6-Bromo-2-(4-chloro­phen­yl)-3-[(1-octyl-1H-1,2,3-triazol-4-yl)meth­yl]-3H-imidazo[4,5-b]pyridine

Bourichi, S.; Kandri Rodi, Y.; Hökelek, T.; Chakroune, S.; Ouzidan, Y.; Capet, F.

doi:10.1107/S2414314619000531

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 1| January 2019| x190053

https://doi.org/10.1107/S2414314619000531

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6-Bromo-2-(4-chlorophenyl)-3-[(1-octyl-1H-1,2,3-triazol-4-yl)methyl]-3H-imidazo[4,5-b]pyridine

Selma Bourichi,^a ^* Youssef Kandri Rodi,^a Tuncer Hökelek,^b Said Chakroune,^a Younes Ouzidan ^c and Frédéric Capet ^d

^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, ^cLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route dímmouzzer, BP 2202, Fez, Morocco, and ^dUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, France
^*Correspondence e-mail: said.chakroune20@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 1 January 2019; accepted 9 January 2019; online 15 January 2019)

In the title compound, C₂₃H₂₆BrClN₆, the imidazo[4,5-b]pyridine ring system (r.m.s. deviation = 0.012 Å) is inclined at angles of 19.37 (12) and 89.27 (13)° to the phenyl and triazole rings, respectively, while the phenyl and triazole rings subtend a dihedral angle of 71.23 (15)°. In the crystal, the molecules are linked by C—H⋯N_I and bifurcated C—H⋯(N_T,N_T) (I = imidazo[4,5-b]pyridine and T = triazole) hydrogen bonds into a double-column structure propagating along the b-axis direction.

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

CCDC reference: 1889816

Structure description

Some imidazopyridine derivatives have a significant inhibitory effect on target enzymes (Palmer et al., 2007 ; Katritzky et al., 2003 ). The most popular synthetic approach to these compounds involves the cyclo-condensation of 2,3-pyridinediamine with carboxylic acid derivatives or with aldehydes (Dubey et al., 2004 ). On the other hand, there is increasing interest in the design of new synthetic routes such as an eco-friendly synthesis by oxidation in aqueous medium (Kale et al., 2009 ). As a continuation of our studies in this area (Bourichi et al., 2016 ), we now report the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

The imidazo[4,5-b]pyridine unit is planar to within 0.026 (5) Å (for atom C7), and the r.m.s. deviation of the fitted atoms is 0.012 Å. It is inclined by 19.37 (12) and 89.27 (13)° to the phenyl and triazole rings, respectively, while phenyl and triazole rings are oriented at a dihedral angle of 71.23 (15)°. Atoms Br1, Cl1 and C13 and C16 are displaced by −0.037 (1), 0.024 (2), −0.017 (4) and 0.031 (5) Å, respectively, away from their attached rings.

In the crystal, the molecules are linked via C—H⋯N hydrogen bonds (Table 1), enclosing R₃³(20), R₃³(21) and R₃³(22) ring motifs (Figs. 2 and 3) as part of a double-column structure (Fig. 2) running along the b-axis direction (Fig. 3). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are H⋯H (57.2%), H⋯N/N⋯H (17.6%), H⋯C/C⋯H (9.6%), H⋯Cl/Cl⋯H (7.9%) and H⋯Br/Br⋯H (7.0%) interactions. No significant π–π or C—H⋯π interactions are observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N4ⁱ	0.93	2.60	3.452 (6)	153
C15—H15⋯N5ⁱ	0.93	2.38	3.293 (6)	168
C16—H16B⋯N3ⁱⁱ	0.97	2.53	3.444 (6)	157
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Detail of the crystal structure showing C—H⋯N_I and bifurcated C—H⋯(N_T,N_T) (I = imidazo[4,5-b]pyridine and T = triazole) hydrogen bonds, enclosing R₃³(20), R₃³(21) and R₃³(22) ring motifs, are shown as dashed lines. Non-bonding hydrogen atoms have been omitted for clarity.

Figure 3
Packing viewed along the b-axis direction. C—H⋯N_I hydrogen bonds are shown by dashed lines.

