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

Tachallait, H.; Karrouchi, K.; Bougrin, K.; Mague, J.T.; Ramli, Y.

doi:10.1107/S2414314616010415

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161041

https://doi.org/10.1107/S2414314616010415

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

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

^aLaboratoire de Chimie des Plantes et de Synthese Organique et Bioorganique, Faculty of Sciences, Mohammed V University, Rabat, Morocco, ^bLaboratoire National de Controle des Medicaments, D M P, Ministere de la Santé, Madinat Al Irfane, BP, 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 24 June 2016; accepted 27 June 2016; online 5 July 2016)

In the title compound, C₁₅H₁₅NO₅S, the benzene and heterocyclic rings are close to being coplanar [dihedral angle = 1.49 (6)°]. In the crystal, pairwise C—H⋯O hydrogen bonds form dimers, which are arranged into `stair-step' rows by way of C=O–π interactions between a carbonyl group and the benzene ring [O⋯π = 3.3837 (12) Å].

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

CCDC reference: 1487873

Structure description

As a continuation of our studies of the structures of thiazolidine-2,4-dione derivatives (Karrouchi et al., 2016 ), we report on the N-alkylation of 5-(4 methoxybenzylidene)thiazolidine-2,4-dione with ethyl bromoacetate which gave title compound (Fig. 1) which was characterized by single-crystal X-ray diffraction.

Figure 1
The title molecule, showing the atom-labelling scheme and 50% probability displacement ellipsoids.

The benzene ring and the heterocyclic ring (r.m.s. deviation = 0.018 Å) are close to being coplanar, the dihedral angle between their mean planes being 1.49 (6)°. In the crystal, the molecules form dimers via pairwise C8—H8⋯O2ⁱ [symmetry code: (i) −x, −y + 1, −z + 1] hydrogen bonds (Table 1 and Fig. 2). These units are formed into `stair-step' rows through C=O–π interactions between the C10=O2 carbonyl group and the benzene ring at (∓x, y, z) [O⋯π = 3.370 (1) Å and C=O⋯π = 83.56 (8)°] (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.95	2.42	3.3157 (15)	156
Symmetry code: (i) -x, -y+1, -z+1.

Figure 2
The packing, viewed along the b axis, with complementary C—H⋯O hydrogen bonds shown as dotted lines.

Figure 3
Detail of the complementary C=O–π stacking between one carbonyl group and the benzene ring in an adjacent molecule.

Synthesis and crystallization

To a solution of 5-(4-methoxybenzylidene)thiazolidine-2,4-dione (1 mmol) in acetone (30 ml) an excess of triethylamine (1.5 mmol) was added and the mixture was stirred for 10 min at 25°C. Ethyl bromoacetate (1.5 mmol) was added slowly and the reaction mixture was refluxed for 10 h. The progress was monitored by TLC and, when complete, the reaction mixture was cooled to room temperature, filtered and the volatiles removed under reduced pressure. The residue was dissolved in ethanol, concentrated and cooled to afford crystals which were filtered off, washed with ethanol and recrystallized from ethanol solution. Yield 84%; m.p. 130–132°C.

Refinement

Details of crystal data and refinement are presented in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₅S
M_r	321.34
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	6.1957 (2), 10.6460 (3), 12.2909 (3)
α, β, γ (°)	68.845 (1), 78.971 (1), 84.919 (1)
V (Å³)	741.93 (4)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.16
Crystal size (mm)	0.21 × 0.11 × 0.04

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.80, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	10428, 2884, 2690
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.05
No. of reflections	2884
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1487873

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616010415/hb4063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010415/hb4063Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010415/hb4063Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); 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-methoxybenzylidene)-2,4-dioxo-1,3-thiazolidin-3-yl]acetate top

Crystal data top

C₁₅H₁₅NO₅S	Z = 2
M_r = 321.34	F(000) = 336
Triclinic, P1	D_x = 1.438 Mg m⁻³
a = 6.1957 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.6460 (3) Å	Cell parameters from 8632 reflections
c = 12.2909 (3) Å	θ = 3.9–72.0°
α = 68.845 (1)°	µ = 2.16 mm⁻¹
β = 78.971 (1)°	T = 150 K
γ = 84.919 (1)°	Plate, colourless
V = 741.93 (4) Å³	0.21 × 0.11 × 0.04 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2884 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2690 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.1°, θ_min = 3.9°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −12→13
T_min = 0.80, T_max = 0.92	l = −12→14
10428 measured reflections

