3-Acetyl-4-hydroxy­quinolin-2(1H)-one: resonance-assisted O—H...O hydrogen bonding

The molecule of the title compound, C₁₁H₉NO₃, a pharmacologically important quinoline derivative, adopts an overall planar shape. The structure is stabilized by an intra­molecular O—H...O=C hydrogen bond, forming an S(6) hydrogen-bonded ring pattern. The O—H...O inter­action results in delocalization of the electron density within the dihydro­pyridine ring, as observed for resonance-assisted hydrogen bonds, leading to lengthening of the carbonyl O=C and pyridyl C=C bonds, and shortening of the C—OH bond in this hydrogen-bonded S(6) ring structure. The cooperative inter­molecular N—H...O hydrogen bonds cluster mol­ecules into closed dimers, characterized by an R₂²(8) ring pattern. Aromatic–aromatic stacking inter­actions are also observed in the packing, with an inter­planar distance of 3.352 Å and a slippage of 1.855 Å

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.048
• wR factor = 0.124
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

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S1. Comment

Quinoline-2,4-dione derivatives are useful molecules for the synthesis of many pharmacologically active compounds including glycine NMDA and serotonin (5-HT₃) receptor antagonists (Detsi et al., 1996; Lange et al., 2001; Sarveswari & Raja, 2006). The title compound, 3-acetyl-4-hydroxyquinolin-2(1H)-one, (I), is one such derivative having antimalarial and antimicrobial properties, where acetyl group is substituted at the position-3. A search of quinoline-2,4-dione derivatives, substituted at the position-3 in Cambridge Structural Database (CSD, Version 5.28; Allen, 2002) reveled following 18 similar compounds (the CSD entry numbers are provided within the braces): N-methyl-N-phenyl-1,2-dihydro-4-hydroxy-1-methyl-2-oxoquinoline- 3-carboxamide (BEHDUO), 3-(1,2-dimethyl-2-hydroxypropyl)-4-hydroxy-1-methylquinolin-2(1H)-one (CEPTAS), ethyl-1-phenyl-2-oxo-4-hydroxyquinoline-3-carboxylate (EYOTUH), 1-ethyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid (FACVUB) 1-Propyl-2-oxo-3-ethoxycarbonyl-4-hydroxyquinoline (FOWKIL), N-(6-hydroxybenzothiazol-2-yl)-1-ethyl-4-hydroxy-2-oxo-1,2- dihydroquinolinyl-3-carboxamide (IBEGAY), 4-hydroxy-1-methyl-2-oxo-N-(4-oxo-2-propyl-3,4-dihydroquinazolin-3-yl)-1, 2-dihydroquinoline-3-carboxamide (KOBZOQ), 6-bromo-1-isopentyl-2-oxo-3-(N-(1-phenylethyl)carboxamido)-4- hydroxyquinoline (LOHFOD), 2-oxo-4-hydroxy-3-(1-phenylethylaminocarbonyl)-1-pentylquinoline (LOHNIF), 1-ethyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid 3-chloro-benzylidenehydrazide (NAMYIK), 6-bromo-4-hydroxy-2-oxo-1-phenyl-3-ethoxycarbonyl-1,2-dihydroquinoline (NANFIS), N-(2-diethylaminoethyl) 1-allyl–4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carbox amide hydrochloride (NANFOY), 3-ethoxycarbonyl-4-hydroxy-6-(methoxymethoxy)-1-methyl-2-quinolone (OJILIC), 3-(1-hydroxyiminoethyl)-4-hydroxyquinolin-2(1H)-one (QONPOY), N-(1-adamantyl)-4-hydroxy-1-(2-methylpropyl)-2-oxo-1,2-dihydroquinoline- 3-carboxamide 2-propanol solvate (QOQQUI), 3-benzoyl-1-ethyl-4-hydroxy-2-quinolone (TEZHAH), 3-(N,N-dibutylaminocarbonylmethyl)-2-oxo-1,2-dihydro-4- hydroxyquinoline (XEPPEN), 1,1,3,6-tetramethyl-1,2,4a,11,12,12a-hexahydro-12-(4-hydroxy-1- methylquinolin-2-one-3-yl)-2-benzopyrano(3,4 - c)quinolin-5-one chloroform (YIVMIZ).

