2-Methyl-1,2-benzisothia­zol-3(2H)-one 1,1-dioxide

Siddiqui, W.A.; Ahmad, S.; Siddiqui, H.L.; Parvez, M.

doi:10.1107/S1600536808004637

organic compounds

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Volume 64| Part 4| April 2008| Page o724

doi:10.1107/S1600536808004637

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2-Methyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide

Waseeq Ahmad Siddiqui,^a Saeed Ahmad,^b Hamid Latif Siddiqui ^c and Masood Parvez ^d ^*

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, ^bDepartment of Chemistry, University of Science and Technology, Bannu, Pakistan, ^cInstitute of Chemistry, University of the Punjab, Lahore, Pakistan, and ^dDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
^*Correspondence e-mail: parvez@ucalgary.ca

(Received 12 February 2008; accepted 16 February 2008; online 20 March 2008)

All atoms of the title molecule, C₈H₇NO₃S, except the two oxide O atoms and two H atoms of the methyl group, lie on a crystallographic mirror plane. The crystal structure is stabilized by weak inter- and intramolecular C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Hu et al. (2004 ); Kap-Sun & Nicholas (1998 ); Liang et al. (2006 ); Masashi et al. (1999 ); Nagasawa et al. (1995 ); Siddiqui et al. (2006 , 2007a ,b ,c ); Siddiqui, Ahmad, Khan & Siddiqui (2007 ); Siddiqui, Ahmad, Khan, Siddiqui & Ahmad (2007 ); Siddiqui, Ahmad, Khan, Siddiqui & Parvez (2007 ).

Experimental

Crystal data

C₈H₇NO₃S
M_r = 197.21
Monoclinic, P 2₁ /m
a = 7.463 (7) Å
b = 6.761 (6) Å
c = 8.748 (8) Å
β = 103.78 (3)°
V = 428.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 173 (2) K
0.12 × 0.08 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ) T_min = 0.960, T_max = 0.976
1724 measured reflections
1045 independent reflections
889 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.106
S = 1.03
1045 reflections
76 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1	0.96	2.49	2.869 (4)	104
C2—H2⋯O1ⁱ	0.95	2.29	3.227 (4)	169
C8—H8B⋯O2ⁱⁱ	0.96	2.49	3.358 (3)	151
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004637/lh2597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004637/lh2597Isup2.hkl

checkCIF report

Comment top

Benzisothiazolone-1,1-dioxide is part of a class of heterocycles which has been investigated in pharmaceutical research (Kap-Sun & Nicholas, 1998). 1,2-benzisothiazole-3-one 1,1-dioxide (saccharin) has been widely incorporated into a variety of biologically active compounds. It has been identified as an important molecular component in various classes of 5-HTla antagonists, analgesics and human mast cell tryptase inhibitors (Liang et al., 2006). In particular, N-substituted derivatives, e.g with N-hydroxy and N-alkyl substituents, have shown important biological activites (Nagasawa et al., 1995). Among N-alkyl derivatives, various synthetic routes have been reported for the synthesis of the title compound involving ionic liquids and free radical mechanisms (Hu et al., 2004; Masashi et al., 1999). In continuation of our research on the synthesis of 1,2-benzothiazine 1,1-dioxide derivatives, we have in addtion, embarked on the synthesis of benzisothiazole derivatives (Siddiqui et al., 2006; Siddiqui et al., 2007a,b,c; Siddiqui, Ahmad, Khan & Siddiqui, 2007; Siddiqui, Ahmad, Khan, Siddiqui & Ahmad, 2007; Siddiqui, Ahmad, Khan, Siddiqui & Parvez, 2007). Herein, we report the synthesis and crystal structure of the title compound, (I).

With the exception atoms O2 and H8B, all atoms of the molecule of (I) (Fig. 1) lie on a crystallographic mirror plane. The benzisothiazole moiety is exactly planar. The molecular dimensions are in accord with the corresponding dimensions reported in similar structures (Siddiqui et al., 2007a-c; Siddiqui, Ahmad, Khan, Siddiqui & Parvez, 2007). The structure is stabilized by one intramolecular and two intermolecular interactions of the type C—H···O (details are in Table).

