1-All­yl-4-hydr­oxy-2-oxo-1,2,5,6,7,8-hexa­hydro­quinoline-3-carboxylic acid

An X-ray diffraction study of the title compound, C₁₃H₁₅NO₄, has demonstrated that the formation of intra­molecular O—H...O=C hydrogen bonds leads to the lengthening of the carbon­yl C=O bonds, shortening of the (C=)C—O(—H) bond and delocalization of the electron density within the dihydro­pyridine ring.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.132
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         45 Perc.
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     -   C13     ..       5.04 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1991); software used to prepare material for publication: SHELXL97.

1-Allyl-4-hydroxy-2-oxo-1,2,5,6,7,8-hexahydroquinoline-3-carboxylic acid

Crystal data

C13H15NO4	F(000) = 1056
Mr = 249.26	Dx = 1.381 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 24 reflections
a = 16.823 (4) Å	θ = 10–11°
b = 7.179 (2) Å	µ = 0.10 mm^−1
c = 19.847 (5) Å	T = 293 K
V = 2397.0 (11) Å^3	Needle, colourless
Z = 8	0.30 × 0.10 × 0.10 mm

Data collection

Siemens P3/PC diffractometer	Rint = 0.03
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 2.1°
Graphite monochromator	h = 0→20
θ–2θ scans	k = 0→8
2087 measured reflections	l = −23→0
2086 independent reflections	2 standard reflections every 98 reflections
935 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0714P)^2] where P = (Fo^2 + 2Fc^2)/3
2086 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	1.05775 (12)	0.3007 (3)	0.41713 (11)	0.0417 (6)
O1	1.14931 (12)	0.3376 (3)	0.50184 (11)	0.0639 (7)
O2	0.98629 (15)	0.2277 (3)	0.64867 (11)	0.0736 (7)
O3	1.11128 (14)	0.2978 (4)	0.62195 (11)	0.0714 (7)
H3O	1.1380	0.3103	0.5877	0.086*
O4	0.88264 (12)	0.1831 (3)	0.55454 (9)	0.0604 (6)
H4O	0.8993	0.1951	0.5931	0.072*
C1	1.07847 (18)	0.3009 (4)	0.48444 (14)	0.0448 (8)
C2	1.01776 (16)	0.2601 (4)	0.53308 (13)	0.0397 (7)
C3	0.94084 (16)	0.2223 (4)	0.51073 (14)	0.0409 (8)
C4	0.92086 (16)	0.2244 (4)	0.44117 (13)	0.0382 (7)
C5	0.83565 (17)	0.1906 (4)	0.42068 (14)	0.0535 (8)
H5A	0.8009	0.2627	0.4496	0.064*
H5B	0.8231	0.0599	0.4272	0.064*