The crystal structure of (I) is discussed in this report. The molecular structure with atom numbering scheme is shown in Fig 1. A l l the non-hydrogen atoms in (I) are coplanar with maximum deviation of -0.07 (1)Å for C11. The acetyl group is slighly tilted with respect to the quinoline ring with the torsion angle C3—C2—C10—C11 of -177.4 (2)°. An intra-molecular O2—H2···O3 hydrogen bond stabilize the structure, which form a hydrogen-bonded S(6) closed-ring structure. Hydrogen bond parameters are provided in Table 2. The intramolecular hydrogen bond leads to delocalization of the electron density within the dihydropyridine ring thereby affecting bond distances in S(6) ring-pattern as also observed in an analogus structure of methyl 1-acetonyl-4-hydroxy-2-oxo-1,2-dihydro-quinoline-3-carboxylate (Shishkina et al., 2005). Such hydrogen bonds, observed first by Gilli et al. (1989) are referred to as resonance-assisted hydrogen bond (RAHB), which are formed betweeen conjugated multiple π-bonds (Jeffrey, 1997). The relevent bond distances are listed in Table 1. A s a result of RAHB in (I), the carbonyl O3?C10 and C2?C3 bonds are longer than standard values for O?C (1.210 Å) and C?C (1.334 Å), respectively (Bürgi & Dunitz, 1994). On the other hand, hydroxyl O2—C3, and C3—C4 bonds in the pyridine ring are shorter than their respective standard values (C_sp²—O = 1.362 Å; C_sp²—C_sp² = 1.455 Å). There is no significant change observed in the bond length C2—C10 as compared to the standard value.

Crystal packing diagram is shown in Fig. 2. In the crystal, the molecules cluster into closed dimers via cooperative intermolecular N1—H1···O1ⁱ hydrogen bonds [symmetry code (i): -x, -y, -z]. The dimeric assembly is characterized by R₂²(8) ring pattern. Significant π···π interactions were also observed in the packing. Cg1 (centeroid of C4—C9 ring) makes a parallel stacking interaction with Cg1 of the molecule, related by a center of inversion with Cg1···Cg1ⁱⁱ [symmetry code (ii): -x, 1 - y, -z] 3.352Å apart and a slippage of 1.855 Å. The center-to-center distance is 3.831 (1) Å.

Related literature

Quinoline-2,4-dione derivatives are useful molecules for the synthesis of many pharmacologically active compounds (Detsi et al., 1996; Lange et al., 2001; Sarveswari & Raja, 2006). 18 analogous structures have been reported in the Cambridge Structural Database (Version 5.28; Allen, 2002). For relevent literature for resonance-assisted hydrogen bonds, see Gilli et al. (1989), Jeffrey (1997) and Shishkina et al. (2005). Molecular bond distances are reported by Bürgi & Dunitz (1994).

S2. Experimental

A mixture of methylanthranilate(3.85 ml, 25 mmol), ethylacetoacetate (4 ml, 5 mmol) and a catalytic amount of sodium ethoxide was irradiated under microwave at 360 W for 3 minutes. The solid obtained, following the cooling was then dissolved in water and acidified with dilute acetic acid. The product was filtered, dried and recrystallized from acetic acid [melting point 261–263°C].

S3. Refinement

All the parameters of heavy atoms and polar H atoms (NH and OH) were freely refined except that the O–H distance, in the final cycle of refinement was restrained to 0.86 (2) Å. Rest of the H atoms were positioned geometrically and refined as riding on their carrier atoms. The distances with hydrogen atoms were C_ar—H = 0.93 Å, methyl C—H = 0.96Å with U_iso (H) = 1.2 U_eq(C) [= 1.5 U_eq(C) for methyl H atoms], N—H = 0.92 (2) Å.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997)and PLATON (Spek,2003).

Figures

	Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing, showing the cooperative N—H···O hydrogen bonds forming molecular dimers and aromatic–aromatic stacking interactions. For clarity, only selected molecules and H atoms involved in the interactions are shown.

