Ethyl 2-[(Z)-2-cyano­imino-1,3-thiazolidin-3-yl]acetate

Xie, B.

doi:10.1107/S1600536808015663

organic compounds

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Volume 64| Part 7| July 2008| Page o1237

doi:10.1107/S1600536808015663

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Ethyl 2-[(Z)-2-cyanoimino-1,3-thiazolidin-3-yl]acetate

Bing Xie ^a ^*

^aHenan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: bingxie_2008@yahoo.cn

(Received 23 May 2008; accepted 24 May 2008; online 7 June 2008)

In the title molecule, C₈H₁₁N₃O₂S, the puckering amplitude of the thiazolidine ring is q₂ = 0.3011 (5) Å and the conformation is an envelope. There are weak intermolecular C—H⋯O interactions which stabilize the crystal structure.

Related literature

For the crystal structures of related compounds, see: Dai et al. (2007 ). For details of the biological activities of thiazolidine-containing compounds, see: Iwata et al. (1988 ). For bond-length data, see: Allen et al. (1987 ). For puckering amplitude definitions, see: Cremer & Pople (1975 ). For conformation definitions, see: Duax et al. (1976 ).

Experimental

Crystal data

C₈H₁₁N₃O₂S
M_r = 213.26
Monoclinic, C 2/c
a = 30.862 (6) Å
b = 4.9376 (10) Å
c = 14.067 (3) Å
β = 105.09 (3)°
V = 2069.7 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 (2) K
0.34 × 0.21 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.907, T_max = 0.958
7488 measured reflections
1826 independent reflections
1491 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.117
S = 1.10
1826 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2C⋯O2ⁱ	0.97	2.56	3.284 (3)	132
C4—H4B⋯O2ⁱⁱ	0.97	2.50	3.431 (3)	162
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) x, y+1, z.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015663/hg2405sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015663/hg2405Isup2.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). Here, we report the crystal structure of (I).

In (I) (Fig. 1), all bond lengths are normal (Allen et al., 1987) and in a good agreement with those reported previously (Dai et al., 2007). The plane I (C7/C8/N1–N3/S1) makes the dihedral angles of 86.11 (3)° with ethyl acetate group (C1–C4/O1/O2). The Cremer & Pople (1975) puckering amplitude of the thiazolidine ring is q2 = 0.3011 (5) Å. According to Duax et al. (1976), the conformation is an envelope with a local pseudo-mirror passing through C6 and the mid-point of the N1—C7 bond. There are some weak C—H···O intermolecular interactions (see Table 1) which stabilize the title structure.

Related literature top

For the crystal structures of related compounds, see: Dai et al. (2007). For details of the biological activities of thiazolidine-containing compounds, see: Iwata et al. (1988). For bond-length data, see: Allen et al. (1987). For puckering amplitude definitions, see: Cremer & Pople (1975). For conformation definitions, see: Duax et al. (1976).

Experimental top

A solution of (Z)-(thiazolidin-2-ylideneamino)formonitrile 1.27 g (10 mmol) and sodium hydride 0.3 g dissolved in anhydrous acetonitrile (20 ml), and dropwise added over a period of 10 min to a solution of ethyl 2-chloroacetate 1.23 (10 mmol) in acetonitrile (10 ml) at 273 K. The mixture was stirred at 353 K for 3 h. The solvent was removed and the residue was purified by recrystall from ethanol to give I as a white solid (1.92 g, 90%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 (I), with atom labels and 40% probability displacement ellipsoids for non-H atoms.

Ethyl 2-[(Z)-2-cyanoimino-1,3-thiazolidin-3-yl]acetate top

Crystal data top

C₈H₁₁N₃O₂S	F(000) = 896
M_r = 213.26	D_x = 1.369 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1021 reflections
a = 30.862 (6) Å	θ = 2.9–26.4°
b = 4.9376 (10) Å	µ = 0.29 mm⁻¹
c = 14.067 (3) Å	T = 293 K
β = 105.09 (3)°	Block, colourless
V = 2069.7 (7) Å³	0.34 × 0.21 × 0.15 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1826 independent reflections
Radiation source: rotating anode	1491 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω oscillation scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −36→36
T_min = 0.907, T_max = 0.958	k = −5→5
7488 measured reflections	l = −16→15

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0531P)² + 1.3476P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1826 reflections	Δρ_max = 0.25 e Å⁻³
128 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 20018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (9)

