2-(4-Bromo­phen­yl)-1-ethyl-1H-1,3-benzodiazole

Dong, S.-L.; Cheng, X.-C.

doi:10.1107/S1600536811001097

organic compounds

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Volume 67| Part 2| February 2011| Page o379

doi:10.1107/S1600536811001097

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2-(4-Bromophenyl)-1-ethyl-1H-1,3-benzodiazole

Su-Lan Dong ^a ^* and Xiao-Chun Cheng ^a

^aCollege of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, Jiangsu, People's Republic of China
^*Correspondence e-mail: dsl710221@163.com

(Received 4 January 2011; accepted 8 January 2011; online 15 January 2011)

In the title compound, C₁₅H₁₃BrN₂, the benzimidazole group is almost planar, as indicated by the dihedral angle of 2.6 (3)° between the best planes through the benzene and imidazole rings. The best plane through the attached benzene makes an angle of 44.5 (2)° with the best plane through the benzimidazole system. C—H⋯π interactions are observed in the crystal structure.

Related literature

For the synthesis, see: Kakimoto et al. (2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₃BrN₂
M_r = 301.18
Triclinic, $[P \overline 1]$
a = 9.0780 (18) Å
b = 9.1480 (18) Å
c = 9.2750 (19) Å
α = 76.72 (3)°
β = 78.44 (3)°
γ = 61.05 (3)°
V = 652.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.573, T_max = 0.745
2550 measured reflections
2388 independent reflections
1322 reflections with I > 2σ(I)
R_int = 0.068
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.111
S = 1.00
2388 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the imidazolyl and C1–C6 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯Cg2ⁱ	0.93	2.80	3.364 (2)	120
C13—H13A⋯Cg1ⁱ	0.93	2.93	3.429 (5)	115
Symmetry code: (i) -x+1, -y-2, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 I, global. DOI: 10.1107/S1600536811001097/vm2072sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001097/vm2072Isup2.hkl

checkCIF report

Comment top

The tittle compound, (I), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole is an important intermediate organic intermediate which can be used for many fields such as OLED materials (Kakimoto et al., 2008). Here we report the crystal structure of (I). The molecular structure of (I) is shown in Fig. 1, the bond lengths and angles are within normal ranges (Allen et al., 1987).

In the benzimidazolyl group, the best planes through the phenyl ring and imidazolyl ring make an angle of 2.6 (2) °. Phenyl ring C8—C13 (connected with Br atom) makes an angle of 45.2 (3) ° and 43.3 (3) ° with phenyl ring C1—C6 and the imidazolyl ring, respectively.

In the crystal packing of (I), there were no classic intramolecular or intermolecular hydrogen bonds. Two C—H···ring interactions are present (Table 1, Fig.2).

Related literature top

For the synthetic procedure, see: Kakimoto et al. (2008). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Kakimoto et al., 2008). The crystals were obtained by dissolving (I) (0.5 g, 1.61 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. The molecular structure of title compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Packing diagram for (I) showing C—H···ring interactions.

2-(4-Bromophenyl)-1-ethyl-1H-1,3-benzodiazole top

Crystal data top

C₁₅H₁₃BrN₂	Z = 2
M_r = 301.18	F(000) = 304
Triclinic, P1	D_x = 1.533 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0780 (18) Å	Cell parameters from 25 reflections
b = 9.1480 (18) Å	θ = 10–14°
c = 9.2750 (19) Å	µ = 3.13 mm⁻¹
α = 76.72 (3)°	T = 293 K
β = 78.44 (3)°	Block, colourless
γ = 61.05 (3)°	0.20 × 0.10 × 0.10 mm
V = 652.4 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1322 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −9→11
T_min = 0.573, T_max = 0.745	l = −10→11
2550 measured reflections	3 standard reflections every 200 reflections
2388 independent reflections	intensity decay: 1%

