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

Shen, W.-T.; Yao, C.

doi:10.1107/S1600536809007727

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o716

doi:10.1107/S1600536809007727

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

Wen-Tong Shen ^a and Cheng Yao ^a ^*

^aCollege of Science, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: yaocheng@njut.edu.cn

(Received 27 February 2009; accepted 3 March 2009; online 6 March 2009)

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.

Related literature

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

Experimental

Crystal data

C₁₁H₁₀ClNO₃S
M_r = 271.71
Monoclinic, P 2₁ /c
a = 5.4830 (11) Å
b = 19.410 (4) Å
c = 11.060 (2) Å
β = 95.16 (3)°
V = 1172.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.907, T_max = 0.952
2363 measured reflections
2132 independent reflections
1460 reflections with I > 2σ(I)
R_int = 0.044
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.172
S = 1.00
2132 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O3	0.97	2.36	2.768 (5)	105
C4—H4B⋯Cl	0.97	2.63	3.105 (4)	110

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007727/hk2637sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007727/hk2637Isup2.hkl

checkCIF report

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.

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

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

C₁₁H₁₀ClNO₃S	F(000) = 560
M_r = 271.71	D_x = 1.539 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 5.4830 (11) Å	θ = 10–12°
b = 19.410 (4) Å	µ = 0.50 mm⁻¹
c = 11.060 (2) Å	T = 294 K
β = 95.16 (3)°	Block, colorless
V = 1172.3 (4) Å³	0.20 × 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 tube	R_int = 0.044
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→23
T_min = 0.907, T_max = 0.952	l = −13→13
2363 measured reflections	3 standard reflections every 120 min
2132 independent reflections	intensity decay: 1%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.14P] where P = (F_o² + 2F_c²)/3
2132 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₁H₁₀ClNO₃S	V = 1172.3 (4) Å³
M_r = 271.71	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.4830 (11) Å	µ = 0.50 mm⁻¹
b = 19.410 (4) Å	T = 294 K
c = 11.060 (2) Å	0.20 × 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)	R_int = 0.044
T_min = 0.907, T_max = 0.952	3 standard reflections every 120 min
2363 measured reflections	intensity decay: 1%
2132 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.00	Δρ_max = 0.34 e Å⁻³
2132 reflections	Δρ_min = −0.28 e Å⁻³
154 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
Cl	−0.37482 (19)	0.59357 (6)	0.35838 (10)	0.0538 (4)
S	0.41735 (19)	0.71164 (6)	0.58220 (10)	0.0472 (3)
O1	−0.1295 (5)	0.67435 (15)	0.0880 (3)	0.0510 (8)
O2	0.1424 (5)	0.61068 (17)	0.2030 (3)	0.0568 (8)
O3	0.3832 (6)	0.78020 (17)	0.3753 (3)	0.0574 (8)
N	0.0918 (5)	0.69736 (17)	0.4015 (3)	0.0394 (8)
C1	−0.2905 (10)	0.5683 (3)	−0.0001 (5)	0.0751 (16)
H1A	−0.2854	0.5377	−0.0681	0.113*
H1B	−0.4543	0.5853	0.0030	0.113*
H1C	−0.2413	0.5438	0.0735	0.113*
C2	−0.1232 (10)	0.6264 (2)	−0.0132 (4)	0.0595 (12)
H2A	0.0422	0.6091	−0.0163	0.071*
H2B	−0.1699	0.6502	−0.0888	0.071*
C3	0.0067 (7)	0.6585 (2)	0.1892 (4)	0.0410 (9)
C4	−0.0388 (7)	0.7124 (2)	0.2852 (3)	0.0443 (10)
H4A	0.0119	0.7572	0.2577	0.053*
H4B	−0.2128	0.7146	0.2945	0.053*
C5	0.2972 (7)	0.7356 (2)	0.4359 (4)	0.0434 (10)
C6	0.1986 (7)	0.6473 (2)	0.5897 (3)	0.0400 (9)
C7	0.1815 (9)	0.6014 (2)	0.6847 (4)	0.0522 (11)
H7A	0.2950	0.6021	0.7525	0.063*
C8	−0.0084 (9)	0.5547 (2)	0.6758 (4)	0.0542 (11)
H8A	−0.0245	0.5236	0.7386	0.065*
C9	−0.1741 (9)	0.5536 (2)	0.5752 (4)	0.0541 (11)
H9A	−0.3022	0.5221	0.5708	0.065*
C10	−0.1530 (7)	0.5992 (2)	0.4797 (4)	0.0419 (9)
C11	0.0334 (7)	0.64719 (19)	0.4852 (3)	0.0384 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0421 (6)	0.0549 (7)	0.0633 (7)	−0.0090 (5)	−0.0018 (5)	−0.0008 (5)
S	0.0446 (6)	0.0507 (7)	0.0456 (6)	−0.0038 (5)	−0.0001 (5)	−0.0043 (5)
O1	0.0571 (18)	0.0488 (18)	0.0446 (16)	0.0022 (14)	−0.0087 (14)	−0.0003 (14)
O2	0.0544 (18)	0.059 (2)	0.0563 (19)	0.0132 (16)	−0.0005 (15)	−0.0047 (15)
O3	0.0624 (19)	0.056 (2)	0.0527 (18)	−0.0162 (16)	0.0011 (15)	0.0084 (15)
N	0.0380 (17)	0.0366 (18)	0.0427 (18)	−0.0012 (14)	−0.0014 (14)	0.0015 (15)
C1	0.081 (4)	0.069 (4)	0.076 (4)	−0.017 (3)	0.005 (3)	−0.010 (3)
C2	0.075 (3)	0.059 (3)	0.044 (2)	−0.009 (3)	0.000 (2)	−0.007 (2)
C3	0.034 (2)	0.043 (2)	0.046 (2)	−0.0049 (18)	−0.0014 (17)	0.0029 (19)
C4	0.045 (2)	0.042 (2)	0.045 (2)	0.0046 (19)	−0.0004 (18)	0.0060 (19)
C5	0.042 (2)	0.045 (2)	0.043 (2)	0.0010 (19)	0.0037 (18)	−0.0022 (19)
C6	0.041 (2)	0.038 (2)	0.042 (2)	0.0050 (18)	0.0049 (17)	−0.0026 (17)
C7	0.067 (3)	0.046 (3)	0.043 (2)	0.005 (2)	0.007 (2)	0.005 (2)
C8	0.066 (3)	0.041 (3)	0.056 (3)	−0.001 (2)	0.011 (2)	0.009 (2)
C9	0.065 (3)	0.040 (2)	0.059 (3)	−0.009 (2)	0.018 (2)	0.001 (2)
C10	0.0351 (19)	0.040 (2)	0.050 (2)	0.0047 (18)	0.0011 (17)	−0.0030 (19)
C11	0.041 (2)	0.032 (2)	0.043 (2)	0.0057 (17)	0.0079 (17)	−0.0037 (17)

