Ethyl 2-[(5Z)-5-(4-methyl­benzyl­idene)-2,4-dioxo-1,3-thia­zolidin-3-yl]acetate

Khalid, K.; Tachallait, H.; Khalid, B.; Mague, J.T.; Ramli, Y.

doi:10.1107/S2414314616008518

organic compounds

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ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160851

doi:10.1107/S2414314616008518

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Ethyl 2-[(5Z)-5-(4-methylbenzylidene)-2,4-dioxo-1,3-thiazolidin-3-yl]acetate

Karrouchi Khalid,^a Hamza Tachallait,^b Bougrin Khalid,^b Joel T. Mague ^c and Youssef Ramli ^d ^*

^aLaboratoire National de Controle des Médicaments, D M P, Ministère de la Santé, Madinat Al Irfane, BP, Rabat, Morocco, ^bLaboratoire de Chimie des Plantes et de Synthèse Organique et Bioorganique, Faculty of Sciences, Mohammed V University, Rabat, Morocco, ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and ^dLaboratory of Medicinal Chemistry, Faculty of Medicine and Pharmacy, Mohammed V University, Rabat, Morocco
^*Correspondence e-mail: yramli76@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 25 May 2016; accepted 25 May 2016; online 17 June 2016)

In the title molecule, C₁₅H₁₅NO₄S, the dihedral angle between the almost planar heterocyclic ring (r.m.s. deviation = 0.027 Å) and the benzene ring is 5.33 (8)°. The chain of the ester group adopts an extended conformation [C—O—C—C = −174.80 (14)°]. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R₂²(10) loops and further such bonds connect the dimers into `stair-step' chains propagating in [100].

Keywords: crystal structure; thiazolidinone; C—H ⋯O hydrogen bonds.

CCDC reference: 1481951

Structure description

The 2,4-thiazolidinone ring system is a core structure in various synthetic pharmaceutical agents, displaying a broad spectrum of biological activities such as antidiabetic (Sohda et al., 1992 ), anticancer (Kaminskyy et al., 2016 ) and anti-tubercular (Narute et al., 2008 ) activities. In this study, we report the N-alkylation of 5-(4-methylbenzylidene)thiazolidine-2,4-dione, with ethyl bromoacetate, which gave the title compound (Fig. 1) whose crystal structure is reported here.

Figure 1
The title molecule with 50% probability ellipsoids.

The molecule exists in an `extended' conformation with a dihedral angle of 5.3 (1)° between the benzene and heterocyclic rings. In the crystal, pairwise C8—H8⋯O1ⁱ [symmetry code: (i) −x, −y + 1, −z + 1] hydrogen bonds form dimers (Table 1 and Fig. 2), which are further associated by pairwise C12—H12A⋯O3ⁱⁱ [symmetry code: (ii) x + 1, y, z] into `stair-step' chains propagating in [100] (Table 1 and Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1ⁱ	0.95	2.46	3.3612 (18)	159
C12—H12A⋯O3ⁱⁱ	0.99	2.31	3.2757 (19)	166
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z.

Figure 2
A portion of the packing projected onto (100) showing two dimers connected by C—H⋯O hydrogen bonds (dotted lines).

Figure 3
Packing projected onto (1 11 $[\overline{4}]$ ) showing a portion of the stepped stack of dimers with C—H⋯O hydrogen bonds shown as dotted lines.

Synthesis and crystallization

To a solution of 5-(4-methylbenzylidene)thiazolidine-2,4-dione (1 mmol) in acetone (30 ml), an excess of triethylamine (1.5 mmol) was added and stirred for 10 min at RT. The alkylating agent, ethyl bromoacetate (1.5 mmol), was added slowly. The reaction mixture was then refluxed for 10 h. The progress of reaction was monitored by TLC. The reaction mixture was allowed to attain RT, filtered and concentrated on a rotary evaporator. The residue was dissolved in ethanol. The formed crystals were filtered off, washed with ethanol and recrystallized from ethanol solution. Yield 77%; m.p. 127–129°C.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Trial refinements using the single-component reflection extracted with TWINABS and the full, two-component data showed the former refinement to be superior. The crystal did not diffract well at high angles, possibly as the result of the twinning. For this reason, the completeness of the data is somewhat less than optimal but, nevertheless, all features of chemical interest are quite satisfactorily determined.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₄S
M_r	305.34
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	4.7310 (1), 11.9082 (3), 13.2907 (4)
α, β, γ (°)	87.354 (1), 82.381 (1), 85.283 (1)
V (Å³)	739.17 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.09
Crystal size (mm)	0.19 × 0.08 × 0.08

