Isopropyl 3-oxo-2,3-dihydro-1,2-benzothia­zole-2-carboxyl­ate

Wang, X.; Lin, Q.; Yang, J.

doi:10.1107/S1600536811034209

organic compounds

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Volume 67| Part 9| September 2011| Page o2477

doi:10.1107/S1600536811034209

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Isopropyl 3-oxo-2,3-dihydro-1,2-benzothiazole-2-carboxylate

Xiang-hui Wang,^a Qiang Lin ^b,^c ^* and Jian-xin Yang ^d

^aInstitute of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093, People's Republic of China, ^bHainan Provincial Fine Chemical Engineering Center, Hainan University, Haikou 570228, People's Republic of China, ^cCollege of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571100, People's Republic of China, and ^dInstitute of Materials and Chemical Engineering, Hainan University, Haikou 570228, People's Republic of China
^*Correspondence e-mail: linqianggroup@163.com

(Received 5 August 2011; accepted 20 August 2011; online 27 August 2011)

The title compound, C₁₁H₁₁NO₃S, was synthesized by the reaction of benzo[d]isothiazol-3(2H)-one with isopropanol in toluene. The benzoisothiazolone ring system is essentially planar, with a mean deviation of 0.018 (2) Å from the least–squares plane defined by the nine constituent atoms. In the crystal, molecules are linked by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For background to the sythesis of benzoisothiazolone derivatives, see: Davis (1972 ); Elgazwy & Abdel-Sattar (2003 ). For the biological activity of 1, 2–benzoisothiazolone derivatives, see: Taubert et al. (2002 ). For structural studies of related alkyl 3-oxo-2,3-dihydro-1,2-benzothiazole-2-carboxylate derivatives, see: Wang et al. (2011a ,b ).

Experimental

Crystal data

C₁₁H₁₁NO₃S
M_r = 237.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.6218 (19) Å
b = 11.621 (5) Å
c = 20.510 (9) Å
V = 1101.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 153 K
0.68 × 0.12 × 0.07 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.830, T_max = 0.980
9436 measured reflections
2897 independent reflections
2245 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.078
S = 1.00
2897 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack, (1983 ), 1150 Friedel pairs
Flack parameter: −0.02 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.47	3.225 (3)	137
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811034209/lx2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034209/lx2199Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034209/lx2199Isup3.cml

checkCIF report

Comment top

1,2-benzoisothiazol-3(2H)-ones are a class of compounds with a wide spectrum of biological activities (Davis, 1972; Elgazwy & Abdel-Sattar, 2003). 1, 2-Benzisothiazolone derivatives have been reported to possess high antibacterial and antifungal activity (Taubert et al., 2002). As a part of our ongoing study of the substituent effect on the solid state structures of alkyl 3-oxo-2,3-dihydro-1,2-benzothiazole-2-carboxylate analogues (Wang, et al., 2011a,b), we report herein the crystal structure of the title compound.

The title compound crystallizes as the non–centrosymmetric space group P _{21 21 21} in spite of having no asymmetric C atoms. In the title molecule (Fig. 1), the benzoisothiazolone ring system is essentially planar, with a mean deviation of 0.018 (2) Å from the least–squares plane defined by the nine constituent atoms and the C8–C2–C9–C11 torsion angle is 156.63 (18)°. The crystal packing is stabilized by weak intermolecular C—H···O hydrogen bonds between a benzene H atom and the O atom of the carbonyl group (Table 1; C2—H2···O1ⁱ).

Related literature top

For background to the sythesis of benzoisothiazolone derivatives, see: Davis (1972); Elgazwy & Abdel-Sattar (2003). For the biological activity of 1, 2–benzoisothiazolone derivatives, see: Taubert et al. (2002). For structural studies of related alkyl 3-oxo-2,3-dihydro-1,2-benzothiazole-2-carboxylate derivatives, see: Wang et al. (2011a,b).

