(Z)-3-Chloro­methyl­idene-5,6-dimeth­oxy-2-methyl-2,3-dihydro-1,2-benzothia­zole 1,1-dioxide

Bassin, J.P.; Shah, V.P.; Martin, L.; Clegg, W.; Harrington, R.W.

doi:10.1107/S1600536810049561

organic compounds

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Volume 67| Part 1| January 2011| Page o12

https://doi.org/10.1107/S1600536810049561

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(Z)-3-Chloromethylidene-5,6-dimethoxy-2-methyl-2,3-dihydro-1,2-benzothiazole 1,1-dioxide

Jatinder P. Bassin,^a ^* Virender P. Shah,^a Lee Martin,^a William Clegg ^b and Ross W. Harrington ^b

^aSchool of Pharmacy, University of Hertfordshire, College Lane, Hatfield AL10 9AB, England, and ^bSchool of Chemistry, Newcastle University, Newcastle upon Tyne NE1 7RU, England
^*Correspondence e-mail: j.p.bassin@herts.ac.uk

(Received 17 November 2010; accepted 26 November 2010; online 4 December 2010)

The title compound, C₁₁H₁₂ClNO₄S, adopts a Z configuration about the C=C double bond. The benzisothiazole system is essentially planar [maximum deviation of 0.235 (2) Å for the S atom]. In the crystal, the molecules stack parallel to each other in the b-axis direction, with interplanar spacings for the benzene and thiazole rings ranging from 3.402 (2) to 3.702 (2) Å.

Related literature

3-Substituted 1,2-benzisothiazole-1,1-dioxides are an important class of heterocycles with a broad range of biological activity, see: Feit et al. (1973 ); Shutske et al. (1983 ); Bachman et al. (1978 ); Vicini et al. (2003 ); Sharmeen et al. (2001 ). Various synthetic routes have been developed for the synthesis of 1,2-benzisothiazole-1,1-dioxides, see: Chapman & Peart (1996 ). Carbonation of ortho-lithiated sulfonamides is the most common method for the preparation of substituted saccharins; however, this results in poor yields (Lombardino, 1971 ) and is limited by the availability of starting materials. A recent improved synthesis of 1,2-benzisothiazole-1,1-dioxides involved cyclization of N-acyl-benzenesulfonamides using LDA, see: Hermann et al. (1992 ).

Experimental

Crystal data

C₁₁H₁₂ClNO₄S
M_r = 289.73
Triclinic, $[P \overline 1]$
a = 7.578 (5) Å
b = 7.904 (6) Å
c = 10.002 (7) Å
α = 88.875 (11)°
β = 86.293 (10)°
γ = 84.176 (11)°
V = 594.7 (7) Å³
Z = 2
Synchrotron radiation
λ = 0.6937 Å
μ = 0.50 mm⁻¹
T = 120 K
0.20 × 0.04 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.905, T_max = 0.990
4651 measured reflections
2237 independent reflections
1671 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.177
S = 1.02
2237 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 1.29 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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 and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810049561/jh2234sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049561/jh2234Isup2.hkl

checkCIF report

Related literature top

3-Substituted 1,2-benzisothiazole-1,1-dioxides are an important class of heterocycles with a broad range of biological activity, see: Feit et al. (1973); Shutske et al. (1983); Bachman et al. (1978); Vicini et al. (2003); Sharmeen et al. (2001). Various synthetic routes have been developed for the synthesis of 1,2-benzisothiazole-1,1-dioxides, see: Chapman & Peart (1996). Carbonation of ortho-lithiated sulfonamides is the most common method for the preparation of substituted saccharins; however, this results in poor yields (Lombardino, 1971) and is limited by the availability of starting materials. A recent improved synthesis of 1,2-benzisothiazole-1,1-dioxides involved cyclization of N-acyl-benzenesulfonamides using LDA, see: Hermann et al. (1992).

Experimental top

The title compound was synthesized by reacting 2-(5,6-dimethoxy-2-methyl-1,1-dioxido-2,3-dihydrobenzo [d]isothiazol-3-yl)-1-phenylethanone (1 g; 2.77 mmol), dissolved in pyridine (10 ml), with sodium hypochlorite (10 ml). An exothermic reaction occurred and with time the solution became turbid. The reaction mixture was stirred for a total of 30 minutes and then poured onto crushed ice. The resulting light yellow solid was filtered by suction filtration and air dried. It was re-crystallized from ethanol to afford a creamy white solid which was re-crystallized a second time to give 1 as a colourless crystalline product [yield: 87%, m.p.: 457 K].

