(Z)-Methyl 4-(1,3-benzothia­zol-2-yl­sulfan­yl)-2-(methoxy­imino)-3-oxo­butanoate

Li, Q.-Z.; Song, B.-A.; Yang, S.; Zheng, Y.-G.; Guo, Q.-Q.

doi:10.1107/S1600536808040658

organic compounds

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doi:10.1107/S1600536808040658

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(Z)-Methyl 4-(1,3-benzothiazol-2-ylsulfanyl)-2-(methoxyimino)-3-oxobutanoate

Qian-Zhu Li,^a,^b ^* Bao-An Song,^a Song Yang,^a Yu-Guo Zheng ^a and Qing-Qing Guo ^a

^aCenter for Research and Development of Fine Chemicals, Guizhou University, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guiyang 550025, People's Republic of China, and ^bDepartment of Chemistry, Bijie University, Bijie 551700, People's Republic of China
^*Correspondence e-mail: qianzhuli@126.com

(Received 1 December 2008; accepted 3 December 2008; online 6 December 2008)

In the molecular structure of the title compound, C₁₃H₁₂N₂O₄S₂, there is a dihedral angle of 0.41 (13)° between the benzene and thiazole rings. In the crystal, inversion dimers linked by two C—H⋯O interactions together with π–π stacking between the parallel benzene rings of adjacent molecules [centroid–centroid distance = 3.673 (2) Å].

Related literature

For general background to benzothiazole derivatives and their biological activities, see: Bradshaw et al. (2008 ); Moharram (1990 ); Spillane et al. (2007 ).

Experimental

Crystal data

C₁₃H₁₂N₂O₄S₂
M_r = 324.39
Triclinic, $[P \overline 1]$
a = 8.019 (3) Å
b = 10.037 (4) Å
c = 10.662 (5) Å
α = 76.44 (2)°
β = 67.997 (14)°
γ = 74.964 (15)°
V = 759.3 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 (2) K
0.22 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.913, T_max = 0.939
7739 measured reflections
2620 independent reflections
2278 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.101
S = 1.10
2620 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.55	3.398 (3)	152
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040658/at2688sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040658/at2688Isup2.hkl

checkCIF report

Comment top

A wide range of biological activities have been attributed to compounds containing benzothiazole moiety such as anticancer (Bradshaw et al., 2008), antibacterial (Moharram et al., 1990) and cytotoxic activity (Spillane et al., 2007), Herein we present the crystal structure of the title benzothiazole derivative (I).

The crystal structure of the title compound (I) is represented in Fig. 1. There is a dihedral angle of 0.41 (13)° between the benzene ring and thiazole ring. In the crystal structure, weak intermolecular C—H···O interactions (Table 1), together with π-π stacking between parallel benzene rings of adjacent molecules stabilize the packing, the centroid-to-centroid distance of two benzene rings is 3.673 (2)Å (symmetry codes: 1 - x,-y,1 - z).

Related literature top

For general background to benzothiazole derivatives and their biological activities, see: Bradshaw et al. (2008); Moharram et al. (1990); Spillane et al. (2007).

Experimental top

A solution of (Z)-methyl-4-bromo-2-(methoxyimino)-3-oxobutanoate 30 ml (2.38 g, 0.01 mol) in methanol (10 ml) was added dropwise to a stirred solution of benzothiazole-2-thiol (1.67 g, 0.01 mol) and sodium hydroxide (0.40 g, 0.01 mol) in water (25 ml). The resulting mixture was stirred at room temperature for 3 h, the mixture was filtered and the residue was dissolved in 30 ml e thanol, Single crystals of (I) were obtained after several days.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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).