3-Acetyl-4-hydroxyquinolin-2(1H)-one

Crystal data

C11H9NO3	F(000) = 424
Mr = 203.19	Dx = 1.466 Mg m^−3
Monoclinic, P21/n	Melting point: 261(2) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.914 (3) Å	Cell parameters from 1119 reflections
b = 5.2297 (12) Å	θ = 3.5–24.5°
c = 14.946 (3) Å	µ = 0.11 mm^−1
β = 98.555 (4)°	T = 295 K
V = 920.9 (4) Å^3	Needle, colorless
Z = 4	0.3 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1812 independent reflections
Radiation source: fine-focus sealed tube	1209 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω–scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.95, Tmax = 0.98	k = −6→6
6736 measured reflections	l = −18→18

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0575P)^2 + 0.1258P] where P = (Fo^2 + 2Fc^2)/3
1812 reflections	(Δ/σ)max < 0.001
144 parameters	Δρmax = 0.18 e Å^−3
1 restraint	Δρmin = −0.12 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.

Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric.Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d

Plane 1 m1 = -0.50700(0.00021) m2 = 0.60194(0.00025) m3 = -0.61695(0.00021) D = -0.10597(0.00110) Atom d s d/s (d/s)**2 N1 * 0.0083 0.0016 5.067 25.673 O1 * 0.0131 0.0014 9.641 92.953 O2 * 0.0038 0.0015 2.461 6.055 O3 * 0.0102 0.0016 6.322 39.968 C1 * 0.0062 0.0019 3.297 10.873 C2 * 0.0048 0.0018 2.638 6.959 C3 * 0.0101 0.0019 5.207 27.112 C4 * 0.0108 0.0019 5.612 31.497 C5 * 0.0034 0.0022 1.524 2.323 C6 * -0.0105 0.0025 - 4.150 17.226 C7 * -0.0224 0.0024 - 9.321 86.872 C8 * -0.0161 0.0022 - 7.329 53.707 C9 * -0.0049 0.0019 - 2.549 6.497 C10 * -0.0117 0.0021 - 5.673 32.181 C11 * -0.0747 0.0025 - 30.230 913.870 ============ Sum((d/s)**2) for starred atoms 1353.766 Chi-squared at 95% for 12 degrees of freedom: 21.00 The group of atoms deviates significantly from planarity

Plane 2 m1 = -0.50314(0.00026) m2 = 0.60226(0.00028) m3 = -0.61979(0.00030) D = -0.10111(0.00121) Atom d s d/s (d/s)**2 N1 * 0.0060 0.0016 3.654 13.355 O1 * 0.0008 0.0014 0.587 0.344 O2 * -0.0046 0.0015 - 2.940 8.646 C1 * -0.0026 0.0019 - 1.362 1.854 C2 * -0.0063 0.0018 - 3.419 11.690 C3 * 0.0035 0.0019 1.805 3.259 C4 * 0.0110 0.0019 5.697 32.456 C5 * 0.0081 0.0022 3.691 13.624 C6 * 0.0007 0.0025 0.266 0.071 C7 * -0.0092 0.0024 - 3.846 14.794 C8 * -0.0074 0.0022 - 3.347 11.202 C9 * -0.0027 0.0019 - 1.416 2.006 C10 - 0.0296 0.0021 - 14.379 206.766 O3 - 0.0094 0.0016 - 5.870 34.458 C11 - 0.0978 0.0025 - 39.563 1565.243 ============ Sum((d/s)**2) for starred atoms 113.302 Chi-squared at 95% for 9 degrees of freedom: 16.90 The group of atoms deviates significantly from planarity

Plane 3 m1 = -0.53467(0.00105) m2 = 0.57611(0.00100) m3 = -0.61824(0.00080) D = -0.16756(0.00482) Atom d s d/s (d/s)**2 O3 * -0.0011 0.0016 - 0.688 0.473 C2 * -0.0013 0.0018 - 0.714 0.510 C10 * 0.0050 0.0021 2.444 5.975 C11 * -0.0023 0.0025 - 0.922 0.849 C1 0.0302 0.0019 15.947 254.299 C3 - 0.0490 0.0019 - 25.144 632.222 O1 0.0840 0.0014 61.747 3812.751 O2 - 0.0847 0.0016 - 54.488 2968.986 ============ Sum((d/s)**2) for starred atoms 7.807 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity

Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 0.28 (0.02) 179.72 (0.02) 1 3 2.17 (0.06) 177.83 (0.06) 2 3 2.35 (0.06) 177.65 (0.06)