Synthesis and crystallization

1-Azido-octane (0.18 mg, 1.16 mmol) was added to a solution of 6-bromo-2-(4-chlorophenyl)-3-(prop-2-yn-1-yl)-3H-imidazo[4,5-b] pyridine (0.2 g, 0.58 mmol) in ethanol (20 ml). The mixture was stirred under reflux for 48 h. After completion of reaction (monitored by TLC), the solution was concentrated and the residue was purified by column chromatography on silica gel by using a hexane/ethyl acetate (3/1) mixture. Colourless needles of the title compound were obtained when the solvent was allowed to evaporate.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₃H₂₆BrClN₆
M_r	501.86
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	16.252 (3), 5.3787 (9), 27.109 (4)
β (°)	90.551 (12)
V (Å³)	2369.6 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.87
Crystal size (mm)	0.26 × 0.06 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.662, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	26673, 4359, 2265
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.124, 1.01
No. of reflections	4359
No. of parameters	281
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2015 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/1 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX publication routines (Farrugia, 2012 ) and PLATON (Spek, 2015 ).

Structural data

CCDC reference: 1889816

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314619000531/hb4278sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619000531/hb4278Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619000531/hb4278Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and PLATON (Spek, 2015).

6-Bromo-2-(4-chlorophenyl)-3-[(1-octyl-1H-1,2,3-triazol-4-yl)methyl]-3H-imidazo[4,5-b]pyridine top

Crystal data top

C₂₃H₂₆BrClN₆	F(000) = 1032
M_r = 501.86	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 16.252 (3) Å	Cell parameters from 2998 reflections
b = 5.3787 (9) Å	θ = 2.5–17.9°
c = 27.109 (4) Å	µ = 1.87 mm⁻¹
β = 90.551 (12)°	T = 296 K
V = 2369.6 (7) Å³	Needle, colourless
Z = 4	0.26 × 0.06 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	2265 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.074
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.4°, θ_min = 1.5°
T_min = 0.662, T_max = 0.745	h = −19→19
26673 measured reflections	k = −6→6
4359 independent reflections	l = −32→31

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0335P)² + 3.1135P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
4359 reflections	Δρ_max = 0.26 e Å⁻³
281 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints

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.

Refinement. The C-bound H-atoms were positioned geometrically with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methine and methyl hydrogen atoms and refined as riding with U_iso(H) = k × U_eq(C), where k = 1.2 for aromatic and methine H atoms and k = 1.5 for methyl H atoms.

