Ethyl 2-(4-hydr-oxy-1-methyl-2-oxo-1,2-dihydro-quinolin-3-yl)acetate.

In the title compound, C(14)H(15)NO(4), the bicyclic fragment and the ester group form a dihedral angle of 86.7 (2)°. Inter-molecular O-H⋯O and C-H⋯O hydrogen bonding connects mol-ecules 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 = 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

Δρmax = 0.28 e Å−3

Δρmin = −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.

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

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

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

C14H15NO4	Dx = 1.366 Mg m−3
Mr = 261.27	Melting point: 455 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.608 (2) Å	Cell parameters from 8736 reflections
b = 9.2155 (9) Å	θ = 4–32°
c = 14.6795 (12) Å	µ = 0.10 mm−1
β = 119.632 (9)°	T = 293 K
V = 2540.8 (4) Å3	Block, colourless
Z = 8	0.30 × 0.30 × 0.20 mm
F(000) = 1104

Oxford Diffraction Xcalibur3 diffractometer	2376 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.030
graphite	θmax = 27.5°, θmin = 3.2°
Detector resolution: 16.1827 pixels mm-1	h = −28→28
ω scans	k = −11→11
13114 measured reflections	l = −19→19
2862 independent 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)] = 0.060	Hydrogen site location: difference Fourier map
wR(F2) = 0.171	All H-atom parameters refined
S = 1.19	w = 1/[σ2(Fo2) + (0.0943P)2] where P = (Fo2 + 2Fc2)/3
2862 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

	x	y	z	Uiso*/Ueq
N1	0.12615 (8)	0.48562 (16)	0.00279 (10)	0.0447 (4)
O1	0.23317 (6)	0.38519 (13)	0.11389 (9)	0.0511 (4)
O2	0.14804 (7)	0.78108 (14)	0.22763 (10)	0.0528 (4)
H2O	0.1932 (14)	0.807 (3)	0.284 (2)	0.086 (8)*
O3	0.21567 (7)	0.39416 (16)	0.34316 (11)	0.0651 (4)
O4	0.32312 (6)	0.48690 (14)	0.45168 (9)	0.0525 (4)
C1	0.07158 (8)	0.58298 (18)	−0.01697 (12)	0.0434 (4)
C2	0.00694 (10)	0.5816 (2)	−0.11336 (15)	0.0566 (5)
H2	0.0020 (13)	0.511 (3)	−0.161 (2)	0.077 (7)*
C3	−0.04624 (10)	0.6786 (3)	−0.13061 (17)	0.0652 (6)
H3	−0.0931 (15)	0.677 (3)	−0.195 (2)	0.102 (9)*
C4	−0.03752 (10)	0.7799 (3)	−0.05606 (18)	0.0638 (6)
H4	−0.0737 (14)	0.850 (3)	−0.064 (2)	0.087 (7)*
C5	0.02492 (9)	0.7826 (2)	0.03876 (16)	0.0541 (5)
H5	0.0334 (10)	0.852 (2)	0.0948 (15)	0.054 (5)*
C6	0.07974 (8)	0.68292 (17)	0.05940 (13)	0.0419 (4)
C7	0.14509 (8)	0.68166 (17)	0.15888 (12)	0.0393 (4)
C8	0.19716 (8)	0.58370 (17)	0.17776 (12)	0.0390 (4)
C9	0.18749 (9)	0.47940 (18)	0.09900 (12)	0.0407 (4)
C10	0.26583 (8)	0.57643 (19)	0.28059 (12)	0.0413 (4)
H10B	0.3055 (9)	0.5445 (19)	0.2663 (13)	0.042 (4)*
H10A	0.2774 (9)	0.668 (2)	0.3117 (14)	0.044 (5)*
C11	0.26352 (8)	0.47532 (18)	0.35929 (13)	0.0416 (4)
C12	0.32854 (11)	0.3976 (2)	0.53692 (15)	0.0564 (5)
H12B	0.2882 (13)	0.416 (3)	0.5450 (19)	0.082 (7)*
H12A	0.3291 (12)	0.291 (3)	0.5182 (18)	0.084 (7)*
C13	0.39738 (15)	0.4393 (3)	0.63283 (17)	0.0757 (7)
H13C	0.3974 (17)	0.546 (4)	0.658 (2)	0.132 (12)*
H13B	0.4378 (17)	0.416 (4)	0.623 (3)	0.119 (11)*
H13A	0.4017 (15)	0.380 (3)	0.688 (2)	0.105 (9)*
C14	0.11943 (14)	0.3847 (3)	−0.07860 (17)	0.0627 (5)
H14C	0.1113 (13)	0.444 (3)	−0.1404 (19)	0.084 (7)*
H14B	0.1627 (16)	0.332 (3)	−0.050 (2)	0.105 (10)*
H14A	0.0770 (14)	0.324 (3)	−0.0999 (19)	0.080 (7)*

