organic compounds
Ethyl 1-methyl-2-oxo-1,2-dihydroquinoline-4-carboxylate
aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014, Avenue Ibn Batouta, Rabat, Morocco
*Correspondence e-mail: yassir.filali.baba@gmail.com
The title compound, C13H13NO3, lies on a mirror plane with an intramolecular C—H⋯O hydrogen bond enclosing an S(6) ring. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into zigzag chains along the a-axis direction and π–π interactions, with a centroid-to-centroid distance of 3.7003 (2) Å, involving the pyridine and benzene rings of the oxoquinoline ring system, pack the molecules into parallel layers.
Keywords: crystal structure; quinoxaline; alkylation.
CCDC reference: 1556969
Structure description
Quinolone derivatives are a versatile class of nitrogen-containing ), anti-inflammatory (Ratheesh et al., 2013) and antibacterial properties (Beena & Rawat, 2013; Chai et al., 2011). Some quinoline derivatives have also been reported as corrosion inhibitors for steel in an acidic medium (Ebenso et al. 2010). Following on from our research in the field of substituted pyrido[2,3-b]pyrazine derivatives (Filali Baba et al., 2016), we report here the synthesis of the title compound by the condensation reaction of iodomethane with ethyl 1,2-dihydro-2-oxoquinoline-4-carboxylate and its crystal structure.
and they are useful intermediates in organic synthesis. They possess a broad spectrum of biological activities including anti-cancer (Elderfield & LeVon, 1960The title compound lies on a mirror plane and crystallizes with one independent molecule in the ). Only the hydrogen atoms of the methylene and methyl groups lie out of this plane. An intramolecular C5—H5⋯O2 hydrogen bond generates an S(6) ring motif. In the crystal, weak C8—H8⋯O1i hydrogen bonds link the molecules into zigzag chains along the a-axis direction (Table 1, Fig. 2). In addition, π–π interactions involving the pyridine and benzene rings of the oxoquinoline ring system stack the molecules into parallel layers [Cg1⋯Cg2 = 3.7003 (2) Å, symmetry operations 1 − x, −y, 1 − z; 1 − x, 1 − y, 1 − z; 1 − x, − + y, 1 − z; 1 − x, + y, 1 − z; Cg1 and Cg2 are the centroids of the N1/C1–C4/C9 and C4–C9 rings, respectively].
(Fig. 1Synthesis and crystallization
A solution of ethyl 1,2-dihydro-2-oxoquinoline-4-carboxylate (1 g 4.6 mmol) in 15 ml of DMF was mixed with iodomethane (0.34 ml, 5.5 mmol), K2CO3 (0.82 g, 6 mmol) and TBAB(0.03 g, 0.1 mmol). The reaction mixture was stirred at room temperature in DMF for 6 h. After removal of salts by filtration, the DMF was evaporated under reduced pressure and the residue obtained was dissolved in dichloromethane. The organic phase was dried over Na2SO4 then concentrated in vacuo. The title compound was obtained after recrystallization from a dichloromethane/hexane (1/3) solvent mixture, yield = 81%.
Refinement
Crystal data, data collection and structure . H atoms on the C12 and C13 methyl groups were generated using the PART −1 and AFIX 137 functions in SHELXL.
details are summarized in Table 2Structural data
CCDC reference: 1556969
https://doi.org/10.1107/S2414314617009178/sj4124sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009178/sj4124Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617009178/sj4124Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314617009178/sj4124Isup4.cml
Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell
CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C13H13NO3 | Dx = 1.331 Mg m−3 |
Mr = 231.24 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, Pnma | Cell parameters from 2463 reflections |
a = 12.2269 (4) Å | θ = 4.8–71.5° |
b = 6.7034 (3) Å | µ = 0.78 mm−1 |
c = 14.0817 (5) Å | T = 293 K |
V = 1154.16 (8) Å3 | Plate, yellow |
Z = 4 | 0.16 × 0.12 × 0.04 mm |
F(000) = 488 |
Rigaku Oxford Diffraction diffractometer | 1219 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source | 1036 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 16.0416 pixels mm-1 | θmax = 71.5°, θmin = 4.8° |
ω scans | h = −14→15 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | k = −5→8 |
Tmin = 0.751, Tmax = 1.000 | l = −15→17 |
6979 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.071P)2 + 0.1102P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1219 reflections | Δρmax = 0.28 e Å−3 |
105 parameters | Δρmin = −0.15 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.36454 (11) | 0.2500 | 0.25521 (9) | 0.0580 (4) | |
O2 | 0.36344 (10) | 0.2500 | 0.67503 (9) | 0.0544 (4) | |
O3 | 0.22613 (9) | 0.2500 | 0.57140 (8) | 0.0446 (4) | |
N1 | 0.52409 (11) | 0.2500 | 0.33834 (9) | 0.0352 (4) | |
C1 | 0.41212 (13) | 0.2500 | 0.33222 (12) | 0.0386 (4) | |
C2 | 0.35321 (13) | 0.2500 | 0.42157 (12) | 0.0367 (4) | |
H2 | 0.2772 | 0.2500 | 0.4198 | 0.044* | |
C3 | 0.40269 (13) | 0.2500 | 0.50701 (11) | 0.0313 (4) | |
C4 | 0.52145 (12) | 0.2500 | 0.51177 (11) | 0.0303 (4) | |
C5 | 0.58205 (13) | 0.2500 | 0.59667 (12) | 0.0370 (4) | |
H5 | 0.5454 | 0.2500 | 0.6546 | 0.044* | |
C6 | 0.69501 (14) | 0.2500 | 0.59553 (13) | 0.0439 (4) | |
H6 | 0.7339 | 0.2500 | 0.6523 | 0.053* | |
C7 | 0.75009 (14) | 0.2500 | 0.50994 (13) | 0.0447 (4) | |
H7 | 0.8262 | 0.2500 | 0.5096 | 0.054* | |
C8 | 0.69445 (13) | 0.2500 | 0.42541 (12) | 0.0390 (4) | |
H8 | 0.7328 | 0.2500 | 0.3684 | 0.047* | |
C9 | 0.57974 (13) | 0.2500 | 0.42483 (11) | 0.0312 (4) | |
C10 | 0.33175 (13) | 0.2500 | 0.59438 (12) | 0.0346 (4) | |
C11 | 0.14893 (14) | 0.2500 | 0.64993 (14) | 0.0491 (5) | |
H11A | 0.1592 | 0.3675 | 0.6891 | 0.059* | 0.5 |
H11B | 0.1592 | 0.1325 | 0.6891 | 0.059* | 0.5 |
C12 | 0.03753 (17) | 0.2500 | 0.60706 (19) | 0.0834 (9) | |
H12A | 0.0232 | 0.3779 | 0.5790 | 0.125* | 0.5 |
H12B | −0.0158 | 0.2236 | 0.6555 | 0.125* | 0.5 |
H12C | 0.0334 | 0.1485 | 0.5591 | 0.125* | 0.5 |
C13 | 0.58549 (16) | 0.2500 | 0.24866 (12) | 0.0499 (5) | |
H13A | 0.6393 | 0.1458 | 0.2500 | 0.075* | 0.5 |
H13B | 0.6212 | 0.3764 | 0.2406 | 0.075* | 0.5 |
H13C | 0.5361 | 0.2278 | 0.1967 | 0.075* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0450 (7) | 0.0960 (12) | 0.0330 (7) | 0.000 | −0.0106 (5) | 0.000 |
O2 | 0.0409 (7) | 0.0905 (11) | 0.0318 (7) | 0.000 | 0.0003 (5) | 0.000 |
O3 | 0.0309 (6) | 0.0647 (8) | 0.0380 (7) | 0.000 | 0.0030 (4) | 0.000 |
N1 | 0.0342 (7) | 0.0434 (8) | 0.0281 (7) | 0.000 | 0.0005 (5) | 0.000 |
C1 | 0.0354 (9) | 0.0466 (9) | 0.0339 (8) | 0.000 | −0.0076 (6) | 0.000 |
C2 | 0.0281 (7) | 0.0452 (9) | 0.0368 (9) | 0.000 | −0.0027 (6) | 0.000 |
C3 | 0.0312 (8) | 0.0308 (8) | 0.0319 (8) | 0.000 | −0.0011 (6) | 0.000 |
C4 | 0.0305 (8) | 0.0282 (8) | 0.0323 (8) | 0.000 | −0.0019 (6) | 0.000 |
C5 | 0.0353 (9) | 0.0441 (9) | 0.0318 (8) | 0.000 | −0.0025 (6) | 0.000 |
C6 | 0.0376 (9) | 0.0556 (11) | 0.0385 (9) | 0.000 | −0.0116 (7) | 0.000 |
C7 | 0.0265 (7) | 0.0562 (11) | 0.0514 (10) | 0.000 | −0.0044 (7) | 0.000 |
C8 | 0.0321 (8) | 0.0469 (10) | 0.0379 (9) | 0.000 | 0.0034 (6) | 0.000 |
C9 | 0.0310 (8) | 0.0303 (8) | 0.0324 (8) | 0.000 | −0.0031 (6) | 0.000 |
C10 | 0.0310 (8) | 0.0353 (8) | 0.0376 (8) | 0.000 | −0.0003 (6) | 0.000 |
C11 | 0.0355 (9) | 0.0700 (13) | 0.0418 (10) | 0.000 | 0.0086 (7) | 0.000 |
C12 | 0.0352 (11) | 0.149 (3) | 0.0661 (16) | 0.000 | 0.0053 (10) | 0.000 |
C13 | 0.0450 (10) | 0.0733 (13) | 0.0313 (9) | 0.000 | 0.0031 (7) | 0.000 |
O1—C1 | 1.231 (2) | C6—H6 | 0.9300 |
O2—C10 | 1.200 (2) | C6—C7 | 1.381 (3) |
O3—C10 | 1.3312 (19) | C7—H7 | 0.9300 |
O3—C11 | 1.454 (2) | C7—C8 | 1.371 (2) |
N1—C1 | 1.372 (2) | C8—H8 | 0.9300 |
N1—C9 | 1.3952 (19) | C8—C9 | 1.403 (2) |
N1—C13 | 1.469 (2) | C11—H11A | 0.9700 |
C1—C2 | 1.450 (2) | C11—H11B | 0.9700 |
C2—H2 | 0.9300 | C11—C12 | 1.490 (3) |
C2—C3 | 1.347 (2) | C12—H12A | 0.9600 |
C3—C4 | 1.454 (2) | C12—H12B | 0.9600 |
C3—C10 | 1.505 (2) | C12—H12C | 0.9600 |
C4—C5 | 1.407 (2) | C13—H13A | 0.9600 |
C4—C9 | 1.417 (2) | C13—H13B | 0.9600 |
C5—H5 | 0.9300 | C13—H13C | 0.9600 |
C5—C6 | 1.381 (2) | ||
C10—O3—C11 | 116.42 (13) | C7—C8—C9 | 120.08 (15) |
C1—N1—C9 | 122.79 (13) | C9—C8—H8 | 120.0 |
C1—N1—C13 | 117.13 (13) | N1—C9—C4 | 120.60 (14) |
C9—N1—C13 | 120.08 (14) | N1—C9—C8 | 119.52 (13) |
O1—C1—N1 | 121.81 (15) | C8—C9—C4 | 119.88 (13) |
O1—C1—C2 | 122.00 (15) | O2—C10—O3 | 122.91 (15) |
N1—C1—C2 | 116.19 (14) | O2—C10—C3 | 125.97 (14) |
C1—C2—H2 | 118.2 | O3—C10—C3 | 111.12 (13) |
C3—C2—C1 | 123.52 (15) | O3—C11—H11A | 110.4 |
C3—C2—H2 | 118.2 | O3—C11—H11B | 110.4 |
C2—C3—C4 | 119.33 (14) | O3—C11—C12 | 106.58 (17) |
C2—C3—C10 | 118.12 (14) | H11A—C11—H11B | 108.6 |
C4—C3—C10 | 122.55 (13) | C12—C11—H11A | 110.4 |
C5—C4—C3 | 124.43 (14) | C12—C11—H11B | 110.4 |
C5—C4—C9 | 118.00 (14) | C11—C12—H12A | 109.5 |
C9—C4—C3 | 117.57 (13) | C11—C12—H12B | 109.5 |
C4—C5—H5 | 119.4 | C11—C12—H12C | 109.5 |
C6—C5—C4 | 121.12 (15) | H12A—C12—H12B | 109.5 |
C6—C5—H5 | 119.4 | H12A—C12—H12C | 109.5 |
C5—C6—H6 | 120.1 | H12B—C12—H12C | 109.5 |
C7—C6—C5 | 119.86 (15) | N1—C13—H13A | 109.5 |
C7—C6—H6 | 120.1 | N1—C13—H13B | 109.5 |
C6—C7—H7 | 119.5 | N1—C13—H13C | 109.5 |
C8—C7—C6 | 121.05 (16) | H13A—C13—H13B | 109.5 |
C8—C7—H7 | 119.5 | H13A—C13—H13C | 109.5 |
C7—C8—H8 | 120.0 | H13B—C13—H13C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2 | 0.93 | 2.24 | 2.892 (2) | 126 |
C8—H8···O1i | 0.93 | 2.37 | 3.285 (2) | 168 |
Symmetry code: (i) x+1/2, −y+1/2, −z+1/2. |
Acknowledgements
JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.
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