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)] = 0.030	H-atom parameters constrained
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0403P)² + 0.2407P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2884 reflections	Δρ_max = 0.29 e Å⁻³
202 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0071 (7)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
S1	0.34156 (5)	0.50355 (3)	0.12596 (3)	0.02452 (11)
O1	1.10838 (15)	0.14727 (10)	0.45592 (8)	0.0287 (2)
O2	−0.08424 (15)	0.60296 (10)	0.35429 (8)	0.0266 (2)
O3	0.09830 (17)	0.64516 (10)	−0.03482 (8)	0.0320 (2)
O4	−0.01087 (16)	0.89843 (10)	0.13494 (10)	0.0346 (2)
O5	−0.37526 (16)	0.92434 (10)	0.13243 (11)	0.0374 (3)
N1	−0.02628 (17)	0.63167 (11)	0.15778 (9)	0.0230 (2)
C1	0.5290 (2)	0.36877 (12)	0.38833 (11)	0.0214 (3)
C2	0.5793 (2)	0.32201 (13)	0.50296 (11)	0.0237 (3)
H2	0.4799	0.3421	0.5640	0.028*
C3	0.7695 (2)	0.24723 (13)	0.53029 (11)	0.0249 (3)
H3	0.7995	0.2163	0.6088	0.030*
C4	0.9158 (2)	0.21833 (13)	0.44081 (12)	0.0234 (3)
C5	0.8693 (2)	0.26387 (13)	0.32566 (12)	0.0247 (3)
H5	0.9693	0.2440	0.2648	0.030*
C6	0.6797 (2)	0.33731 (13)	0.30007 (11)	0.0234 (3)
H6	0.6499	0.3673	0.2215	0.028*
C7	1.1601 (2)	0.09656 (15)	0.57301 (13)	0.0314 (3)
H7A	1.3016	0.0475	0.5725	0.047*
H7B	1.0448	0.0356	0.6268	0.047*
H7C	1.1691	0.1719	0.5998	0.047*
C8	0.3265 (2)	0.44693 (12)	0.36890 (11)	0.0215 (3)
H8	0.2416	0.4593	0.4375	0.026*
C9	0.2398 (2)	0.50466 (12)	0.26949 (11)	0.0211 (3)
C10	0.0297 (2)	0.58171 (12)	0.27051 (11)	0.0211 (3)
C11	0.1182 (2)	0.60538 (13)	0.06821 (11)	0.0239 (3)
C12	−0.2200 (2)	0.71737 (13)	0.13586 (12)	0.0256 (3)
H12A	−0.3461	0.6765	0.1984	0.031*
H12B	−0.2561	0.7244	0.0588	0.031*
C13	−0.1837 (2)	0.85685 (13)	0.13435 (11)	0.0251 (3)
C14	−0.3745 (3)	1.06523 (15)	0.12095 (16)	0.0402 (4)
H14A	−0.3447	1.1233	0.0363	0.048*
H14B	−0.2590	1.0798	0.1605	0.048*
C15	−0.5960 (3)	1.09868 (16)	0.17802 (16)	0.0425 (4)
H15A	−0.6077	1.1957	0.1632	0.064*
H15B	−0.6160	1.0490	0.2635	0.064*
H15C	−0.7098	1.0734	0.1448	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02626 (17)	0.02999 (18)	0.01769 (17)	0.00376 (12)	−0.00117 (11)	−0.01115 (12)
O1	0.0259 (5)	0.0305 (5)	0.0301 (5)	0.0060 (4)	−0.0074 (4)	−0.0111 (4)
O2	0.0257 (5)	0.0333 (5)	0.0208 (5)	0.0036 (4)	0.0003 (3)	−0.0125 (4)
O3	0.0410 (6)	0.0357 (5)	0.0186 (5)	0.0038 (4)	−0.0062 (4)	−0.0094 (4)
O4	0.0270 (5)	0.0307 (5)	0.0455 (6)	−0.0021 (4)	−0.0066 (4)	−0.0124 (4)
O5	0.0257 (5)	0.0259 (5)	0.0628 (7)	0.0040 (4)	−0.0082 (5)	−0.0190 (5)
N1	0.0247 (5)	0.0243 (5)	0.0201 (5)	0.0033 (4)	−0.0044 (4)	−0.0087 (4)
C1	0.0219 (6)	0.0219 (6)	0.0206 (6)	−0.0025 (5)	−0.0019 (5)	−0.0083 (5)
C2	0.0242 (6)	0.0266 (6)	0.0208 (6)	−0.0013 (5)	−0.0011 (5)	−0.0102 (5)
C3	0.0278 (6)	0.0263 (6)	0.0212 (6)	−0.0021 (5)	−0.0056 (5)	−0.0079 (5)
C4	0.0216 (6)	0.0212 (6)	0.0278 (7)	−0.0006 (5)	−0.0048 (5)	−0.0086 (5)
C5	0.0247 (6)	0.0257 (6)	0.0234 (6)	0.0005 (5)	0.0000 (5)	−0.0107 (5)
C6	0.0253 (6)	0.0250 (6)	0.0199 (6)	−0.0012 (5)	−0.0026 (5)	−0.0083 (5)
C7	0.0311 (7)	0.0308 (7)	0.0332 (7)	0.0034 (5)	−0.0123 (6)	−0.0099 (6)
C8	0.0215 (6)	0.0236 (6)	0.0198 (6)	−0.0023 (5)	0.0007 (5)	−0.0095 (5)
C9	0.0213 (6)	0.0228 (6)	0.0193 (6)	−0.0014 (5)	0.0010 (4)	−0.0095 (5)
C10	0.0228 (6)	0.0211 (6)	0.0196 (6)	−0.0019 (5)	−0.0023 (4)	−0.0078 (5)
C11	0.0293 (6)	0.0226 (6)	0.0202 (6)	−0.0023 (5)	−0.0022 (5)	−0.0086 (5)
C12	0.0241 (6)	0.0267 (7)	0.0276 (7)	0.0034 (5)	−0.0075 (5)	−0.0108 (5)
C13	0.0249 (6)	0.0263 (6)	0.0220 (6)	0.0013 (5)	−0.0023 (5)	−0.0074 (5)
C14	0.0355 (8)	0.0243 (7)	0.0595 (10)	0.0015 (6)	−0.0029 (7)	−0.0162 (7)
C15	0.0392 (8)	0.0338 (8)	0.0548 (10)	0.0057 (6)	−0.0022 (7)	−0.0204 (7)