C6	0.81978 (18)	0.2430 (5)	0.34751 (14)	0.0607 (9)
H6A	0.7693	0.1907	0.3333	0.073*
H6B	0.8164	0.3774	0.3435	0.073*
C7	0.88517 (18)	0.1710 (5)	0.30240 (14)	0.0585 (9)
H7A	0.8727	0.2007	0.2559	0.070*
H7B	0.8883	0.0366	0.3064	0.070*
C8	0.96555 (18)	0.2560 (4)	0.32073 (14)	0.0520 (8)
H8A	1.0073	0.1851	0.2989	0.062*
H8B	0.9678	0.3824	0.3035	0.062*
C9	0.98082 (16)	0.2595 (4)	0.39514 (13)	0.0395 (7)
C10	1.12272 (17)	0.3462 (4)	0.36924 (15)	0.0524 (8)
H10A	1.1550	0.4452	0.3881	0.063*
H10B	1.0998	0.3915	0.3275	0.063*
C11	1.17457 (19)	0.1818 (4)	0.35433 (16)	0.0580 (9)
H11	1.2008	0.1262	0.3903	0.070*
C12	1.18556 (19)	0.1116 (5)	0.29535 (18)	0.0763 (11)
H12A	1.1603	0.1634	0.2581	0.092*
H12B	1.2187	0.0090	0.2900	0.092*
C13	1.0371 (2)	0.2601 (4)	0.60523 (17)	0.0555 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0347 (13)	0.0456 (16)	0.0450 (16)	0.0021 (11)	0.0063 (11)	−0.0005 (11)
O1	0.0432 (13)	0.0742 (17)	0.0745 (15)	−0.0006 (12)	−0.0098 (11)	−0.0106 (12)
O2	0.0930 (18)	0.0883 (18)	0.0394 (13)	0.0126 (15)	0.0036 (13)	0.0016 (12)
O3	0.0775 (16)	0.0765 (17)	0.0601 (14)	0.0034 (15)	−0.0270 (13)	−0.0065 (14)
O4	0.0603 (13)	0.0812 (16)	0.0397 (12)	−0.0070 (12)	0.0148 (11)	0.0064 (12)
C1	0.0451 (19)	0.042 (2)	0.047 (2)	0.0021 (15)	−0.0063 (15)	−0.0064 (14)
C2	0.0468 (17)	0.0340 (16)	0.0383 (17)	0.0098 (15)	−0.0016 (15)	−0.0030 (13)
C3	0.0465 (18)	0.0368 (18)	0.0393 (19)	0.0047 (14)	0.0070 (14)	0.0034 (14)
C4	0.0420 (16)	0.0384 (16)	0.0342 (16)	0.0012 (13)	0.0013 (13)	−0.0004 (13)
C5	0.0432 (17)	0.061 (2)	0.056 (2)	−0.0081 (15)	−0.0021 (15)	−0.0057 (15)
C6	0.0512 (19)	0.071 (2)	0.0594 (19)	0.0001 (19)	−0.0191 (17)	−0.0029 (18)
C7	0.067 (2)	0.070 (2)	0.0382 (17)	−0.0010 (18)	−0.0118 (17)	−0.0056 (16)
C8	0.0575 (19)	0.061 (2)	0.0374 (16)	0.0074 (18)	0.0016 (15)	−0.0026 (16)
C9	0.0419 (16)	0.0367 (17)	0.0401 (17)	0.0038 (14)	0.0028 (14)	−0.0006 (14)
C10	0.0469 (17)	0.050 (2)	0.0605 (19)	−0.0029 (16)	0.0152 (16)	0.0016 (16)
C11	0.0521 (19)	0.065 (2)	0.057 (2)	0.0042 (17)	0.0136 (16)	0.0014 (18)
C12	0.070 (2)	0.086 (3)	0.073 (2)	0.007 (2)	0.0205 (19)	−0.004 (2)
C13	0.071 (3)	0.0444 (19)	0.051 (2)	0.0117 (19)	−0.016 (2)	−0.0055 (17)