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

	x	y	z	U_iso*/U_eq
Br1	0.91417 (3)	1.26424 (11)	0.49714 (2)	0.0850 (2)
Cl1	0.37541 (9)	−0.1921 (3)	0.58798 (6)	0.1026 (5)
N1	0.6829 (2)	0.5770 (8)	0.53176 (13)	0.0591 (10)
N2	0.7471 (2)	0.4450 (7)	0.60069 (12)	0.0515 (9)
N3	0.8640 (2)	0.7240 (8)	0.59990 (14)	0.0648 (11)
N4	0.6885 (2)	0.6629 (6)	0.69399 (14)	0.0567 (10)
N5	0.6355 (3)	0.6816 (7)	0.73019 (15)	0.0600 (11)
N6	0.6209 (2)	0.4516 (7)	0.74655 (13)	0.0529 (10)
C1	0.6048 (3)	0.0529 (9)	0.60623 (17)	0.0641 (14)
H1	0.6513	0.0047	0.6240	0.077*
C2	0.5331 (3)	−0.0841 (10)	0.61021 (18)	0.0729 (15)
H2	0.5316	−0.2218	0.6309	0.087*
C3	0.4649 (3)	−0.0182 (10)	0.58390 (19)	0.0642 (14)
C4	0.4666 (3)	0.1848 (11)	0.5548 (2)	0.0860 (18)
H4	0.4200	0.2305	0.5368	0.103*
C5	0.5372 (3)	0.3244 (10)	0.55179 (19)	0.0777 (17)
H5	0.5371	0.4675	0.5325	0.093*
C6	0.6082 (3)	0.2576 (9)	0.57660 (15)	0.0511 (11)
C7	0.6790 (3)	0.4233 (8)	0.56938 (16)	0.0503 (11)
C8	0.7946 (3)	0.6337 (9)	0.58096 (16)	0.0518 (12)
C9	0.7545 (3)	0.7123 (9)	0.53840 (16)	0.0535 (12)
C10	0.7887 (3)	0.9040 (9)	0.51141 (17)	0.0608 (13)
H10	0.7645	0.9638	0.4825	0.073*
C11	0.8606 (3)	0.9999 (9)	0.53016 (18)	0.0582 (13)
C12	0.8965 (3)	0.9066 (11)	0.57280 (19)	0.0682 (14)
H12	0.9463	0.9750	0.5833	0.082*
C13	0.7649 (3)	0.3372 (9)	0.64894 (16)	0.0588 (13)
H13A	0.8202	0.3842	0.6591	0.071*
H13B	0.7632	0.1574	0.6464	0.071*
C14	0.7059 (3)	0.4188 (8)	0.68720 (15)	0.0447 (11)
C15	0.6636 (3)	0.2859 (9)	0.72059 (17)	0.0580 (12)
H15	0.6641	0.1143	0.7247	0.070*
C16	0.5635 (3)	0.4089 (10)	0.78608 (18)	0.0769 (16)
H16A	0.5462	0.5681	0.7992	0.092*
H16B	0.5915	0.3194	0.8124	0.092*
C17	0.4894 (4)	0.2660 (13)	0.7708 (2)	0.105 (2)
H17A	0.5068	0.1010	0.7609	0.126*
H17B	0.4544	0.2469	0.7993	0.126*
C18	0.4402 (3)	0.3708 (12)	0.7310 (2)	0.0955 (19)
H18A	0.4732	0.3734	0.7014	0.115*
H18B	0.4273	0.5418	0.7393	0.115*
C19	0.3599 (4)	0.2355 (13)	0.7193 (2)	0.112 (2)
H19A	0.3726	0.0667	0.7093	0.134*
H19B	0.3276	0.2261	0.7491	0.134*
C20	0.3094 (4)	0.3534 (13)	0.6802 (2)	0.103 (2)
H20A	0.3408	0.3505	0.6499	0.124*
H20B	0.3017	0.5265	0.6890	0.124*
C21	0.2271 (4)	0.2445 (13)	0.6694 (2)	0.105 (2)
H21A	0.2340	0.0706	0.6609	0.126*
H21B	0.1944	0.2518	0.6991	0.126*
C22	0.1813 (4)	0.3678 (15)	0.6293 (3)	0.123 (2)
H22A	0.2136	0.3574	0.5994	0.148*
H22B	0.1756	0.5425	0.6374	0.148*
C23	0.0973 (4)	0.2647 (16)	0.6184 (3)	0.152 (3)
H23A	0.0753	0.3414	0.5892	0.227*
H23B	0.0617	0.2984	0.6457	0.227*
H23C	0.1011	0.0883	0.6135	0.227*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0782 (4)	0.0744 (4)	0.1029 (4)	−0.0149 (3)	0.0270 (3)	−0.0023 (4)
Cl1	0.0844 (11)	0.0859 (12)	0.1374 (14)	−0.0342 (9)	−0.0044 (9)	0.0181 (10)
N1	0.054 (3)	0.069 (3)	0.054 (2)	−0.006 (2)	−0.0109 (19)	0.008 (2)
N2	0.046 (2)	0.062 (3)	0.047 (2)	−0.001 (2)	−0.0078 (19)	−0.002 (2)
N3	0.049 (2)	0.084 (3)	0.062 (3)	−0.010 (2)	−0.003 (2)	−0.012 (2)
N4	0.073 (3)	0.033 (2)	0.064 (3)	0.0015 (19)	−0.002 (2)	0.0066 (19)
N5	0.082 (3)	0.031 (2)	0.067 (3)	0.006 (2)	−0.003 (2)	0.0022 (19)
N6	0.072 (3)	0.040 (2)	0.047 (2)	−0.001 (2)	−0.003 (2)	0.004 (2)
C1	0.072 (4)	0.054 (3)	0.066 (3)	−0.002 (3)	−0.019 (3)	0.002 (3)
C2	0.086 (4)	0.056 (3)	0.076 (4)	−0.015 (3)	−0.010 (3)	0.016 (3)
C3	0.060 (3)	0.060 (3)	0.073 (3)	−0.015 (3)	−0.005 (3)	0.001 (3)
C4	0.066 (4)	0.087 (5)	0.105 (4)	−0.018 (3)	−0.029 (3)	0.037 (4)
C5	0.058 (3)	0.076 (4)	0.099 (4)	−0.018 (3)	−0.029 (3)	0.040 (3)
C6	0.054 (3)	0.052 (3)	0.047 (3)	−0.003 (3)	−0.002 (2)	0.004 (3)
C7	0.048 (3)	0.049 (3)	0.053 (3)	0.000 (2)	−0.004 (2)	−0.003 (3)
C8	0.049 (3)	0.062 (3)	0.045 (3)	0.004 (3)	0.001 (2)	−0.012 (2)
C9	0.046 (3)	0.060 (3)	0.054 (3)	−0.006 (3)	0.004 (2)	−0.003 (3)
C10	0.057 (3)	0.072 (4)	0.053 (3)	−0.003 (3)	0.007 (2)	−0.005 (3)
C11	0.052 (3)	0.061 (3)	0.062 (3)	−0.008 (3)	0.019 (3)	−0.009 (3)
C12	0.052 (3)	0.086 (4)	0.067 (4)	−0.014 (3)	0.007 (3)	−0.015 (3)
C13	0.058 (3)	0.057 (3)	0.062 (3)	0.005 (2)	−0.017 (2)	0.003 (3)
C14	0.048 (3)	0.039 (3)	0.047 (3)	0.004 (2)	−0.018 (2)	0.002 (2)
C15	0.086 (4)	0.032 (3)	0.055 (3)	−0.002 (3)	−0.007 (3)	0.004 (3)
C16	0.097 (4)	0.074 (4)	0.060 (3)	0.001 (3)	0.011 (3)	0.006 (3)
C17	0.106 (5)	0.117 (6)	0.091 (4)	−0.025 (5)	0.019 (4)	0.021 (4)
C18	0.075 (4)	0.097 (5)	0.115 (5)	0.000 (4)	0.010 (4)	0.023 (4)
C19	0.100 (5)	0.126 (6)	0.110 (5)	−0.035 (5)	0.008 (4)	0.008 (5)
C20	0.097 (5)	0.110 (5)	0.103 (5)	−0.021 (4)	0.004 (4)	0.003 (4)
C21	0.096 (5)	0.120 (6)	0.100 (5)	−0.027 (5)	0.001 (4)	0.004 (4)
C22	0.115 (6)	0.135 (6)	0.120 (6)	−0.029 (5)	−0.005 (5)	0.008 (5)
C23	0.121 (6)	0.190 (9)	0.143 (6)	−0.060 (6)	−0.017 (5)	0.012 (6)