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (TWINABS; Sheldrick, 2009 )
T_min, T_max	0.54, 0.85
No. of measured, independent and observed [I > 2σ(I)] reflections	11328, 2825, 2648
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.096, 1.07
No. of reflections	2825
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.27
Computer programs: APEX3 and SAINT (Bruker, 2016 ), CELL_NOW (Sheldrick, 2009), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1481951

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616008518/hb4050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616008518/hb4050Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616008518/hb4050Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016) and CELL_NOW (Sheldrick, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Ethyl 2-[(5Z)-5-(4-methylbenzylidene)-2,4-dioxo-1,3-thiazolidin-3-yl]acetate top

Crystal data top

C₁₅H₁₅NO₄S	Z = 2
M_r = 305.34	F(000) = 320
Triclinic, P1	D_x = 1.372 Mg m⁻³
a = 4.7310 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.9082 (3) Å	Cell parameters from 5760 reflections
c = 13.2907 (4) Å	θ = 3.4–74.5°
α = 87.354 (1)°	µ = 2.09 mm⁻¹
β = 82.381 (1)°	T = 150 K
γ = 85.283 (1)°	Column, colourless
V = 739.17 (3) Å³	0.19 × 0.08 × 0.08 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2825 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2648 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.5°, θ_min = 3.7°
ω scans	h = −5→5
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −14→14
T_min = 0.54, T_max = 0.85	l = −15→12
11328 measured reflections

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)] = 0.037	Hydrogen site location: mixed
wR(F²) = 0.096	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0496P)² + 0.290P] where P = (F_o² + 2F_c²)/3
2825 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Special details top

