2-(2H-1,3-Benzodioxol-5-yl)-1,3-benzo­thia­zole

D Lakshmanan; S Murugavel; R Selvakumar; M Bakthadoss

doi:10.1107/S1600536812008914

. 2012 Mar 3;68(Pt 4):o961. doi: 10.1107/S1600536812008914

2-(2H-1,3-Benzodioxol-5-yl)-1,3-benzothiazole

D Lakshmanan ^a, S Murugavel ^b,^*, R Selvakumar ^c, M Bakthadoss ^c,^‡

PMCID: PMC3343939 PMID: 22590020

Abstract

In the title compound, C₁₄H₉O₂S, the benzothiazole unit is oriented at a dihedral angle of 7.1 (1)° with respect to the benzodioxole unit. The dioxole ring adopts flattened envelope conformation with the methylene C atom at the flap. The crystal packing is stabilized by π–π interactions [centroid–centroid distances = 3.705 (1) and 3.752 (1) Å], C—H⋯π interactions and a short S⋯S contact of 3.485 (1) Å.

Related literature

For background to the applications of benzothiazoles in the chemical industry, see: Bradshaw et al. (2002 ▶); Delmas et al. (2002 ▶); Hutchinson et al. (2002 ▶). For the pharmacological activity of benzothiazole derivatives, see: Repiĉ et al. (2001 ▶); Schwartz et al. (1992 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For related structures, see: Baryala et al. (2010 ▶); Zhang et al. (2008 ▶).

Experimental

Crystal data

C₁₄H₉NO₂S
M _r = 255.28
Orthorhombic,
a = 6.3356 (2) Å
b = 16.3222 (5) Å
c = 22.0471 (7) Å
V = 2279.91 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.934, T _max = 0.952
15338 measured reflections
3135 independent reflections
2243 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.105
S = 1.02
3135 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812008914/gk2459sup1.cif

e-68-0o961-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008914/gk2459Isup2.hkl

e-68-0o961-Isup2.hkl^{(150.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812008914/gk2459Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the dioxole ring and Cg2 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cg1ⁱ	0.93	2.79	3.624 (2)	150
C14—H14B⋯Cg2ⁱⁱ	0.97	2.84	3.580 (2)	134

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Benzothiazoles are remarkable heterocyclic ring systems. They possess therapeutic value, are synthetic intermediates in the preparation of medicinal compounds and find numerous applications in chemical industry (Bradshaw et al., 2002; Hutchinson et al., 2002; Delmas et al., 2002). Benzothiazole nucleus is associated with several pharmacological activities such as anti-tumor (Repiĉ et al., 2001) and antimicrobial (Schwartz et al., 1992). In view of this biological importance, the crystal structure of the title compound has been determined and the results are presented here.

Fig. 1. shows a displacement ellipsoid plot of (I), with the atom numbering scheme. The benzothiazole moiety is essentially planar [maximum deviation = -0.016 (1) Å for the C14 atom] and lies at an angle 7.1 (1)° with respect to the benzodioxole unit. The dioxole (O1/O2/C11/C12/C14) ring adopts an envelope conformation with the C14 (displacement = 0.03 (18) Å) atom as the flap atom and with puckering parameters (Cremer & Pople, 1975), q₂ = 0.0882 (16) Å and φ₂ = 143.8 (1)°. The geometric parameters of the title molecule agree well with those reported for similar structures (Baryala et al., 2010; Zhang et al., 2008).

The crystal packing is stabilized by π—π interactions with Cg3···Cg4ⁱ and Cg1···Cg4ⁱ seperations of 3.705 (1) Å and 3.752 (1) Å, respectively (Fig. 2; Cg1, Cg3 and Cg4 are the centroids of the N1/S1/C1/C2/C7 thiazole ring, C2–C7 benzene ring and C8–C13 benzene ring, respectively, symmetry code as in Fig. 2). The crystal packing (Fig. 3) is further stabilized by a short contact S1···S1ⁱⁱⁱ [3.485 (1) Å; symmetry code: (iii) = -x, 1 - y, 1 - z], which is shorter than the sum of the van der Waals radii of these atoms [3.60 Å].

Experimental

A mixture of benzo[d][1,3]dioxole-5-carbaldehyde (0.15 g, 1 mmol), 2-aminobenzenethiol (0.125 g, 1 mmol), H₂O₂ (0.013 g, 0.4 mmol) and NH₄Ce(NO₃)₆ (0.053 g, 0.1 mmol) was heated at 50°C for 12 h. After completion of the reaction, the reaction mixture was dissolved in EtOH and then poured into ice–water. The products were filtered, washed with ice-water, and subsequently dried. Recystallization of the product from ethyl acetate: hexanes (1: 10) yielded colourless crystals of the title compound (0.22 g; yield: 91%).