organic compounds
Ethyl 2-[(5Z)-5-(4-methoxybenzylidene)-2,4-dioxo-1,3-thiazolidin-3-yl]acetate
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
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.
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).
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
are presented in Table 2Structural data
CCDC reference: 1487873
https://doi.org/10.1107/S2414314616010415/hb4063sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX3 (Bruker, 2016); cell
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).C15H15NO5S | Z = 2 |
Mr = 321.34 | F(000) = 336 |
Triclinic, P1 | Dx = 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 |
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 | Rint = 0.027 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 72.1°, θmin = 3.9° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −12→13 |
Tmin = 0.80, Tmax = 0.92 | l = −12→14 |
10428 measured reflections |
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(Fo2) + (0.0403P)2 + 0.2407P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2884 reflections | Δρmax = 0.29 e Å−3 |
202 parameters | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Karrouchi, K., Tachallait, H., Bougrin, K., Mague, J. T. & Ramli, Y. (2016). IUCrData, 1, x160851. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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