Crystal data top

C₈H₁₁N₃O₂S	V = 2069.7 (7) Å³
M_r = 213.26	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 30.862 (6) Å	µ = 0.29 mm⁻¹
b = 4.9376 (10) Å	T = 293 K
c = 14.067 (3) Å	0.34 × 0.21 × 0.15 mm
β = 105.09 (3)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1826 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1491 reflections with I > 2σ(I)
T_min = 0.907, T_max = 0.958	R_int = 0.045
7488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.10	Δρ_max = 0.25 e Å⁻³
1826 reflections	Δρ_min = −0.31 e Å⁻³
128 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	0.462350 (18)	0.24900 (11)	0.03972 (4)	0.0520 (2)
O1	0.27777 (5)	0.6328 (3)	−0.12161 (13)	0.0627 (5)
O2	0.31720 (5)	0.3188 (3)	−0.02097 (14)	0.0670 (5)
N1	0.39666 (6)	0.5821 (3)	−0.01316 (12)	0.0453 (4)
N2	0.40242 (6)	0.2991 (4)	−0.13944 (13)	0.0514 (5)
N3	0.44256 (9)	−0.0586 (5)	−0.20421 (18)	0.0847 (7)
C1	0.19858 (10)	0.6384 (8)	−0.1823 (3)	0.0959 (10)
H1A	0.1712	0.5457	−0.1828	0.144*
H1B	0.2017	0.6507	−0.2483	0.144*
H1C	0.1979	0.8173	−0.1559	0.144*
C2	0.23648 (8)	0.4890 (6)	−0.1212 (2)	0.0781 (8)
H2B	0.2373	0.3074	−0.1471	0.094*
H2C	0.2335	0.4751	−0.0545	0.094*
C3	0.31533 (7)	0.5240 (4)	−0.06723 (16)	0.0498 (5)
C4	0.35509 (7)	0.6959 (4)	−0.07168 (18)	0.0525 (6)
H4A	0.3565	0.7112	−0.1396	0.063*
H4B	0.3513	0.8765	−0.0479	0.063*
C5	0.40994 (8)	0.6115 (5)	0.09383 (16)	0.0553 (6)
H5A	0.3904	0.5060	0.1235	0.066*
H5B	0.4084	0.7998	0.1122	0.066*
C6	0.45751 (8)	0.5090 (5)	0.12722 (15)	0.0557 (6)
H6A	0.4634	0.4343	0.1931	0.067*
H6B	0.4786	0.6545	0.1273	0.067*
C7	0.41698 (6)	0.3814 (4)	−0.04819 (14)	0.0413 (5)
C8	0.42527 (8)	0.1075 (5)	−0.17063 (16)	0.0572 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0464 (4)	0.0506 (4)	0.0556 (4)	0.0037 (2)	0.0072 (3)	0.0093 (2)
O1	0.0403 (9)	0.0630 (10)	0.0806 (11)	−0.0003 (7)	0.0080 (8)	0.0119 (9)
O2	0.0538 (10)	0.0559 (10)	0.0910 (13)	−0.0012 (8)	0.0182 (9)	0.0175 (9)
N1	0.0406 (10)	0.0458 (9)	0.0491 (9)	0.0004 (7)	0.0109 (7)	−0.0011 (8)
N2	0.0505 (11)	0.0558 (11)	0.0465 (10)	−0.0031 (8)	0.0101 (8)	−0.0021 (8)
N3	0.109 (2)	0.0805 (16)	0.0738 (14)	0.0062 (15)	0.0411 (14)	−0.0142 (13)
C1	0.0479 (16)	0.121 (3)	0.110 (2)	0.0012 (17)	0.0040 (16)	0.013 (2)
C2	0.0450 (14)	0.0844 (18)	0.103 (2)	−0.0084 (13)	0.0157 (14)	0.0109 (16)
C3	0.0440 (12)	0.0441 (12)	0.0618 (13)	0.0041 (9)	0.0147 (10)	−0.0015 (10)
C4	0.0422 (12)	0.0447 (11)	0.0694 (14)	0.0037 (9)	0.0121 (10)	0.0062 (10)
C5	0.0601 (14)	0.0567 (13)	0.0515 (12)	−0.0083 (11)	0.0186 (10)	−0.0062 (10)
C6	0.0595 (14)	0.0600 (13)	0.0433 (11)	−0.0119 (11)	0.0058 (10)	0.0036 (10)
C7	0.0379 (11)	0.0413 (11)	0.0460 (11)	−0.0057 (8)	0.0128 (8)	0.0061 (8)
C8	0.0664 (16)	0.0598 (14)	0.0473 (12)	−0.0082 (12)	0.0183 (11)	−0.0048 (11)