Geometric parameters (Å, º) top

Br1—C11	1.896 (5)	C12—H12	0.9300
Cl1—C3	1.733 (5)	C13—H13A	0.9700
N1—C7	1.315 (5)	C13—H13B	0.9700
N1—C9	1.382 (5)	C14—C15	1.347 (6)
N2—C7	1.394 (5)	C14—C13	1.486 (6)
N2—C8	1.385 (5)	C15—H15	0.9300
N2—C13	1.457 (5)	C16—H16A	0.9700
N3—C8	1.327 (5)	C16—H16B	0.9700
N3—C12	1.338 (6)	C16—C17	1.485 (7)
N4—N5	1.317 (5)	C17—H17A	0.9700
N4—C14	1.356 (5)	C17—H17B	0.9700
N6—N5	1.336 (5)	C18—H18A	0.9700
N6—C15	1.334 (5)	C18—H18B	0.9700
N6—C16	1.446 (6)	C18—C17	1.450 (7)
C1—H1	0.9300	C18—C19	1.525 (8)
C1—C2	1.383 (6)	C19—H19A	0.9700
C2—H2	0.9300	C19—H19B	0.9700
C3—C2	1.361 (6)	C20—H20A	0.9700
C3—C4	1.347 (6)	C20—H20B	0.9700
C4—H4	0.9300	C20—C21	1.488 (8)
C5—H5	0.9300	C20—C19	1.477 (8)
C5—C4	1.375 (6)	C21—H21A	0.9700
C6—C1	1.365 (6)	C21—H21B	0.9700
C6—C5	1.378 (6)	C21—C22	1.471 (8)
C7—C6	1.469 (6)	C22—H22A	0.9700
C8—C9	1.386 (6)	C22—H22B	0.9700
C9—C10	1.384 (6)	C22—C23	1.499 (8)
C10—H10	0.9300	C23—H23A	0.9600
C11—C10	1.371 (6)	C23—H23B	0.9600
C11—C12	1.384 (6)	C23—H23C	0.9600

