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

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, mol-ecules are linked via a pair of weak inter-molecular C-H⋯N hydrogen bonds, forming an inversion dimer with an R 2 2(20) ring motif. The dimers are further connected by π-π stacking inter-actions 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.

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.

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.

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 (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) .

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.

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.

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. 5 ▸ f) 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.

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.

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
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[F 2 > 2σ(F 2)], wR(F 2), S	0.035, 0.089, 1.03
No. of reflections	4288
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018017322/is5505sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018017322/is5505Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018017322/is5505Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018017322/is5505Isup4.cml

CCDC reference: 1883384

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

C15H11BrClN3	Z = 2
Mr = 348.63	F(000) = 348
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0395P)2 + 0.2342P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.002
4288 reflections	Δρmax = 0.57 e Å−3
181 parameters	Δρmin = −0.47 e Å−3

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

	x	y	z	Uiso*/Ueq
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*

	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)

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···H10iv	3.1682	C6···C12ii	3.470 (3)
Cl1···H12v	2.8304	C7···C8ii	3.512 (3)
Cl1···H14vi	3.1002	C7···C10iii	3.499 (3)
Cl1···H15Bvii	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)

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