2-Ethyl-2,3-dihydro-1,2-benzothia­zole-1,1,3-trione

Abstract

In the title mol­ecule, C₉H₉NO₃S, the bond lengths and angles fall within normal ranges. All nine ring atoms almost lie in a common plane (r.m.s. deviation 0.021 Å). In the crystal, symmetry-related mol­ecules are linked via C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For related literature on benzisothia­zolone-1,1-dioxide derivatives, see: Hu et al. (2004 ▶); Kap-Sun & Nicholas (1998 ▶); Liang et al. (2006 ▶); Masashi et al. (1999 ▶); Nagasawa et al. (1995 ▶). For related structures, see: Hu et al. (2006 ▶); Xu et al. (2005 ▶); Wen et al. (2006 ▶).

Experimental

Crystal data

• C₉H₉NO₃S

• M _r = 211.24

• Monoclinic,

• a = 10.4559 (5) Å

• b = 7.5484 (5) Å

• c = 12.9408 (7) Å

• β = 105.863 (2)°

• V = 982.46 (10) ų

• Z = 4

• Mo Kα radiation

• μ = 0.31 mm⁻¹

• T = 296 K

• 0.19 × 0.18 × 0.09 mm

Data collection

• Bruker APEXII CCD diffractometer

• 9319 measured reflections

• 2429 independent reflections

• 1822 reflections with I > 2σ(I)

• R _int = 0.081

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.144

• S = 1.08

• 2429 reflections

• 129 parameters

• H-atom parameters constrained

• Δρ_max = 0.34 e Å⁻³

• Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.93	2.37	3.265 (2)	162
C3—H3⋯O2ii	0.93	2.53	3.295 (3)	140
C8—H8A⋯O3iii	0.97	2.45	3.139 (3)	128

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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 activity (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 the molecule of the title compound (Fig. 1), all the bond lengths and bond angles agree with the corresponding values in similar structures containing benzisothiazole group (Hu et al., 2006; Xu et al., 2005; Wen et al., 2006).

Atoms C1–C7, S1, O1 and N1 of the title molecule are essentially coplanar, with a maximum deviation of 0.020 (1) Å for S1. The packing of the molecules is stabilized by intermolecular C—H···O intermolecular hydrogen bonds (Table 1, Fig. 2).

Experimental

Sodium sacharrin (0.5 g, 2.439 mmol) was taken in round bottom flask and 20 ml DMF was added to it. It was kept for stirring at room temperature for 5 minutes then ethyl iodide (0.195 ml, 2.439 mmol) was added to the solution. Then reaction mixture was kept under reflux for 3 h at 333 K and after 3 h the TLC confirmed the completion of reaction. The product was obtained in ice-water, filtered and dried. Dried precipitates were dissolved in methanol for crystallization (yield: 93%).

Refinement

In the last cycles of the refinement, 3 reflections (1 0 1), (-1 0 1) and (-2 2 2) were eliminated due to being poorly measured in the vicinity of the beam stop. All H atoms were positioned geometrically with C—H = 0.93 - 0.97 Å, and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) for aromatic and methylene, and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Figures

Fig. 1.

View of the title molecule with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

Fig. 2.

A view of the packing and hydrogen bonding interactions of the title compound down the b axis. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C9H9NO3S	F(000) = 440
Mr = 211.24	Dx = 1.428 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3812 reflections
a = 10.4559 (5) Å	θ = 2.7–28.3°
b = 7.5484 (5) Å	µ = 0.31 mm−1
c = 12.9408 (7) Å	T = 296 K
β = 105.863 (2)°	Plate, colourless
V = 982.46 (10) Å3	0.19 × 0.18 × 0.09 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	1822 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.081
graphite	θmax = 28.3°, θmin = 3.2°
φ and ω scans	h = −13→13
9319 measured reflections	k = −10→10
2429 independent reflections	l = −17→17