C7—N1—C9	106.0 (4)	C15—C14—N4	108.3 (4)
C7—N2—C13	131.5 (4)	C15—C14—C13	130.5 (4)
C8—N2—C7	105.6 (4)	N6—C15—C14	105.8 (4)
C8—N2—C13	122.1 (4)	N6—C15—H15	127.1
C8—N3—C12	113.2 (4)	C14—C15—H15	127.1
N5—N4—C14	108.3 (4)	N6—C16—H16A	108.8
N4—N5—N6	107.2 (3)	N6—C16—H16B	108.8
N5—N6—C16	120.7 (4)	N6—C16—C17	113.7 (4)
C15—N6—N5	110.4 (4)	H16A—C16—H16B	107.7
C15—N6—C16	128.9 (4)	C17—C16—H16A	108.8
C6—C1—H1	119.5	C17—C16—H16B	108.8
C6—C1—C2	121.0 (5)	C16—C17—H17A	108.2
C2—C1—H1	119.5	C16—C17—H17B	108.2
C1—C2—H2	119.9	C18—C17—C16	116.6 (5)
C3—C2—C1	120.2 (5)	C18—C17—H17A	108.2
C3—C2—H2	119.9	C18—C17—H17B	108.2
C2—C3—Cl1	120.4 (4)	H17A—C17—H17B	107.3
C4—C3—Cl1	119.8 (4)	H18A—C18—H18B	107.4
C4—C3—C2	119.8 (5)	C17—C18—H18A	108.4
C3—C4—C5	120.0 (5)	C17—C18—H18B	108.4
C3—C4—H4	120.0	C17—C18—C19	115.7 (6)
C5—C4—H4	120.0	C19—C18—H18A	108.4
C6—C5—H5	119.2	C19—C18—H18B	108.4
C4—C5—C6	121.6 (5)	C18—C19—H19A	108.7
C4—C5—H5	119.2	C18—C19—H19B	108.7
C1—C6—C7	127.2 (4)	C20—C19—C18	114.4 (6)
C1—C6—C5	117.3 (4)	C20—C19—H19A	108.7
C5—C6—C7	115.5 (4)	C20—C19—H19B	108.7
N2—C7—C6	126.0 (4)	H19A—C19—H19B	107.6
N1—C7—N2	112.1 (4)	H20A—C20—H20B	107.2
N1—C7—C6	121.9 (4)	C21—C20—H20A	107.9
N2—C8—C9	106.6 (4)	C21—C20—H20B	107.9
N3—C8—N2	126.4 (4)	C19—C20—H20A	107.9
N3—C8—C9	127.0 (5)	C19—C20—H20B	107.9
N1—C9—C8	109.7 (4)	C19—C20—C21	117.7 (6)
N1—C9—C10	131.7 (4)	C20—C21—H21A	108.6
C10—C9—C8	118.6 (4)	C20—C21—H21B	108.6
C9—C10—H10	122.3	H21A—C21—H21B	107.6
C11—C10—C9	115.4 (4)	C22—C21—C20	114.6 (6)
C11—C10—H10	122.3	C22—C21—H21A	108.6
C10—C11—Br1	120.0 (4)	C22—C21—H21B	108.6
C10—C11—C12	121.6 (5)	C21—C22—H22A	108.4
C12—C11—Br1	118.3 (4)	C21—C22—H22B	108.4
N3—C12—C11	124.0 (5)	C21—C22—C23	115.5 (6)
N3—C12—H12	118.0	H22A—C22—H22B	107.5
C11—C12—H12	118.0	C23—C22—H22A	108.4
N2—C13—C14	112.6 (4)	C23—C22—H22B	108.4
N2—C13—H13A	109.1	C22—C23—H23A	109.5
N2—C13—H13B	109.1	C22—C23—H23B	109.5
C14—C13—H13A	109.1	C22—C23—H23C	109.5
C14—C13—H13B	109.1	H23A—C23—H23B	109.5
H13A—C13—H13B	107.8	H23A—C23—H23C	109.5
N4—C14—C13	121.2 (4)	H23B—C23—H23C	109.5