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.049P)²] where P = (F_o² + 2F_c²)/3
2388 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₅H₁₃BrN₂	γ = 61.05 (3)°
M_r = 301.18	V = 652.4 (2) Å³
Triclinic, P1	Z = 2
a = 9.0780 (18) Å	Mo Kα radiation
b = 9.1480 (18) Å	µ = 3.13 mm⁻¹
c = 9.2750 (19) Å	T = 293 K
α = 76.72 (3)°	0.20 × 0.10 × 0.10 mm
β = 78.44 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1322 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.068
T_min = 0.573, T_max = 0.745	3 standard reflections every 200 reflections
2550 measured reflections	intensity decay: 1%
2388 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.00	Δρ_max = 0.28 e Å⁻³
2388 reflections	Δρ_min = −0.32 e Å⁻³
163 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Br	0.32320 (8)	−0.57697 (8)	0.48665 (6)	0.0929 (3)
N1	0.1726 (4)	−0.8039 (4)	−0.1030 (4)	0.0524 (9)
C1	0.2103 (5)	−1.0699 (6)	−0.0928 (5)	0.0519 (12)
N2	0.2453 (4)	−1.0570 (5)	0.0412 (4)	0.0486 (9)
C2	0.2144 (6)	−1.2057 (7)	−0.1407 (6)	0.0698 (14)
H2A	0.2384	−1.3083	−0.0784	0.084*
C3	0.1808 (7)	−1.1794 (9)	−0.2856 (7)	0.0872 (19)
H3A	0.1828	−1.2662	−0.3234	0.105*
C4	0.1437 (6)	−1.0237 (9)	−0.3760 (6)	0.0827 (18)
H4A	0.1248	−1.0112	−0.4741	0.099*
C5	0.1337 (5)	−0.8882 (7)	−0.3275 (5)	0.0694 (14)
H5A	0.1054	−0.7847	−0.3892	0.083*
C6	0.1682 (5)	−0.9129 (6)	−0.1804 (5)	0.0524 (12)
C7	0.2206 (5)	−0.8950 (6)	0.0272 (5)	0.0461 (10)
C8	0.2462 (5)	−0.8272 (5)	0.1432 (4)	0.0439 (10)
C9	0.1320 (6)	−0.6632 (6)	0.1667 (5)	0.0538 (11)
H9A	0.0382	−0.6028	0.1131	0.065*
C10	0.1543 (6)	−0.5881 (6)	0.2670 (5)	0.0631 (13)
H10A	0.0761	−0.4783	0.2818	0.076*
C11	0.2940 (6)	−0.6771 (6)	0.3456 (5)	0.0552 (12)
C12	0.4095 (6)	−0.8382 (6)	0.3237 (4)	0.0563 (12)
H12A	0.5034	−0.8977	0.3773	0.068*
C13	0.3864 (5)	−0.9121 (6)	0.2220 (4)	0.0515 (11)
H13A	0.4665	−1.0209	0.2061	0.062*
C14	0.2964 (6)	−1.1962 (6)	0.1673 (5)	0.0588 (12)
H14A	0.2218	−1.2480	0.1842	0.071*
H14B	0.2831	−1.1505	0.2564	0.071*
C15	0.4772 (6)	−1.3301 (6)	0.1421 (5)	0.0673 (13)
H15A	0.5041	−1.4173	0.2274	0.101*
H15B	0.5519	−1.2802	0.1271	0.101*
H15C	0.4905	−1.3781	0.0556	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.1271 (6)	0.1207 (6)	0.0706 (4)	−0.0799 (5)	0.0003 (3)	−0.0424 (3)
N1	0.052 (2)	0.057 (2)	0.044 (2)	−0.018 (2)	−0.0118 (18)	−0.0083 (19)
C1	0.042 (3)	0.064 (3)	0.056 (3)	−0.022 (3)	0.000 (2)	−0.030 (3)
N2	0.046 (2)	0.055 (3)	0.047 (2)	−0.0224 (19)	−0.0062 (17)	−0.0112 (19)
C2	0.057 (3)	0.079 (4)	0.085 (4)	−0.033 (3)	0.001 (3)	−0.037 (3)
C3	0.069 (4)	0.128 (6)	0.098 (5)	−0.055 (4)	0.006 (3)	−0.068 (4)
C4	0.057 (4)	0.138 (6)	0.072 (4)	−0.045 (4)	−0.006 (3)	−0.051 (4)
C5	0.050 (3)	0.102 (4)	0.051 (3)	−0.024 (3)	−0.006 (2)	−0.028 (3)
C6	0.036 (3)	0.067 (4)	0.052 (3)	−0.019 (2)	−0.005 (2)	−0.019 (3)
C7	0.040 (3)	0.051 (3)	0.047 (3)	−0.020 (2)	0.000 (2)	−0.014 (2)
C8	0.045 (3)	0.048 (3)	0.037 (2)	−0.021 (2)	−0.002 (2)	−0.007 (2)
C9	0.057 (3)	0.048 (3)	0.051 (3)	−0.018 (3)	−0.013 (2)	−0.005 (2)
C10	0.075 (4)	0.048 (3)	0.066 (3)	−0.025 (3)	0.001 (3)	−0.022 (2)
C11	0.068 (3)	0.065 (3)	0.046 (3)	−0.039 (3)	0.001 (2)	−0.017 (2)
C12	0.050 (3)	0.072 (4)	0.047 (3)	−0.025 (3)	−0.005 (2)	−0.017 (2)
C13	0.045 (3)	0.052 (3)	0.053 (3)	−0.014 (2)	−0.006 (2)	−0.017 (2)
C14	0.065 (3)	0.057 (3)	0.058 (3)	−0.035 (3)	0.000 (2)	−0.007 (3)
C15	0.060 (3)	0.060 (3)	0.075 (3)	−0.023 (3)	−0.005 (3)	−0.012 (3)

