Methyl 1-acetonyl-4-hydr­oxy-2-oxo-1,2-dihydro­quinoline-3-carboxyl­ate

The title compound, C₁₄H₁₃NO₅, exhibits a resonance-assisted hydrogen bond O—H...O=C [2.505 (4) Å], which leads to a lengthening of the carbonyl C=O bond, a shortening of the C—OH 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) = 0.006 Å
• R factor = 0.049
• wR factor = 0.138
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         38 Perc.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1991); software used to prepare material for publication: SHELXL97.

Methyl 1-acetonyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylate

Crystal data

C14H13NO5	F(000) = 576
Mr = 275.25	Dx = 1.425 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 12 reflections
a = 11.084 (4) Å	θ = 2–25°
b = 15.120 (5) Å	µ = 0.11 mm^−1
c = 8.133 (3) Å	T = 293 K
β = 109.77 (3)°	Plate, colourless
V = 1282.7 (8) Å^3	0.40 × 0.20 × 0.20 mm
Z = 4

Data collection

Siemens P3/PC diffractometer	Rint = 0.069
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 2.0°
Graphite monochromator	h = −13→12
ω–2θ scans	k = −18→0
2406 measured reflections	l = 0→9
2238 independent reflections	2 standard reflections every 98 reflections
857 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0631P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.88	(Δ/σ)max < 0.001
2238 reflections	Δρmax = 0.17 e Å^−3
185 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (13)