Experimental top

A solution (20 ml) containing benzo[d]isothiazol-3(2H)-one (1.51 g, 0.01 mol) was added dropwise to a solution of isopropanol (0.61 g, 0.01 mol) and bis(triehloromethyl)Carbonate in toluene (20 ml) under stirring on an ice-water bath. The reaction mixture was stirred at room temperature for 4.5 h to afford the title compound (1.72 g, yield 72.6%). Single crystals suitable for X-ray measurements were obtained by recrystallization of the title compound from cyclohexane at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

Isopropyl 3-oxo-2,3-dihydro-1,2-benzothiazole-2-carboxylate top

Crystal data top

C₁₁H₁₁NO₃S	F(000) = 496
M_r = 237.27	D_x = 1.431 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3268 reflections
a = 4.6218 (19) Å	θ = 2.7–29.1°
b = 11.621 (5) Å	µ = 0.28 mm⁻¹
c = 20.510 (9) Å	T = 153 K
V = 1101.6 (8) Å³	Prism, colorless
Z = 4	0.68 × 0.12 × 0.07 mm

Data collection top

AFC10/Saturn724+ diffractometer	2897 independent reflections
Radiation source: Rotating Anode	2245 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 28.5714 pixels mm^-1	θ_max = 29.1°, θ_min = 3.5°
phi and ω scans	h = −6→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→15
T_min = 0.830, T_max = 0.980	l = −28→26
9436 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0289P)² + 0.116P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2897 reflections	Δρ_max = 0.26 e Å⁻³
147 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Absolute structure: Flack, (1983), 1150 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (8)

Crystal data top

C₁₁H₁₁NO₃S	V = 1101.6 (8) Å³
M_r = 237.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.6218 (19) Å	µ = 0.28 mm⁻¹
b = 11.621 (5) Å	T = 153 K
c = 20.510 (9) Å	0.68 × 0.12 × 0.07 mm

Data collection top

AFC10/Saturn724+ diffractometer	2897 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2245 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.980	R_int = 0.045
9436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.078	Δρ_max = 0.26 e Å⁻³
S = 1.00	Δρ_min = −0.22 e Å⁻³
2897 reflections	Absolute structure: Flack, (1983), 1150 Friedel pairs
147 parameters	Absolute structure parameter: −0.02 (8)
0 restraints

