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

Bourichi, S.; Kandri Rodi, Y.; Hökelek, T.; Haoudi, A.; Renard, C.; Capet, F.

doi:10.1107/S2056989018017322

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ISSN: 2056-9890

Volume 75| Part 1| January 2019| Pages 43-48

https://doi.org/10.1107/S2056989018017322

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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 Renard ^c and Frédéric Capet ^c

^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

Edited by H. Ishida, Okayama University, Japan (Received 21 November 2018; accepted 6 December 2018; online 1 January 2019)

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 R₂²(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.

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

CCDC reference: 1883384

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 ).

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-chlorophenyl)-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 1
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, molecules are linked via a pair of weak intermolecular C—H⋯N hydrogen bonds [C15—H15A⋯N1ⁱ; 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 π–π stacking interactions between the imidazo[4,5-b]pyridine ring systems. The centroid–centroid distances, Cg1⋯Cg1ⁱⁱ and Cg1⋯Cg2ⁱ [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.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯N1ⁱ	0.93	2.59	3.454 (4)	155
Symmetry code: (i) -x, -y+1, -z+1.

Figure 2
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.

4. Database survey

A non-para-substituated 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, 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 d_norm (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 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 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 ∼ 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)].

Figure 3
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1373 to 1.1294 a.u.

Figure 4
Hirshfeld surface of the title compound plotted over shape index.

Figure 5
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_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

Figure 6
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.

6. 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.

7. 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).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₁BrClN₃
M_r	348.63
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.6218 (5), 8.5238 (5), 11.1093 (7)
α, β, γ (°)	95.739 (3), 98.880 (3), 94.979 (3)
V (Å³)	705.66 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.09
Crystal size (mm)	0.3 × 0.23 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.591, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	31084, 4288, 3226
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.03
No. of reflections	4288
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.47
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 ).

Supporting information

CCDC reference: 1883384

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018017322/is5505sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018017322/is5505Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018017322/is5505Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989018017322/is5505Isup4.cml

checkCIF report

Computing details top

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 top

Crystal data top

C₁₅H₁₁BrClN₃	Z = 2
M_r = 348.63	F(000) = 348
Triclinic, P1	D_x = 1.641 Mg m⁻³
a = 7.6218 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5238 (5) Å	Cell parameters from 9961 reflections
c = 11.1093 (7) Å	θ = 2.4–25.8°
α = 95.739 (3)°	µ = 3.09 mm⁻¹
β = 98.880 (3)°	T = 296 K
γ = 94.979 (3)°	Plate, colourless
V = 705.66 (8) Å³	0.3 × 0.23 × 0.06 mm

Data collection top

Bruker APEX-II CCD diffractometer	3226 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.033
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 30.5°, θ_min = 1.9°
T_min = 0.591, T_max = 0.746	h = −10→10
31084 measured reflections	k = −12→12
4288 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0395P)² + 0.2342P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
4288 reflections	Δρ_max = 0.57 e Å⁻³
181 parameters	Δρ_min = −0.47 e Å⁻³