Related literature top

For related literature, see: Hu et al. (2004); Kap-Sun & Nicholas (1998); Liang et al. (2006); Masashi et al. (1999); Nagasawa et al. (1995); Siddiqui et al. (2006, 2007a,b,c); Siddiqui, Ahmad, Khan & Siddiqui (2007); Siddiqui, Ahmad, Khan, Siddiqui & Ahmad (2007); Siddiqui, Ahmad, Khan, Siddiqui & Parvez (2007).

Experimental top

Saccharin (2.0 g, 11.0 mmol.) was added to a solution of sodium hydroxide (0.875 g, 22.0 mmol.) in distilled water (25 ml) under constant stirring to give a transparent solution. A solution of dimethylsulfate (2.08 ml, 22.0 mmol.) in methanol (10.0 ml) was then added dropwise over 2 minutes. Precipitates started appearing within 5 minutes and stirring was continued for 20 min. at room temperature. The precipitates were filtered, washed with cold water and dried (343 K) to get 1.75 g of (I) (8.9 mmol. 81%). Recrystallization Solvent: CHCl₃. The solution was subjected to slow evaporation at 313 K to obtain colourless crystals.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEPII (Johnson, 1976) drawing of (I) with displacement ellipsoids plotted at 50% probability level. Symmetry code: (iii) x, -y + 1/2, z.

2-Methyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide top

Crystal data top

C₈H₇NO₃S	F(000) = 204
M_r = 197.21	D_x = 1.528 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1724 reflections
a = 7.463 (7) Å	θ = 3.2–27.4°
b = 6.761 (6) Å	µ = 0.35 mm⁻¹
c = 8.748 (8) Å	T = 173 K
β = 103.78 (3)°	Prism, colorless
V = 428.7 (7) Å³	0.12 × 0.08 × 0.07 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	1045 independent reflections
Radiation source: fine-focus sealed tube	889 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and ϕ scans	θ_max = 27.4°, θ_min = 3.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −9→9
T_min = 0.960, T_max = 0.976	k = −8→8
1724 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0455P)² + 0.2966P] where P = (F_o² + 2F_c²)/3
1045 reflections	(Δ/σ)_max < 0.001
76 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₈H₇NO₃S	V = 428.7 (7) Å³
M_r = 197.21	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.463 (7) Å	µ = 0.35 mm⁻¹
b = 6.761 (6) Å	T = 173 K
c = 8.748 (8) Å	0.12 × 0.08 × 0.07 mm
β = 103.78 (3)°