Geometric parameters (Å, º)

N1—C1	1.381 (3)	C5—H5B	0.9700
N1—C9	1.397 (3)	C6—C7	1.510 (4)
N1—C10	1.485 (3)	C6—H6A	0.9700
O1—C1	1.268 (3)	C6—H6B	0.9700
O2—C13	1.236 (4)	C7—C8	1.528 (4)
O3—C13	1.320 (4)	C7—H7A	0.9700
O3—H3O	0.8200	C7—H7B	0.9700
O4—C3	1.339 (3)	C8—C9	1.499 (4)
O4—H4O	0.8200	C8—H8A	0.9700
C1—C2	1.436 (4)	C8—H8B	0.9700
C2—C3	1.395 (4)	C10—C11	1.497 (4)
C2—C13	1.468 (4)	C10—H10A	0.9700
C3—C4	1.421 (4)	C10—H10B	0.9700
C4—C9	1.384 (4)	C11—C12	1.288 (4)
C4—C5	1.510 (4)	C11—H11	0.9300
C5—C6	1.524 (4)	C12—H12A	0.9300
C5—H5A	0.9700	C12—H12B	0.9300
C1—N1—C9	122.4 (2)	C6—C7—H7A	109.3
C1—N1—C10	115.7 (2)	C8—C7—H7A	109.3
C9—N1—C10	121.9 (2)	C6—C7—H7B	109.3
C13—O3—H3O	109.5	C8—C7—H7B	109.3
C3—O4—H4O	109.5	H7A—C7—H7B	108.0
O1—C1—N1	120.1 (3)	C9—C8—C7	113.1 (2)
O1—C1—C2	121.9 (3)	C9—C8—H8A	109.0
N1—C1—C2	118.1 (2)	C7—C8—H8A	109.0
C3—C2—C1	119.1 (3)	C9—C8—H8B	109.0
C3—C2—C13	121.0 (3)	C7—C8—H8B	109.0
C1—C2—C13	119.9 (3)	H8A—C8—H8B	107.8
O4—C3—C2	120.8 (3)	C4—C9—N1	120.5 (3)
O4—C3—C4	117.4 (2)	C4—C9—C8	121.5 (3)
C2—C3—C4	121.8 (3)	N1—C9—C8	118.0 (2)
C9—C4—C3	118.1 (3)	N1—C10—C11	112.5 (2)
C9—C4—C5	122.9 (2)	N1—C10—H10A	109.1
C3—C4—C5	119.0 (2)	C11—C10—H10A	109.1
C4—C5—C6	112.5 (2)	N1—C10—H10B	109.1
C4—C5—H5A	109.1	C11—C10—H10B	109.1
C6—C5—H5A	109.1	H10A—C10—H10B	107.8
C4—C5—H5B	109.1	C12—C11—C10	124.9 (3)
C6—C5—H5B	109.1	C12—C11—H11	117.6
H5A—C5—H5B	107.8	C10—C11—H11	117.6
C7—C6—C5	110.7 (3)	C11—C12—H12A	120.0
C7—C6—H6A	109.5	C11—C12—H12B	120.0
C5—C6—H6A	109.5	H12A—C12—H12B	120.0
C7—C6—H6B	109.5	O2—C13—O3	121.1 (3)
C5—C6—H6B	109.5	O2—C13—C2	121.8 (3)
H6A—C6—H6B	108.1	O3—C13—C2	117.0 (3)
C6—C7—C8	111.5 (2)
C9—N1—C1—O1	179.3 (2)	C5—C6—C7—C8	−61.7 (4)
C10—N1—C1—O1	−0.3 (4)	C6—C7—C8—C9	44.6 (4)
C9—N1—C1—C2	−1.1 (4)	C3—C4—C9—N1	−3.2 (4)
C10—N1—C1—C2	179.3 (2)	C5—C4—C9—N1	176.2 (3)
O1—C1—C2—C3	179.5 (3)	C3—C4—C9—C8	177.3 (3)
N1—C1—C2—C3	0.0 (4)	C5—C4—C9—C8	−3.3 (4)
O1—C1—C2—C13	0.0 (4)	C1—N1—C9—C4	2.8 (4)
N1—C1—C2—C13	−179.6 (3)	C10—N1—C9—C4	−177.6 (2)
C1—C2—C3—O4	179.8 (2)	C1—N1—C9—C8	−177.7 (3)
C13—C2—C3—O4	−0.7 (4)	C10—N1—C9—C8	2.0 (4)
C1—C2—C3—C4	−0.5 (4)	C7—C8—C9—C4	−12.4 (4)
C13—C2—C3—C4	179.0 (2)	C7—C8—C9—N1	168.1 (3)
O4—C3—C4—C9	−178.2 (2)	C1—N1—C10—C11	81.7 (3)
C2—C3—C4—C9	2.1 (4)	C9—N1—C10—C11	−98.0 (3)
O4—C3—C4—C5	2.4 (4)	N1—C10—C11—C12	120.3 (3)
C2—C3—C4—C5	−177.3 (3)	C3—C2—C13—O2	−0.3 (5)
C9—C4—C5—C6	−13.3 (4)	C1—C2—C13—O2	179.2 (3)
C3—C4—C5—C6	166.1 (3)	C3—C2—C13—O3	−179.9 (3)
C4—C5—C6—C7	44.9 (4)	C1—C2—C13—O3	−0.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	0.82	1.73	2.485 (3)	153
O4—H4O···O2	0.82	1.85	2.576 (3)	147