Special details top

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

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

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

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.05960 (16)	0.03754 (12)	0.08491 (19)	0.00970 (9)	0.01673 (12)	0.00593 (10)
Cl1	0.0863 (5)	0.0732 (4)	0.0594 (3)	0.0184 (3)	0.0175 (3)	−0.0136 (3)
N1	0.0482 (9)	0.0466 (9)	0.0414 (8)	0.0074 (7)	0.0058 (7)	0.0105 (7)
N2	0.0446 (9)	0.0398 (8)	0.0399 (8)	0.0079 (7)	0.0079 (7)	0.0090 (6)
N3	0.0486 (9)	0.0397 (8)	0.0383 (8)	0.0076 (7)	0.0078 (7)	0.0100 (6)
C1	0.0462 (11)	0.0510 (11)	0.0425 (10)	0.0094 (9)	0.0090 (8)	0.0066 (8)
C2	0.0508 (12)	0.0515 (12)	0.0511 (11)	0.0131 (9)	0.0133 (9)	0.0050 (9)
C3	0.0479 (11)	0.0554 (12)	0.0489 (11)	0.0053 (9)	0.0158 (9)	−0.0042 (9)
C4	0.0542 (12)	0.0648 (14)	0.0407 (10)	0.0030 (10)	0.0055 (9)	0.0041 (9)
C5	0.0487 (11)	0.0521 (12)	0.0464 (10)	0.0054 (9)	0.0033 (9)	0.0092 (9)
C6	0.0370 (9)	0.0468 (11)	0.0426 (9)	0.0016 (8)	0.0086 (8)	0.0058 (8)
C7	0.0369 (9)	0.0427 (10)	0.0419 (9)	0.0040 (8)	0.0082 (7)	0.0094 (8)
C8	0.0390 (9)	0.0395 (9)	0.0410 (9)	0.0042 (7)	0.0095 (7)	0.0117 (7)
C9	0.0394 (10)	0.0421 (10)	0.0441 (9)	0.0056 (8)	0.0096 (8)	0.0145 (8)
C10	0.0441 (10)	0.0407 (10)	0.0546 (11)	0.0079 (8)	0.0094 (9)	0.0182 (9)
C11	0.0436 (10)	0.0347 (9)	0.0584 (11)	0.0048 (8)	0.0161 (9)	0.0094 (8)
C12	0.0508 (11)	0.0403 (10)	0.0458 (10)	0.0038 (8)	0.0130 (9)	0.0054 (8)
C13	0.0532 (12)	0.0523 (12)	0.0416 (10)	0.0121 (9)	0.0019 (9)	0.0107 (9)
C14	0.0662 (15)	0.0521 (12)	0.0472 (11)	0.0093 (10)	0.0024 (10)	0.0170 (9)
C15	0.0673 (17)	0.0755 (18)	0.0765 (17)	0.0097 (13)	0.0144 (13)	0.0348 (14)

Geometric parameters (Å, º) top

Br1—C11	1.886 (2)	C6—C1	1.395 (3)
Cl1—C3	1.744 (2)	C6—C5	1.401 (3)
N1—C7	1.342 (3)	C7—C6	1.464 (3)
N1—C9	1.371 (3)	C8—C9	1.431 (3)
N2—C7	1.375 (2)	C9—C10	1.373 (3)
N2—C8	1.327 (2)	C10—H10	0.9300
N3—C8	1.352 (2)	C11—C10	1.399 (3)
N3—C12	1.355 (3)	C11—C12	1.373 (3)
N3—C13	1.477 (2)	C12—H12	0.9300
C1—H1	0.9300	C13—H13A	0.9700
C1—C2	1.381 (3)	C13—H13B	0.9700
C2—H2	0.9300	C13—C14	1.480 (3)
C2—C3	1.384 (3)	C14—H14	0.9300
C4—H4	0.9300	C14—C15	1.287 (4)
C4—C3	1.378 (3)	C15—H15A	0.9300
C5—H5	0.9300	C15—H15B	0.9300
C5—C4	1.377 (3)

Br1···C14ⁱ	3.624 (2)	N3···H15A	2.5350
Br1···C15ⁱ	3.660 (3)	C1···C11ⁱⁱ	3.532 (3)
Br1···C2ⁱⁱ	3.677 (2)	C1···C12ⁱⁱ	3.472 (3)
Br1···C6ⁱⁱⁱ	3.729 (2)	C5···C13ⁱⁱ	3.595 (3)
Br1···H10^iv	3.1682	C6···C12ⁱⁱ	3.470 (3)
Cl1···H12^v	2.8304	C7···C8ⁱⁱ	3.512 (3)
Cl1···H14^vi	3.1002	C7···C10ⁱⁱⁱ	3.499 (3)
Cl1···H15B^vii	2.9750	C8···C15	3.559 (4)
N3···C6ⁱⁱ	3.437 (3)	C9···C9ⁱⁱⁱ	3.473 (3)
N1···H5	2.6087	C12···C15	3.378 (3)
N1···H15Aⁱⁱⁱ	2.5889	C5···H13Aⁱⁱ	2.8677
N2···H13B	2.5360	C12···H15A	2.8971
N2···H1	2.5251	H12···H13A	2.4427