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	0.09377 (13)	0.2592 (3)	0.04347 (11)	0.0403 (4)
H1	0.0852 (16)	0.139 (4)	−0.0022 (14)	0.048*
O1	−0.05886 (11)	0.1058 (3)	0.09779 (9)	0.0491 (4)
O2	0.14531 (14)	0.8292 (3)	0.22959 (10)	0.0552 (5)
H2	0.0905 (16)	0.813 (5)	0.2603 (15)	0.078 (9)*
O3	−0.02021 (14)	0.6819 (3)	0.29588 (10)	0.0628 (5)
C1	0.01820 (16)	0.2671 (4)	0.10394 (12)	0.0385 (5)
C2	0.03497 (16)	0.4702 (4)	0.17146 (12)	0.0394 (5)
C3	0.12517 (17)	0.6416 (4)	0.17013 (13)	0.0408 (5)
C4	0.20119 (16)	0.6217 (4)	0.10472 (13)	0.0404 (5)
C5	0.29257 (18)	0.7891 (4)	0.10253 (15)	0.0514 (6)
H5	0.3054	0.9213	0.1444	0.062*
C6	0.3628 (2)	0.7584 (5)	0.03905 (17)	0.0622 (7)
H6	0.4232	0.8703	0.0377	0.075*
C7	0.34452 (19)	0.5602 (5)	−0.02366 (16)	0.0598 (7)
H7	0.3931	0.5408	−0.0665	0.072*
C8	0.25622 (18)	0.3942 (4)	−0.02310 (14)	0.0506 (6)
H8	0.2444	0.2631	−0.0655	0.061*
C9	0.18338 (16)	0.4227 (4)	0.04178 (13)	0.0395 (5)
C10	−0.03790 (17)	0.5005 (4)	0.24056 (13)	0.0459 (5)
C11	−0.1327 (2)	0.3222 (5)	0.24988 (16)	0.0624 (7)
H11A	−0.1715	0.3790	0.2982	0.094*
H11B	−0.1030	0.1536	0.2631	0.094*
H11C	−0.1849	0.3190	0.1944	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0464 (10)	0.0384 (10)	0.0377 (9)	−0.0026 (8)	0.0115 (8)	−0.0061 (8)
O1	0.0508 (8)	0.0500 (9)	0.0489 (9)	−0.0089 (7)	0.0147 (7)	−0.0074 (7)
O2	0.0673 (11)	0.0479 (9)	0.0499 (9)	−0.0026 (8)	0.0065 (8)	−0.0147 (8)
O3	0.0813 (12)	0.0613 (11)	0.0490 (9)	0.0115 (9)	0.0202 (8)	−0.0135 (8)
C1	0.0413 (11)	0.0379 (11)	0.0359 (11)	0.0055 (9)	0.0044 (8)	0.0038 (9)
C2	0.0474 (12)	0.0367 (11)	0.0342 (11)	0.0070 (9)	0.0060 (9)	0.0031 (9)
C3	0.0529 (12)	0.0330 (11)	0.0344 (11)	0.0076 (9)	−0.0001 (9)	−0.0017 (9)
C4	0.0446 (11)	0.0382 (11)	0.0374 (11)	0.0029 (9)	0.0024 (9)	0.0037 (9)
C5	0.0538 (13)	0.0451 (13)	0.0531 (13)	−0.0067 (10)	0.0012 (10)	−0.0004 (11)
C6	0.0533 (14)	0.0644 (16)	0.0698 (16)	−0.0137 (12)	0.0121 (12)	0.0082 (13)
C7	0.0547 (14)	0.0711 (18)	0.0573 (15)	−0.0015 (12)	0.0203 (11)	0.0056 (13)
C8	0.0538 (13)	0.0551 (14)	0.0454 (12)	0.0019 (11)	0.0160 (10)	−0.0001 (11)
C9	0.0432 (11)	0.0396 (12)	0.0352 (11)	0.0030 (9)	0.0047 (9)	0.0065 (9)
C10	0.0542 (13)	0.0474 (13)	0.0373 (11)	0.0149 (10)	0.0107 (10)	0.0040 (10)
C11	0.0682 (15)	0.0688 (17)	0.0566 (15)	0.0083 (13)	0.0301 (12)	0.0044 (12)