Experimental. Analysis of 1664 reflections having I/σ(I) > 13 and chosen from the full data set with CELL_NOW (Sheldrick, 2009) showed the crystal to belong to the triclinic system and to be twinned by a 180° rotation about the c* axis. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Trial refinements using the single- component reflection extracted with TWINABS and the full, two- component data showed the former refinement to be superior.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.46791 (8)	0.80982 (3)	0.58528 (3)	0.02562 (13)
O1	0.2523 (2)	0.50494 (9)	0.59713 (8)	0.0284 (3)
O2	0.7768 (3)	0.74899 (10)	0.73387 (9)	0.0338 (3)
O3	0.1983 (2)	0.55164 (10)	0.85155 (9)	0.0325 (3)
O4	0.4985 (2)	0.39867 (9)	0.87431 (8)	0.0300 (3)
N1	0.5379 (3)	0.61154 (10)	0.67263 (9)	0.0233 (3)
C1	0.0634 (3)	0.78637 (12)	0.39196 (11)	0.0238 (3)
C2	0.1525 (4)	0.89592 (14)	0.38704 (14)	0.0337 (4)
H2	0.2683	0.9172	0.4351	0.040*
C3	0.0744 (4)	0.97353 (14)	0.31324 (14)	0.0362 (4)
H3	0.1379	1.0473	0.3115	0.043*
C4	−0.0950 (4)	0.94608 (14)	0.24161 (13)	0.0323 (4)
C5	−0.1872 (4)	0.83785 (15)	0.24710 (14)	0.0384 (4)
H5	−0.3059	0.8174	0.1997	0.046*
C6	−0.1092 (4)	0.75930 (13)	0.32051 (13)	0.0315 (4)
H6	−0.1742	0.6858	0.3223	0.038*
C7	−0.1802 (5)	1.03219 (16)	0.16215 (15)	0.0483 (5)
H7A	−0.1061	1.0093	0.0931	0.072*	0.66 (3)
H7B	−0.3884	1.0447	0.1647	0.072*	0.66 (3)
H7C	−0.1089	1.1058	0.1703	0.072*	0.66 (3)
H7D	−0.2954	1.0010	0.1156	0.072*	0.34 (3)
H7E	−0.0138	1.0611	0.1201	0.072*	0.34 (3)
H7F	−0.2941	1.0976	0.1923	0.072*	0.34 (3)
C8	0.1368 (3)	0.69861 (12)	0.46601 (11)	0.0232 (3)
H8	0.0588	0.6288	0.4591	0.028*
C9	0.2959 (3)	0.69950 (11)	0.54241 (11)	0.0220 (3)
C10	0.3506 (3)	0.59488 (12)	0.60384 (11)	0.0218 (3)
C11	0.6206 (3)	0.71986 (13)	0.67685 (12)	0.0250 (3)
C12	0.6377 (3)	0.52013 (13)	0.73800 (11)	0.0250 (3)
H12A	0.8126	0.5405	0.7640	0.030*
H12B	0.6885	0.4517	0.6978	0.030*
C13	0.4152 (3)	0.49421 (12)	0.82666 (11)	0.0224 (3)
C14	0.3050 (4)	0.36299 (16)	0.96293 (13)	0.0365 (4)
H14A	0.1216	0.3443	0.9421	0.044*
H14B	0.2651	0.4241	1.0120	0.044*
C15	0.4510 (5)	0.26072 (17)	1.01043 (15)	0.0461 (5)
H15A	0.3232	0.2321	1.0683	0.069*
H15B	0.6272	0.2813	1.0338	0.069*
H15C	0.4976	0.2022	0.9601	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0323 (2)	0.01908 (19)	0.0270 (2)	−0.00486 (14)	−0.00876 (14)	0.00268 (13)
O1	0.0349 (6)	0.0206 (5)	0.0311 (6)	−0.0083 (4)	−0.0077 (4)	0.0044 (4)
O2	0.0405 (7)	0.0318 (6)	0.0328 (6)	−0.0108 (5)	−0.0152 (5)	0.0030 (5)
O3	0.0259 (6)	0.0396 (6)	0.0299 (6)	0.0046 (5)	−0.0013 (4)	0.0024 (5)
O4	0.0347 (6)	0.0270 (5)	0.0258 (6)	−0.0007 (4)	0.0009 (4)	0.0082 (4)
N1	0.0253 (6)	0.0213 (6)	0.0234 (7)	−0.0027 (5)	−0.0051 (5)	0.0042 (5)
C1	0.0273 (7)	0.0210 (7)	0.0225 (8)	−0.0001 (5)	−0.0030 (6)	0.0009 (5)
C2	0.0427 (9)	0.0247 (8)	0.0373 (9)	−0.0076 (7)	−0.0173 (7)	0.0056 (7)
C3	0.0452 (10)	0.0242 (8)	0.0407 (10)	−0.0062 (7)	−0.0122 (8)	0.0083 (7)
C4	0.0427 (9)	0.0272 (8)	0.0262 (8)	0.0033 (7)	−0.0064 (7)	0.0045 (6)
C5	0.0569 (11)	0.0300 (8)	0.0316 (9)	0.0003 (8)	−0.0212 (8)	0.0000 (7)
C6	0.0442 (9)	0.0217 (7)	0.0306 (9)	−0.0029 (6)	−0.0128 (7)	−0.0001 (6)
C7	0.0719 (14)	0.0365 (10)	0.0374 (11)	0.0028 (9)	−0.0195 (9)	0.0110 (8)
C8	0.0262 (7)	0.0195 (7)	0.0236 (8)	−0.0021 (5)	−0.0027 (5)	0.0008 (5)
C9	0.0245 (7)	0.0176 (6)	0.0233 (7)	−0.0024 (5)	−0.0012 (5)	0.0015 (5)
C10	0.0221 (7)	0.0220 (7)	0.0208 (7)	−0.0023 (5)	−0.0008 (5)	0.0012 (5)
C11	0.0273 (7)	0.0238 (7)	0.0242 (8)	−0.0048 (6)	−0.0030 (6)	0.0018 (5)
C12	0.0241 (7)	0.0247 (7)	0.0250 (8)	0.0007 (5)	−0.0030 (6)	0.0061 (6)
C13	0.0240 (7)	0.0243 (7)	0.0201 (7)	−0.0043 (5)	−0.0061 (5)	0.0005 (5)
C14	0.0418 (9)	0.0432 (10)	0.0238 (9)	−0.0121 (8)	0.0009 (7)	0.0092 (7)
C15	0.0704 (13)	0.0395 (10)	0.0302 (10)	−0.0148 (9)	−0.0113 (9)	0.0136 (8)

Geometric parameters (Å, º) top

S1—C9	1.7553 (15)	C5—H5	0.9500
S1—C11	1.7708 (16)	C6—H6	0.9500
O1—C10	1.2140 (18)	C7—H7A	0.9800
O2—C11	1.2066 (19)	C7—H7B	0.9801
O3—C13	1.2025 (18)	C7—H7C	0.9800
O4—C13	1.3329 (18)	C7—H7D	0.9800
O4—C14	1.4619 (19)	C7—H7E	0.9801
N1—C11	1.3840 (19)	C7—H7F	0.9800
N1—C10	1.3858 (19)	C8—C9	1.343 (2)
N1—C12	1.4490 (18)	C8—H8	0.9500
C1—C6	1.396 (2)	C9—C10	1.4816 (19)
C1—C2	1.400 (2)	C12—C13	1.511 (2)
C1—C8	1.455 (2)	C12—H12A	0.9900
C2—C3	1.382 (2)	C12—H12B	0.9900
C2—H2	0.9500	C14—C15	1.505 (3)
C3—C4	1.389 (2)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.390 (2)	C15—H15A	0.9800
C4—C7	1.508 (2)	C15—H15B	0.9800
C5—C6	1.385 (2)	C15—H15C	0.9800

