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Acta Cryst. (2009). E65, o716    [ doi:10.1107/S1600536809007727 ]

Ethyl 2-(4-chloro-2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate

W.-T. Shen and C. Yao

Abstract top

In the molecule of the title compound, C11H10ClNO3S, the benzene and thiazole rings are oriented at a dihedral angle of 1.25 (3)°. Intramolecular C-H...O and C-H...Cl interactions result in the formation of two five-membered rings which both adopt envelope conformations.

Comment top

The title compound is widely used in preventing cole from pest and is also useful to kill broad-leaved weed. It is likely to be decomposed in the soil. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C6-C11) and B (S/N/C5/C6/C11) are, of course, planar, and they are oriented at a dihedral angle 1.25 (3)°. So, they are also coplanar. The intramolecular C-H···O and C-H···Cl interactions (Table 1) result in the formations of two five-membered rings C (O3/N/C4/C5/H4A) and D (Cl/N/C4/C10/C11/H4B), adopting envelope conformations with H4A and H4B atoms displaced by -0.284 (3) and -0.661 (3) Å from the planes of the other ring atoms, respectively.

Related literature top

For a related structure, see: Shao et al. (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 4-chlorobenzothiazol-2(3H)-one (10.7 g, 57.5 mmol), ethyl choroacetate (4.3 g, 50 mmol), and the catalyst of potassium iodide (0.63 g, 3 mmol) were added to butyl acetate solution (200 ml) of potassium carbonate (2.72 g, 20 ml) as acid-binding at 353 K. It was stirred for 8 h, and then cooled to room temperature. Water (150 ml) was added to dissolve the product, and inorganic salts were generated. The separated aqueous phase was extracted three times by butyl acetate, and then combined with organic phase product, treated with vacuum distillation at 353 K. Some anhydrous ethanol (about 40 ml) was added to the residual products, the combination was heated into homogeneous phase. Thereafter, precipitated products were cooled (Shao et al., 2001). Crystals suitable for X-ray analysis were obtained by evaporating the solvent slowly at room temperature for about 15 d.