Figures top

Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

(Z)-Methyl 4-(1,3-benzothiazol-2-ylsulfanyl)-2-(methoxyimino)-3-oxobutanoate top

Crystal data top

C₁₃H₁₂N₂O₄S₂	Z = 2
M_r = 324.39	F(000) = 336
Triclinic, P1	D_x = 1.419 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.019 (3) Å	Cell parameters from 2679 reflections
b = 10.037 (4) Å	θ = 2.1–25.0°
c = 10.662 (5) Å	µ = 0.37 mm⁻¹
α = 76.44 (2)°	T = 293 K
β = 67.997 (14)°	Block, colourless
γ = 74.964 (15)°	0.22 × 0.19 × 0.18 mm
V = 759.3 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2620 independent reflections
Radiation source: fine-focus sealed tube	2278 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
T_min = 0.913, T_max = 0.939	k = −11→11
7739 measured reflections	l = −12→12

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0551P)² + 0.1857P] where P = (F_o² + 2F_c²)/3
2620 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₃H₁₂N₂O₄S₂	γ = 74.964 (15)°
M_r = 324.39	V = 759.3 (6) Å³
Triclinic, P1	Z = 2
a = 8.019 (3) Å	Mo Kα radiation
b = 10.037 (4) Å	µ = 0.37 mm⁻¹
c = 10.662 (5) Å	T = 293 K
α = 76.44 (2)°	0.22 × 0.19 × 0.18 mm
β = 67.997 (14)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2620 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2278 reflections with I > 2σ(I)
T_min = 0.913, T_max = 0.939	R_int = 0.020
7739 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.10	Δρ_max = 0.23 e Å⁻³
2620 reflections	Δρ_min = −0.27 e Å⁻³
190 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
C1	0.2301 (4)	0.0381 (3)	0.4741 (3)	0.0665 (7)
H1	0.1206	0.0298	0.5455	0.080*
C2	0.3264 (5)	−0.0698 (2)	0.3972 (3)	0.0788 (9)
H2	0.2803	−0.1514	0.4185	0.095*
C3	0.4890 (4)	−0.0581 (3)	0.2898 (3)	0.0735 (8)
H3	0.5497	−0.1320	0.2407	0.088*
C4	0.5617 (4)	0.0593 (3)	0.2549 (3)	0.0635 (6)
H4	0.6707	0.0670	0.1829	0.076*
C5	0.4664 (3)	0.1679 (2)	0.3314 (2)	0.0472 (5)
C6	0.3029 (3)	0.1583 (2)	0.4407 (2)	0.0452 (5)
C7	0.3251 (3)	0.3681 (2)	0.45184 (18)	0.0387 (4)
C8	0.0771 (3)	0.5086 (2)	0.65173 (19)	0.0436 (5)
H8A	0.0138	0.5988	0.6798	0.052*
H8B	−0.0068	0.4706	0.6302	0.052*
C9	0.1277 (3)	0.41269 (19)	0.76915 (19)	0.0399 (4)
C10	−0.0218 (3)	0.3515 (2)	0.88308 (19)	0.0403 (4)
C11	0.0216 (3)	0.2738 (2)	1.0097 (2)	0.0443 (5)
C12	−0.4696 (3)	0.3219 (3)	0.9528 (3)	0.0694 (7)
