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

Abstract

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,

• a = 11.2459 (19) Å

• b = 9.1554 (16) Å

• c = 14.2842 (18) Å

• β = 118.159 (9)°

• V = 1296.6 (4) ų

• 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[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811034842/xu5299Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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 U_iso(H)= 1.2 U_eq(C).

Figures

Fig. 1.

The molecular structure.

Crystal data

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

Data collection

Bruker APEXII CCD diffractometer	2533 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
graphite	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

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)

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	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, °)

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)