C7—N1—C9	102.65 (16)	N2—C8—C9	111.53 (16)
C8—N2—C7	101.17 (15)	N3—C8—C9	120.81 (17)
C8—N3—C12	119.16 (16)	N1—C9—C8	107.12 (17)
C8—N3—C13	120.08 (16)	N1—C9—C10	132.60 (18)
C12—N3—C13	120.76 (16)	C10—C9—C8	120.27 (18)
C6—C1—H1	119.5	C9—C10—C11	116.59 (18)
C2—C1—C6	120.95 (19)	C9—C10—H10	121.7
C2—C1—H1	119.5	C11—C10—H10	121.7
C1—C2—H2	120.5	C10—C11—Br1	120.71 (15)
C1—C2—C3	118.9 (2)	C12—C11—Br1	117.03 (16)
C3—C2—H2	120.5	C12—C11—C10	122.18 (18)
C4—C3—Cl1	119.49 (17)	N3—C12—C11	120.99 (18)
C4—C3—C2	121.6 (2)	N3—C12—H12	119.5
C2—C3—Cl1	118.93 (18)	C11—C12—H12	119.5
C5—C4—H4	120.4	N3—C13—H13A	108.8
C5—C4—C3	119.2 (2)	N3—C13—H13B	108.8
C3—C4—H4	120.4	N3—C13—C14	113.74 (18)
C6—C5—H5	119.5	H13A—C13—H13B	107.7
C4—C5—C6	120.9 (2)	C14—C13—H13A	108.8
C4—C5—H5	119.5	C14—C13—H13B	108.8
C1—C6—C7	120.23 (17)	C13—C14—H14	116.6
C1—C6—C5	118.48 (19)	C15—C14—C13	126.8 (2)
C5—C6—C7	121.28 (18)	C15—C14—H14	116.6
N2—C7—C6	120.09 (17)	C14—C15—H15A	120.0
N1—C7—N2	117.53 (17)	C14—C15—H15B	120.0
N1—C7—C6	122.39 (17)	H15A—C15—H15B	120.0
N2—C8—N3	127.66 (17)

C9—N1—C7—N2	−0.3 (2)	C6—C5—C4—C3	1.1 (3)
C9—N1—C7—C6	−179.75 (17)	C5—C6—C1—C2	0.0 (3)
C7—N1—C9—C8	0.5 (2)	C7—C6—C1—C2	−179.96 (19)
C7—N1—C9—C10	179.6 (2)	C1—C6—C5—C4	−0.8 (3)
C8—N2—C7—N1	0.0 (2)	C7—C6—C5—C4	179.11 (19)
C8—N2—C7—C6	179.45 (17)	N1—C7—C6—C1	−177.28 (18)
C7—N2—C8—N3	−178.58 (19)	N1—C7—C6—C5	2.8 (3)
C7—N2—C8—C9	0.3 (2)	N2—C7—C6—C1	3.3 (3)
C12—N3—C8—N2	178.81 (19)	N2—C7—C6—C5	−176.66 (18)
C12—N3—C8—C9	0.0 (3)	N2—C8—C9—N1	−0.5 (2)
C13—N3—C8—N2	−0.5 (3)	N2—C8—C9—C10	−179.82 (17)
C13—N3—C8—C9	−179.29 (18)	N3—C8—C9—N1	178.47 (17)
C8—N3—C12—C11	0.8 (3)	N3—C8—C9—C10	−0.8 (3)
C13—N3—C12—C11	−179.93 (19)	N1—C9—C10—C11	−178.3 (2)
C8—N3—C13—C14	−97.3 (2)	C8—C9—C10—C11	0.8 (3)
C12—N3—C13—C14	83.4 (2)	C12—C11—C10—C9	0.0 (3)
C6—C1—C2—C3	0.6 (3)	Br1—C11—C10—C9	176.73 (14)
C1—C2—C3—Cl1	−178.98 (17)	Br1—C11—C12—N3	−177.67 (15)
C1—C2—C3—C4	−0.4 (3)	C10—C11—C12—N3	−0.8 (3)
C5—C4—C3—Cl1	178.14 (17)	N3—C13—C14—C15	1.2 (4)
C5—C4—C3—C2	−0.5 (3)

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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···N1ⁱⁱⁱ	0.93	2.59	3.454 (4)	155

Symmetry code: (iii) −x, −y+1, −z+1.

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); Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004, to TH).

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