(E)-Ethyl 2-cyano-2-(thia­zolidin-2-yl­idene)acetate

Wang, J.-G.; Jian, F.-F.

doi:10.1107/S1600536808032984

organic compounds

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doi:10.1107/S1600536808032984

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(E)-Ethyl 2-cyano-2-(thiazolidin-2-ylidene)acetate

Jian-Gang Wang ^a and Fang-Fang Jian ^b ^*

^aMicroscale Science Institute, Biology Department, Weifang University, Weifang 261061, People's Republic of China, and ^bMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 8 October 2008; accepted 12 October 2008; online 18 October 2008)

The title compound, C₈H₁₀N₂O₂S, was prepared by the reaction of 2-cyano-3,3-bis(methylsulfanyl)acrylate and 2-aminoethanethiol at 350 K. The molecular structure and packing are stabilized by N—H⋯O hydrogen-bond interactions. All the non-H atoms are nearly in the same plane with the maximum deviation being 0.08 Å.

Related literature

For biological properties of compounds containing thiazolidine groups, see: Huang & Shi (1990 ); Iwata et al. (1988 ). For related compounds, see: Schroth et al. (1997 ).

Experimental

Crystal data

C₈H₁₀N₂O₂S
M_r = 198.24
Monoclinic, P 2₁ /c
a = 4.0676 (8) Å
b = 15.460 (3) Å
c = 14.581 (3) Å
β = 90.03 (3)°
V = 916.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 (2) K
0.20 × 0.12 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
6717 measured reflections
1577 independent reflections
1484 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.112
S = 1.24
1577 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.33	2.955 (3)	129
N1—H1A⋯O1	0.86	2.12	2.723 (3)	127
Symmetry code: (i) -x, -y+2, -z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032984/at2647sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032984/at2647Isup2.hkl

checkCIF report

Comment top

Thiazolidine is an important kind of group in organic chemistry. Many compounds containing thiazolidine groups possess a broad spectrum of biological activities (Iwata et al., 1988; Huang & Shi, 1990). Here, we report the crystal structure of the title compound (I).

In the crystal structure of (I) (Fig. 1), the torsion angle formed by the N1, C3, S1 and C1 is 4.5 (3)°. All the non-H atoms are nearly the same plane with the maximum deviation of atoms being 0.08 Å. The C—S bond lengths of 1.745 (3) and 1.806 (3) Å are in agreement with those observed before (Schroth et al., 1997). In the crystal structure, there are N—H···O hydrogen-bond interactions to stabilize the crystal structure (Table 12).

Related literature top

For biological properties of compounds containing thiazolidine groups, see: Huang & Shi (1990); Iwata et al. (1988). For related compounds, see: Schroth et al. (1997). [Please check amended text]

Experimental top

A mixture of ethyl 2-cyano-3,3-bis(methylthio)acrylate 4 mmol (0.87 g) and 2-amino-ethanethiol (0.32 g, 4.1 mmol) is refluxed in absolute EtOH (25 ml) for 4 h. On cooling, the product crystallized and is filtered, and recrystallized from absolute EtOH [yield 0.67 g (85%)]. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.

(E)-Ethyl 2-cyano-2-(thiazolidin-2-ylidene)acetate top

Crystal data top

C₈H₁₀N₂O₂S	F(000) = 416
M_r = 198.24	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2422 reflections
a = 4.0676 (8) Å	θ = 2.3–25.1°
b = 15.460 (3) Å	µ = 0.32 mm⁻¹
c = 14.581 (3) Å	T = 293 K
β = 90.03 (3)°	Needle, colourless
V = 916.9 (3) Å³	0.20 × 0.12 × 0.09 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1484 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 25.0°, θ_min = 3.1°
ϕ and ω scans	h = −4→4
6717 measured reflections	k = −18→18
1577 independent reflections	l = −17→17

Refinement top

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)] = 0.051	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + 2.059P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
1577 reflections	Δρ_max = 0.26 e Å⁻³
119 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.041 (3)