H12A	−0.5552	0.2765	1.0303	0.104*
H12B	−0.4454	0.2809	0.8734	0.104*
H12C	−0.5204	0.4195	0.9369	0.104*
C13	0.1207 (5)	0.0538 (3)	1.1217 (3)	0.0890 (9)
H13A	0.1554	−0.0424	1.1090	0.134*
H13B	0.0174	0.0646	1.2040	0.134*
H13C	0.2215	0.0828	1.1287	0.134*
N1	0.2241 (2)	0.27441 (17)	0.50850 (16)	0.0448 (4)
N2	−0.1769 (2)	0.36936 (18)	0.86710 (16)	0.0451 (4)
O1	0.28034 (19)	0.38332 (16)	0.77643 (15)	0.0530 (4)
O2	0.0143 (3)	0.32938 (19)	1.09837 (17)	0.0774 (5)
O3	0.0721 (2)	0.13890 (16)	1.00578 (16)	0.0638 (4)
O4	−0.30078 (19)	0.30477 (17)	0.97942 (15)	0.0568 (4)
S1	0.52463 (7)	0.32799 (6)	0.31355 (5)	0.05263 (18)
S2	0.27235 (7)	0.53273 (5)	0.50010 (5)	0.04578 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0938 (19)	0.0544 (14)	0.0641 (14)	−0.0322 (13)	−0.0349 (13)	0.0011 (11)
C2	0.138 (3)	0.0375 (13)	0.093 (2)	−0.0260 (15)	−0.074 (2)	0.0004 (13)
C3	0.103 (2)	0.0500 (14)	0.0869 (19)	0.0087 (14)	−0.0594 (18)	−0.0267 (13)
C4	0.0734 (16)	0.0570 (14)	0.0702 (15)	0.0041 (12)	−0.0340 (13)	−0.0302 (12)
C5	0.0562 (12)	0.0444 (11)	0.0480 (11)	−0.0042 (9)	−0.0252 (10)	−0.0131 (9)
C6	0.0596 (12)	0.0385 (11)	0.0474 (11)	−0.0108 (9)	−0.0292 (10)	−0.0048 (8)
C7	0.0414 (10)	0.0418 (10)	0.0358 (9)	−0.0071 (8)	−0.0154 (8)	−0.0082 (8)
C8	0.0432 (11)	0.0490 (11)	0.0406 (10)	0.0008 (9)	−0.0174 (8)	−0.0155 (8)
C9	0.0420 (11)	0.0403 (10)	0.0438 (10)	0.0002 (8)	−0.0203 (8)	−0.0174 (8)
C10	0.0438 (10)	0.0413 (10)	0.0424 (10)	−0.0005 (8)	−0.0213 (8)	−0.0155 (8)
C11	0.0440 (11)	0.0488 (12)	0.0439 (10)	−0.0041 (9)	−0.0188 (9)	−0.0127 (9)
C12	0.0513 (13)	0.0842 (18)	0.0843 (17)	−0.0193 (12)	−0.0342 (13)	−0.0082 (14)
C13	0.127 (3)	0.0679 (18)	0.0844 (19)	−0.0117 (17)	−0.068 (2)	0.0130 (15)
N1	0.0484 (9)	0.0457 (10)	0.0433 (9)	−0.0136 (8)	−0.0150 (7)	−0.0077 (7)
N2	0.0446 (9)	0.0497 (10)	0.0449 (9)	−0.0089 (7)	−0.0185 (7)	−0.0088 (7)
O1	0.0438 (8)	0.0620 (9)	0.0594 (9)	−0.0054 (7)	−0.0272 (7)	−0.0094 (7)
O2	0.1180 (15)	0.0696 (11)	0.0605 (10)	0.0034 (10)	−0.0516 (10)	−0.0270 (9)
O3	0.0931 (12)	0.0467 (9)	0.0642 (10)	−0.0046 (8)	−0.0473 (9)	−0.0069 (7)
O4	0.0463 (8)	0.0745 (11)	0.0546 (9)	−0.0184 (7)	−0.0238 (7)	0.0000 (7)
S1	0.0523 (3)	0.0552 (4)	0.0485 (3)	−0.0167 (3)	−0.0037 (2)	−0.0193 (2)
S2	0.0515 (3)	0.0413 (3)	0.0472 (3)	−0.0109 (2)	−0.0144 (2)	−0.0131 (2)