Geometric parameters (Å, º) top

Br—C11	1.883 (4)	C8—C13	1.383 (5)
N1—C7	1.319 (5)	C8—C9	1.388 (6)
N1—C6	1.374 (5)	C9—C10	1.372 (6)
C1—N2	1.386 (5)	C9—H9A	0.9300
C1—C6	1.388 (6)	C10—C11	1.379 (6)
C1—C2	1.394 (6)	C10—H10A	0.9300
N2—C7	1.365 (5)	C11—C12	1.367 (6)
N2—C14	1.472 (5)	C12—C13	1.379 (5)
C2—C3	1.379 (7)	C12—H12A	0.9300
C2—H2A	0.9300	C13—H13A	0.9300
C3—C4	1.394 (8)	C14—C15	1.510 (6)
C3—H3A	0.9300	C14—H14A	0.9700
C4—C5	1.370 (7)	C14—H14B	0.9700
C4—H4A	0.9300	C15—H15A	0.9600
C5—C6	1.404 (6)	C15—H15B	0.9600
C5—H5A	0.9300	C15—H15C	0.9600
C7—C8	1.464 (5)

C7—N1—C6	104.7 (4)	C10—C9—C8	121.6 (4)
N2—C1—C6	105.7 (4)	C10—C9—H9A	119.2
N2—C1—C2	130.8 (5)	C8—C9—H9A	119.2
C6—C1—C2	123.5 (4)	C9—C10—C11	119.2 (4)
C7—N2—C1	105.7 (4)	C9—C10—H10A	120.4
C7—N2—C14	130.3 (3)	C11—C10—H10A	120.4
C1—N2—C14	123.9 (4)	C12—C11—C10	120.5 (4)
C3—C2—C1	116.3 (5)	C12—C11—Br	119.9 (4)
C3—C2—H2A	121.9	C10—C11—Br	119.6 (4)
C1—C2—H2A	121.9	C11—C12—C13	119.7 (4)
C2—C3—C4	120.6 (5)	C11—C12—H12A	120.1
C2—C3—H3A	119.7	C13—C12—H12A	120.1
C4—C3—H3A	119.7	C12—C13—C8	121.1 (4)
C5—C4—C3	123.2 (5)	C12—C13—H13A	119.4
C5—C4—H4A	118.4	C8—C13—H13A	119.4
C3—C4—H4A	118.4	N2—C14—C15	112.8 (4)
C4—C5—C6	117.0 (5)	N2—C14—H14A	109.0
C4—C5—H5A	121.5	C15—C14—H14A	109.0
C6—C5—H5A	121.5	N2—C14—H14B	109.0
N1—C6—C1	110.4 (4)	C15—C14—H14B	109.0
N1—C6—C5	130.2 (5)	H14A—C14—H14B	107.8
C1—C6—C5	119.4 (4)	C14—C15—H15A	109.5
N1—C7—N2	113.5 (4)	C14—C15—H15B	109.5
N1—C7—C8	122.5 (4)	H15A—C15—H15B	109.5
N2—C7—C8	124.1 (4)	C14—C15—H15C	109.5
C13—C8—C9	117.8 (4)	H15A—C15—H15C	109.5
C13—C8—C7	123.5 (4)	H15B—C15—H15C	109.5
C9—C8—C7	118.5 (4)

