organic compounds
3-Hydroxy-7,8-dimethoxyquinolin-2(1H)-one
aSchool of Pharmacy, Guangdong Pharmaceutical University, Guangzhou 510006, People's Republic of China, bSchool of Chemistry and Chemical Engineering, Sun Yat-sun University, Guangzhou 510275, People's Republic of China, and cDepartment of Applied Biology and Chemistry Technology, Polytechnic University of Hong Kong, Hong Kong, People's Republic of China
*Correspondence e-mail: zsusj@yahoo.com.cn
In the 11H11NO4, intramolecular O—H⋯O hydrogen bonding results in the formation of a planar five-membered ring, which is nearly coplanar with the quinoline group. Intermolecular N—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers.
of the title compound, CRelated literature
For general background, see: Beak (1977); Nimlos et al. (1987); Rajnikant et al. (2002); Johnson (1996). For related literature, see: Lin et al. (2000); Song et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808011549/hk2455sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011549/hk2455Isup2.hkl
The title compound, (I), was prepared according to our reported procedure (Song et al., 2006). Suitable crystals were obtained by recrystallization from chloroform/ethyl acetate (1:1) solution (m.p. 436-437 K). Spectroscopic analysis: IR (KBr, νcm-1): 3442, 3169, 1665, 1638, 1116; 1H NMR (CDCl3, δ, p.p.m.): 7.14–7.17(d, 1H, J = 9.0 Hz), 7.07(s, 1H), 6.85-6.88 (d, 1H, J = 9.0 Hz), 6.61(br, OH),3.97 (s, 3H), 3.93 (s, 3H); 13C NMR (CDCl3, δ, p.p.m.): 159.0, 150.2, 143.7, 134.2,127.2,121.1,115.7,112.2, 108.8,60.6,56.0; analysis, calculated for C11H11N1O4: C 59.73, H 5.01, N 6.33%; found: C 59.98, H 5.23, N 6.14%.
H atom (for NH) was located in a difference syntheses and refined [N-H = 0.90 (3) Å and Uiso(H) = 0.068 (7) Å2]. The remaining H atoms were positioned geometrically, with O-H = 0.82 Å (for OH) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,O), where x = 1.2 for aromatic H, and x = 1.5 for all other H atoms.
Data collection: SMART (Bruker, 1998); cell
SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C11H11NO4 | F(000) = 464 |
Mr = 221.21 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 886 reflections |
a = 4.9655 (16) Å | θ = 3.1–27.1° |
b = 14.084 (5) Å | µ = 0.11 mm−1 |
c = 14.888 (5) Å | T = 294 K |
β = 96.208 (6)° | Block, colorless |
V = 1035.1 (6) Å3 | 0.60 × 0.37 × 0.31 mm |
Z = 4 |
Bruker CCD area-detector diffractometer | 2228 independent reflections |
Radiation source: fine-focus sealed tube | 1761 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 27.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→5 |
Tmin = 0.937, Tmax = 0.967 | k = −17→15 |
6788 measured reflections | l = −18→18 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0907P)2 + 0.3738P] where P = (Fo2 + 2Fc2)/3 |
2228 reflections | (Δ/σ)max < 0.001 |
150 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C11H11NO4 | V = 1035.1 (6) Å3 |
