2-[(1H-Benzimidazol-2-yl)imino­meth­yl]-4,6-dibromo­phenol ethanol hemisolvate

Liu, J.; Liu, Z.; Yuan, S.

doi:10.1107/S1600536813002031

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o362

doi:10.1107/S1600536813002031

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2-[(1H-Benzimidazol-2-yl)iminomethyl]-4,6-dibromophenol ethanol hemisolvate

Jie Liu,^a ^* Zheng Liu ^a and Shuai Yuan ^a

^aKey Laboratory of Nonferrous Metal Materials and Processing Technology, Department of Material and Chemical Engineering, Guilin University of Technology, Ministry of Education, Guilin 541004, People's Republic of China
^*Correspondence e-mail: lisa4.6@163.com

(Received 23 October 2012; accepted 21 January 2013; online 9 February 2013)

The title compound, C₁₄H₉Br₂N₃O·0.5C₂H₅OH, crystallizes with two 2-[(1H-benzimidazol-2-yl)iminomethyl]-4,6-dibromophenol molecules and one ethanol solvent molecule in the asymmetric unit. The benzene and benzimidazole rings subtend dihedral angles of 4.5 (3) and 5.2 (2)° in the two molecules. In the crystal, one molecule presents π–π stacking with the equivalent molecule related by inversion, at a distance of 3.30 Å (separation between molecular mean planes). A three-dimensional network is formed through N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For background to benzimidazole compounds, see: Zhang et al. (2008 , 2011 ).

Experimental

Crystal data

C₁₄H₉Br₂N₃O·0.5C₂H₆O
M_r = 836.19
Monoclinic, P 2₁ /c
a = 14.5300 (15) Å
b = 16.8190 (14) Å
c = 13.8491 (17) Å
β = 111.656 (13)°
V = 3145.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.16 mm⁻¹
T = 293 K
0.23 × 0.22 × 0.21 mm

Data collection

Agilent SuperNova Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.436, T_max = 1.000
19465 measured reflections
6390 independent reflections
4189 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.133
S = 1.03
6390 reflections
392 parameters
H-atom parameters constrained
Δρ_max = 1.55 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯N3	0.86	2.14	2.997 (4)	172
N2—H2A⋯O3ⁱ	0.86	2.00	2.816 (4)	157
O1—H1⋯N1	0.82	1.90	2.618 (6)	146
O2—H2⋯N4	0.82	1.92	2.640 (6)	147
O3—H3⋯N6ⁱⁱ	0.82	2.08	2.900 (5)	176
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813002031/bh2461sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813002031/bh2461Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813002031/bh2461Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536813002031/bh2461Isup4.cml

checkCIF report

Comment top

Benzimidazole compounds exhibit a large range of biological activities and so far various types of benzimidazole drugs have been extensively used in clinic practice (Zhang et al., 2008, 2011). Herein, we have synthesized a new benzimidazole compound.

In the title compound, the benzene and benzimidazole rings are almost in the same plane, and the dihedral angle between the benzene and benzimidazole rings is 4.5 (3) and 5.2 (2)° for each crystallographically independent molecule (Fig. 1). π–π stacking interactions are observed between the benzene and benzimidazole rings of molecules C1···C14 related by inversion: the dihedral angle between stacked molecules is 0°, and the separation between mean planes formed by the benzene and the benzimidazole rings in the molecules is 3.487 Å (Fig. 2). The title compound forms a three-dimensional network in the crystal structure, through N—H···N, N—H···O and O—H···N hydrgoen bonds (Fig. 3).

Related literature top

For background to benzimidazole compounds, see: Zhang et al. (2008, 2011).

Experimental top

3,5-Dibromosalicylaldehyde (3.0 mmol) was dissolved in a round bottom flask containing ethanol (20 ml). To this solution, an ethanolic solution (10 ml) of 2-aminobenzimidazole (3.0 mmol) was then added dropwise, and the mixture was refluxed for 4 h. After cooling down to room temperature, the resulting orange precipitate was filtered off, and recrystallized from ethanol. Orange block-like crystals of the title compound were obtained by slow evaporation of the filtrate at room temperature.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of one independent molecule in the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. Perspective view of the stacking of two inversion-related molecules in the title compound.
	Fig. 3. Three-dimensional network of the title compound, with dashed lines showing hydrogen bonds.