C14—N4—N5—N6	1.1 (5)	C7—N1—C9—C8	0.8 (5)
N4—N5—N6—C15	−0.7 (5)	N3—C8—C9—N1	−178.3 (4)
N4—N5—N6—C16	−178.9 (4)	N2—C8—C9—N1	0.5 (5)
C6—C1—C2—C3	0.9 (8)	N3—C8—C9—C10	0.5 (7)
C1—C2—C3—C4	−1.6 (8)	N2—C8—C9—C10	179.2 (4)
C1—C2—C3—Cl1	179.0 (4)	N1—C9—C10—C11	178.2 (5)
C2—C3—C4—C5	0.0 (9)	C8—C9—C10—C11	−0.2 (6)
Cl1—C3—C4—C5	179.5 (4)	C9—C10—C11—C12	1.0 (7)
C3—C4—C5—C6	2.3 (9)	C9—C10—C11—Br1	−179.8 (3)
C2—C1—C6—C5	1.3 (7)	C8—N3—C12—C11	2.1 (7)
C2—C1—C6—C7	178.8 (4)	C10—C11—C12—N3	−2.1 (8)
C4—C5—C6—C1	−2.9 (8)	Br1—C11—C12—N3	178.7 (4)
C4—C5—C6—C7	179.3 (5)	C8—N2—C13—C14	105.9 (5)
C9—N1—C7—N2	−1.8 (5)	C7—N2—C13—C14	−62.4 (6)
C9—N1—C7—C6	176.4 (4)	N5—N4—C14—C15	−1.1 (5)
C8—N2—C7—N1	2.1 (5)	N5—N4—C14—C13	−179.4 (4)
C13—N2—C7—N1	171.8 (4)	N2—C13—C14—C15	131.6 (5)
C8—N2—C7—C6	−176.0 (4)	N2—C13—C14—N4	−50.5 (5)
C13—N2—C7—C6	−6.3 (7)	N5—N6—C15—C14	0.1 (5)
C1—C6—C7—N1	163.1 (5)	C16—N6—C15—C14	178.0 (4)
C5—C6—C7—N1	−19.4 (6)	N4—C14—C15—N6	0.6 (5)
C1—C6—C7—N2	−19.0 (7)	C13—C14—C15—N6	178.7 (4)
C5—C6—C7—N2	158.5 (4)	C15—N6—C16—C17	−63.3 (7)
C12—N3—C8—N2	−179.9 (4)	N5—N6—C16—C17	114.5 (5)
C12—N3—C8—C9	−1.4 (7)	N6—C16—C17—C18	−57.7 (7)
C7—N2—C8—N3	177.3 (4)	C16—C17—C18—C19	−174.1 (5)
C13—N2—C8—N3	6.4 (7)	C17—C18—C19—C20	177.3 (6)
C7—N2—C8—C9	−1.5 (5)	C18—C19—C20—C21	−175.2 (6)
C13—N2—C8—C9	−172.4 (4)	C19—C20—C21—C22	−178.6 (6)
C7—N1—C9—C10	−177.8 (5)	C20—C21—C22—C23	−178.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···N4ⁱ	0.93	2.60	3.452 (6)	153
C15—H15···N5ⁱ	0.93	2.38	3.293 (6)	168
C16—H16B···N3ⁱⁱ	0.97	2.53	3.444 (6)	157

Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, −z+3/2.

Funding information

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

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