Mr = 221.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.9655 (16) Å | µ = 0.11 mm−1 |
b = 14.084 (5) Å | T = 294 K |
c = 14.888 (5) Å | 0.60 × 0.37 × 0.31 mm |
β = 96.208 (6)° |
Bruker CCD area-detector diffractometer | 2228 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1761 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.967 | Rint = 0.015 |
6788 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.50 e Å−3 |
2228 reflections | Δρmin = −0.25 e Å−3 |
150 parameters |
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 > 2sigma(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 | ||
O1 | −0.1615 (3) | 0.39255 (11) | 1.01266 (11) | 0.0616 (5) | |
O2 | −0.2273 (3) | 0.20136 (9) | 0.97741 (9) | 0.0514 (4) | |
H2 | −0.2816 | 0.2327 | 1.0182 | 0.077* | |
O3 | 0.6647 (4) | 0.48962 (12) | 0.67193 (12) | 0.0681 (5) | |
O4 | 0.3678 (3) | 0.54717 (9) | 0.80367 (10) | 0.0498 (4) | |
N1 | 0.1136 (3) | 0.41905 (11) | 0.90243 (11) | 0.0439 (4) | |
H1 | 0.119 (5) | 0.481 (2) | 0.9155 (17) | 0.068 (7)* | |
C1 | −0.0380 (4) | 0.36225 (14) | 0.95063 (13) | 0.0458 (5) | |
C2 | −0.0452 (4) | 0.26212 (14) | 0.92587 (13) | 0.0483 (5) | |
C3 | 0.0957 (4) | 0.22783 (14) | 0.86147 (14) | 0.0500 (5) | |
H3A | 0.0912 | 0.1632 | 0.8488 | 0.060* | |
C4 | 0.2532 (4) | 0.28997 (13) | 0.81204 (13) | 0.0442 (4) | |
C5 | 0.2543 (4) | 0.38754 (13) | 0.83327 (12) | 0.0404 (4) | |
C6 | 0.4035 (5) | 0.26022 (15) | 0.74343 (15) | 0.0535 (5) | |
H6A | 0.4079 | 0.1960 | 0.7290 | 0.064* | |
C7 | 0.5456 (5) | 0.32376 (16) | 0.69650 (15) | 0.0544 (5) | |
H7A | 0.6462 | 0.3021 | 0.6514 | 0.065* | |
C8 | 0.5392 (4) | 0.42049 (15) | 0.71632 (14) | 0.0490 (5) | |
C9 | 0.3942 (4) | 0.45222 (12) | 0.78474 (13) | 0.0427 (4) | |
C10 | 0.6032 (5) | 0.58783 (16) | 0.85291 (18) | 0.0617 (6) | |
H10A | 0.5711 | 0.6538 | 0.8638 | 0.093* | |
H10B | 0.7547 | 0.5816 | 0.8184 | 0.093* | |
H10C | 0.6416 | 0.5554 | 0.9095 | 0.093* | |
C11 | 0.8222 (6) | 0.4614 (2) | 0.60194 (19) | 0.0789 (8) | |
H11A | 0.8986 | 0.5166 | 0.5766 | 0.118* | |
H11B | 0.7088 | 0.4286 | 0.5557 | 0.118* | |
H11C | 0.9653 | 0.4200 | 0.6265 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0712 (10) | 0.0546 (9) | 0.0639 (9) | −0.0102 (7) | 0.0302 (8) | −0.0133 (7) |
O2 | 0.0809 (10) | 0.0349 (7) | 0.0397 (7) | −0.0015 (6) | 0.0119 (6) | −0.0009 (5) |
O3 | 0.0819 (12) | 0.0579 (10) | 0.0713 (10) | 0.0009 (8) | 0.0395 (9) | 0.0048 (7) |
O4 | 0.0549 (8) | 0.0341 (7) | 0.0615 (8) | 0.0020 (6) | 0.0117 (6) | −0.0013 (6) |
N1 | 0.0498 (9) | 0.0337 (8) | 0.0496 (9) | −0.0009 (6) | 0.0118 (7) | −0.0058 (6) |
C1 | 0.0491 (10) | 0.0431 (10) | 0.0463 (10) | −0.0035 (8) | 0.0096 (8) | −0.0056 (8) |
C2 | 0.0559 (12) | 0.0403 (10) | 0.0488 (10) | −0.0069 (8) | 0.0063 (9) | 0.0001 (8) |
C3 | 0.0620 (12) | 0.0332 (9) | 0.0552 (11) | −0.0018 (8) | 0.0076 (9) | −0.0039 (8) |