Crystal data top

C₈H₁₀N₂O₂S	V = 916.9 (3) Å³
M_r = 198.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.0676 (8) Å	µ = 0.32 mm⁻¹
b = 15.460 (3) Å	T = 293 K
c = 14.581 (3) Å	0.20 × 0.12 × 0.09 mm
β = 90.03 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1484 reflections with I > 2σ(I)
6717 measured reflections	R_int = 0.025
1577 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.24	Δρ_max = 0.26 e Å⁻³
1577 reflections	Δρ_min = −0.33 e Å⁻³
119 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
S1	0.2265 (2)	0.70109 (5)	0.01523 (5)	0.0285 (3)
O2	−0.2856 (6)	0.91026 (13)	0.24156 (14)	0.0250 (5)
O1	−0.1022 (6)	0.97114 (14)	0.11080 (15)	0.0325 (6)
N2	−0.1952 (7)	0.68892 (17)	0.23236 (18)	0.0304 (7)
N1	0.1928 (7)	0.86360 (17)	−0.01208 (17)	0.0279 (7)
H1A	0.1440	0.9171	−0.0037	0.034*
C3	0.1091 (7)	0.80489 (19)	0.0489 (2)	0.0209 (6)
C6	−0.1433 (8)	0.9071 (2)	0.1582 (2)	0.0226 (7)
C7	−0.3933 (9)	0.9959 (2)	0.2710 (2)	0.0270 (7)
H7A	−0.5582	1.0182	0.2291	0.032*
H7B	−0.2088	1.0356	0.2717	0.032*
C1	0.3729 (10)	0.7390 (2)	−0.0946 (2)	0.0337 (8)
H1B	0.5946	0.7182	−0.1053	0.040*
H1C	0.2324	0.7174	−0.1433	0.040*
C4	−0.0547 (8)	0.82003 (19)	0.13177 (19)	0.0213 (7)
C5	−0.1330 (7)	0.7482 (2)	0.18828 (19)	0.0220 (7)
C2	0.3686 (8)	0.8366 (2)	−0.0937 (2)	0.0263 (7)
H2A	0.5914	0.8590	−0.0926	0.032*
H2B	0.2593	0.8584	−0.1481	0.032*
C8	−0.5358 (9)	0.9868 (2)	0.3661 (2)	0.0330 (8)
H8A	−0.6097	1.0423	0.3873	0.049*
H8B	−0.3703	0.9650	0.4069	0.049*
H8C	−0.7180	0.9474	0.3645	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0436 (5)	0.0177 (4)	0.0241 (4)	0.0040 (4)	0.0121 (3)	0.0002 (3)
O2	0.0389 (13)	0.0167 (10)	0.0192 (10)	0.0020 (9)	0.0100 (9)	−0.0013 (8)
O1	0.0527 (15)	0.0197 (11)	0.0251 (12)	0.0021 (11)	0.0141 (11)	0.0033 (9)
N2	0.0444 (17)	0.0255 (14)	0.0215 (14)	0.0008 (13)	0.0075 (12)	0.0017 (12)
N1	0.0421 (17)	0.0182 (13)	0.0234 (14)	0.0058 (12)	0.0128 (12)	0.0028 (10)
C3	0.0237 (15)	0.0194 (14)	0.0197 (15)	0.0003 (13)	−0.0012 (12)	0.0001 (12)
C6	0.0272 (17)	0.0223 (16)	0.0183 (14)	−0.0010 (13)	0.0039 (12)	−0.0021 (12)
C7	0.0385 (19)	0.0182 (15)	0.0244 (16)	0.0012 (14)	0.0057 (14)	−0.0035 (12)
C1	0.051 (2)	0.0258 (17)	0.0245 (17)	0.0088 (16)	0.0135 (15)	0.0034 (13)
C4	0.0274 (16)	0.0180 (15)	0.0183 (14)	−0.0005 (13)	0.0030 (12)	0.0010 (11)
C5	0.0254 (16)	0.0240 (16)	0.0166 (14)	0.0029 (13)	0.0033 (12)	−0.0030 (12)
C2	0.0312 (17)	0.0266 (17)	0.0212 (15)	0.0000 (14)	0.0076 (13)	0.0001 (13)
C8	0.045 (2)	0.0264 (17)	0.0275 (17)	0.0059 (16)	0.0109 (15)	−0.0042 (13)