Geometric parameters (Å, º) top

S1—C9	1.7602 (12)	C4—C5	1.3989 (18)
S1—C11	1.7745 (13)	C5—C6	1.3755 (18)
O1—C4	1.3617 (15)	C5—H5	0.9500
O1—C7	1.4318 (16)	C6—H6	0.9500
O2—C10	1.2131 (15)	C7—H7A	0.9800
O3—C11	1.2089 (16)	C7—H7B	0.9800
O4—C13	1.1966 (17)	C7—H7C	0.9800
O5—C13	1.3315 (16)	C8—C9	1.3453 (18)
O5—C14	1.4553 (17)	C8—H8	0.9500
N1—C11	1.3757 (16)	C9—C10	1.4763 (17)
N1—C10	1.3937 (16)	C12—C13	1.5144 (18)
N1—C12	1.4482 (15)	C12—H12A	0.9900
C1—C2	1.4014 (18)	C12—H12B	0.9900
C1—C6	1.4070 (17)	C14—C15	1.493 (2)
C1—C8	1.4523 (17)	C14—H14A	0.9900
C2—C3	1.3888 (18)	C14—H14B	0.9900
C2—H2	0.9500	C15—H15A	0.9800
C3—C4	1.3924 (18)	C15—H15B	0.9800
C3—H3	0.9500	C15—H15C	0.9800