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	0.3973 (2)	0.6718 (2)	0.0847 (3)	0.0402 (8)
C1	0.3563 (3)	0.7574 (2)	0.0954 (4)	0.0424 (10)
O1	0.3812 (2)	0.52387 (17)	0.1113 (4)	0.0651 (9)
O2	0.0598 (2)	0.71380 (18)	0.1722 (4)	0.0700 (9)
H2O	0.0291	0.6674	0.1922	0.105*
C2	0.4280 (4)	0.8300 (3)	0.0789 (4)	0.0553 (11)
H2	0.5050	0.8215	0.0589	0.066*
O3	0.0352 (2)	0.55035 (19)	0.1995 (4)	0.0700 (9)
C3	0.3860 (5)	0.9144 (3)	0.0920 (5)	0.0665 (13)
H3	0.4348	0.9626	0.0808	0.080*
O4	0.1956 (2)	0.46152 (18)	0.2068 (3)	0.0632 (8)
C4	0.2727 (5)	0.9283 (3)	0.1213 (5)	0.0700 (13)
H4	0.2450	0.9856	0.1296	0.084*
C5	0.2009 (4)	0.8583 (3)	0.1382 (5)	0.0612 (12)
H5	0.1239	0.8680	0.1576	0.073*
O5	0.6342 (2)	0.67652 (19)	0.3442 (4)	0.0686 (9)
C6	0.2422 (3)	0.7712 (2)	0.1265 (5)	0.0445 (10)
C7	0.1695 (3)	0.6971 (3)	0.1468 (5)	0.0483 (10)
C8	0.2147 (3)	0.6118 (2)	0.1475 (4)	0.0415 (9)
C9	0.3341 (3)	0.5963 (3)	0.1141 (5)	0.0439 (9)
C10	0.1411 (4)	0.5399 (3)	0.1835 (5)	0.0513 (10)
C11	0.1276 (4)	0.3896 (3)	0.2520 (7)	0.0998 (18)
H11A	0.0491	0.3789	0.1576	0.150*
H11B	0.1088	0.4046	0.3555	0.150*
H11C	0.1797	0.3373	0.2732	0.150*
C12	0.5136 (3)	0.6553 (2)	0.0440 (4)	0.0462 (10)
H12B	0.5175	0.6972	−0.0444	0.055*
H12A	0.5086	0.5964	−0.0054	0.055*
C13	0.6354 (3)	0.6624 (2)	0.1989 (5)	0.0446 (9)
C14	0.7553 (3)	0.6508 (2)	0.1574 (5)	0.0608 (11)
H14A	0.7531	0.5948	0.1007	0.091*
H14B	0.8278	0.6525	0.2635	0.091*
H14C	0.7623	0.6975	0.0813	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0312 (16)	0.053 (2)	0.0397 (19)	0.0038 (15)	0.0155 (16)	−0.0036 (16)
C1	0.041 (2)	0.047 (3)	0.036 (2)	−0.002 (2)	0.009 (2)	−0.0008 (19)
O1	0.0575 (18)	0.0483 (18)	0.097 (2)	0.0129 (15)	0.0364 (18)	−0.0009 (16)
O2	0.0434 (17)	0.080 (2)	0.096 (2)	0.0146 (15)	0.0358 (17)	−0.003 (2)
C2	0.062 (3)	0.063 (3)	0.040 (2)	−0.007 (2)	0.016 (2)	0.002 (2)
O3	0.0402 (17)	0.092 (2)	0.083 (2)	−0.0078 (15)	0.0277 (16)	0.0004 (17)
C3	0.091 (4)	0.055 (3)	0.047 (3)	−0.013 (3)	0.014 (3)	−0.002 (2)
O4	0.0543 (17)	0.0568 (19)	0.078 (2)	−0.0060 (16)	0.0212 (16)	0.0135 (17)
C4	0.103 (4)	0.041 (3)	0.063 (3)	0.012 (3)	0.024 (3)	0.002 (2)
C5	0.069 (3)	0.056 (3)	0.057 (3)	0.014 (3)	0.019 (2)	−0.004 (2)
O5	0.0513 (18)	0.106 (2)	0.0484 (17)	0.0154 (16)	0.0167 (15)	−0.0058 (17)
C6	0.045 (2)	0.043 (3)	0.042 (2)	0.004 (2)	0.010 (2)	−0.007 (2)
C7	0.031 (2)	0.065 (3)	0.045 (2)	0.009 (2)	0.0089 (19)	−0.001 (2)
C8	0.030 (2)	0.049 (3)	0.043 (2)	−0.001 (2)	0.0077 (18)	−0.001 (2)
C9	0.035 (2)	0.053 (3)	0.042 (2)	0.000 (2)	0.0110 (19)	0.003 (2)
C10	0.041 (2)	0.056 (3)	0.052 (3)	0.000 (2)	0.009 (2)	0.000 (2)
C11	0.091 (4)	0.090 (4)	0.115 (5)	−0.030 (3)	0.030 (4)	0.026 (3)
C12	0.045 (2)	0.058 (3)	0.042 (2)	−0.0052 (19)	0.023 (2)	−0.007 (2)
C13	0.038 (2)	0.044 (2)	0.056 (3)	−0.0007 (17)	0.021 (2)	−0.002 (2)
C14	0.040 (2)	0.065 (3)	0.085 (3)	0.0035 (19)	0.032 (2)	−0.002 (2)

Geometric parameters (Å, º)