Geometric parameters (Å, º) top

S1—C7	1.736 (2)	C1—H1B	0.9600
S1—C6	1.811 (2)	C1—H1C	0.9600
O1—C3	1.325 (3)	C2—H2B	0.9700
O1—C2	1.460 (3)	C2—H2C	0.9700
O2—C3	1.198 (3)	C3—C4	1.507 (3)
N1—C7	1.334 (3)	C4—H4A	0.9700
N1—C4	1.446 (3)	C4—H4B	0.9700
N1—C5	1.460 (3)	C5—C6	1.508 (3)
N2—C7	1.309 (3)	C5—H5A	0.9700
N2—C8	1.322 (3)	C5—H5B	0.9700
N3—C8	1.145 (3)	C6—H6A	0.9700
C1—C2	1.459 (4)	C6—H6B	0.9700
C1—H1A	0.9600

C7—S1—C6	91.34 (10)	N1—C4—H4A	109.3
C3—O1—C2	115.73 (19)	C3—C4—H4A	109.3
C7—N1—C4	120.76 (17)	N1—C4—H4B	109.3
C7—N1—C5	114.95 (17)	C3—C4—H4B	109.3
C4—N1—C5	121.17 (18)	H4A—C4—H4B	108.0
C7—N2—C8	118.10 (19)	N1—C5—C6	106.08 (18)
C2—C1—H1A	109.5	N1—C5—H5A	110.5
C2—C1—H1B	109.5	C6—C5—H5A	110.5
H1A—C1—H1B	109.5	N1—C5—H5B	110.5
C2—C1—H1C	109.5	C6—C5—H5B	110.5
H1A—C1—H1C	109.5	H5A—C5—H5B	108.7
H1B—C1—H1C	109.5	C5—C6—S1	105.78 (15)
C1—C2—O1	108.6 (2)	C5—C6—H6A	110.6
C1—C2—H2B	110.0	S1—C6—H6A	110.6
O1—C2—H2B	110.0	C5—C6—H6B	110.6
C1—C2—H2C	110.0	S1—C6—H6B	110.6
O1—C2—H2C	110.0	H6A—C6—H6B	108.7
H2B—C2—H2C	108.4	N2—C7—N1	121.22 (19)
O2—C3—O1	124.6 (2)	N2—C7—S1	126.07 (17)
O2—C3—C4	125.1 (2)	N1—C7—S1	112.71 (14)
O1—C3—C4	110.33 (18)	N3—C8—N2	174.8 (3)
N1—C4—C3	111.65 (18)

C3—O1—C2—C1	178.6 (2)	C7—S1—C6—C5	21.72 (16)
C2—O1—C3—O2	1.4 (3)	C8—N2—C7—N1	177.09 (19)
C2—O1—C3—C4	−178.3 (2)	C8—N2—C7—S1	−3.9 (3)
C7—N1—C4—C3	81.0 (2)	C4—N1—C7—N2	6.6 (3)
C5—N1—C4—C3	−78.0 (2)	C5—N1—C7—N2	166.86 (19)
O2—C3—C4—N1	0.4 (3)	C4—N1—C7—S1	−172.54 (15)
O1—C3—C4—N1	−179.87 (18)	C5—N1—C7—S1	−12.3 (2)
C7—N1—C5—C6	28.7 (2)	C6—S1—C7—N2	174.48 (19)
C4—N1—C5—C6	−171.18 (17)	C6—S1—C7—N1	−6.41 (16)
N1—C5—C6—S1	−30.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2C···O2ⁱ	0.97	2.56	3.284 (3)	132
C4—H4B···O2ⁱⁱ	0.97	2.50	3.431 (3)	162

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

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₃O₂S
M_r	213.26
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	30.862 (6), 4.9376 (10), 14.067 (3)
β (°)	105.09 (3)
V (Å³)	2069.7 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.34 × 0.21 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.907, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	7488, 1826, 1491
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.117, 1.10
No. of reflections	1826
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.31

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2C···O2ⁱ	0.97	2.56	3.284 (3)	131.7
C4—H4B···O2ⁱⁱ	0.97	2.50	3.431 (3)	161.9

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

References

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. CrossRef Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Dai, H., Zhang, X., Qin, X., Qin, Z.-F. & Fang, J.-X. (2007). Acta Cryst. E63, o4283. Web of Science CSD CrossRef IUCr Journals Google Scholar
Duax, W. L., Weeks, C. M. & Rohrer, D. C. (1976). Topics in Stereochemistry, Vol. 9, edited by E. L. Eliel & N. Allinger, pp. 271–383. New York: John Wiley. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Iwata, C., Watanabe, M., Okamoto, S., Fujimoto, M., Sakae, M., Katsurada, M. & Imanishi, T. (1988). Synthesis, 3, 261–262. Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. 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
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1237

doi:10.1107/S1600536808015663

Open

access