	U11	U22	U33	U12	U13	U23
N1	0.0472 (8)	0.0479 (8)	0.0323 (7)	−0.0083 (6)	0.0145 (6)	0.0011 (6)
O1	0.0542 (7)	0.0477 (7)	0.0450 (7)	0.0045 (5)	0.0196 (6)	0.0028 (5)
O2	0.0436 (7)	0.0519 (7)	0.0528 (7)	−0.0003 (5)	0.0160 (6)	−0.0072 (6)
O3	0.0505 (8)	0.0751 (10)	0.0550 (8)	−0.0127 (6)	0.0149 (6)	0.0126 (7)
O4	0.0458 (7)	0.0627 (8)	0.0352 (6)	0.0027 (5)	0.0095 (5)	0.0072 (5)
C1	0.0368 (8)	0.0472 (9)	0.0359 (8)	−0.0093 (7)	0.0101 (7)	0.0112 (7)
C2	0.0476 (10)	0.0667 (13)	0.0378 (9)	−0.0157 (9)	0.0075 (8)	0.0124 (9)
C3	0.0387 (10)	0.0794 (15)	0.0531 (11)	−0.0089 (9)	0.0040 (8)	0.0275 (11)
C4	0.0373 (10)	0.0654 (13)	0.0707 (13)	0.0015 (9)	0.0129 (9)	0.0215 (11)
C5	0.0400 (9)	0.0511 (11)	0.0597 (11)	−0.0004 (8)	0.0159 (8)	0.0127 (9)
C6	0.0345 (8)	0.0410 (9)	0.0417 (8)	−0.0051 (6)	0.0123 (7)	0.0121 (7)
C7	0.0356 (8)	0.0383 (8)	0.0380 (8)	−0.0068 (6)	0.0137 (6)	0.0032 (6)
C8	0.0356 (8)	0.0384 (8)	0.0337 (8)	−0.0037 (6)	0.0100 (6)	0.0046 (6)
C9	0.0420 (9)	0.0398 (8)	0.0356 (8)	−0.0045 (6)	0.0156 (7)	0.0050 (6)
C10	0.0340 (8)	0.0394 (9)	0.0380 (9)	−0.0014 (6)	0.0084 (7)	−0.0008 (6)
C11	0.0365 (8)	0.0442 (9)	0.0372 (8)	0.0059 (6)	0.0128 (7)	−0.0017 (6)
C12	0.0600 (12)	0.0693 (14)	0.0412 (10)	0.0198 (9)	0.0259 (9)	0.0129 (9)
C13	0.0800 (17)	0.0909 (19)	0.0360 (10)	0.0189 (14)	0.0134 (10)	0.0088 (11)
C14	0.0691 (14)	0.0706 (14)	0.0398 (10)	−0.0091 (11)	0.0204 (10)	−0.0092 (10)