2-[(1H-Benzimidazol-2-yl)iminomethyl]-4,6-dibromophenol ethanol hemisolvate top

Crystal data top

C₁₄H₉Br₂N₃O·0.5C₂H₆O	F(000) = 1640
M_r = 836.19	D_x = 1.766 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6390 reflections
a = 14.5300 (15) Å	θ = 2.8–29.1°
b = 16.8190 (14) Å	µ = 5.16 mm⁻¹
c = 13.8491 (17) Å	T = 293 K
β = 111.656 (13)°	Block, orange
V = 3145.5 (6) Å³	0.23 × 0.22 × 0.21 mm
Z = 4

Data collection top

Agilent SuperNova Eos diffractometer	6390 independent reflections
Radiation source: fine-focus sealed tube	4189 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 26.4°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −17→18
T_min = 0.436, T_max = 1.000	k = −12→21
19465 measured reflections	l = −17→16

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0525P)² + 1.2028P] where P = (F_o² + 2F_c²)/3
6390 reflections	(Δ/σ)_max = 0.001
392 parameters	Δρ_max = 1.55 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³
0 constraints

Crystal data top

C₁₄H₉Br₂N₃O·0.5C₂H₆O	V = 3145.5 (6) Å³
M_r = 836.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.5300 (15) Å	µ = 5.16 mm⁻¹
b = 16.8190 (14) Å	T = 293 K
c = 13.8491 (17) Å	0.23 × 0.22 × 0.21 mm
β = 111.656 (13)°

