Ethyl 2-(4-hydr­oxy-1-methyl-2-oxo-1,2-dihydro­quinolin-3-yl)acetate

Igor V Ukrainets; Svetlana V Shishkina; Oleg V Shishkin; Alexandra A Davidenko; Andrei A Tkach

doi:10.1107/S1600536809011921

. 2009 Apr 8;65(Pt 5):o968. doi: 10.1107/S1600536809011921

Ethyl 2-(4-hydroxy-1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)acetate

Igor V Ukrainets ^a,^*, Svetlana V Shishkina ^b, Oleg V Shishkin ^b, Alexandra A Davidenko ^a, Andrei A Tkach ^a

PMCID: PMC2977667 PMID: 21584010

Abstract

In the title compound, C₁₄H₁₅NO₄, the bicyclic fragment and the ester group form a dihedral angle of 86.7 (2)°. Intermolecular O—H⋯O and C—H⋯O hydrogen bonding connects molecules into a helix along the crystallographic b axis.

Related literature

For esters of 4-hydroxy-2-oxo-1,2-dihydroquinolin-3-acetic acids as non-steroidal anti-inflammatory drugs, see: Ukrainets et al. (2001 ▶). For their use in the synthesis of natural alkaloids, see: Ramesh & Shanmugam (1985 ▶); Geismann & Cho (1959 ▶) and in highly active antithyroid substances, see: Ukrainets et al. (1997 ▶). For van der Waals radii, see: Zefirov (1997 ▶). For related structures, see: Jurd et al. (1983 ▶); Ukrainets et al. (2000 ▶). For bond-length data, see: Bürgi & Dunitz (1994 ▶).

Experimental

Crystal data

C₁₄H₁₅NO₄
M _r = 261.27
Monoclinic,
a = 21.608 (2) Å
b = 9.2155 (9) Å
c = 14.6795 (12) Å
β = 119.632 (9)°
V = 2540.8 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur3 diffractometer
Absorption correction: none
13114 measured reflections
2862 independent reflections
2376 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.171
S = 1.19
2862 reflections
232 parameters
All H-atom parameters refined
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP (Siemens, 1998 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011921/kp2212sup1.cif

e-65-0o968-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011921/kp2212Isup2.hkl

e-65-0o968-Isup2.hkl^{(140.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1ⁱ	0.95 (3)	1.71 (3)	2.649 (2)	169 (2)
C10—H10a⋯O1ⁱ	0.94 (2)	2.34 (3)	3.235 (2)	159 (2)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Esters of 4-hydroxy-2-oxo-1,2-dihydroquinolin-3-acetic acids can be considered as non-steroid anti-inflammatory drugs (Ukrainets et al., 2001). However they are of great interest for synthesis of natural alkaloids (Ramesh & Shanmugam, 1985; Geismann & Cho, 1959) and highly active antithyroid substances (Ukrainets et al., 1997). In the present paper, we report the crystal structure of the (4-hydroxy-1-methyl-2-oxo-1,2-dihydro- quinolin-3-yl)-acetic acid ethyl ester (I) (Fig. 1). The bicyclic fragment and the C14, O1, C10 and O2 atoms are coplanar within 0.02 Å. The planar ester group at the C10 atom has orthogonal orientation with respect to the plane of quinolone bicycle (the C7—C8—C10—C11 torsion angle is 90.8 (2) %A) whereas the C8—C10—C11—O3 torsion angle is 7.3 (3) %A). The C9—O1 bond (1.250 (2) Å) is elongated as compared with its mean value (1.210 Å; Bürgi & Dunitz, 1994) owing to the formation of the intermolecular hydrogen bond O2—H2O···O1' (Table 1). The presence of hydrogen bond affects the orientation of the hydrogen atom of hydroxy group despite of strong repulsion with hydrogen atom of neighbouring methylene group: distance H10a···H2O is 2.09 Å [the van der Waals radii sum is 2.34 Å (Zefirov, 1997)]. It should be noted that the C7—O2 bond length (1.341 (2) Å) is close to its mean value 1.333 Å observed in earlier investigated compounds (Jurd et al., 1983; Ukrainets et al., 2000). In the crystal the molecules form the infinite helix along the [0 1 0] direction (Fig. 2) via the O2—H2O···O1 intermolecular hydrogen bond between hydroxyl group of one molecule and carbonyl group of quinolone fragment of neighbouring molecule. The C10—H10a···O1' intermolecular hydrogen bond (Table 1) occurs as well.

Experimental

(4-Hydroxy-1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)-acetic acid is synthesized from the methyl N-methyl anthranilate using the known method (Geismann & Cho, 1959) and then is esterified by ethanol (Ukrainets et al., 2001). Yield 96%. M.p. 454–457 K.