Geometric parameters (Å, º) top

C1—C6	1.389 (3)	C8—H8A	0.9700
C1—C2	1.397 (4)	C8—H8B	0.9700
C1—H1	0.9300	C9—O1	1.210 (2)
C2—C3	1.387 (4)	C9—C10	1.493 (3)
C2—H2	0.9300	C10—N2	1.279 (2)
C3—C4	1.362 (4)	C10—C11	1.506 (3)
C3—H3	0.9300	C11—O2	1.182 (2)
C4—C5	1.398 (3)	C11—O3	1.315 (3)
C4—H4	0.9300	C12—O4	1.445 (3)
C5—C6	1.398 (3)	C12—H12A	0.9600
C5—S1	1.736 (2)	C12—H12B	0.9600
C6—N1	1.397 (3)	C12—H12C	0.9600
C7—N1	1.291 (2)	C13—O3	1.450 (3)
C7—S2	1.745 (2)	C13—H13A	0.9600
C7—S1	1.753 (2)	C13—H13B	0.9600
C8—C9	1.507 (3)	C13—H13C	0.9600
C8—S2	1.800 (2)	N2—O4	1.386 (2)

C6—C1—C2	118.0 (3)	O1—C9—C10	118.71 (17)
C6—C1—H1	121.0	O1—C9—C8	124.10 (19)
C2—C1—H1	121.0	C10—C9—C8	117.19 (16)
C3—C2—C1	121.5 (2)	N2—C10—C9	118.18 (17)
C3—C2—H2	119.3	N2—C10—C11	124.72 (18)
C1—C2—H2	119.3	C9—C10—C11	117.11 (16)
C4—C3—C2	121.3 (2)	O2—C11—O3	125.40 (19)
C4—C3—H3	119.3	O2—C11—C10	123.41 (19)
C2—C3—H3	119.3	O3—C11—C10	111.17 (16)
C3—C4—C5	117.6 (3)	O4—C12—H12A	109.5
C3—C4—H4	121.2	O4—C12—H12B	109.5
C5—C4—H4	121.2	H12A—C12—H12B	109.5
C6—C5—C4	122.2 (2)	O4—C12—H12C	109.5
C6—C5—S1	109.43 (15)	H12A—C12—H12C	109.5
C4—C5—S1	128.4 (2)	H12B—C12—H12C	109.5
C1—C6—N1	124.8 (2)	O3—C13—H13A	109.5
C1—C6—C5	119.4 (2)	O3—C13—H13B	109.5
N1—C6—C5	115.76 (18)	H13A—C13—H13B	109.5
N1—C7—S2	124.48 (15)	O3—C13—H13C	109.5
N1—C7—S1	117.24 (15)	H13A—C13—H13C	109.5
S2—C7—S1	118.25 (11)	H13B—C13—H13C	109.5
C9—C8—S2	113.07 (14)	C7—N1—C6	109.26 (17)
C9—C8—H8A	109.0	C10—N2—O4	111.87 (15)
S2—C8—H8A	109.0	C11—O3—C13	115.94 (19)
C9—C8—H8B	109.0	N2—O4—C12	109.46 (16)
S2—C8—H8B	109.0	C5—S1—C7	88.31 (10)
H8A—C8—H8B	107.8	C7—S2—C8	98.95 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.55	3.398 (3)	152

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂O₄S₂
M_r	324.39
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.019 (3), 10.037 (4), 10.662 (5)
α, β, γ (°)	76.44 (2), 67.997 (14), 74.964 (15)
V (Å³)	759.3 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.22 × 0.19 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.913, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	7739, 2620, 2278
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.101, 1.10
No. of reflections	2620
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.27

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.55	3.398 (3)	151.8

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The authors acknowledge the National Key Technologies R&D Program of China (2006BAE01A01–13) for supporting this work.

References

Bradshaw, T. D., Stone, E. L., Trapani, V., leong, C. O., Matthews, C. S., Poele, R. T. & Stevens, M. G. (2008). Breast Cancer Res. Treat. 110, 57–68. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Moharram, H. H. (1990). Arch. Pharm. Res. 13, 14–18. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spillane, C. B., Fletcher, N. C., Rountree, S. M., Berg, H. V., Chanduloy, S., Morgan, J. L. & Keene, F. R. (2007). J. Biol. Inorg. Chem. 12, 797–807. Web of Science CrossRef PubMed CAS Google Scholar

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(Z)-Methyl 4-(1,3-benzo­thia­zol-2-yl­sulfan­yl)-2-(meth­oxy­imino)-3-oxo­butanoate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(Z)-Methyl 4-(1,3-benzothiazol-2-ylsulfanyl)-2-(methoxyimino)-3-oxobutanoate