C9—S1—C11	92.06 (7)	H7E—C7—H7F	106.7
C13—O4—C14	115.90 (12)	C9—C8—C1	130.99 (14)
C11—N1—C10	116.74 (12)	C9—C8—H8	114.5
C11—N1—C12	121.85 (12)	C1—C8—H8	114.5
C10—N1—C12	121.40 (12)	C8—C9—C10	119.93 (13)
C6—C1—C2	117.54 (14)	C8—C9—S1	130.02 (11)
C6—C1—C8	117.54 (13)	C10—C9—S1	110.04 (10)
C2—C1—C8	124.92 (14)	O1—C10—N1	122.54 (13)
C3—C2—C1	120.88 (15)	O1—C10—C9	126.79 (13)
C3—C2—H2	119.6	N1—C10—C9	110.67 (12)
C1—C2—H2	119.6	O2—C11—N1	125.07 (14)
C2—C3—C4	121.47 (15)	O2—C11—S1	124.62 (12)
C2—C3—H3	119.3	N1—C11—S1	110.31 (11)
C4—C3—H3	119.3	N1—C12—C13	112.17 (12)
C3—C4—C5	117.82 (15)	N1—C12—H12A	109.2
C3—C4—C7	120.74 (16)	C13—C12—H12A	109.2
C5—C4—C7	121.42 (16)	N1—C12—H12B	109.2
C6—C5—C4	121.16 (16)	C13—C12—H12B	109.2
C6—C5—H5	119.4	H12A—C12—H12B	107.9
C4—C5—H5	119.4	O3—C13—O4	125.07 (14)
C5—C6—C1	121.11 (15)	O3—C13—C12	125.38 (13)
C5—C6—H6	119.4	O4—C13—C12	109.54 (12)
C1—C6—H6	119.4	O4—C14—C15	107.17 (15)
C4—C7—H7A	112.1	O4—C14—H14A	110.3
C4—C7—H7B	112.1	C15—C14—H14A	110.3
H7A—C7—H7B	106.7	O4—C14—H14B	110.3
C4—C7—H7C	112.2	C15—C14—H14B	110.3
H7A—C7—H7C	106.7	H14A—C14—H14B	108.5
H7B—C7—H7C	106.7	C14—C15—H15A	109.5
C4—C7—H7D	112.1	C14—C15—H15B	109.5
C4—C7—H7E	112.1	H15A—C15—H15B	109.5
H7D—C7—H7E	106.7	C14—C15—H15C	109.5
C4—C7—H7F	112.1	H15A—C15—H15C	109.5
H7D—C7—H7F	106.7	H15B—C15—H15C	109.5

C6—C1—C2—C3	−0.7 (3)	C12—N1—C10—C9	−176.67 (12)
C8—C1—C2—C3	179.36 (15)	C8—C9—C10—O1	−4.5 (2)
C1—C2—C3—C4	0.1 (3)	S1—C9—C10—O1	176.30 (13)
C2—C3—C4—C5	0.8 (3)	C8—C9—C10—N1	174.96 (13)
C2—C3—C4—C7	179.48 (18)	S1—C9—C10—N1	−4.26 (15)
C3—C4—C5—C6	−1.0 (3)	C10—N1—C11—O2	178.32 (14)
C7—C4—C5—C6	−179.73 (18)	C12—N1—C11—O2	−0.6 (2)
C4—C5—C6—C1	0.4 (3)	C10—N1—C11—S1	−2.44 (16)
C2—C1—C6—C5	0.5 (2)	C12—N1—C11—S1	178.60 (10)
C8—C1—C6—C5	−179.61 (16)	C9—S1—C11—O2	179.04 (15)
C6—C1—C8—C9	179.98 (16)	C9—S1—C11—N1	−0.21 (11)
C2—C1—C8—C9	−0.1 (3)	C11—N1—C12—C13	101.44 (16)
C1—C8—C9—C10	−176.52 (14)	C10—N1—C12—C13	−77.47 (17)
C1—C8—C9—S1	2.5 (3)	C14—O4—C13—O3	0.5 (2)
C11—S1—C9—C8	−176.60 (15)	C14—O4—C13—C12	179.43 (13)
C11—S1—C9—C10	2.52 (11)	N1—C12—C13—O3	−11.2 (2)
C11—N1—C10—O1	−176.16 (14)	N1—C12—C13—O4	169.83 (12)
C12—N1—C10—O1	2.8 (2)	C13—O4—C14—C15	−174.80 (14)
C11—N1—C10—C9	4.37 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.95	2.46	3.3612 (18)	159
C12—H12A···O3ⁱⁱ	0.99	2.31	3.2757 (19)	166

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

Acknowledgements

The support of NSF-MRI Grant #1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

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