Structure description top

3-Substituted 1,2-benzisothiazole-1,1-dioxides are an important class of heterocycles with a broad range of biological activity, see: Feit et al. (1973); Shutske et al. (1983); Bachman et al. (1978); Vicini et al. (2003); Sharmeen et al. (2001). Various synthetic routes have been developed for the synthesis of 1,2-benzisothiazole-1,1-dioxides, see: Chapman & Peart (1996). Carbonation of ortho-lithiated sulfonamides is the most common method for the preparation of substituted saccharins; however, this results in poor yields (Lombardino, 1971) and is limited by the availability of starting materials. A recent improved synthesis of 1,2-benzisothiazole-1,1-dioxides involved cyclization of N-acyl-benzenesulfonamides using LDA, see: Hermann et al. (1992).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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) and local programs.

Figures top

Fig. 1. Ellipsoid plot.

(Z)-3-Chloromethylidene-5,6-dimethoxy-2-methyl-2,3- dihydro-1,2-benzothiazole 1,1-dioxide top

Crystal data top

C₁₁H₁₂ClNO₄S	Z = 2
M_r = 289.73	F(000) = 300
Triclinic, P1	D_x = 1.618 Mg m⁻³
Hall symbol: -P 1	Synchrotron radiation, λ = 0.6937 Å
a = 7.578 (5) Å	Cell parameters from 974 reflections
b = 7.904 (6) Å	θ = 2.6–24.5°
c = 10.002 (7) Å	µ = 0.50 mm⁻¹
α = 88.875 (11)°	T = 120 K
β = 86.293 (10)°	Needle, colourless
γ = 84.176 (11)°	0.20 × 0.04 × 0.01 mm
V = 594.7 (7) Å³

Data collection top

Bruker APEXII CCD diffractometer	2237 independent reflections
Radiation source: Daresbury SRS station 9.8	1671 reflections with I > 2σ(I)
Silicon 111 monochromator	R_int = 0.038
thin–slice ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→9
T_min = 0.905, T_max = 0.990	k = −9→9
4651 measured reflections	l = −12→12

Refinement top

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)] = 0.065	H-atom parameters constrained
wR(F²) = 0.177	w = 1/[σ²(F_o²) + (0.0319P)² + 1.6618P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2237 reflections	Δρ_max = 1.29 e Å⁻³
167 parameters	Δρ_min = −0.43 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: 0.084 (15)

Crystal data top

C₁₁H₁₂ClNO₄S	γ = 84.176 (11)°
M_r = 289.73	V = 594.7 (7) Å³
Triclinic, P1	Z = 2
a = 7.578 (5) Å	Synchrotron radiation, λ = 0.6937 Å
b = 7.904 (6) Å	µ = 0.50 mm⁻¹
c = 10.002 (7) Å	T = 120 K
α = 88.875 (11)°	0.20 × 0.04 × 0.01 mm
β = 86.293 (10)°

Data collection top

Bruker APEXII CCD diffractometer	2237 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1671 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.990	R_int = 0.038
4651 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.02	Δρ_max = 1.29 e Å⁻³
2237 reflections	Δρ_min = −0.43 e Å⁻³
167 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.

