3-(2-Bromo­phen­yl)thia­zolo[3,2-a]benzimidazole

Wang, Z.-M.; Yu, B.; Cui, Y.; Zhang, X.-Q.; Sun, X.-Q.

doi:10.1107/S1600536811034842

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2540

doi:10.1107/S1600536811034842

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3-(2-Bromophenyl)thiazolo[3,2-a]benzimidazole

Zhi-Ming Wang,^a Bin Yu,^b Yuan Cui,^a Xiu-Qing Zhang ^b and Xiao-Qiang Sun ^a ^*

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, People's Republic of China, and ^bHigh Technology Research Institute of Nanjing University, Changzhou 213162, People's Republic of China
^*Correspondence e-mail: wzmmol@hotmail.com

(Received 17 August 2011; accepted 25 August 2011; online 31 August 2011)

The title compound, C₁₅H₉BrN₂S, was prepared by the reaction of 1-bromo-2-(2,2-dibromovinyl)benzene with 1H-benzo[d]imidazole-2(3H)-thione. The thiazolo[3,2-a]benzimidazole fused-ring system is nearly planar, the maximum atomic deviation being 0.049 (4) Å. This mean plane is oriented at a dihedral angle of 71.55 (17)° with respect ot the bromophenyl ring. π–π stacking is observed in the crystal structure, the centroid–centroid distance between the thiazole and imidazole rings of adjacent molecules being 3.582 (2) Å.

Related literature

For the biological activity of imidazoles and their use as inhibitors of neurodegenerative disorders and as antitumor drugs, see: Park et al. (1977 ); Schuckmann et al. (1979 ). For related imidazole compounds, see: Andreani et al. (2005 ); Xu et al. (2010 ).

Experimental

Crystal data

C₁₅H₉BrN₂S
M_r = 329.21
Monoclinic, P 2₁ /c
a = 11.2459 (19) Å
b = 9.1554 (16) Å
c = 14.2842 (18) Å
β = 118.159 (9)°
V = 1296.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.32 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.456, T_max = 0.483
7492 measured reflections
2533 independent reflections
1977 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.120
S = 1.01
2533 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −1.20 e Å⁻³

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811034842/xu5299sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034842/xu5299Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034842/xu5299Isup3.cml

checkCIF report

Comment top

Owing to the promising biological activities as inhibitors of neurodegenerative disorders and antitumor drugs, such compound structures have been studied (Park et al., 1977; Schuckmann et al., 1979). In the past decades, most of these investigations were carried out with imidazole (Andreani et al., 2005; Xu et al., 2010). We herein present the structure of 3-(2-bromopheny)thiazolo[3,2-a]benzimidazole(Fig. 1).

In the title compound, the benzene imidazole ring and thiazole ring are almost in the same plane. In the crystal structure, π-π interactions contribute the crystal packing.

Related literature top

For the biological activity of imidazoles and their use as inhibitors of neurodegenerative disorders and as antitumor drugs, see: Park et al. (1977); Schuckmann et al. (1979). For related imidazole compounds, see: Andreani et al. (2005); Xu et al. (2010).

Experimental top

1-Bromo-2-(2,2-dibromovinyl)benzene(1.2 mmol) in 1.0 ml of DMF were added to a stirred solution of 1H-benzo[d]imidazole-2(3H)-thione(1.0 mmol), Cs₂CO₃(2 mmol), CuI(0.1 mmol) and dmeda(0.2 mmol) in DMF(3 ml) under nitrogen. The resulting mixture was stirred at 100 °C for 4 h. After being cooled to room temperature, the reaction mixture was diluted with water and extracted with CHCl_3, the combined organic layer were dried over Na₂SO₄ and concentrated. The crude product was further purified by flash column chromatography using petroleum ether (PE) and CH₂Cl₂ as a white solid (90% yield). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure.

3-(2-Bromophenyl)thiazolo[3,2-a]benzimidazole top

Crystal data top

C₁₅H₉BrN₂S	F(000) = 656
M_r = 329.21	D_x = 1.686 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3173 reflections
a = 11.2459 (19) Å	θ = 2.8–27.3°
b = 9.1554 (16) Å	µ = 3.32 mm⁻¹
c = 14.2842 (18) Å	T = 296 K
β = 118.159 (9)°	Block, colourless
V = 1296.6 (4) Å³	0.24 × 0.22 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2533 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −13→11
T_min = 0.456, T_max = 0.483	k = −11→10
7492 measured reflections	l = −11→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0717P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
2533 reflections	Δρ_max = 0.52 e Å⁻³
173 parameters	Δρ_min = −1.20 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.198 (7)