C6—C1—N2—C7	0.7 (4)	C14—N2—C7—N1	−179.2 (4)
C2—C1—N2—C7	−179.9 (4)	C1—N2—C7—C8	−179.0 (4)
C6—C1—N2—C14	−179.8 (4)	C14—N2—C7—C8	1.5 (7)
C2—C1—N2—C14	−0.3 (7)	N1—C7—C8—C13	−133.5 (4)
N2—C1—C2—C3	−176.6 (4)	N2—C7—C8—C13	45.7 (6)
C6—C1—C2—C3	2.7 (6)	N1—C7—C8—C9	40.5 (6)
C1—C2—C3—C4	−0.6 (7)	N2—C7—C8—C9	−140.3 (4)
C2—C3—C4—C5	−1.8 (8)	C13—C8—C9—C10	−1.5 (6)
C3—C4—C5—C6	2.0 (7)	C7—C8—C9—C10	−175.9 (4)
C7—N1—C6—C1	1.5 (5)	C8—C9—C10—C11	0.5 (7)
C7—N1—C6—C5	−176.5 (4)	C9—C10—C11—C12	0.2 (7)
N2—C1—C6—N1	−1.4 (5)	C9—C10—C11—Br	−178.6 (3)
C2—C1—C6—N1	179.1 (4)	C10—C11—C12—C13	0.1 (7)
N2—C1—C6—C5	176.9 (3)	Br—C11—C12—C13	179.0 (3)
C2—C1—C6—C5	−2.6 (6)	C11—C12—C13—C8	−1.2 (6)
C4—C5—C6—N1	178.1 (4)	C9—C8—C13—C12	1.9 (6)
C4—C5—C6—C1	0.2 (6)	C7—C8—C13—C12	175.9 (4)
C6—N1—C7—N2	−1.1 (5)	C7—N2—C14—C15	−106.0 (5)
C6—N1—C7—C8	178.2 (4)	C1—N2—C14—C15	74.6 (5)
C1—N2—C7—N1	0.2 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the imidazolyl and C1–C6 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···Cg2ⁱ	0.93	2.80	3.364 (2)	120
C13—H13A···Cg1ⁱ	0.93	2.93	3.429 (5)	115

Symmetry code: (i) −x+1, −y−2, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃BrN₂
M_r	301.18
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.0780 (18), 9.1480 (18), 9.2750 (19)
α, β, γ (°)	76.72 (3), 78.44 (3), 61.05 (3)
V (Å³)	652.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.13
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.573, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	2550, 2388, 1322
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.111, 1.00
No. of reflections	2388
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.32

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the imidazolyl and C1–C6 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···Cg2ⁱ	0.93	2.80	3.364 (2)	120
C13—H13A···Cg1ⁱ	0.93	2.93	3.429 (5)	115

Symmetry code: (i) −x+1, −y−2, −z.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection. We also thank the Contract grant sponsors, the Natural Science Foundation of Jiangsu Province of China (BK2008195) and the Science Research Foundation of Huaiyin Institute of Technology (2517045), for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Kakimoto, M., Ge, Z. Y., Hayakawa, T., Ando, S. & Ueda, M. (2008). Adv. Funct. Mater. A18, 584–590. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536811001097

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