Refinement

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0789P)2 + 0.0563P] where P = (Fo2 + 2Fc2)/3
2429 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.45672 (5)	0.21780 (7)	0.19351 (3)	0.0544 (2)
O1	0.27985 (14)	0.1334 (2)	−0.09326 (10)	0.0684 (5)
O2	0.50046 (15)	0.0632 (2)	0.25648 (10)	0.0770 (6)
O3	0.42257 (17)	0.3675 (2)	0.24709 (11)	0.0771 (6)
N1	0.33045 (15)	0.1647 (2)	0.08810 (12)	0.0540 (5)
C1	0.55956 (17)	0.2745 (2)	0.11296 (13)	0.0442 (5)
C2	0.68739 (19)	0.3429 (3)	0.14490 (15)	0.0568 (6)
C3	0.74791 (19)	0.3782 (3)	0.06576 (17)	0.0620 (6)
C4	0.68513 (19)	0.3479 (3)	−0.04052 (16)	0.0591 (7)
C5	0.55651 (19)	0.2815 (2)	−0.07236 (14)	0.0515 (6)
C6	0.49424 (17)	0.2447 (2)	0.00599 (13)	0.0417 (5)
C7	0.35743 (17)	0.1749 (2)	−0.00979 (13)	0.0473 (5)
C8	0.2068 (2)	0.0906 (3)	0.10313 (19)	0.0704 (8)
C9	0.0967 (3)	0.2234 (3)	0.0851 (3)	0.0977 (13)
H2	0.73010	0.36390	0.21690	0.0680*
H3	0.83380	0.42380	0.08450	0.0740*
H4	0.72950	0.37220	−0.09210	0.0710*
H5	0.51370	0.26240	−0.14450	0.0620*
H8A	0.22420	0.04450	0.17560	0.0840*
H8B	0.17840	−0.00750	0.05380	0.0840*
H9A	0.12320	0.31940	0.13500	0.1470*
H9B	0.01870	0.16790	0.09560	0.1470*
H9C	0.07780	0.26810	0.01300	0.1470*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0641 (3)	0.0629 (4)	0.0381 (3)	0.0102 (2)	0.0174 (2)	0.0029 (2)
O1	0.0600 (8)	0.0833 (10)	0.0532 (8)	−0.0087 (7)	0.0010 (6)	−0.0090 (7)
O2	0.0932 (11)	0.0822 (10)	0.0543 (8)	0.0116 (9)	0.0179 (7)	0.0255 (7)
O3	0.0937 (11)	0.0869 (10)	0.0586 (8)	0.0168 (9)	0.0343 (8)	−0.0156 (8)
N1	0.0505 (8)	0.0625 (9)	0.0515 (8)	0.0006 (7)	0.0181 (7)	0.0040 (7)
C1	0.0481 (9)	0.0458 (9)	0.0371 (8)	0.0107 (7)	0.0092 (7)	−0.0022 (6)
C2	0.0524 (10)	0.0596 (11)	0.0503 (10)	0.0075 (8)	0.0001 (8)	−0.0070 (8)
C3	0.0456 (9)	0.0604 (11)	0.0789 (13)	0.0027 (8)	0.0150 (9)	−0.0019 (10)
C4	0.0577 (11)	0.0601 (11)	0.0665 (12)	0.0051 (9)	0.0287 (9)	0.0037 (9)
C5	0.0611 (11)	0.0547 (10)	0.0406 (8)	0.0067 (8)	0.0172 (8)	−0.0013 (7)
C6	0.0464 (8)	0.0406 (8)	0.0372 (8)	0.0068 (7)	0.0098 (6)	−0.0015 (6)
C7	0.0484 (9)	0.0475 (9)	0.0439 (9)	0.0047 (7)	0.0092 (7)	−0.0008 (7)
C8	0.0610 (12)	0.0704 (14)	0.0886 (14)	−0.0035 (10)	0.0356 (11)	0.0074 (11)
C9	0.0638 (14)	0.0892 (18)	0.149 (3)	0.0057 (13)	0.0440 (17)	0.0024 (17)

Geometric parameters (Å, °)