Refinement top

H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bonds are shown as dashed lines.
Ethyl 2-(4-chloro-2-oxo-2,3-dihydro-1,3-benzothiazol-3-yl)acetate top
Crystal data top
C11H10ClNO3SF(000) = 560
Mr = 271.71Dx = 1.539 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 5.4830 (11) Åθ = 10–12°
b = 19.410 (4) ŵ = 0.50 mm−1
c = 11.060 (2) ÅT = 294 K
β = 95.16 (3)°Block, colorless
V = 1172.3 (4) Å30.20 × 0.10 × 0.10 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		1460 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.044
graphiteθmax = 25.3°, θmin = 2.1°
ω/2θ scansh = 0→6
Absorption correction: ψ scan
(North et al., 1968)		k = 0→23
Tmin = 0.907, Tmax = 0.952l = −13→13
2363 measured reflections3 standard reflections every 120 min
2132 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1P)2 + 0.14P]
where P = (Fo2 + 2Fc2)/3
2132 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C11H10ClNO3SV = 1172.3 (4) Å3
Mr = 271.71Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.4830 (11) ŵ = 0.50 mm−1
b = 19.410 (4) ÅT = 294 K
c = 11.060 (2) Å0.20 × 0.10 × 0.10 mm
β = 95.16 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1460 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.044
Tmin = 0.907, Tmax = 0.952θmax = 25.3°
2363 measured reflections3 standard reflections every 120 min
2132 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.172Δρmax = 0.34 e Å−3
S = 1.00Δρmin = −0.28 e Å−3
2132 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cl−0.37482 (19)0.59357 (6)0.35838 (10)0.0538 (4)
S0.41735 (19)0.71164 (6)0.58220 (10)0.0472 (3)
O1−0.1295 (5)0.67435 (15)0.0880 (3)0.0510 (8)
O20.1424 (5)0.61068 (17)0.2030 (3)0.0568 (8)
O30.3832 (6)0.78020 (17)0.3753 (3)0.0574 (8)
N0.0918 (5)0.69736 (17)0.4015 (3)0.0394 (8)
C1−0.2905 (10)0.5683 (3)−0.0001 (5)0.0751 (16)
H1A−0.28540.5377−0.06810.113*
H1B−0.45430.58530.00300.113*
H1C−0.24130.54380.07350.113*
C2−0.1232 (10)0.6264 (2)−0.0132 (4)0.0595 (12)
H2A0.04220.6091−0.01630.071*
H2B−0.16990.6502−0.08880.071*
C30.0067 (7)0.6585 (2)0.1892 (4)0.0410 (9)
C4−0.0388 (7)0.7124 (2)0.2852 (3)0.0443 (10)
H4A0.01190.75720.25770.053*
H4B−0.21280.71460.29450.053*
C50.2972 (7)0.7356 (2)0.4359 (4)0.0434 (10)
C60.1986 (7)0.6473 (2)0.5897 (3)0.0400 (9)
C70.1815 (9)0.6014 (2)0.6847 (4)0.0522 (11)
H7A0.29500.60210.75250.063*
C8−0.0084 (9)0.5547 (2)0.6758 (4)0.0542 (11)
H8A−0.02450.52360.73860.065*
C9−0.1741 (9)0.5536 (2)0.5752 (4)0.0541 (11)
H9A−0.30220.52210.57080.065*
C10−0.1530 (7)0.5992 (2)0.4797 (4)0.0419 (9)
C110.0334 (7)0.64719 (19)0.4852 (3)0.0384 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0421 (6)0.0549 (7)0.0633 (7)−0.0090 (5)−0.0018 (5)−0.0008 (5)
S0.0446 (6)0.0507 (7)0.0456 (6)−0.0038 (5)−0.0001 (5)−0.0043 (5)
O10.0571 (18)0.0488 (18)0.0446 (16)0.0022 (14)−0.0087 (14)−0.0003 (14)
O20.0544 (18)0.059 (2)0.0563 (19)0.0132 (16)−0.0005 (15)−0.0047 (15)
O30.0624 (19)0.056 (2)0.0527 (18)−0.0162 (16)0.0011 (15)0.0084 (15)