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	0.20714 (16)	0.29186 (15)	0.38990 (10)	0.0286 (4)
Cl1	0.72928 (18)	0.01424 (17)	0.14119 (11)	0.0402 (4)
N1	0.3721 (5)	0.2029 (5)	0.2891 (3)	0.0315 (9)
C1	0.3515 (8)	0.2190 (8)	0.1449 (4)	0.0441 (14)
H1A	0.4303	0.3002	0.1058	0.066*
H1B	0.2279	0.2595	0.1290	0.066*
H1C	0.3823	0.1079	0.1031	0.066*
C2	0.5330 (6)	0.1725 (6)	0.3483 (4)	0.0277 (10)
C3	0.6901 (7)	0.0988 (6)	0.2982 (4)	0.0353 (12)
H3	0.7873	0.0931	0.3541	0.042*
C4	0.5098 (6)	0.2358 (5)	0.4871 (4)	0.0255 (10)
C5	0.6343 (6)	0.2194 (6)	0.5848 (4)	0.0270 (10)
H5	0.7509	0.1660	0.5653	0.032*
C6	0.5834 (6)	0.2829 (6)	0.7102 (4)	0.0268 (10)
C7	0.4134 (6)	0.3697 (6)	0.7387 (4)	0.0255 (10)
C8	0.2894 (6)	0.3844 (6)	0.6435 (4)	0.0271 (10)
H8	0.1733	0.4400	0.6615	0.033*
C9	0.3435 (6)	0.3132 (6)	0.5189 (4)	0.0250 (10)
C10	0.8610 (6)	0.1808 (6)	0.7939 (5)	0.0328 (11)
H10A	0.8510	0.0663	0.7612	0.049*
H10B	0.9205	0.1726	0.8782	0.049*
H10C	0.9306	0.2431	0.7271	0.049*
C11	0.2152 (7)	0.5175 (7)	0.8980 (5)	0.0354 (11)
H11A	0.1882	0.6091	0.8329	0.053*
H11B	0.2138	0.5654	0.9878	0.053*
H11C	0.1258	0.4362	0.8971	0.053*
O1	0.0829 (5)	0.1725 (4)	0.4255 (3)	0.0371 (8)
O2	0.1341 (5)	0.4480 (4)	0.3321 (3)	0.0358 (8)
O3	0.6882 (4)	0.2685 (4)	0.8156 (3)	0.0316 (8)
O4	0.3860 (4)	0.4328 (4)	0.8638 (3)	0.0320 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0357 (7)	0.0326 (7)	0.0185 (6)	−0.0065 (5)	−0.0058 (5)	0.0001 (4)
Cl1	0.0493 (8)	0.0498 (8)	0.0204 (6)	0.0003 (6)	−0.0013 (5)	−0.0052 (5)
N1	0.039 (2)	0.043 (2)	0.0123 (17)	−0.0009 (18)	−0.0043 (16)	−0.0005 (16)
C1	0.052 (3)	0.068 (4)	0.012 (2)	−0.006 (3)	−0.008 (2)	0.002 (2)
C2	0.036 (3)	0.027 (2)	0.020 (2)	−0.003 (2)	0.0002 (18)	0.0020 (18)
C3	0.054 (3)	0.036 (3)	0.017 (2)	−0.010 (2)	−0.003 (2)	−0.0034 (19)
C4	0.033 (2)	0.026 (2)	0.018 (2)	−0.0053 (19)	−0.0008 (18)	−0.0002 (17)
C5	0.028 (2)	0.032 (2)	0.020 (2)	−0.0014 (19)	−0.0004 (18)	0.0004 (18)
C6	0.029 (2)	0.034 (2)	0.019 (2)	−0.0067 (19)	−0.0039 (17)	0.0038 (18)
C7	0.034 (2)	0.029 (2)	0.0132 (19)	−0.0050 (19)	0.0020 (17)	−0.0001 (16)
C8	0.030 (2)	0.030 (2)	0.022 (2)	−0.0059 (19)	−0.0021 (18)	0.0008 (18)
C9	0.029 (2)	0.029 (2)	0.017 (2)	−0.0033 (19)	−0.0032 (17)	0.0023 (17)
C10	0.034 (3)	0.036 (3)	0.029 (2)	−0.001 (2)	−0.011 (2)	0.001 (2)
C11	0.039 (3)	0.042 (3)	0.024 (2)	−0.002 (2)	0.005 (2)	−0.006 (2)
O1	0.041 (2)	0.042 (2)	0.0306 (18)	−0.0136 (16)	−0.0048 (15)	−0.0041 (15)
O2	0.044 (2)	0.0359 (19)	0.0287 (17)	−0.0017 (15)	−0.0140 (15)	0.0039 (14)
O3	0.0333 (18)	0.0432 (19)	0.0182 (15)	−0.0007 (15)	−0.0065 (13)	−0.0009 (13)
O4	0.0385 (19)	0.0414 (19)	0.0159 (15)	−0.0035 (15)	−0.0008 (13)	−0.0020 (13)

Geometric parameters (Å, º) top

S1—N1	1.661 (4)	C5—C6	1.377 (6)
S1—C9	1.725 (4)	C6—C7	1.411 (7)
S1—O1	1.424 (4)	C6—O3	1.357 (5)
S1—O2	1.427 (3)	C7—C8	1.376 (6)
Cl1—C3	1.715 (5)	C7—O4	1.352 (5)
N1—C1	1.463 (5)	C8—H8	0.950
N1—C2	1.387 (6)	C8—C9	1.398 (6)
C1—H1A	0.980	C10—H10A	0.980
C1—H1B	0.980	C10—H10B	0.980
C1—H1C	0.980	C10—H10C	0.980
C2—C3	1.342 (7)	C10—O3	1.424 (6)
C2—C4	1.478 (6)	C11—H11A	0.980
C3—H3	0.950	C11—H11B	0.980
C4—C5	1.397 (6)	C11—H11C	0.980
C4—C9	1.365 (6)	C11—O4	1.420 (6)
C5—H5	0.950

