Methyl (Z)-2-[(2,4-dioxothia­zolidin-3-yl)meth­yl]-3-(2-methyl­phen­yl)prop-2-enoate

S Vijayakumar; S Murugavel; D Kannan; M Bakthadoss

doi:10.1107/S1600536811053682

. 2011 Dec 17;68(Pt 1):o156–o157. doi: 10.1107/S1600536811053682

Methyl (Z)-2-[(2,4-dioxothiazolidin-3-yl)methyl]-3-(2-methylphenyl)prop-2-enoate

S Vijayakumar ^a, S Murugavel ^b,^*, D Kannan ^c, M Bakthadoss ^c,^‡

PMCID: PMC3254499 PMID: 22259442

Abstract

The C=C bond in the title compound, C₁₅H₁₅NO₄S, has a Z configuration. The thiazolidine ring is essentially planar [maximum deviation = 0.008 (1) Å for the N atom] and is oriented at a dihedral angle of 59.1 (1)° with respect to the benzene ring. In the crystal, pairs of C—H⋯O hydrogen bonds link centrosymmetrically related molecules into dimers, generating R ₂ ²(18) ring motifs. The crystal packing is further stabilized by C—H⋯π and C—O⋯π [O⋯centroid = 3.412 (2) Å and C—O⋯centroid = 115.0 (1)°] interactions.

Related literature

For the biolgical activity of thiazolidine derivatives, see: Chen et al. (2000 ▶); Jacop & Kutty (2004 ▶); Kalia et al. (2007 ▶); Vicentini et al. (1998 ▶); Vigorita et al. (1992 ▶). For resonance effects of acrylate, see: Merlino (1971 ▶); Varghese et al. (1986 ▶). For closely related structures, see: Fun et al. (2009 ▶); Vennila et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₅H₁₅NO₄S
M _r = 305.34
Monoclinic,
a = 21.3744 (10) Å
b = 6.9762 (3) Å
c = 20.3084 (10) Å
β = 103.361 (2)°
V = 2946.3 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.941, T _max = 0.959
18757 measured reflections
4354 independent reflections
2966 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.135
S = 1.04
4354 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811053682/bt5747sup1.cif

e-68-0o156-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053682/bt5747Isup2.hkl

e-68-0o156-Isup2.hkl^{(209.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811053682/bt5747Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C7–C12 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.55	3.379 (2)	148
C9—H9⋯Cg1ⁱⁱ	0.93	2.90	3.677 (2)	142

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Thiazolidine derivatives exhibit herbicidal (Chen et al., 2000; Vicentini et al., 1998), antineoplastic (Vigorita et al., 1992), hypolipidemic (Jacop & Kutty, 2004) and anti-inflammatory (Kalia et al., 2007) activities. In view of this importance, the crystal structure of the title compound has been carried out and the results are presented here.

Fig. 1. shows a displacement ellipsoid plot of (I), with the atom numbering scheme. The molecules of the title compound display a Z– configuration about the C6═C5 double bond. The thiazolidine moiety (S1/N1/C1-C3) is essentially planar [maximum deviation = -0.008 (1) Å for the N1 atom] and lies at an angle 59.1 (1)° with respect to the benzene ring. The significant difference in length of the C13—O4 = 1.334 (2) Å and C14—O4 = 1.446 (2) Å bonds is attributed to a partial contribution from the O^-–C = O⁺–C resonance structure of the O3═C13—O4—C14 group (Merlino, 1971). This feature, commonly observed in the carboxylic ester group of the substituents in various compounds gives average values of 1.340 Å and 1.447 Å respectively for these bonds (Varghese et al., 1986). The sum of bond angles around N1 (360°) indicates that N1 is in sp² hybridization. The geometric parameters of the title molecule agrees well with those reported for similar structures (Fun et al., 2009, Vennila et al., 2011).

In the crystal packing (Fig. 2), the molecules at x, y, z and 1-x, y, 1/2-z are linked by C8—H8···O2 hydrogen bonds into cyclic centrosymmetric R₂²(18) dimers (Bernstein et al., 1995). The crystal packing is further stabilized by C—H···π and C—O···π interactions, the first one between a H9 atom and neighbouring benene ring (C7–C12), with a C9—H9···Cg1ⁱⁱ seperation of 2.90 Å (Fig. 3 and Table 1; Cg1 is the centroid of the C7–C12 benzene ring, Symmetry code as in Fig.3), and the second one between oxygen atom O1 and neighbouring thiazolidine ring (N1/S1/C1–C3), with a Ol···centroid(Cg2ⁱⁱⁱ) distance of 3.412 (2) Å and a C1—O1···Cg2ⁱⁱⁱ angle of 115.0 (1)° (Fig. 3; Cg2 is the centroid of the N1/S1/C1—C3 thiazolidine ring, Symmetry code as in Fig. 3).

Experimental

A solution of thiazolidine-2,4-dione (1 mmol, 0.117 g) and potassium carbonate (1.5 mmol, 0.207 g) in acetonitrile solvent was stirred for 15 minutes at room temperature. To this solution, (Z)-methyl-2 -(bromomethyl)-3-(2-methylphenyl)-prop-2-enoate (1 mmol, 0.269 g) was added dropwise till the addition is complete. After the completion of the reaction, as indicated by TLC, acetonitrile was evaporated. Ethyl acetate (15 ml) and water (15 ml) were added to the crude mass. The organic layer was dried over anhydrous sodium sulfate. Removal of solvent led to the crude product, which was purified through pad of silica gel (100–200 mesh) using ethylacetate and hexanes (1:9) as solvents. The pure title compound was obtained as a colourless solid (0.290 g, 95% yield). Recrystallization was carried out using ethylacetate as solvent.