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organic compounds
3-(2-Bromophenyl)thiazolo[3,2-a]benzimidazole
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
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 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
|
Data collection: APEX2 (Bruker, 2006); cell 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
10.1107/S1600536811034842/xu5299sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811034842/xu5299Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811034842/xu5299Isup3.cml
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 CHCl3, the combined organic layer were dried over Na2SO4 and concentrated. The crude product was further purified by flash
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.All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 Å, and with Uiso(H)= 1.2 Ueq(C).
Data collection: APEX2 (Bruker, 2006); cell
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).C15H9BrN2S | F(000) = 656 |
Mr = 329.21 | Dx = 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 |
Bruker APEXII CCD diffractometer | 2533 independent reflections |
Radiation source: fine-focus sealed tube | 1977 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −13→11 |
Tmin = 0.456, Tmax = 0.483 | k = −11→10 |
7492 measured reflections | l = −11→17 |
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(Fo2) + (0.0717P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
2533 reflections | Δρmax = 0.52 e Å−3 |
173 parameters | Δρmin = −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) |
C15H9BrN2S | V = 1296.6 (4) Å3 |
Mr = 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)° |
Bruker APEXII CCD diffractometer | 2533 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 1977 reflections with I > 2σ(I) |
Tmin = 0.456, Tmax = 0.483 | Rint = 0.073 |
7492 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.52 e Å−3 |
2533 reflections | Δρmin = −1.20 e Å−3 |
173 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.456, 0.483 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7492, 2533, 1977 |
Rint | 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 |
Δρmax, Δρmin (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
Andreani, A., Granaiola, M., Leoni, A., Locatelli, A., Morigi, R., Rambaldi, M., Garaliene, V., Welsh, W., Arora, S., Farruggia, G. & Masotti, L. (2005). J. Med. Chem. 48, 5604–5607. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2006). APEX2, SMART and SADABS. Bruker AXS Inc., Madison Wisconsin, USA. Google Scholar
Park, S. W., Reid, W. & Schuckmann, W. (1977). Liebigs Ann. Chem. pp. 106–115. CrossRef Google Scholar
Schuckmann, W., Fuess, H., Park, S. W. & Reid, W. (1979). Acta Cryst. B35, 96–100. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, H., Zhang, Y., Huang, J.-Q. & Chen, W.-Z. (2010). Org. Lett. 12, 3704–3707. CSD CrossRef CAS PubMed Google Scholar
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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.