N1—C1	1.385 (4)	C5—C6	1.408 (5)
N1—C9	1.402 (4)	C5—H5	0.9300
N1—C12	1.457 (4)	O5—C13	1.205 (4)
C1—C6	1.386 (4)	C6—C7	1.422 (5)
C1—C2	1.388 (5)	C7—C8	1.384 (5)
O1—C9	1.216 (4)	C8—C10	1.447 (5)
O2—C7	1.324 (4)	C8—C9	1.457 (5)
O2—H2O	0.8200	C11—H11A	0.9600
C2—C3	1.375 (5)	C11—H11B	0.9600
C2—H2	0.9300	C11—H11C	0.9600
O3—C10	1.234 (4)	C12—C13	1.507 (5)
C3—C4	1.370 (5)	C12—H12B	0.9700
C3—H3	0.9300	C12—H12A	0.9700
O4—C10	1.315 (4)	C13—C14	1.488 (4)
O4—C11	1.440 (4)	C14—H14A	0.9600
C4—C5	1.358 (5)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C1—N1—C9	123.9 (3)	C10—C8—C9	121.8 (4)
C1—N1—C12	120.6 (3)	O1—C9—N1	119.2 (3)
C9—N1—C12	115.5 (3)	O1—C9—C8	124.8 (4)
N1—C1—C6	119.4 (3)	N1—C9—C8	116.0 (4)
N1—C1—C2	121.5 (3)	O3—C10—O4	120.4 (4)
C6—C1—C2	119.1 (4)	O3—C10—C8	123.2 (4)
C7—O2—H2O	109.5	O4—C10—C8	116.3 (3)
C3—C2—C1	120.4 (4)	O4—C11—H11A	109.5
C3—C2—H2	119.8	O4—C11—H11B	109.5
C1—C2—H2	119.8	H11A—C11—H11B	109.5
C4—C3—C2	120.6 (4)	O4—C11—H11C	109.5
C4—C3—H3	119.7	H11A—C11—H11C	109.5
C2—C3—H3	119.7	H11B—C11—H11C	109.5
C10—O4—C11	117.6 (3)	N1—C12—C13	114.1 (3)
C5—C4—C3	120.1 (4)	N1—C12—H12B	108.7
C5—C4—H4	119.9	C13—C12—H12B	108.7
C3—C4—H4	119.9	N1—C12—H12A	108.7
C4—C5—C6	120.4 (4)	C13—C12—H12A	108.7
C4—C5—H5	119.8	H12B—C12—H12A	107.6
C6—C5—H5	119.8	O5—C13—C14	123.4 (4)
C1—C6—C5	119.4 (4)	O5—C13—C12	121.9 (3)
C1—C6—C7	119.4 (3)	C14—C13—C12	114.7 (3)
C5—C6—C7	121.2 (4)	C13—C14—H14A	109.5
O2—C7—C8	121.8 (4)	C13—C14—H14B	109.5
O2—C7—C6	117.0 (3)	H14A—C14—H14B	109.5
C8—C7—C6	121.1 (3)	C13—C14—H14C	109.5
C7—C8—C10	118.2 (3)	H14A—C14—H14C	109.5
C7—C8—C9	120.0 (3)	H14B—C14—H14C	109.5
C9—N1—C1—C6	−4.1 (5)	O2—C7—C8—C9	178.3 (3)
C12—N1—C1—C6	177.1 (3)	C6—C7—C8—C9	−4.6 (5)
C9—N1—C1—C2	174.7 (3)	C1—N1—C9—O1	−175.9 (3)
C12—N1—C1—C2	−4.1 (5)	C12—N1—C9—O1	3.0 (5)
N1—C1—C2—C3	−179.3 (3)	C1—N1—C9—C8	3.6 (5)
C6—C1—C2—C3	−0.5 (5)	C12—N1—C9—C8	−177.4 (3)
C1—C2—C3—C4	−0.1 (6)	C7—C8—C9—O1	−179.7 (4)
C2—C3—C4—C5	0.2 (6)	C10—C8—C9—O1	0.9 (6)
C3—C4—C5—C6	0.2 (6)	C7—C8—C9—N1	0.7 (5)
N1—C1—C6—C5	179.7 (3)	C10—C8—C9—N1	−178.7 (3)
C2—C1—C6—C5	0.9 (5)	C11—O4—C10—O3	−0.4 (6)
N1—C1—C6—C7	0.0 (5)	C11—O4—C10—C8	176.8 (3)
C2—C1—C6—C7	−178.8 (3)	C7—C8—C10—O3	6.1 (5)
C4—C5—C6—C1	−0.8 (5)	C9—C8—C10—O3	−174.5 (4)
C4—C5—C6—C7	178.9 (4)	C7—C8—C10—O4	−170.9 (3)
C1—C6—C7—O2	−178.5 (3)	C9—C8—C10—O4	8.5 (5)
C5—C6—C7—O2	1.9 (5)	C1—N1—C12—C13	82.2 (4)
C1—C6—C7—C8	4.3 (5)	C9—N1—C12—C13	−96.8 (3)
C5—C6—C7—C8	−175.4 (4)	N1—C12—C13—O5	3.2 (5)
O2—C7—C8—C10	−2.3 (5)	N1—C12—C13—C14	−176.6 (3)
C6—C7—C8—C10	174.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.82	1.77	2.505 (4)	148