N1—S1—C9	93.3 (2)	C5—C6—C7	121.5 (4)
N1—S1—O1	110.3 (2)	C5—C6—O3	124.1 (4)
N1—S1—O2	109.9 (2)	C7—C6—O3	114.4 (4)
C9—S1—O1	110.6 (2)	C6—C7—C8	120.6 (4)
C9—S1—O2	115.1 (2)	C6—C7—O4	114.7 (4)
O1—S1—O2	115.4 (2)	C8—C7—O4	124.7 (4)
S1—N1—C1	117.1 (3)	C7—C8—H8	121.8
S1—N1—C2	114.2 (3)	C7—C8—C9	116.3 (4)
C1—N1—C2	125.1 (4)	H8—C8—C9	121.8
N1—C1—H1A	109.5	S1—C9—C4	110.2 (3)
N1—C1—H1B	109.5	S1—C9—C8	125.5 (4)
N1—C1—H1C	109.5	C4—C9—C8	124.1 (4)
H1A—C1—H1B	109.5	H10A—C10—H10B	109.5
H1A—C1—H1C	109.5	H10A—C10—H10C	109.5
H1B—C1—H1C	109.5	H10A—C10—O3	109.5
N1—C2—C3	129.9 (4)	H10B—C10—H10C	109.5
N1—C2—C4	108.7 (4)	H10B—C10—O3	109.5
C3—C2—C4	121.4 (4)	H10C—C10—O3	109.5
Cl1—C3—C2	125.2 (4)	H11A—C11—H11B	109.5
Cl1—C3—H3	117.4	H11A—C11—H11C	109.5
C2—C3—H3	117.4	H11A—C11—O4	109.5
C2—C4—C5	127.5 (4)	H11B—C11—H11C	109.5
C2—C4—C9	113.3 (4)	H11B—C11—O4	109.5
C5—C4—C9	119.3 (4)	H11C—C11—O4	109.5
C4—C5—H5	120.9	C6—O3—C10	117.2 (4)
C4—C5—C6	118.2 (4)	C7—O4—C11	116.7 (4)
H5—C5—C6	120.9

C9—S1—N1—C1	−155.2 (4)	C5—C6—C7—O4	−176.5 (4)
C9—S1—N1—C2	4.6 (4)	O3—C6—C7—C8	−176.0 (4)
O1—S1—N1—C1	91.4 (4)	O3—C6—C7—O4	3.6 (6)
O1—S1—N1—C2	−108.8 (3)	C6—C7—C8—C9	−1.5 (6)
O2—S1—N1—C1	−37.0 (4)	O4—C7—C8—C9	178.9 (4)
O2—S1—N1—C2	122.8 (3)	C2—C4—C9—S1	6.2 (5)
S1—N1—C2—C3	177.8 (4)	C2—C4—C9—C8	−179.5 (4)
S1—N1—C2—C4	−1.8 (5)	C5—C4—C9—S1	−171.9 (3)
C1—N1—C2—C3	−24.3 (8)	C5—C4—C9—C8	2.5 (7)
C1—N1—C2—C4	156.1 (5)	C7—C8—C9—S1	171.8 (3)
N1—C2—C3—Cl1	−2.1 (7)	C7—C8—C9—C4	−1.6 (7)
C4—C2—C3—Cl1	177.5 (3)	N1—S1—C9—C4	−6.2 (3)
N1—C2—C4—C5	174.9 (4)	N1—S1—C9—C8	179.6 (4)
N1—C2—C4—C9	−2.9 (5)	O1—S1—C9—C4	107.0 (3)
C3—C2—C4—C5	−4.8 (7)	O1—S1—C9—C8	−67.3 (4)
C3—C2—C4—C9	177.4 (4)	O2—S1—C9—C4	−120.0 (3)
C2—C4—C5—C6	−177.8 (4)	O2—S1—C9—C8	65.8 (4)
C9—C4—C5—C6	0.0 (6)	C5—C6—O3—C10	−0.5 (6)
C4—C5—C6—C7	−3.1 (7)	C7—C6—O3—C10	179.4 (4)
C4—C5—C6—O3	176.8 (4)	C6—C7—O4—C11	−178.5 (4)
C5—C6—C7—C8	3.9 (7)	C8—C7—O4—C11	1.1 (6)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClNO₄S
M_r	289.73
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	7.578 (5), 7.904 (6), 10.002 (7)
α, β, γ (°)	88.875 (11), 86.293 (10), 84.176 (11)
V (Å³)	594.7 (7)
Z	2
Radiation type	Synchrotron, λ = 0.6937 Å
µ (mm⁻¹)	0.50
Crystal size (mm)	0.20 × 0.04 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.905, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	4651, 2237, 1671
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.177, 1.02
No. of reflections	2237
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −0.43

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008) and local programs.

Acknowledgements

We thank the EPSRC for funding the National Crystallography Service, and STFC (formerly CCLRC) for access to synchrotron facilities.

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