N0.0380 (17)0.0366 (18)0.0427 (18)−0.0012 (14)−0.0014 (14)0.0015 (15)
C10.081 (4)0.069 (4)0.076 (4)−0.017 (3)0.005 (3)−0.010 (3)
C20.075 (3)0.059 (3)0.044 (2)−0.009 (3)0.000 (2)−0.007 (2)
C30.034 (2)0.043 (2)0.046 (2)−0.0049 (18)−0.0014 (17)0.0029 (19)
C40.045 (2)0.042 (2)0.045 (2)0.0046 (19)−0.0004 (18)0.0060 (19)
C50.042 (2)0.045 (2)0.043 (2)0.0010 (19)0.0037 (18)−0.0022 (19)
C60.041 (2)0.038 (2)0.042 (2)0.0050 (18)0.0049 (17)−0.0026 (17)
C70.067 (3)0.046 (3)0.043 (2)0.005 (2)0.007 (2)0.005 (2)
C80.066 (3)0.041 (3)0.056 (3)−0.001 (2)0.011 (2)0.009 (2)
C90.065 (3)0.040 (2)0.059 (3)−0.009 (2)0.018 (2)0.001 (2)
C100.0351 (19)0.040 (2)0.050 (2)0.0047 (18)0.0011 (17)−0.0030 (19)
C110.041 (2)0.032 (2)0.043 (2)0.0057 (17)0.0079 (17)−0.0037 (17)
Geometric parameters (Å, °) top
S—C61.738 (4)C2—H2A0.9700
S—C51.755 (4)C2—H2B0.9700
Cl—C101.731 (4)C3—C41.527 (6)
O1—C31.325 (5)C4—H4A0.9700
O1—C21.459 (5)C4—H4B0.9700
O2—C31.191 (5)C6—C71.388 (6)
O3—C51.215 (5)C6—C111.403 (5)
N—C51.373 (5)C7—C81.377 (6)
N—C111.400 (5)C7—H7A0.9300
N—C41.445 (5)C8—C91.372 (7)
C1—C21.469 (7)C8—H8A0.9300
C1—H1A0.9600C9—C101.390 (6)
C1—H1B0.9600C9—H9A0.9300
C1—H1C0.9600C10—C111.381 (5)
C6—S—C591.77 (19)C3—C4—H4B109.1
C3—O1—C2116.7 (3)H4A—C4—H4B107.9
C5—N—C11115.1 (3)O3—C5—N125.6 (4)
C5—N—C4117.7 (3)O3—C5—S124.4 (3)
C11—N—C4127.2 (3)N—C5—S110.0 (3)
C2—C1—H1A109.5C7—C6—C11122.7 (4)
C2—C1—H1B109.5C7—C6—S126.3 (3)
H1A—C1—H1B109.5C11—C6—S111.0 (3)
C2—C1—H1C109.5C8—C7—C6118.1 (4)
H1A—C1—H1C109.5C8—C7—H7A121.0
H1B—C1—H1C109.5C6—C7—H7A121.0
O1—C2—C1110.9 (4)C9—C8—C7120.6 (4)
O1—C2—H2A109.5C9—C8—H8A119.7
C1—C2—H2A109.5C7—C8—H8A119.7
O1—C2—H2B109.5C8—C9—C10120.8 (4)
C1—C2—H2B109.5C8—C9—H9A119.6
H2A—C2—H2B108.1C10—C9—H9A119.6
O2—C3—O1126.0 (4)C11—C10—C9120.5 (4)
O2—C3—C4125.7 (4)C11—C10—Cl122.8 (3)
O1—C3—C4108.3 (3)C9—C10—Cl116.6 (3)
N—C4—C3112.4 (3)C10—C11—N130.8 (4)
N—C4—H4A109.1C10—C11—C6117.3 (4)
C3—C4—H4A109.1N—C11—C6112.0 (3)
N—C4—H4B109.1
C3—O1—C2—C182.2 (5)C6—C7—C8—C90.5 (7)
C2—O1—C3—O24.0 (6)C7—C8—C9—C100.5 (7)
C2—O1—C3—C4−176.4 (3)C8—C9—C10—C11−1.1 (7)
C5—N—C4—C3104.5 (4)C8—C9—C10—Cl−179.3 (4)
C11—N—C4—C3−75.3 (5)C9—C10—C11—N179.7 (4)
O2—C3—C4—N−3.7 (6)Cl—C10—C11—N−2.2 (6)
O1—C3—C4—N176.7 (3)C9—C10—C11—C60.5 (6)
C11—N—C5—O3177.8 (4)Cl—C10—C11—C6178.7 (3)
C4—N—C5—O3−2.0 (6)C5—N—C11—C10−178.2 (4)
C11—N—C5—S−3.0 (4)C4—N—C11—C101.6 (7)
C4—N—C5—S177.2 (3)C5—N—C11—C60.9 (5)
C6—S—C5—O3−177.5 (4)C4—N—C11—C6−179.3 (3)
C6—S—C5—N3.3 (3)C7—C6—C11—C100.5 (6)
C5—S—C6—C7177.6 (4)S—C6—C11—C10−179.1 (3)
C5—S—C6—C11−2.8 (3)C7—C6—C11—N−178.8 (4)
C11—C6—C7—C8−1.0 (6)S—C6—C11—N1.6 (4)
S—C6—C7—C8178.5 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O30.972.362.768 (5)105
C4—H4B···Cl0.972.633.105 (4)110
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O30.972.362.768 (5)105
C4—H4B···Cl0.972.633.105 (4)110
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Shao, T., Long, Y. D. & Huang, T. B. (2001). Chin. J. Anal. Chem. 29, 74–76.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.