C12···H15A</td><td>2.8971</td></tr><tr><td>N2···H1</td><td>2.5251</td><td>H12···H13A</td><td>2.4427</td></tr><tr><td>C7—N1—C9</td><td>102.65 (16)</td><td>N2—C8—C9</td><td>111.53 (16)</td></tr><tr><td>C8—N2—C7</td><td>101.17 (15)</td><td>N3—C8—C9</td><td>120.81 (17)</td></tr><tr><td>C8—N3—C12</td><td>119.16 (16)</td><td>N1—C9—C8</td><td>107.12 (17)</td></tr><tr><td>C8—N3—C13</td><td>120.08 (16)</td><td>N1—C9—C10</td><td>132.60 (18)</td></tr><tr><td>C12—N3—C13</td><td>120.76 (16)</td><td>C10—C9—C8</td><td>120.27 (18)</td></tr><tr><td>C6—C1—H1</td><td>119.5</td><td>C9—C10—C11</td><td>116.59 (18)</td></tr><tr><td>C2—C1—C6</td><td>120.95 (19)</td><td>C9—C10—H10</td><td>121.7</td></tr><tr><td>C2—C1—H1</td><td>119.5</td><td>C11—C10—H10</td><td>121.7</td></tr><tr><td>C1—C2—H2</td><td>120.5</td><td>C10—C11—Br1</td><td>120.71 (15)</td></tr><tr><td>C1—C2—C3</td><td>118.9 (2)</td><td>C12—C11—Br1</td><td>117.03 (16)</td></tr><tr><td>C3—C2—H2</td><td>120.5</td><td>C12—C11—C10</td><td>122.18 (18)</td></tr><tr><td>C4—C3—C11</td><td>119.49 (17)</td><td>N3—C12—C11</td><td>120.99 (18)</td></tr><tr><td>C4—C3—C2</td><td>121.6 (2)</td><td>N3—C12—H12</td><td>119.5</td></tr><tr><td>C2—C3—C11</td><td>118.93 (18)</td><td>C11—C12—H12</td><td>119.5</td></tr><tr><td>C5—C4—H4</td><td>120.4</td><td>N3—C13—H13A</td><td>108.8</td></tr><tr><td>C5—C4—C3</td><td>119.2 (2)</td><td>N3—C13—H13B</td><td>108.8</td></tr><tr><td>C3—C4—H4</td><td>120.4</td><td>N3—C13—C14</td><td>113.74 (18)</td></tr><tr><td>C6—C5—H5</td><td>119.5</td><td>H13A—C13—H13B</td><td>107.7</td></tr><tr><td>C4—C5—C6</td><td>120.9 (2)</td><td>C14—C13—H13A</td><td>108.8</td></tr><tr><td>C4—C5—H5</td><td>119.5</td><td>C14—C13—H13B</td><td>108.8</td></tr><tr><td>C1—C6—C7</td><td>120.23 (17)</td><td>C13—C14—H14</td><td>116.6</td></tr><tr><td>C1—C6—C5</td><td>118.48 (19)</td><td>C15—C14—C13</td><td>126.8 (2)</td></tr><tr><td>C5—C6—C7</td><td>121.28 (18)</td><td>C15—C14—H14</td><td>116.6</td></tr><tr><td>N2—C7—C6</td><td>120.09 (17)</td><td>C14—C15—H15A</td><td>120.0</td></tr><tr><td>N1—C7—N2</td><td>117.53 (17)</td><td>C14—C15—H15B</td><td>120.0</td></tr><tr><td>N1—C7—C6</td><td>122.39 (17)</td><td>H15A—C15—H15B</td><td>120.0</td></tr><tr><td>N2—C8—N3</td><td>127.66 (17)</td><td></td><td></td></tr><tr><td>C9—N1—C7—N2</td><td>-0.3 (2)</td><td>C6—C5—C4—C3</td><td>1.1 (3)</td></tr><tr><td>C9—N1—C7—C6</td><td>-179.75 (17)</td><td>C5—C6—C1—C2</td><td>0.0 (3)</td></tr><tr><td>C7—N1—C9—C8</td><td>0.5 (2)</td><td>C7—C6—C1—C2</td><td>-179.96 (19)</td></tr><tr><td>C7—N1—C9—C10</td><td>179.6 (2)</td><td>C1—C6—C5—C4</td><td>-0.8 (3)</td></tr><tr><td>C8—N2—C7—N1</td><td>0.0 (2)</td><td>C7—C6—C5—C4</td><td>179.11 (19)</td></tr><tr><td>C8—N2—C7—C6</td><td>179.45 (17)</td><td>N1—C7—C6—C1</td><td>-177.28 (18)</td></tr><tr><td>C7—N2—C8—N3</td><td>-178.58 (19)</td><td>N1—C7—C6—C5</td><td>2.8 (3)</td></tr><tr><td>C7—N2—C8—C9</td><td>0.3 (2)</td><td>N2—C7—C6—C1</td><td>3.3 (3)</td></tr><tr><td>C12—N3—C8—N2</td><td>178.81 (19)</td><td>N2—C7—C6—C5</td><td>-176.66 (18)</td></tr><tr><td>C12—N3—C8—C9</td><td>0.0 (3)</td><td>N2—C8—C9—N1</td><td>-0.5 (2)</td></tr><tr><td>C13—N3—C8—N2</td><td>-0.5 (3)</td><td>N2—C8—C9—C10</td><td>-179.82 (17)</td></tr><tr><td>C13—N3—C8—C9</td><td>-179.29 (18)</td><td>N3—C8—C9—N1</td><td>178.47 (17)</td></tr><tr><td>C8—N3—C12—C11</td><td>0.8 (3)</td><td>N3—C8—C9—C10</td><td>-0.8 (3)</td></tr><tr><td>C13—N3—C12—C11</td><td>-179.93 (19)</td><td>N1—C9—C10—C11</td><td>-178.3 (2)</td></tr><tr><td>C8—N3—C13—C14</td><td>-97.3 (2)</td><td>C8—C9—C10—C11</td><td>0.8 (3)</td></tr><tr><td>C12—N3—C13—C14</td><td>83.4 (2)</td><td>C12—C11—C10—C9</td><td>0.0 (3)</td></tr><tr><td>C6—C1—C2—C3</td><td>0.6 (3)</td><td>Br1—C11—C10—C9</td><td>176.73 (14)</td></tr></tbody></table>
<table><tr><td>C1—C2—C3—Cl1</td><td>-178.98 (17)</td></tr><tr><td>C1—C2—C3—C4</td><td>-0.4 (3)</td></tr><tr><td>C5—C4—C3—Cl1</td><td>178.14 (17)</td></tr><tr><td>C5—C4—C3—C2</td><td>-0.5 (3)</td></tr></table>

<table><tr><td>Br1—C11—C12—N3</td><td>-177.67 (15)</td></tr><tr><td>C10—C11—C12—N3</td><td>-0.8 (3)</td></tr><tr><td>N3—C13—C14—C15</td><td>1.2 (4)</td></tr></table>

Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1; (iv) -x, -y+2, -z+1; (v) x, y-1, z-1; (vi) -x+1, -y, -z+1; (vii) -x, -y, -z+1.

Hydrogen-bond geometry (Å, °)

<table><tr><td>D—H···A</td><td>D—H</td><td>H···A</td><td>D···A</td><td>D—H···A</td></tr><tr><td>C15—H15A···N1<sup>iii</sup></td><td>0.93</td><td>2.59</td><td>3.454 (4)</td><td>155</td></tr></table>

Symmetry code: (iii) -x, -y+1, -z+1.