C9—S1—C11	92.26 (6)	C1—C8—H8	114.8
C4—O1—C7	117.16 (10)	C8—C9—C10	120.98 (11)
C13—O5—C14	117.70 (11)	C8—C9—S1	129.07 (10)
C11—N1—C10	117.36 (10)	C10—C9—S1	109.95 (9)
C11—N1—C12	122.13 (11)	O2—C10—N1	122.09 (11)
C10—N1—C12	120.30 (10)	O2—C10—C9	127.40 (11)
C2—C1—C6	117.48 (11)	N1—C10—C9	110.50 (10)
C2—C1—C8	117.80 (11)	O3—C11—N1	125.70 (12)
C6—C1—C8	124.71 (11)	O3—C11—S1	124.43 (10)
C3—C2—C1	122.14 (12)	N1—C11—S1	109.87 (9)
C3—C2—H2	118.9	N1—C12—C13	111.19 (10)
C1—C2—H2	118.9	N1—C12—H12A	109.4
C2—C3—C4	118.96 (12)	C13—C12—H12A	109.4
C2—C3—H3	120.5	N1—C12—H12B	109.4
C4—C3—H3	120.5	C13—C12—H12B	109.4
O1—C4—C3	124.62 (12)	H12A—C12—H12B	108.0
O1—C4—C5	115.40 (11)	O4—C13—O5	126.15 (13)
C3—C4—C5	119.98 (12)	O4—C13—C12	125.21 (12)
C6—C5—C4	120.38 (11)	O5—C13—C12	108.64 (11)
C6—C5—H5	119.8	O5—C14—C15	107.30 (12)
C4—C5—H5	119.8	O5—C14—H14A	110.3
C5—C6—C1	121.05 (12)	C15—C14—H14A	110.3
C5—C6—H6	119.5	O5—C14—H14B	110.3
C1—C6—H6	119.5	C15—C14—H14B	110.3
O1—C7—H7A	109.5	H14A—C14—H14B	108.5
O1—C7—H7B	109.5	C14—C15—H15A	109.5
H7A—C7—H7B	109.5	C14—C15—H15B	109.5
O1—C7—H7C	109.5	H15A—C15—H15B	109.5
H7A—C7—H7C	109.5	C14—C15—H15C	109.5
H7B—C7—H7C	109.5	H15A—C15—H15C	109.5
C9—C8—C1	130.43 (11)	H15B—C15—H15C	109.5
C9—C8—H8	114.8

C6—C1—C2—C3	−0.04 (19)	C11—N1—C10—C9	−1.53 (15)
C8—C1—C2—C3	−179.58 (11)	C12—N1—C10—C9	−176.34 (10)
C1—C2—C3—C4	0.3 (2)	C8—C9—C10—O2	0.6 (2)
C7—O1—C4—C3	1.50 (19)	S1—C9—C10—O2	−179.72 (11)
C7—O1—C4—C5	−178.81 (11)	C8—C9—C10—N1	179.97 (11)
C2—C3—C4—O1	179.34 (12)	S1—C9—C10—N1	−0.33 (13)
C2—C3—C4—C5	−0.33 (19)	C10—N1—C11—O3	−177.26 (12)
O1—C4—C5—C6	−179.66 (11)	C12—N1—C11—O3	−2.6 (2)
C3—C4—C5—C6	0.0 (2)	C10—N1—C11—S1	2.64 (14)
C4—C5—C6—C1	0.3 (2)	C12—N1—C11—S1	177.35 (9)
C2—C1—C6—C5	−0.26 (19)	C9—S1—C11—O3	177.61 (12)
C8—C1—C6—C5	179.24 (12)	C9—S1—C11—N1	−2.30 (10)
C2—C1—C8—C9	179.20 (13)	C11—N1—C12—C13	−101.22 (14)
C6—C1—C8—C9	−0.3 (2)	C10—N1—C12—C13	73.34 (15)
C1—C8—C9—C10	−179.34 (12)	C14—O5—C13—O4	5.0 (2)
C1—C8—C9—S1	1.0 (2)	C14—O5—C13—C12	−175.08 (13)
C11—S1—C9—C8	−178.85 (13)	N1—C12—C13—O4	9.47 (19)
C11—S1—C9—C10	1.48 (9)	N1—C12—C13—O5	−170.46 (11)
C11—N1—C10—O2	177.90 (12)	C13—O5—C14—C15	−152.82 (14)
C12—N1—C10—O2	3.09 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.95	2.42	3.3157 (15)	156

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

The support of NSF–MRI grant No. 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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