Data collection top

Nonius KappaCCD diffractometer	1045 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	889 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.976	R_int = 0.023
1724 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.03	Δρ_max = 0.41 e Å⁻³
1045 reflections	Δρ_min = −0.42 e Å⁻³
76 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.68037 (10)	0.2500	0.26611 (7)	0.0314 (2)
O1	0.2425 (3)	0.2500	0.4038 (3)	0.0416 (5)
O2	0.7324 (2)	0.0698 (2)	0.20266 (16)	0.0445 (4)
N1	0.4534 (3)	0.2500	0.2520 (3)	0.0314 (5)
C1	0.7314 (4)	0.2500	0.4722 (3)	0.0254 (5)
C2	0.9043 (4)	0.2500	0.5750 (3)	0.0337 (6)
H2	1.0141	0.2500	0.5381	0.040*
C3	0.9090 (4)	0.2500	0.7337 (3)	0.0403 (7)
H3	1.0249	0.2500	0.8079	0.048*
C4	0.7486 (4)	0.2500	0.7873 (3)	0.0379 (7)
H4	0.7566	0.2500	0.8974	0.045*
C5	0.5767 (4)	0.2500	0.6832 (3)	0.0308 (6)
H5	0.4670	0.2500	0.7203	0.037*
C6	0.5690 (3)	0.2500	0.5235 (3)	0.0251 (5)
C7	0.4012 (4)	0.2500	0.3931 (3)	0.0289 (6)
C8	0.3218 (5)	0.2500	0.0986 (3)	0.0455 (8)
H8A	0.1982	0.2500	0.1130	0.055*
H8B	0.3405	0.1341	0.0410	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0415 (4)	0.0319 (4)	0.0237 (3)	0.000	0.0133 (3)	0.000
O1	0.0284 (10)	0.0449 (13)	0.0521 (13)	0.000	0.0107 (9)	0.000
O2	0.0587 (10)	0.0435 (9)	0.0369 (8)	0.0058 (7)	0.0223 (7)	−0.0101 (7)
N1	0.0355 (12)	0.0301 (12)	0.0266 (11)	0.000	0.0031 (9)	0.000
C1	0.0319 (13)	0.0222 (12)	0.0237 (12)	0.000	0.0099 (10)	0.000
C2	0.0276 (13)	0.0367 (16)	0.0371 (14)	0.000	0.0085 (11)	0.000
C3	0.0402 (16)	0.0417 (17)	0.0340 (15)	0.000	−0.0010 (12)	0.000
C4	0.0553 (18)	0.0343 (16)	0.0238 (13)	0.000	0.0087 (12)	0.000
C5	0.0392 (15)	0.0257 (13)	0.0324 (14)	0.000	0.0181 (12)	0.000
C6	0.0280 (12)	0.0189 (12)	0.0297 (13)	0.000	0.0093 (10)	0.000
C7	0.0330 (14)	0.0221 (13)	0.0320 (13)	0.000	0.0086 (11)	0.000
C8	0.0551 (19)	0.0452 (19)	0.0284 (15)	0.000	−0.0053 (13)	0.000

Geometric parameters (Å, º) top

S1—O2ⁱ	1.430 (2)	C2—H2	0.9500
S1—O2	1.430 (2)	C3—C4	1.386 (4)
S1—N1	1.668 (3)	C3—H3	0.9500
S1—C1	1.752 (3)	C4—C5	1.385 (4)
O1—C7	1.211 (3)	C4—H4	0.9500
N1—C7	1.380 (4)	C5—C6	1.384 (4)
N1—C8	1.462 (4)	C5—H5	0.9500
C1—C2	1.386 (4)	C6—C7	1.479 (4)
C1—C6	1.389 (4)	C8—H8A	0.9600
C2—C3	1.380 (4)	C8—H8B	0.9600

O2ⁱ—S1—O2	116.79 (14)	C4—C3—H3	119.2
O2ⁱ—S1—N1	109.63 (8)	C5—C4—C3	121.1 (3)
O2—S1—N1	109.63 (8)	C5—C4—H4	119.5
O2ⁱ—S1—C1	112.76 (8)	C3—C4—H4	119.5
O2—S1—C1	112.76 (8)	C6—C5—C4	118.2 (2)
N1—S1—C1	92.54 (12)	C6—C5—H5	120.9
C7—N1—C8	123.3 (2)	C4—C5—H5	120.9
C7—N1—S1	115.6 (2)	C5—C6—C1	119.7 (2)
C8—N1—S1	121.1 (2)	C5—C6—C7	127.0 (2)
C2—C1—C6	122.7 (2)	C1—C6—C7	113.2 (2)
C2—C1—S1	127.5 (2)	O1—C7—N1	124.0 (3)
C6—C1—S1	109.9 (2)	O1—C7—C6	127.2 (3)
C3—C2—C1	116.7 (3)	N1—C7—C6	108.8 (2)
C3—C2—H2	121.6	N1—C8—H8A	109.6
C1—C2—H2	121.6	N1—C8—H8B	109.4
C2—C3—C4	121.6 (3)	H8A—C8—H8B	109.5
C2—C3—H3	119.2