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
S1	0.56113 (12)	0.76406 (4)	0.72970 (2)	0.02649 (13)
O1	0.3920 (3)	0.45795 (12)	0.67074 (7)	0.0339 (4)
O2	0.7876 (3)	0.55858 (12)	0.59264 (7)	0.0289 (3)
O3	0.9282 (3)	0.73722 (11)	0.62359 (6)	0.0303 (3)
N1	0.5743 (4)	0.64449 (13)	0.67914 (8)	0.0231 (4)
C1	0.3073 (4)	0.69457 (17)	0.77902 (10)	0.0258 (5)
C2	0.1822 (4)	0.73839 (18)	0.83559 (10)	0.0285 (5)
H2	0.2327	0.8124	0.8516	0.034*
C3	−0.0175 (5)	0.67062 (18)	0.86754 (11)	0.0333 (6)
H3	−0.1053	0.6986	0.9063	0.040*
C4	−0.0940 (5)	0.56146 (18)	0.84420 (10)	0.0319 (5)
H4	−0.2360	0.5175	0.8666	0.038*
C5	0.0350 (5)	0.51759 (17)	0.78915 (10)	0.0283 (5)
H5	−0.0128	0.4428	0.7738	0.034*
C6	0.2375 (5)	0.58518 (16)	0.75632 (10)	0.0236 (4)
C7	0.3987 (4)	0.55027 (18)	0.69814 (10)	0.0246 (4)
C8	0.7810 (5)	0.65258 (17)	0.62952 (10)	0.0248 (5)
C9	0.9960 (4)	0.56000 (18)	0.53842 (10)	0.0293 (5)
H9	1.1790	0.5981	0.5529	0.035*
C10	0.8682 (6)	0.62614 (19)	0.48198 (11)	0.0400 (6)
H10A	0.6858	0.5902	0.4687	0.048*
H10B	1.0041	0.6254	0.4453	0.048*
H10C	0.8318	0.7058	0.4954	0.048*
C11	1.0554 (6)	0.43512 (19)	0.52321 (12)	0.0432 (6)
H11A	1.1449	0.3982	0.5611	0.052*
H11B	1.1866	0.4299	0.4858	0.052*
H11C	0.8731	0.3961	0.5128	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0236 (2)	0.0281 (3)	0.0277 (2)	−0.0018 (2)	0.0024 (2)	−0.0002 (2)
O1	0.0339 (9)	0.0294 (8)	0.0386 (9)	−0.0041 (7)	0.0053 (8)	−0.0039 (7)
O2	0.0272 (8)	0.0338 (8)	0.0256 (8)	−0.0021 (7)	0.0072 (6)	−0.0037 (7)
O3	0.0312 (8)	0.0314 (8)	0.0284 (7)	−0.0096 (8)	0.0033 (7)	−0.0001 (6)
N1	0.0192 (8)	0.0240 (8)	0.0261 (9)	−0.0014 (8)	0.0021 (8)	−0.0011 (7)
C1	0.0184 (10)	0.0304 (11)	0.0286 (11)	0.0032 (8)	−0.0010 (9)	0.0056 (9)
C2	0.0284 (11)	0.0292 (11)	0.0277 (10)	−0.0002 (10)	0.0001 (9)	−0.0004 (9)
C3	0.0330 (14)	0.0401 (13)	0.0267 (11)	0.0055 (10)	0.0060 (9)	0.0043 (9)
C4	0.0271 (12)	0.0346 (12)	0.0341 (12)	0.0014 (11)	0.0050 (10)	0.0105 (10)
C5	0.0234 (11)	0.0239 (11)	0.0376 (12)	0.0004 (9)	−0.0024 (10)	0.0040 (9)
C6	0.0181 (10)	0.0255 (11)	0.0273 (11)	0.0031 (8)	−0.0042 (8)	0.0048 (8)
C7	0.0172 (10)	0.0290 (11)	0.0275 (10)	−0.0003 (9)	−0.0023 (9)	0.0047 (8)
C8	0.0218 (11)	0.0313 (12)	0.0215 (10)	0.0023 (9)	−0.0029 (9)	0.0028 (9)
C9	0.0262 (13)	0.0373 (12)	0.0244 (10)	−0.0021 (10)	0.0055 (9)	−0.0009 (9)
C10	0.0405 (16)	0.0507 (14)	0.0289 (12)	−0.0036 (12)	−0.0017 (11)	0.0002 (11)
C11	0.0464 (15)	0.0454 (13)	0.0377 (13)	0.0011 (14)	0.0115 (13)	−0.0039 (11)

Geometric parameters (Å, º) top

S1—N1	1.7349 (17)	C4—C5	1.375 (3)
S1—C1	1.747 (2)	C4—H4	0.9500
O1—C7	1.212 (2)	C5—C6	1.395 (3)
O2—C8	1.329 (2)	C5—H5	0.9500
O2—C9	1.472 (2)	C6—C7	1.464 (3)
O3—C8	1.202 (2)	C9—C11	1.509 (3)
N1—C8	1.399 (3)	C9—C10	1.510 (3)
N1—C7	1.418 (3)	C9—H9	1.0000
C1—C6	1.392 (3)	C10—H10A	0.9800
C1—C2	1.393 (3)	C10—H10B	0.9800
C2—C3	1.379 (3)	C10—H10C	0.9800
C2—H2	0.9500	C11—H11A	0.9800
C3—C4	1.401 (3)	C11—H11B	0.9800
C3—H3	0.9500	C11—H11C	0.9800