Data collection top

Agilent SuperNova Eos diffractometer	6390 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	4189 reflections with I > 2σ(I)
T_min = 0.436, T_max = 1.000	R_int = 0.051
19465 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.03	Δρ_max = 1.55 e Å⁻³
6390 reflections	Δρ_min = −0.76 e Å⁻³
392 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.18346 (5)	0.58511 (4)	0.49389 (5)	0.0651 (2)
Br2	0.16183 (5)	0.34709 (4)	0.19662 (5)	0.0773 (2)
Br3	0.20356 (4)	0.66995 (4)	0.13312 (5)	0.0682 (2)
Br4	0.02247 (4)	0.43016 (4)	−0.16402 (5)	0.0687 (2)
O1	0.3836 (3)	0.6096 (2)	0.4833 (3)	0.0523 (9)
H1	0.4378	0.6170	0.4793	0.078*
O2	0.3869 (3)	0.5833 (2)	0.1429 (3)	0.0509 (9)
H2	0.4369	0.5579	0.1491	0.076*
O3	0.5513 (3)	0.7478 (2)	0.0641 (3)	0.0584 (10)
H3	0.5114	0.7166	0.0249	0.088*
N1	0.5251 (3)	0.5886 (2)	0.4114 (3)	0.0410 (10)
N2	0.6683 (3)	0.6647 (2)	0.4789 (3)	0.0391 (9)
H2A	0.6473	0.6908	0.5201	0.047*
N3	0.6673 (3)	0.5779 (2)	0.3570 (3)	0.0383 (9)
N4	0.4902 (3)	0.4627 (2)	0.1140 (3)	0.0380 (9)
N5	0.6607 (3)	0.4473 (2)	0.2074 (3)	0.0398 (9)
H5	0.6654	0.4877	0.2470	0.048*
N6	0.5910 (3)	0.3573 (2)	0.0821 (3)	0.0365 (9)
C1	0.2409 (3)	0.5300 (3)	0.4110 (4)	0.0430 (12)
C2	0.1890 (3)	0.4700 (3)	0.3465 (4)	0.0463 (13)
H2B	0.1258	0.4567	0.3430	0.056*
C3	0.2322 (4)	0.4295 (3)	0.2863 (4)	0.0438 (12)
C4	0.3270 (3)	0.4493 (3)	0.2931 (4)	0.0448 (12)
H4	0.3557	0.4217	0.2533	0.054*
C5	0.3790 (3)	0.5090 (3)	0.3576 (3)	0.0380 (11)
C6	0.3357 (3)	0.5508 (3)	0.4174 (4)	0.0383 (11)
C7	0.4786 (3)	0.5289 (3)	0.3606 (3)	0.0395 (11)
H7	0.5078	0.4973	0.3248	0.047*
C8	0.6193 (3)	0.6076 (3)	0.4121 (4)	0.0351 (10)
C9	0.7585 (3)	0.6735 (3)	0.4691 (4)	0.0425 (12)
C10	0.8406 (4)	0.7209 (3)	0.5210 (4)	0.0565 (14)
H10	0.8415	0.7560	0.5732	0.068*
C11	0.9220 (4)	0.7126 (4)	0.4902 (5)	0.0679 (18)
H11	0.9792	0.7420	0.5233	0.081*
C12	0.9177 (4)	0.6611 (4)	0.4110 (5)	0.0677 (18)
H12	0.9721	0.6580	0.3912	0.081*
C13	0.8372 (4)	0.6143 (3)	0.3604 (5)	0.0574 (15)
H13	0.8368	0.5802	0.3074	0.069*
C14	0.7557 (3)	0.6193 (3)	0.3904 (4)	0.0392 (11)
C15	0.2131 (4)	0.5794 (3)	0.0568 (4)	0.0447 (13)
C16	0.1299 (4)	0.5450 (3)	−0.0139 (4)	0.0472 (13)
H16	0.0680	0.5671	−0.0260	0.057*
C17	0.1377 (3)	0.4775 (3)	−0.0673 (4)	0.0444 (12)
C18	0.2293 (3)	0.4427 (3)	−0.0496 (4)	0.0434 (12)
H18	0.2339	0.3970	−0.0855	0.052*
C19	0.3148 (3)	0.4774 (3)	0.0231 (3)	0.0367 (11)
C20	0.3075 (3)	0.5466 (3)	0.0751 (4)	0.0387 (11)
C21	0.4092 (3)	0.4375 (3)	0.0437 (4)	0.0410 (12)
H21	0.4111	0.3926	0.0053	0.049*
C22	0.5779 (3)	0.4202 (3)	0.1318 (4)	0.0351 (11)
C23	0.6906 (3)	0.3406 (3)	0.1292 (3)	0.0341 (10)
C24	0.7478 (4)	0.2809 (3)	0.1087 (4)	0.0473 (13)
H24	0.7189	0.2432	0.0573	0.057*
C25	0.8469 (4)	0.2791 (3)	0.1662 (4)	0.0517 (14)
H25	0.8857	0.2395	0.1535	0.062*
C26	0.8919 (4)	0.3357 (3)	0.2441 (4)	0.0478 (13)
H26	0.9598	0.3326	0.2811	0.057*
C27	0.8391 (3)	0.3952 (3)	0.2674 (4)	0.0440 (12)
H27	0.8690	0.4325	0.3191	0.053*
C28	0.7368 (3)	0.3966 (3)	0.2085 (3)	0.0357 (11)
C29	0.5640 (5)	0.7298 (4)	0.1691 (5)	0.0677 (17)
H29A	0.6296	0.7466	0.2143	0.081*
H29B	0.5602	0.6726	0.1762	0.081*
C30	0.4904 (6)	0.7678 (4)	0.2036 (5)	0.089 (2)
H30A	0.4263	0.7453	0.1665	0.134*
H30B	0.4888	0.8239	0.1900	0.134*
H30C	0.5081	0.7592	0.2767	0.134*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0689 (4)	0.0622 (4)	0.0823 (5)	0.0184 (3)	0.0492 (4)	0.0108 (3)
Br2	0.0635 (4)	0.0832 (5)	0.0757 (5)	−0.0212 (3)	0.0146 (4)	−0.0247 (4)
Br3	0.0597 (4)	0.0671 (4)	0.0849 (5)	0.0064 (3)	0.0350 (4)	−0.0178 (3)
Br4	0.0352 (3)	0.0942 (5)	0.0658 (4)	−0.0026 (3)	0.0059 (3)	−0.0097 (3)
O1	0.048 (2)	0.055 (2)	0.058 (2)	0.0017 (18)	0.025 (2)	−0.0100 (19)
O2	0.046 (2)	0.055 (2)	0.048 (2)	0.0020 (17)	0.0122 (19)	−0.0030 (18)
O3	0.062 (3)	0.062 (3)	0.047 (2)	−0.0218 (19)	0.016 (2)	−0.0002 (19)
N1	0.038 (2)	0.043 (3)	0.039 (2)	0.0001 (18)	0.011 (2)	0.0035 (19)
N2	0.039 (2)	0.041 (2)	0.038 (2)	0.0034 (18)	0.015 (2)	−0.0022 (18)
N3	0.036 (2)	0.041 (2)	0.040 (2)	0.0040 (17)	0.016 (2)	0.0000 (18)
N4	0.032 (2)	0.050 (3)	0.031 (2)	0.0020 (18)	0.0109 (19)	0.0026 (18)
N5	0.033 (2)	0.049 (3)	0.038 (2)	0.0006 (18)	0.0135 (19)	−0.0110 (19)
N6	0.028 (2)	0.044 (2)	0.036 (2)	−0.0030 (17)	0.0102 (18)	−0.0009 (18)
C1	0.039 (3)	0.052 (3)	0.038 (3)	0.011 (2)	0.014 (2)	0.011 (2)
C2	0.032 (3)	0.055 (3)	0.051 (3)	0.004 (2)	0.014 (3)	0.017 (3)
C3	0.037 (3)	0.053 (3)	0.034 (3)	−0.002 (2)	0.004 (2)	0.007 (2)
C4	0.038 (3)	0.062 (4)	0.033 (3)	0.000 (2)	0.012 (2)	0.002 (2)
C5	0.034 (3)	0.046 (3)	0.032 (3)	0.002 (2)	0.010 (2)	0.008 (2)
C6	0.039 (3)	0.037 (3)	0.034 (3)	0.005 (2)	0.007 (2)	0.010 (2)
C7	0.036 (3)	0.052 (3)	0.029 (3)	0.011 (2)	0.011 (2)	0.004 (2)
C8	0.029 (2)	0.037 (3)	0.035 (3)	0.001 (2)	0.007 (2)	0.003 (2)
C9	0.032 (3)	0.046 (3)	0.043 (3)	0.003 (2)	0.006 (2)	0.010 (2)
C10	0.052 (4)	0.051 (4)	0.051 (3)	−0.006 (3)	0.001 (3)	0.002 (3)
C11	0.037 (3)	0.071 (4)	0.081 (5)	−0.015 (3)	0.006 (3)	0.023 (4)
C12	0.033 (3)	0.077 (5)	0.092 (5)	0.002 (3)	0.022 (3)	0.020 (4)
C13	0.047 (3)	0.060 (4)	0.072 (4)	0.008 (3)	0.031 (3)	0.009 (3)
C14	0.033 (3)	0.041 (3)	0.041 (3)	0.007 (2)	0.010 (2)	0.008 (2)
C15	0.047 (3)	0.049 (3)	0.045 (3)	0.010 (2)	0.025 (3)	0.011 (2)
C16	0.033 (3)	0.062 (4)	0.048 (3)	0.010 (2)	0.017 (3)	0.009 (3)
C17	0.034 (3)	0.058 (3)	0.038 (3)	0.003 (2)	0.011 (2)	0.008 (2)
C18	0.039 (3)	0.049 (3)	0.043 (3)	0.002 (2)	0.016 (3)	0.003 (2)
C19	0.031 (3)	0.043 (3)	0.035 (3)	0.007 (2)	0.011 (2)	0.009 (2)
C20	0.031 (3)	0.049 (3)	0.033 (3)	−0.001 (2)	0.009 (2)	0.008 (2)
C21	0.040 (3)	0.049 (3)	0.036 (3)	0.003 (2)	0.016 (2)	−0.001 (2)
C22	0.030 (3)	0.042 (3)	0.033 (3)	−0.001 (2)	0.011 (2)	0.002 (2)
C23	0.031 (2)	0.039 (3)	0.030 (3)	−0.001 (2)	0.009 (2)	0.002 (2)
C24	0.051 (3)	0.041 (3)	0.051 (3)	0.004 (2)	0.020 (3)	−0.006 (2)
C25	0.044 (3)	0.051 (3)	0.064 (4)	0.017 (3)	0.025 (3)	0.007 (3)
C26	0.032 (3)	0.057 (4)	0.052 (3)	0.011 (2)	0.014 (3)	0.011 (3)
C27	0.032 (3)	0.059 (3)	0.039 (3)	0.000 (2)	0.010 (2)	−0.002 (2)
C28	0.029 (2)	0.047 (3)	0.033 (3)	0.006 (2)	0.013 (2)	0.000 (2)
C29	0.076 (4)	0.061 (4)	0.057 (4)	−0.012 (3)	0.013 (3)	0.008 (3)
C30	0.122 (6)	0.081 (5)	0.074 (5)	−0.020 (4)	0.047 (5)	−0.007 (4)

Geometric parameters (Å, º) top

Br1—C1	1.893 (5)	C9—C14	1.410 (7)
Br2—C3	1.891 (5)	C10—C11	1.405 (7)
Br3—C15	1.889 (5)	C10—H10	0.9300
Br4—C17	1.891 (5)	C11—C12	1.380 (8)
O1—C6	1.352 (6)	C11—H11	0.9300
O1—H1	0.8200	C12—C13	1.369 (8)
O2—C20	1.340 (5)	C12—H12	0.9300
O2—H2	0.8200	C13—C14	1.396 (6)
O3—C29	1.428 (6)	C13—H13	0.9300
O3—H3	0.8200	C15—C16	1.372 (7)
N1—C7	1.268 (6)	C15—C20	1.411 (6)
N1—C8	1.401 (5)	C16—C17	1.382 (7)
N2—C8	1.342 (6)	C16—H16	0.9300
N2—C9	1.374 (5)	C17—C18	1.389 (6)
N2—H2A	0.8600	C18—C19	1.406 (6)
N3—C8	1.309 (5)	C18—H18	0.9300
N3—C14	1.381 (6)	C19—C20	1.394 (7)
N4—C21	1.291 (6)	C19—C21	1.457 (6)
N4—C22	1.401 (5)	C21—H21	0.9300
N5—C22	1.350 (6)	C23—C24	1.397 (6)
N5—C28	1.392 (5)	C23—C28	1.414 (6)
N5—H5	0.8600	C24—C25	1.365 (7)
N6—C22	1.313 (6)	C24—H24	0.9300
N6—C23	1.380 (5)	C25—C26	1.406 (7)
C1—C2	1.373 (7)	C25—H25	0.9300
C1—C6	1.392 (6)	C26—C27	1.372 (7)
C2—C3	1.391 (7)	C26—H26	0.9300
C2—H2B	0.9300	C27—C28	1.407 (6)
C3—C4	1.386 (6)	C27—H27	0.9300
C4—C5	1.370 (7)	C29—C30	1.469 (8)
C4—H4	0.9300	C29—H29A	0.9700
C5—C6	1.401 (6)	C29—H29B	0.9700
C5—C7	1.470 (6)	C30—H30A	0.9600
C7—H7	0.9300	C30—H30B	0.9600
C9—C10	1.393 (7)	C30—H30C	0.9600

C6—O1—H1	109.5	C16—C15—C20	120.4 (5)
C20—O2—H2	109.5	C16—C15—Br3	120.8 (4)
C29—O3—H3	109.5	C20—C15—Br3	118.8 (4)
C7—N1—C8	120.3 (4)	C15—C16—C17	120.2 (4)
C8—N2—C9	107.0 (4)	C15—C16—H16	119.9
C8—N2—H2A	126.5	C17—C16—H16	119.9
C9—N2—H2A	126.5	C16—C17—C18	120.9 (5)
C8—N3—C14	104.0 (4)	C16—C17—Br4	119.9 (4)
C21—N4—C22	118.8 (4)	C18—C17—Br4	119.2 (4)
C22—N5—C28	106.2 (4)	C17—C18—C19	119.2 (5)
C22—N5—H5	126.9	C17—C18—H18	120.4
C28—N5—H5	126.9	C19—C18—H18	120.4
C22—N6—C23	104.3 (4)	C20—C19—C18	120.1 (4)
C2—C1—C6	121.3 (4)	C20—C19—C21	122.0 (4)
C2—C1—Br1	119.7 (4)	C18—C19—C21	117.9 (4)
C6—C1—Br1	119.1 (4)	O2—C20—C19	122.5 (4)
C1—C2—C3	119.2 (4)	O2—C20—C15	118.3 (5)
C1—C2—H2B	120.4	C19—C20—C15	119.2 (4)
C3—C2—H2B	120.4	N4—C21—C19	121.8 (4)
C4—C3—C2	119.9 (5)	N4—C21—H21	119.1
C4—C3—Br2	120.2 (4)	C19—C21—H21	119.1
C2—C3—Br2	119.9 (4)	N6—C22—N5	114.7 (4)
C5—C4—C3	121.0 (4)	N6—C22—N4	128.1 (4)
C5—C4—H4	119.5	N5—C22—N4	117.1 (4)
C3—C4—H4	119.5	N6—C23—C24	130.5 (4)
C4—C5—C6	119.5 (4)	N6—C23—C28	110.2 (4)
C4—C5—C7	119.1 (4)	C24—C23—C28	119.3 (4)
C6—C5—C7	121.4 (4)	C25—C24—C23	118.4 (5)
O1—C6—C1	118.5 (4)	C25—C24—H24	120.8
O1—C6—C5	122.4 (4)	C23—C24—H24	120.8
C1—C6—C5	119.1 (5)	C24—C25—C26	121.6 (5)
N1—C7—C5	121.0 (4)	C24—C25—H25	119.2
N1—C7—H7	119.5	C26—C25—H25	119.2
C5—C7—H7	119.5	C27—C26—C25	122.2 (5)
N3—C8—N2	114.4 (4)	C27—C26—H26	118.9
N3—C8—N1	129.7 (4)	C25—C26—H26	118.9
N2—C8—N1	115.9 (4)	C26—C27—C28	116.0 (5)
N2—C9—C10	132.6 (5)	C26—C27—H27	122.0
N2—C9—C14	104.5 (4)	C28—C27—H27	122.0
C10—C9—C14	122.9 (5)	N5—C28—C27	132.9 (4)
C9—C10—C11	116.3 (5)	N5—C28—C23	104.6 (4)
C9—C10—H10	121.9	C27—C28—C23	122.5 (4)
C11—C10—H10	121.9	O3—C29—C30	113.7 (5)
C12—C11—C10	120.5 (5)	O3—C29—H29A	108.8
C12—C11—H11	119.8	C30—C29—H29A	108.8
C10—C11—H11	119.8	O3—C29—H29B	108.8
C13—C12—C11	123.2 (5)	C30—C29—H29B	108.8
C13—C12—H12	118.4	H29A—C29—H29B	107.7
C11—C12—H12	118.4	C29—C30—H30A	109.5
C12—C13—C14	118.1 (6)	C29—C30—H30B	109.5
C12—C13—H13	120.9	H30A—C30—H30B	109.5
C14—C13—H13	120.9	C29—C30—H30C	109.5
N3—C14—C13	131.0 (5)	H30A—C30—H30C	109.5
N3—C14—C9	110.1 (4)	H30B—C30—H30C	109.5
C13—C14—C9	118.9 (5)