O2ⁱ—S1—N1—C7	−115.28 (8)	C3—C4—C5—C6	0.000 (1)
O2—S1—N1—C7	115.28 (8)	C4—C5—C6—C1	0.0
C1—S1—N1—C7	0.0	C4—C5—C6—C7	180.0
O2ⁱ—S1—N1—C8	64.72 (8)	C2—C1—C6—C5	0.0
O2—S1—N1—C8	−64.72 (8)	S1—C1—C6—C5	180.0
C1—S1—N1—C8	180.0	C2—C1—C6—C7	180.0
O2ⁱ—S1—C1—C2	−67.46 (9)	S1—C1—C6—C7	0.0
O2—S1—C1—C2	67.46 (9)	C8—N1—C7—O1	0.0
N1—S1—C1—C2	180.0	S1—N1—C7—O1	180.0
O2ⁱ—S1—C1—C6	112.54 (9)	C8—N1—C7—C6	180.0
O2—S1—C1—C6	−112.54 (9)	S1—N1—C7—C6	0.0
N1—S1—C1—C6	0.0	C5—C6—C7—O1	0.0
C6—C1—C2—C3	0.0	C1—C6—C7—O1	180.0
S1—C1—C2—C3	180.0	C5—C6—C7—N1	180.0
C1—C2—C3—C4	0.000 (1)	C1—C6—C7—N1	0.0
C2—C3—C4—C5	0.000 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.96	2.49	2.869 (4)	104
C2—H2···O1ⁱⁱ	0.95	2.29	3.227 (4)	169
C8—H8B···O2ⁱⁱⁱ	0.96	2.49	3.358 (3)	151

Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₈H₇NO₃S
M_r	197.21
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	173
a, b, c (Å)	7.463 (7), 6.761 (6), 8.748 (8)
β (°)	103.78 (3)
V (Å³)	428.7 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.12 × 0.08 × 0.07

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.960, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	1724, 1045, 889
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.106, 1.03
No. of reflections	1045
No. of parameters	76
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.42

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.96	2.49	2.869 (4)	104
C2—H2···O1ⁱ	0.95	2.29	3.227 (4)	169
C8—H8B···O2ⁱⁱ	0.96	2.49	3.358 (3)	151

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z.

References

Blessing, R. H. (1997). J. Appl. Cryst. 30, 421–426. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fan, H.-F. (1991). SAPI91. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Hu, Y., Chen, Z. C., Le, Z. G. & Zheng, Q. G. (2004). J. Chem. Res. 4, 276–278. CrossRef Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Kap-Sun, Y. & Nicholas, A. M. (1998). Tetrahedron Lett. 39, 5309–5312. Google Scholar
Liang, X., Hong, S., Ying, L., Suhong, Z. & Mark, L. T. (2006). Tetrahedron, 62, 7902–7910. Google Scholar
Masashi, K., Hideo, T., Kentaro, Y. & Masataka, Y. (1999). Tetrahedron, 55, 14885–14900. Google Scholar
Nagasawa, H. T., Kawle, S. P., Elberling, J. A., DeMaster, E. G. & Fukuto, J. M. (1995). J. Med. Chem. 38, 1865–1871. CrossRef CAS PubMed Web of Science Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Khan, I. U. & Siddiqui, H. L. (2007). Synth. Commun. 37, 767–773. Web of Science CrossRef CAS Google Scholar
Siddiqui, W. A., Ahmad, S., Khan, I. U., Siddiqui, H. L. & Ahmad, V. U. (2007). J. Chem. Soc. Pak. 29, 44–47. CAS Google Scholar
Siddiqui, W. A., Ahmad, S., Khan, I. U., Siddiqui, H. L. & Parvez, M. (2007). Acta Cryst. E63, o4116. Web of Science CSD CrossRef IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Tariq, M. I. & Parvez, M. (2007a). Acta Cryst. E63, o4001. Web of Science CSD CrossRef IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Tariq, M. I. & Parvez, M. (2007b). Acta Cryst. E63, o4117. Web of Science CSD CrossRef IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Tariq, M. I. & Parvez, M. (2007c). Acta Cryst. E63, o4585. Web of Science CSD CrossRef IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Ullah, I. & Malik, A. (2006). J. Chem. Soc. Pak. 28, 583–589. Google Scholar

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doi:10.1107/S1600536808004637

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