Geometric parameters (Å, º) top

S—C6	1.738 (4)	C2—H2A	0.9700
S—C5	1.755 (4)	C2—H2B	0.9700
Cl—C10	1.731 (4)	C3—C4	1.527 (6)
O1—C3	1.325 (5)	C4—H4A	0.9700
O1—C2	1.459 (5)	C4—H4B	0.9700
O2—C3	1.191 (5)	C6—C7	1.388 (6)
O3—C5	1.215 (5)	C6—C11	1.403 (5)
N—C5	1.373 (5)	C7—C8	1.377 (6)
N—C11	1.400 (5)	C7—H7A	0.9300
N—C4	1.445 (5)	C8—C9	1.372 (7)
C1—C2	1.469 (7)	C8—H8A	0.9300
C1—H1A	0.9600	C9—C10	1.390 (6)
C1—H1B	0.9600	C9—H9A	0.9300
C1—H1C	0.9600	C10—C11	1.381 (5)

C6—S—C5	91.77 (19)	C3—C4—H4B	109.1
C3—O1—C2	116.7 (3)	H4A—C4—H4B	107.9
C5—N—C11	115.1 (3)	O3—C5—N	125.6 (4)
C5—N—C4	117.7 (3)	O3—C5—S	124.4 (3)
C11—N—C4	127.2 (3)	N—C5—S	110.0 (3)
C2—C1—H1A	109.5	C7—C6—C11	122.7 (4)
C2—C1—H1B	109.5	C7—C6—S	126.3 (3)
H1A—C1—H1B	109.5	C11—C6—S	111.0 (3)
C2—C1—H1C	109.5	C8—C7—C6	118.1 (4)
H1A—C1—H1C	109.5	C8—C7—H7A	121.0
H1B—C1—H1C	109.5	C6—C7—H7A	121.0
O1—C2—C1	110.9 (4)	C9—C8—C7	120.6 (4)
O1—C2—H2A	109.5	C9—C8—H8A	119.7
C1—C2—H2A	109.5	C7—C8—H8A	119.7
O1—C2—H2B	109.5	C8—C9—C10	120.8 (4)
C1—C2—H2B	109.5	C8—C9—H9A	119.6
H2A—C2—H2B	108.1	C10—C9—H9A	119.6
O2—C3—O1	126.0 (4)	C11—C10—C9	120.5 (4)
O2—C3—C4	125.7 (4)	C11—C10—Cl	122.8 (3)
O1—C3—C4	108.3 (3)	C9—C10—Cl	116.6 (3)
N—C4—C3	112.4 (3)	C10—C11—N	130.8 (4)
N—C4—H4A	109.1	C10—C11—C6	117.3 (4)
C3—C4—H4A	109.1	N—C11—C6	112.0 (3)
N—C4—H4B	109.1

C3—O1—C2—C1	82.2 (5)	C6—C7—C8—C9	0.5 (7)
C2—O1—C3—O2	4.0 (6)	C7—C8—C9—C10	0.5 (7)
C2—O1—C3—C4	−176.4 (3)	C8—C9—C10—C11	−1.1 (7)
C5—N—C4—C3	104.5 (4)	C8—C9—C10—Cl	−179.3 (4)
C11—N—C4—C3	−75.3 (5)	C9—C10—C11—N	179.7 (4)
O2—C3—C4—N	−3.7 (6)	Cl—C10—C11—N	−2.2 (6)
O1—C3—C4—N	176.7 (3)	C9—C10—C11—C6	0.5 (6)
C11—N—C5—O3	177.8 (4)	Cl—C10—C11—C6	178.7 (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—C10	1.6 (7)
C4—N—C5—S	177.2 (3)	C5—N—C11—C6	0.9 (5)
C6—S—C5—O3	−177.5 (4)	C4—N—C11—C6	−179.3 (3)
C6—S—C5—N	3.3 (3)	C7—C6—C11—C10	0.5 (6)
C5—S—C6—C7	177.6 (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—N	1.6 (4)
S—C6—C7—C8	178.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3	0.97	2.36	2.768 (5)	105
C4—H4B···Cl	0.97	2.63	3.105 (4)	110

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀ClNO₃S
M_r	271.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	5.4830 (11), 19.410 (4), 11.060 (2)
β (°)	95.16 (3)
V (Å³)	1172.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.907, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	2363, 2132, 1460
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.172, 1.00
No. of reflections	2132
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3	0.97	2.36	2.768 (5)	105.00
C4—H4B···Cl	0.97	2.63	3.105 (4)	110.00

Acknowledgements

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

References

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