N1—S1—C1	89.97 (9)	O1—C7—C6	127.63 (19)
C8—O2—C9	115.85 (16)	N1—C7—C6	107.53 (17)
C8—N1—C7	130.00 (17)	O3—C8—O2	127.0 (2)
C8—N1—S1	113.89 (13)	O3—C8—N1	121.00 (19)
C7—N1—S1	115.74 (14)	O2—C8—N1	112.00 (17)
C6—C1—C2	121.1 (2)	O2—C9—C11	105.33 (17)
C6—C1—S1	112.58 (15)	O2—C9—C10	109.20 (17)
C2—C1—S1	126.31 (17)	C11—C9—C10	113.71 (19)
C3—C2—C1	117.7 (2)	O2—C9—H9	109.5
C3—C2—H2	121.1	C11—C9—H9	109.5
C1—C2—H2	121.1	C10—C9—H9	109.5
C2—C3—C4	121.6 (2)	C9—C10—H10A	109.5
C2—C3—H3	119.2	C9—C10—H10B	109.5
C4—C3—H3	119.2	H10A—C10—H10B	109.5
C5—C4—C3	120.5 (2)	C9—C10—H10C	109.5
C5—C4—H4	119.8	H10A—C10—H10C	109.5
C3—C4—H4	119.8	H10B—C10—H10C	109.5
C4—C5—C6	118.6 (2)	C9—C11—H11A	109.5
C4—C5—H5	120.7	C9—C11—H11B	109.5
C6—C5—H5	120.7	H11A—C11—H11B	109.5
C1—C6—C5	120.5 (2)	C9—C11—H11C	109.5
C1—C6—C7	114.09 (18)	H11A—C11—H11C	109.5
C5—C6—C7	125.36 (18)	H11B—C11—H11C	109.5
O1—C7—N1	124.83 (19)

C1—S1—N1—C8	−175.20 (15)	S1—N1—C7—O1	−175.99 (17)
C1—S1—N1—C7	−1.47 (16)	C8—N1—C7—C6	175.40 (19)
N1—S1—C1—C6	−0.54 (15)	S1—N1—C7—C6	2.9 (2)
N1—S1—C1—C2	178.93 (19)	C1—C6—C7—O1	175.6 (2)
C6—C1—C2—C3	−1.3 (3)	C5—C6—C7—O1	−2.9 (3)
S1—C1—C2—C3	179.25 (17)	C1—C6—C7—N1	−3.3 (2)
C1—C2—C3—C4	−0.2 (3)	C5—C6—C7—N1	178.28 (19)
C2—C3—C4—C5	1.6 (3)	C9—O2—C8—O3	−0.8 (3)
C3—C4—C5—C6	−1.6 (3)	C9—O2—C8—N1	179.12 (16)
C2—C1—C6—C5	1.4 (3)	C7—N1—C8—O3	−173.8 (2)
S1—C1—C6—C5	−179.12 (16)	S1—N1—C8—O3	−1.2 (3)
C2—C1—C6—C7	−177.15 (18)	C7—N1—C8—O2	6.3 (3)
S1—C1—C6—C7	2.3 (2)	S1—N1—C8—O2	178.90 (13)
C4—C5—C6—C1	0.1 (3)	C8—O2—C9—C11	156.63 (18)
C4—C5—C6—C7	178.46 (19)	C8—O2—C9—C10	−80.9 (2)
C8—N1—C7—O1	−3.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.47	3.225 (3)	137

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁NO₃S
M_r	237.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	153
a, b, c (Å)	4.6218 (19), 11.621 (5), 20.510 (9)
V (Å³)	1101.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.68 × 0.12 × 0.07

Data collection
Diffractometer	AFC10/Saturn724+ diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.830, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	9436, 2897, 2245
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.078, 1.00
No. of reflections	2897
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22
Absolute structure	Flack, (1983), 1150 Friedel pairs
Absolute structure parameter	−0.02 (8)

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.47	3.225 (3)	136.9

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 20962007) and the Creative Talents Plan of Hainan University 211 Project.

References

Davis, M. (1972). Adv. Heterocycl. Chem. 14, 43–98. CrossRef CAS Google Scholar
Elgazwy, H. & Abdel-Sattar, S. (2003). Tetrahedron, 59, 7445–7463. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taubert, K., Kraus, S. & Schulze, B. (2002). Sulfur Rep. 23, 79–81. CrossRef CAS Google Scholar
Wang, X., Yang, J., You, C. & Lin, Q. (2011a). Acta Cryst. E67, o2237. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, X., Yang, J., You, C. & Lin, Q. (2011b). Acta Cryst. E67, o2238. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar