Ethyl 1-methyl-2-oxo-1,2-di­hydro­quinoline-4-carboxyl­ate

Filali Baba, Y.; Kandri Rodi, Y.; Hayani, S.; Jasinski, J.P.; Kaur, M.; Essassi, E.M.

doi:10.1107/S2414314617009178

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170917

https://doi.org/10.1107/S2414314617009178

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Ethyl 1-methyl-2-oxo-1,2-dihydroquinoline-4-carboxylate

Yassir Filali Baba,^a ^* Youssef Kandri Rodi,^a Sonia Hayani,^a Jerry P. Jasinski,^b Manpreet Kaur ^b and El Mokhtar Essassi ^c

^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

Edited by J. Simpson, University of Otago, New Zealand (Received 16 June 2017; accepted 19 June 2017; online 30 June 2017)

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 heterocyclic compounds and they are useful intermediates in organic synthesis. They possess a broad spectrum of biological activities including anti-cancer (Elderfield & LeVon, 1960 ), 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.

The title compound lies on a mirror plane and crystallizes with one independent molecule in the asymmetric unit (Fig. 1). 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, − $[{1\over 2}]$ + y, 1 − z; 1 − x, $[{1\over 2}]$ + y, 1 − z; Cg1 and Cg2 are the centroids of the N1/C1–C4/C9 and C4–C9 rings, respectively].

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The structure of the title compound, showing the atom-numbering scheme, with displacement ellipsoids drawn at the 30% probability level.

Figure 2
The packing of the title compound, viewed along the b axis. Dashed lines indicate both intra- and intermolecular hydrogen bonds. H atoms not involved in the packing have been omitted for clarity.

Synthesis 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 refinement details are summarized in Table 2. H atoms on the C12 and C13 methyl groups were generated using the PART −1 and AFIX 137 functions in SHELXL.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO₃
M_r	231.24
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	12.2269 (4), 6.7034 (3), 14.0817 (5)
V (Å³)	1154.16 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.78
Crystal size (mm)	0.16 × 0.12 × 0.04

Data collection
Diffractometer	Rigaku Oxford Diffraction
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas, The Woodlands, Texas, USA.]$ )
T_min, T_max	0.751, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6979, 1219, 1036
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 1.05
No. of reflections	1219
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.15
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas, The Woodlands, Texas, USA.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1556969

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009178/sj4124sup1.cif

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

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: 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).

Ethyl 1-methyl-2-oxo-1,2-dihydroquinoline-4-carboxylate top

Crystal data top

C₁₃H₁₃NO₃	D_x = 1.331 Mg m⁻³
M_r = 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

Data collection top

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	R_int = 0.038
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.5°, θ_min = 4.8°
ω scans	h = −14→15
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −5→8
T_min = 0.751, T_max = 1.000	l = −15→17
6979 measured reflections

Refinement top

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(F_o²) + (0.071P)² + 0.1102P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1219 reflections	Δρ_max = 0.28 e Å⁻³
105 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints

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.

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

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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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