Geometric parameters (Å, º)

N1—C1	1.368 (2)	C5—C6	1.365 (3)
N1—C9	1.371 (2)	C5—H5	0.9300
N1—H1	0.92 (2)	C6—C7	1.393 (3)
O1—C1	1.240 (2)	C6—H6	0.9300
O2—C3	1.321 (2)	C7—C8	1.365 (3)
O2—H2	0.856 (10)	C7—H7	0.9300
O3—C10	1.255 (2)	C8—C9	1.402 (3)
C1—C2	1.458 (3)	C8—H8	0.9300
C2—C3	1.402 (3)	C10—C11	1.487 (3)
C2—C10	1.453 (3)	C11—H11A	0.9600
C3—C4	1.432 (3)	C11—H11B	0.9600
C4—C9	1.398 (3)	C11—H11C	0.9600
C4—C5	1.401 (3)
C1—N1—C9	125.76 (17)	C5—C6—H6	119.9
C1—N1—H1	119.9 (12)	C7—C6—H6	119.9
C9—N1—H1	114.4 (12)	C8—C7—C6	120.9 (2)
C3—O2—H2	102.3 (18)	C8—C7—H7	119.6
O1—C1—N1	118.91 (17)	C6—C7—H7	119.6
O1—C1—C2	124.79 (17)	C7—C8—C9	119.6 (2)
N1—C1—C2	116.30 (17)	C7—C8—H8	120.2
C3—C2—C10	118.73 (18)	C9—C8—H8	120.2
C3—C2—C1	118.84 (17)	N1—C9—C4	119.51 (17)
C10—C2—C1	122.44 (18)	N1—C9—C8	120.69 (19)
O2—C3—C2	121.87 (18)	C4—C9—C8	119.80 (18)
O2—C3—C4	116.31 (19)	O3—C10—C2	119.4 (2)
C2—C3—C4	121.82 (17)	O3—C10—C11	117.86 (18)
C9—C4—C5	119.35 (19)	C2—C10—C11	122.72 (19)
C9—C4—C3	117.75 (18)	C10—C11—H11A	109.5
C5—C4—C3	122.89 (19)	C10—C11—H11B	109.5
C6—C5—C4	120.1 (2)	H11A—C11—H11B	109.5
C6—C5—H5	119.9	C10—C11—H11C	109.5
C4—C5—H5	119.9	H11A—C11—H11C	109.5
C5—C6—C7	120.3 (2)	H11B—C11—H11C	109.5
C9—N1—C1—O1	−179.67 (18)	C4—C5—C6—C7	−0.2 (3)
C9—N1—C1—C2	0.7 (3)	C5—C6—C7—C8	0.2 (4)
O1—C1—C2—C3	−179.37 (18)	C6—C7—C8—C9	−0.3 (3)
N1—C1—C2—C3	0.2 (2)	C1—N1—C9—C4	−1.6 (3)
O1—C1—C2—C10	1.1 (3)	C1—N1—C9—C8	179.29 (18)
N1—C1—C2—C10	−179.33 (17)	C5—C4—C9—N1	−179.71 (18)
C10—C2—C3—O2	−0.2 (3)	C3—C4—C9—N1	1.4 (3)
C1—C2—C3—O2	−179.73 (17)	C5—C4—C9—C8	−0.6 (3)
C10—C2—C3—C4	179.27 (18)	C3—C4—C9—C8	−179.47 (19)
C1—C2—C3—C4	−0.3 (3)	C7—C8—C9—N1	179.67 (19)
O2—C3—C4—C9	178.97 (17)	C7—C8—C9—C4	0.5 (3)
C2—C3—C4—C9	−0.5 (3)	C3—C2—C10—O3	1.6 (3)
O2—C3—C4—C5	0.1 (3)	C1—C2—C10—O3	−178.83 (18)
C2—C3—C4—C5	−179.38 (18)	C3—C2—C10—C11	−177.42 (18)
C9—C4—C5—C6	0.4 (3)	C1—C2—C10—C11	2.1 (3)
C3—C4—C5—C6	179.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.86 (2)	1.64 (2)	2.459 (2)	158 (3)
N1—H1···O1^i	0.92 (2)	1.91 (2)	2.831 (2)	177 (2)

Symmetry code: (i) −x, −y, −z.