Geometric parameters (Å, º) top

S1—C3	1.745 (3)	C7—C8	1.510 (4)
S1—C1	1.806 (3)	C7—H7A	0.9700
O2—C6	1.348 (3)	C7—H7B	0.9700
O2—C7	1.459 (4)	C1—C2	1.510 (4)
O1—C6	1.218 (4)	C1—H1B	0.9700
N2—C5	1.147 (4)	C1—H1C	0.9700
N1—C3	1.315 (4)	C4—C5	1.420 (4)
N1—C2	1.450 (4)	C2—H2A	0.9700
N1—H1A	0.8600	C2—H2B	0.9700
C3—C4	1.400 (4)	C8—H8A	0.9600
C6—O1	1.218 (4)	C8—H8B	0.9600
C6—C4	1.446 (4)	C8—H8C	0.9600

C3—S1—C1	92.39 (14)	S1—C1—H1B	110.1
C6—O2—C7	115.3 (2)	C2—C1—H1C	110.1
C3—N1—C2	119.0 (3)	S1—C1—H1C	110.1
C3—N1—H1A	120.5	H1B—C1—H1C	108.4
C2—N1—H1A	120.5	C3—C4—C5	118.5 (3)
N1—C3—C4	126.3 (3)	C3—C4—C6	120.3 (3)
N1—C3—S1	111.9 (2)	C5—C4—C6	121.2 (3)
C4—C3—S1	121.8 (2)	N2—C5—C4	178.5 (3)
O1—C6—O2	122.8 (3)	N1—C2—C1	107.5 (2)
O1—C6—O2	122.8 (3)	N1—C2—H2A	110.2
O1—C6—C4	124.8 (3)	C1—C2—H2A	110.2
O1—C6—C4	124.8 (3)	N1—C2—H2B	110.2
O2—C6—C4	112.4 (3)	C1—C2—H2B	110.2
O2—C7—C8	107.5 (2)	H2A—C2—H2B	108.5
O2—C7—H7A	110.2	C7—C8—H8A	109.5
C8—C7—H7A	110.2	C7—C8—H8B	109.5
O2—C7—H7B	110.2	H8A—C8—H8B	109.5
C8—C7—H7B	110.2	C7—C8—H8C	109.5
H7A—C7—H7B	108.5	H8A—C8—H8C	109.5
C2—C1—S1	108.2 (2)	H8B—C8—H8C	109.5
C2—C1—H1B	110.1

C2—N1—C3—C4	178.7 (3)	S1—C3—C4—C5	−1.6 (4)
C2—N1—C3—S1	−1.4 (4)	N1—C3—C4—C6	−1.1 (5)
C1—S1—C3—N1	−4.5 (3)	S1—C3—C4—C6	178.9 (2)
C1—S1—C3—C4	175.4 (3)	O1—C6—C4—C3	4.2 (5)
O1—O1—C6—O2	0.0 (3)	O1—C6—C4—C3	4.2 (5)
O1—O1—C6—C4	0.0 (3)	O2—C6—C4—C3	−177.2 (3)
C7—O2—C6—O1	1.0 (4)	O1—C6—C4—C5	−175.3 (3)
C7—O2—C6—O1	1.0 (4)	O1—C6—C4—C5	−175.3 (3)
C7—O2—C6—C4	−177.6 (3)	O2—C6—C4—C5	3.3 (4)
C6—O2—C7—C8	−178.4 (3)	C3—N1—C2—C1	8.0 (4)
C3—S1—C1—C2	8.7 (3)	S1—C1—C2—N1	−10.3 (4)
N1—C3—C4—C5	178.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.33	2.955 (3)	129
N1—H1A···O1	0.86	2.12	2.723 (3)	127

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂O₂S
M_r	198.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.0676 (8), 15.460 (3), 14.581 (3)
β (°)	90.03 (3)
V (Å³)	916.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.20 × 0.12 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6717, 1577, 1484
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.112, 1.24
No. of reflections	1577
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.33

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.33	2.955 (3)	129.3
N1—H1A···O1	0.86	2.12	2.723 (3)	126.9

Symmetry code: (i) −x, −y+2, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Huang, Z. T. & Shi, X. (1990). Synthesis, pp. 162–167. CrossRef Google Scholar
Iwata, C., Watanabe, M., Okamoto, S., Fujimoto, M., Sakae, M., Katstrada, M. & Imanishi, T. (1988). Synthesis, pp. 261–262. Google Scholar
Schroth, W., Hintzsche, E., Jordan, H., Jende, T., Spitzner, R. & Thondorf, I. (1997). Tetrahedron, 53, 7509–7528. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2145

doi:10.1107/S1600536808032984

Open

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