Crystal data top

C₁₅H₉BrN₂S	V = 1296.6 (4) Å³
M_r = 329.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.2459 (19) Å	µ = 3.32 mm⁻¹
b = 9.1554 (16) Å	T = 296 K
c = 14.2842 (18) Å	0.24 × 0.22 × 0.22 mm
β = 118.159 (9)°

Data collection top

Bruker APEXII CCD diffractometer	2533 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1977 reflections with I > 2σ(I)
T_min = 0.456, T_max = 0.483	R_int = 0.073
7492 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.01	Δρ_max = 0.52 e Å⁻³
2533 reflections	Δρ_min = −1.20 e Å⁻³
173 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
Br1	0.22834 (4)	0.45478 (5)	0.55293 (3)	0.0445 (2)
C1	0.2162 (3)	0.0447 (4)	0.5360 (3)	0.0337 (9)
H1	0.1460	0.0949	0.4811	0.040*
C2	0.1918 (4)	−0.0647 (4)	0.5901 (3)	0.0414 (10)
H2	0.1033	−0.0901	0.5711	0.050*
C3	0.2968 (4)	−0.1382 (4)	0.6728 (3)	0.0407 (9)
H3	0.2766	−0.2115	0.7082	0.049*
C4	0.4298 (4)	−0.1059 (4)	0.7041 (3)	0.0389 (9)
H4	0.4991	−0.1562	0.7596	0.047*
C5	0.4574 (3)	0.0052 (4)	0.6498 (3)	0.0295 (8)
C6	0.3489 (3)	0.0771 (3)	0.5661 (3)	0.0239 (7)
C7	0.5470 (3)	0.1543 (4)	0.5890 (3)	0.0271 (7)
C8	0.4831 (3)	0.3354 (4)	0.4467 (3)	0.0315 (8)
H8	0.4781	0.4050	0.3975	0.038*
C9	0.3737 (3)	0.2780 (4)	0.4475 (3)	0.0258 (7)
C10	0.2316 (3)	0.3134 (4)	0.3760 (3)	0.0282 (7)
C11	0.1737 (4)	0.2726 (5)	0.2701 (3)	0.0429 (9)
H11	0.2244	0.2219	0.2449	0.052*
C12	0.0396 (5)	0.3077 (5)	0.2014 (4)	0.0592 (13)
H12	0.0014	0.2812	0.1302	0.071*
C13	−0.0352 (4)	0.3798 (6)	0.2377 (4)	0.0589 (13)
H13	−0.1247	0.4020	0.1912	0.071*
C14	0.0187 (4)	0.4208 (5)	0.3418 (4)	0.0474 (11)
H14	−0.0338	0.4697	0.3662	0.057*
C15	0.1524 (3)	0.3888 (4)	0.4105 (3)	0.0297 (8)
N1	0.4104 (2)	0.1755 (3)	0.5283 (2)	0.0250 (6)
N2	0.5811 (3)	0.0540 (3)	0.6619 (2)	0.0322 (7)
S1	0.63442 (8)	0.26789 (10)	0.54574 (8)	0.0354 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0387 (3)	0.0568 (3)	0.0447 (3)	0.00761 (17)	0.0251 (2)	−0.00393 (19)
C1	0.0233 (18)	0.041 (2)	0.031 (2)	0.0051 (15)	0.0084 (16)	0.0037 (16)
C2	0.031 (2)	0.053 (2)	0.043 (2)	−0.0045 (18)	0.0195 (19)	0.0010 (19)
C3	0.039 (2)	0.047 (2)	0.029 (2)	−0.0060 (18)	0.0110 (18)	0.0045 (18)
C4	0.038 (2)	0.042 (2)	0.0250 (19)	0.0043 (18)	0.0055 (17)	0.0051 (17)
C5	0.0222 (17)	0.0344 (17)	0.0216 (17)	0.0006 (15)	0.0019 (15)	−0.0037 (15)
C6	0.0208 (16)	0.0267 (16)	0.0207 (16)	0.0022 (13)	0.0068 (14)	−0.0020 (13)
C7	0.0158 (15)	0.0326 (17)	0.0258 (18)	0.0004 (14)	0.0040 (14)	−0.0081 (15)
C8	0.0235 (17)	0.0360 (19)	0.034 (2)	−0.0002 (15)	0.0129 (16)	−0.0026 (16)
C9	0.0224 (16)	0.0286 (17)	0.0263 (17)	0.0033 (13)	0.0114 (15)	−0.0006 (14)
C10	0.0226 (16)	0.0301 (17)	0.0272 (18)	0.0010 (14)	0.0078 (15)	0.0053 (15)
C11	0.040 (2)	0.049 (2)	0.031 (2)	0.0004 (18)	0.0089 (19)	−0.0024 (18)
C12	0.043 (3)	0.068 (3)	0.035 (2)	−0.001 (2)	−0.008 (2)	0.004 (2)
C13	0.025 (2)	0.067 (3)	0.057 (3)	0.002 (2)	−0.003 (2)	0.012 (3)
C14	0.025 (2)	0.051 (2)	0.063 (3)	0.0114 (18)	0.018 (2)	0.014 (2)
C15	0.0177 (16)	0.0358 (19)	0.0328 (19)	0.0018 (14)	0.0098 (15)	0.0038 (15)
N1	0.0135 (13)	0.0307 (14)	0.0253 (15)	0.0040 (11)	0.0046 (12)	−0.0023 (12)
N2	0.0181 (14)	0.0375 (16)	0.0261 (16)	0.0029 (12)	−0.0017 (13)	−0.0020 (14)
S1	0.0167 (4)	0.0451 (6)	0.0409 (6)	−0.0022 (4)	0.0107 (4)	−0.0042 (4)

