Abstract
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,
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[F 2 > 2σ(F 2)] = 0.065
wR(F 2) = 0.177
S = 1.02
2237 reflections
167 parameters
H-atom parameters constrained
Δρmax = 1.29 e Å−3
Δρmin = −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.
Supplementary Material
Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810049561/jh2234sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049561/jh2234Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
We thank the EPSRC for funding the National Crystallography Service, and STFC (formerly CCLRC) for access to synchrotron facilities.
supplementary crystallographic information
Experimental
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].
Refinement
H atoms were constrained with a riding model, having C—H = 0.95–0.98 Å and Uiso(H) = 1.5eq(H) for methyl groups and 1.2Ueq(C) for other atoms. The largest residual electron density peak lies 1.81 Å from Cl1 and 1.04 Å from C3, but has no structural chemical significance.
Figures
Fig. 1.
Ellipsoid plot.
Crystal data
| C11H12ClNO4S | Z = 2 |
| Mr = 289.73 | F(000) = 300 |
| Triclinic, P1 | Dx = 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
| Bruker APEXII CCD diffractometer | 2237 independent reflections |
| Radiation source: Daresbury SRS station 9.8 | 1671 reflections with I > 2σ(I) |
| silicon 111 | Rint = 0.038 |
| thin–slice ω scans | θmax = 25.0°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −9→9 |
| Tmin = 0.905, Tmax = 0.990 | k = −9→9 |
| 4651 measured reflections | l = −12→12 |
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)] = 0.065 | H-atom parameters constrained |
| wR(F2) = 0.177 | w = 1/[σ2(Fo2) + (0.0319P)2 + 1.6618P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 2237 reflections | Δρmax = 1.29 e Å−3 |
| 167 parameters | Δρmin = −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) |
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 (Å2)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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, °)
| 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) |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JH2234).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810049561/jh2234sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049561/jh2234Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report