N1—C9	1.380 (2)	C5—H5	0.98 (2)
N1—C1	1.393 (2)	C6—C7	1.445 (2)
N1—C14	1.463 (3)	C7—C8	1.360 (2)
O1—C9	1.250 (2)	C8—C9	1.437 (2)
O2—C7	1.341 (2)	C8—C10	1.507 (2)
O2—H2O	0.95 (3)	C10—C11	1.504 (2)
O3—C11	1.201 (2)	C10—H10B	1.021 (18)
O4—C11	1.335 (2)	C10—H10A	0.935 (19)
O4—C12	1.453 (2)	C12—C13	1.507 (3)
C1—C6	1.393 (2)	C12—H12B	0.95 (2)
C1—C2	1.414 (2)	C12—H12A	1.02 (3)
C2—C3	1.377 (3)	C13—H13C	1.05 (4)
C2—H2	0.92 (3)	C13—H13B	0.98 (3)
C3—C4	1.378 (3)	C13—H13A	0.94 (3)
C3—H3	0.99 (3)	C14—H14C	1.00 (3)
C4—C5	1.379 (3)	C14—H14B	0.95 (3)
C4—H4	0.97 (3)	C14—H14A	0.98 (3)
C5—C6	1.409 (2)
C9—N1—C1	121.71 (14)	O1—C9—C8	122.39 (14)
C9—N1—C14	117.82 (16)	N1—C9—C8	118.67 (14)
C1—N1—C14	120.46 (16)	C11—C10—C8	114.00 (13)
C7—O2—H2O	118.5 (15)	C11—C10—H10B	109.2 (10)
C11—O4—C12	117.13 (15)	C8—C10—H10B	108.6 (10)
C6—C1—N1	120.06 (14)	C11—C10—H10A	106.7 (11)
C6—C1—C2	118.72 (17)	C8—C10—H10A	110.0 (10)
N1—C1—C2	121.21 (17)	H10B—C10—H10A	108.2 (14)
C3—C2—C1	120.0 (2)	O3—C11—O4	123.65 (16)
C3—C2—H2	123.1 (16)	O3—C11—C10	125.92 (15)
C1—C2—H2	116.8 (16)	O4—C11—C10	110.43 (14)
C2—C3—C4	121.30 (18)	O4—C12—C13	106.40 (19)
C2—C3—H3	122.3 (17)	O4—C12—H12B	108.5 (15)
C4—C3—H3	116.4 (16)	C13—C12—H12B	112.4 (14)
C3—C4—C5	119.7 (2)	O4—C12—H12A	108.7 (14)
C3—C4—H4	124.4 (15)	C13—C12—H12A	111.0 (13)
C5—C4—H4	115.9 (16)	H12B—C12—H12A	110 (2)
C4—C5—C6	120.3 (2)	C12—C13—H13C	113.3 (18)
C4—C5—H5	122.7 (11)	C12—C13—H13B	110 (2)
C6—C5—H5	117.1 (11)	H13C—C13—H13B	114 (3)
C1—C6—C5	119.99 (15)	C12—C13—H13A	106.8 (18)
C1—C6—C7	118.66 (14)	H13C—C13—H13A	105 (3)
C5—C6—C7	121.36 (17)	H13B—C13—H13A	107 (3)
O2—C7—C8	124.99 (14)	N1—C14—H14C	107.4 (15)
O2—C7—C6	114.46 (14)	N1—C14—H14B	106.9 (18)
C8—C7—C6	120.53 (15)	H14C—C14—H14B	112 (2)
C7—C8—C9	120.23 (14)	N1—C14—H14A	108.7 (15)
C7—C8—C10	122.64 (15)	H14C—C14—H14A	107.6 (19)
C9—C8—C10	117.11 (14)	H14B—C14—H14A	114 (2)
O1—C9—N1	118.92 (15)
C9—N1—C1—C6	3.6 (2)	O2—C7—C8—C9	178.40 (14)
C14—N1—C1—C6	−177.17 (16)	C6—C7—C8—C9	−0.4 (2)
C9—N1—C1—C2	−175.56 (14)	O2—C7—C8—C10	−0.3 (2)
C14—N1—C1—C2	3.7 (2)	C6—C7—C8—C10	−179.14 (14)
C6—C1—C2—C3	0.5 (2)	C1—N1—C9—O1	176.58 (14)
N1—C1—C2—C3	179.68 (15)	C14—N1—C9—O1	−2.7 (2)
C1—C2—C3—C4	1.1 (3)	C1—N1—C9—C8	−4.7 (2)
C2—C3—C4—C5	−1.5 (3)	C14—N1—C9—C8	176.02 (16)
C3—C4—C5—C6	0.2 (3)	C7—C8—C9—O1	−178.23 (15)
N1—C1—C6—C5	179.10 (14)	C10—C8—C9—O1	0.5 (2)
C2—C1—C6—C5	−1.7 (2)	C7—C8—C9—N1	3.1 (2)
N1—C1—C6—C7	−0.8 (2)	C10—C8—C9—N1	−178.10 (13)
C2—C1—C6—C7	178.41 (14)	C7—C8—C10—C11	90.75 (19)
C4—C5—C6—C1	1.4 (3)	C9—C8—C10—C11	−87.98 (19)
C4—C5—C6—C7	−178.75 (16)	C12—O4—C11—O3	−1.4 (2)
C1—C6—C7—O2	−179.69 (13)	C12—O4—C11—C10	178.93 (15)
C5—C6—C7—O2	0.4 (2)	C8—C10—C11—O3	7.3 (3)
C1—C6—C7—C8	−0.7 (2)	C8—C10—C11—O4	−173.09 (13)
C5—C6—C7—C8	179.38 (15)	C11—O4—C12—C13	−175.83 (16)

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)

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)

Symmetry code: (i) .