Geometric parameters (Å, º) top

Br1—C15	1.895 (4)	C8—C9	1.343 (5)
C1—C2	1.370 (5)	C8—S1	1.735 (4)
C1—C6	1.377 (5)	C8—H8	0.9300
C1—H1	0.9300	C9—N1	1.390 (4)
C2—C3	1.388 (6)	C9—C10	1.470 (5)
C2—H2	0.9300	C10—C11	1.386 (5)
C3—C4	1.376 (6)	C10—C15	1.388 (5)
C3—H3	0.9300	C11—C12	1.395 (6)
C4—C5	1.400 (6)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.351 (7)
C5—N2	1.392 (5)	C12—H12	0.9300
C5—C6	1.405 (5)	C13—C14	1.367 (7)
C6—N1	1.391 (4)	C13—H13	0.9300
C7—N2	1.304 (5)	C14—C15	1.385 (5)
C7—N1	1.375 (4)	C14—H14	0.9300
C7—S1	1.732 (4)

C2—C1—C6	117.2 (3)	C8—C9—C10	127.4 (3)
C2—C1—H1	121.4	N1—C9—C10	121.7 (3)
C6—C1—H1	121.4	C11—C10—C15	118.2 (3)
C1—C2—C3	121.3 (4)	C11—C10—C9	119.6 (3)
C1—C2—H2	119.4	C15—C10—C9	122.2 (3)
C3—C2—H2	119.4	C10—C11—C12	120.0 (4)
C4—C3—C2	122.0 (4)	C10—C11—H11	120.0
C4—C3—H3	119.0	C12—C11—H11	120.0
C2—C3—H3	119.0	C13—C12—C11	120.3 (4)
C3—C4—C5	117.9 (3)	C13—C12—H12	119.8
C3—C4—H4	121.1	C11—C12—H12	119.8
C5—C4—H4	121.1	C12—C13—C14	121.0 (4)
N2—C5—C4	129.4 (3)	C12—C13—H13	119.5
N2—C5—C6	111.7 (3)	C14—C13—H13	119.5
C4—C5—C6	118.8 (3)	C13—C14—C15	119.3 (4)
C1—C6—N1	133.0 (3)	C13—C14—H14	120.4
C1—C6—C5	122.9 (3)	C15—C14—H14	120.4
N1—C6—C5	104.1 (3)	C14—C15—C10	121.2 (4)
N2—C7—N1	115.0 (3)	C14—C15—Br1	118.8 (3)
N2—C7—S1	134.9 (3)	C10—C15—Br1	120.0 (2)
N1—C7—S1	110.1 (3)	C7—N1—C9	115.1 (3)
C9—C8—S1	113.8 (3)	C7—N1—C6	106.0 (3)
C9—C8—H8	123.1	C9—N1—C6	138.8 (3)
S1—C8—H8	123.1	C7—N2—C5	103.1 (3)
C8—C9—N1	110.9 (3)	C7—S1—C8	90.07 (16)

Experimental details

Crystal data
Chemical formula	C₁₅H₉BrN₂S
M_r	329.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.2459 (19), 9.1554 (16), 14.2842 (18)
β (°)	118.159 (9)
V (Å³)	1296.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.32
Crystal size (mm)	0.24 × 0.22 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.456, 0.483
No. of measured, independent and observed [I > 2σ(I)] reflections	7492, 2533, 1977
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.120, 1.01
No. of reflections	2533
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −1.20

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported financially by the Priority Academic Development Program of Jiangsu Higher Education Institutions, China.

References

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