organic compounds
Ethyl 2-[(5Z)-5-(4-methylbenzylidene)-2,4-dioxo-1,3-thiazolidin-3-yl]acetate
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
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 is reported here.
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).
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 . Trial refinements using the single-component reflection extracted with TWINABS and the full, two-component data showed the former to be superior. The crystal did not diffract well at high angles, possibly as the result of the For this reason, the completeness of the data is somewhat less than optimal but, nevertheless, all features of chemical interest are quite satisfactorily determined.
details are summarized in Table 2Structural data
CCDC reference: 1481951
10.1107/S2414314616008518/hb4050sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616008518/hb4050Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616008518/hb4050Isup3.cml
Data collection: APEX3 (Bruker, 2016); cell
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).C15H15NO4S | Z = 2 |
Mr = 305.34 | F(000) = 320 |
Triclinic, P1 | Dx = 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 |
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 | Rint = 0.026 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 74.5°, θmin = 3.7° |
ω scans | h = −5→5 |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009) | k = −14→14 |
Tmin = 0.54, Tmax = 0.85 | l = −15→12 |
11328 measured reflections |
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(Fo2) + (0.0496P)2 + 0.290P] where P = (Fo2 + 2Fc2)/3 |
2825 reflections | (Δ/σ)max = 0.001 |
192 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | 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* |
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) |
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) |
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
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kaminskyy, D., den Hartog, G. J. M., Wojtyra, M., Lelyukh, M., Gzella, A., Bast, A. & Lesyk, R. (2016). Eur. J. Med. Chem. 112, 180–195. CSD CrossRef CAS PubMed Google Scholar
Narute, A., Khedekar, P. & Bhusari, K. (2008). Ind. J. Chem. 47, 586. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2009). CELL_NOW and TWINABS. University of Göttingen, Germany. 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
Sohda, T., Mizuno, K., Momose, Y., Ikeda, H., Fujita, T. & Meguro, K. (1992). J. Med. Chem. 35, 2617–2626. CrossRef PubMed CAS Google Scholar
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