C6—C1—C2—C3	−0.1 (7)	C20—C15—C16—C17	0.5 (7)
Br1—C1—C2—C3	−179.6 (3)	Br3—C15—C16—C17	−178.3 (4)
C1—C2—C3—C4	0.8 (7)	C15—C16—C17—C18	0.8 (7)
C1—C2—C3—Br2	−179.8 (4)	C15—C16—C17—Br4	179.6 (3)
C2—C3—C4—C5	−0.7 (7)	C16—C17—C18—C19	−0.5 (7)
Br2—C3—C4—C5	179.9 (4)	Br4—C17—C18—C19	−179.3 (3)
C3—C4—C5—C6	−0.2 (7)	C17—C18—C19—C20	−1.2 (7)
C3—C4—C5—C7	−178.8 (4)	C17—C18—C19—C21	177.1 (4)
C2—C1—C6—O1	−179.2 (4)	C18—C19—C20—O2	−178.1 (4)
Br1—C1—C6—O1	0.3 (6)	C21—C19—C20—O2	3.8 (7)
C2—C1—C6—C5	−0.7 (7)	C18—C19—C20—C15	2.5 (7)
Br1—C1—C6—C5	178.8 (3)	C21—C19—C20—C15	−175.7 (4)
C4—C5—C6—O1	179.2 (4)	C16—C15—C20—O2	178.3 (4)
C7—C5—C6—O1	−2.2 (7)	Br3—C15—C20—O2	−2.8 (6)
C4—C5—C6—C1	0.9 (7)	C16—C15—C20—C19	−2.2 (7)
C7—C5—C6—C1	179.4 (4)	Br3—C15—C20—C19	176.7 (3)
C8—N1—C7—C5	−178.9 (4)	C22—N4—C21—C19	178.2 (4)
C4—C5—C7—N1	173.0 (5)	C20—C19—C21—N4	2.6 (7)
C6—C5—C7—N1	−5.5 (7)	C18—C19—C21—N4	−175.6 (4)
C14—N3—C8—N2	−0.1 (5)	C23—N6—C22—N5	0.6 (5)
C14—N3—C8—N1	179.9 (5)	C23—N6—C22—N4	178.9 (4)
C9—N2—C8—N3	−1.0 (6)	C28—N5—C22—N6	−0.4 (5)
C9—N2—C8—N1	179.0 (4)	C28—N5—C22—N4	−178.9 (4)
C7—N1—C8—N3	8.9 (8)	C21—N4—C22—N6	3.2 (7)
C7—N1—C8—N2	−171.1 (4)	C21—N4—C22—N5	−178.5 (4)
C8—N2—C9—C10	−177.0 (5)	C22—N6—C23—C24	−179.3 (5)
C8—N2—C9—C14	1.6 (5)	C22—N6—C23—C28	−0.5 (5)
N2—C9—C10—C11	178.9 (5)	N6—C23—C24—C25	178.3 (5)
C14—C9—C10—C11	0.5 (7)	C28—C23—C24—C25	−0.4 (7)
C9—C10—C11—C12	1.4 (8)	C23—C24—C25—C26	−0.2 (8)
C10—C11—C12—C13	−1.7 (9)	C24—C25—C26—C27	0.5 (8)
C11—C12—C13—C14	0.1 (9)	C25—C26—C27—C28	−0.2 (7)
C8—N3—C14—C13	−179.8 (5)	C22—N5—C28—C27	178.2 (5)
C8—N3—C14—C9	1.2 (5)	C22—N5—C28—C23	0.0 (5)
C12—C13—C14—N3	−177.1 (5)	C26—C27—C28—N5	−178.5 (5)
C12—C13—C14—C9	1.8 (7)	C26—C27—C28—C23	−0.5 (7)
N2—C9—C14—N3	−1.8 (5)	N6—C23—C28—N5	0.3 (5)
C10—C9—C14—N3	177.0 (4)	C24—C23—C28—N5	179.3 (4)
N2—C9—C14—C13	179.1 (4)	N6—C23—C28—C27	−178.1 (4)
C10—C9—C14—C13	−2.1 (7)	C24—C23—C28—C27	0.8 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N3	0.86	2.14	2.997 (4)	172
N2—H2A···O3ⁱ	0.86	2.00	2.816 (4)	157
O1—H1···N1	0.82	1.90	2.618 (6)	146
O2—H2···N4	0.82	1.92	2.640 (6)	147
O3—H3···N6ⁱⁱ	0.82	2.08	2.900 (5)	176

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉Br₂N₃O·0.5C₂H₆O
M_r	836.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.5300 (15), 16.8190 (14), 13.8491 (17)
β (°)	111.656 (13)
V (Å³)	3145.5 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.16
Crystal size (mm)	0.23 × 0.22 × 0.21

Data collection
Diffractometer	Agilent SuperNova Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.436, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19465, 6390, 4189
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.133, 1.03
No. of reflections	6390
No. of parameters	392
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.55, −0.76

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N3	0.86	2.14	2.997 (4)	172
N2—H2A···O3ⁱ	0.86	2.00	2.816 (4)	157
O1—H1···N1	0.82	1.90	2.618 (6)	146
O2—H2···N4	0.82	1.92	2.640 (6)	147
O3—H3···N6ⁱⁱ	0.82	2.08	2.900 (5)	176

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

Acknowledgements

The authors acknowledge financial support by the National Natural Science Foundation of China (No. 2126606).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, S.-H., Ma, L.-F., Zou, H.-H., Wang, Y.-G., Liang, H. & Zeng, M.-H. (2011). Dalton Trans. 40, 11402–11409. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zhang, S.-H., Zeng, M.-H. & Liang, H. (2008). J. Coord. Chem. 61, 2422–2427. CAS Google Scholar