S1—O2	1.4252 (15)	C5—C6	1.375 (3)
S1—O3	1.4214 (16)	C6—C7	1.485 (3)
S1—N1	1.6673 (16)	C8—C9	1.496 (4)
S1—C1	1.7432 (18)	C2—H2	0.9300
O1—C7	1.202 (2)	C3—H3	0.9300
N1—C7	1.373 (2)	C4—H4	0.9300
N1—C8	1.470 (3)	C5—H5	0.9300
C1—C2	1.386 (3)	C8—H8A	0.9700
C1—C6	1.384 (2)	C8—H8B	0.9700
C2—C3	1.369 (3)	C9—H9A	0.9600
C3—C4	1.372 (3)	C9—H9B	0.9600
C4—C5	1.388 (3)	C9—H9C	0.9600
O2—S1—O3	117.14 (8)	N1—C7—C6	109.03 (14)
O2—S1—N1	109.24 (8)	N1—C8—C9	113.06 (19)
O2—S1—C1	112.89 (9)	C1—C2—H2	121.00
O3—S1—N1	109.99 (9)	C3—C2—H2	122.00
O3—S1—C1	112.01 (9)	C2—C3—H3	119.00
N1—S1—C1	92.85 (8)	C4—C3—H3	119.00
S1—N1—C7	115.14 (13)	C3—C4—H4	119.00
S1—N1—C8	120.78 (13)	C5—C4—H4	119.00
C7—N1—C8	123.60 (16)	C4—C5—H5	121.00
S1—C1—C2	127.97 (13)	C6—C5—H5	121.00
S1—C1—C6	109.98 (13)	N1—C8—H8A	109.00
C2—C1—C6	122.05 (16)	N1—C8—H8B	109.00
C1—C2—C3	117.03 (17)	C9—C8—H8A	109.00
C2—C3—C4	121.7 (2)	C9—C8—H8B	109.00
C3—C4—C5	121.14 (19)	H8A—C8—H8B	108.00
C4—C5—C6	118.02 (17)	C8—C9—H9A	109.00
C1—C6—C5	120.07 (17)	C8—C9—H9B	109.00
C1—C6—C7	112.86 (15)	C8—C9—H9C	109.00
C5—C6—C7	127.07 (15)	H9A—C9—H9B	110.00
O1—C7—N1	123.80 (17)	H9A—C9—H9C	109.00
O1—C7—C6	127.17 (16)	H9B—C9—H9C	110.00
O2—S1—N1—C7	−111.89 (13)	C7—N1—C8—C9	−85.9 (3)
O2—S1—N1—C8	60.49 (17)	C2—C1—C6—C7	−178.70 (16)
O3—S1—N1—C7	118.24 (13)	S1—C1—C6—C5	179.56 (13)
O3—S1—N1—C8	−69.38 (17)	S1—C1—C2—C3	−179.53 (16)
C1—S1—N1—C7	3.57 (13)	C6—C1—C2—C3	−0.8 (3)
C1—S1—N1—C8	175.95 (15)	S1—C1—C6—C7	0.24 (17)
O2—S1—C1—C2	−70.93 (19)	C2—C1—C6—C5	0.6 (3)
O2—S1—C1—C6	110.22 (13)	C1—C2—C3—C4	0.2 (3)
O3—S1—C1—C2	63.88 (19)	C2—C3—C4—C5	0.7 (3)
O3—S1—C1—C6	−114.97 (13)	C3—C4—C5—C6	−0.8 (3)
N1—S1—C1—C2	176.79 (18)	C4—C5—C6—C7	179.41 (17)
N1—S1—C1—C6	−2.06 (13)	C4—C5—C6—C1	0.2 (2)
S1—N1—C7—O1	176.40 (14)	C5—C6—C7—N1	−177.04 (16)
C8—N1—C7—O1	4.3 (3)	C1—C6—C7—O1	−178.07 (17)
S1—N1—C7—C6	−3.89 (17)	C1—C6—C7—N1	2.23 (19)
C8—N1—C7—C6	−176.03 (16)	C5—C6—C7—O1	2.7 (3)
S1—N1—C8—C9	102.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.93	2.37	3.265 (2)	162
C3—H3···O2ii	0.93	2.53	3.295 (3)	140
C8—H8A···O3iii	0.97	2.45	3.139 (3)	128

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2.