C4 | 0.0489 (10) | 0.0360 (9) | 0.0480 (10) | 0.0022 (8) | 0.0058 (8) | −0.0042 (7) |
C5 | 0.0415 (9) | 0.0371 (9) | 0.0427 (9) | 0.0037 (7) | 0.0045 (7) | −0.0038 (7) |
C6 | 0.0606 (13) | 0.0398 (10) | 0.0611 (12) | 0.0061 (9) | 0.0115 (10) | −0.0110 (9) |
C7 | 0.0580 (12) | 0.0521 (12) | 0.0557 (11) | 0.0083 (9) | 0.0177 (9) | −0.0081 (9) |
C8 | 0.0507 (11) | 0.0471 (11) | 0.0507 (11) | 0.0033 (8) | 0.0129 (9) | 0.0029 (8) |
C9 | 0.0452 (10) | 0.0353 (9) | 0.0480 (10) | 0.0039 (7) | 0.0061 (8) | −0.0005 (7) |
C10 | 0.0622 (14) | 0.0469 (11) | 0.0779 (15) | −0.0108 (10) | 0.0157 (11) | −0.0078 (10) |
C11 | 0.0848 (18) | 0.0863 (19) | 0.0728 (16) | −0.0045 (15) | 0.0419 (14) | 0.0001 (14) |
O2—H2 | 0.8200 | C5—C4 | 1.410 (3) |
O3—C11 | 1.425 (3) | C6—C7 | 1.376 (3) |
O4—C9 | 1.376 (2) | C6—C4 | 1.393 (3) |
O4—C10 | 1.430 (3) | C6—H6A | 0.9300 |
N1—C1 | 1.356 (3) | C7—H7A | 0.9300 |
N1—C5 | 1.379 (2) | C8—O3 | 1.365 (3) |
N1—H1 | 0.90 (3) | C8—C9 | 1.384 (3) |
C1—O1 | 1.238 (2) | C8—C7 | 1.395 (3) |
C1—C2 | 1.457 (3) | C10—H10A | 0.9600 |
C2—O2 | 1.513 (2) | C10—H10B | 0.9600 |
C3—C2 | 1.337 (3) | C10—H10C | 0.9600 |
C3—C4 | 1.430 (3) | C11—H11A | 0.9600 |
C3—H3A | 0.9300 | C11—H11B | 0.9600 |
C5—C9 | 1.394 (3) | C11—H11C | 0.9600 |
C2—O2—H2 | 109.5 | C4—C6—H6A | 119.3 |
C8—O3—C11 | 118.1 (2) | C6—C7—C8 | 120.21 (19) |
C9—O4—C10 | 113.78 (16) | C6—C7—H7A | 119.9 |
C1—N1—C5 | 124.09 (16) | C8—C7—H7A | 119.9 |
C1—N1—H1 | 117.9 (17) | O3—C8—C9 | 115.29 (18) |
C5—N1—H1 | 118.0 (17) | O3—C8—C7 | 124.92 (19) |
O1—C1—N1 | 122.64 (18) | C9—C8—C7 | 119.78 (19) |
O1—C1—C2 | 121.43 (18) | O4—C9—C8 | 122.25 (17) |
N1—C1—C2 | 115.93 (17) | O4—C9—C5 | 117.72 (17) |
C3—C2—C1 | 122.03 (18) | C8—C9—C5 | 119.91 (17) |
C3—C2—O2 | 123.18 (17) | O4—C10—H10A | 109.5 |
C1—C2—O2 | 114.78 (17) | O4—C10—H10B | 109.5 |
C2—C3—C4 | 120.40 (18) | H10A—C10—H10B | 109.5 |
C2—C3—H3A | 119.8 | O4—C10—H10C | 109.5 |
C4—C3—H3A | 119.8 | H10A—C10—H10C | 109.5 |
C6—C4—C5 | 117.91 (18) | H10B—C10—H10C | 109.5 |
C6—C4—C3 | 124.03 (18) | O3—C11—H11A | 109.5 |
C5—C4—C3 | 118.06 (17) | O3—C11—H11B | 109.5 |
N1—C5—C9 | 119.87 (16) | H11A—C11—H11B | 109.5 |
N1—C5—C4 | 119.41 (17) | O3—C11—H11C | 109.5 |
C9—C5—C4 | 120.72 (17) | H11A—C11—H11C | 109.5 |
C7—C6—C4 | 121.43 (18) | H11B—C11—H11C | 109.5 |
C7—C6—H6A | 119.3 | ||
C10—O4—C9—C8 | −77.3 (2) | C9—C5—C4—C3 | −177.13 (18) |
C10—O4—C9—C5 | 106.8 (2) | N1—C5—C9—O4 | −5.1 (3) |
C5—N1—C1—O1 | 179.73 (19) | C4—C5—C9—O4 | 174.46 (17) |
C5—N1—C1—C2 | 0.4 (3) | N1—C5—C9—C8 | 178.93 (17) |
C1—N1—C5—C9 | 176.93 (18) | C4—C5—C9—C8 | −1.6 (3) |
C1—N1—C5—C4 | −2.6 (3) | C7—C6—C4—C5 | −1.1 (3) |
O1—C1—C2—C3 | −177.3 (2) | C7—C6—C4—C3 | 178.2 (2) |
N1—C1—C2—C3 | 2.0 (3) | C4—C6—C7—C8 | −0.7 (3) |
O1—C1—C2—O2 | 3.7 (3) | C9—C8—O3—C11 | 178.7 (2) |
N1—C1—C2—O2 | −176.97 (16) | C7—C8—O3—C11 | −2.2 (4) |
C4—C3—C2—C1 | −2.1 (3) | O3—C8—C7—C6 | −177.6 (2) |
C4—C3—C2—O2 | 176.75 (17) | C9—C8—C7—C6 | 1.4 (3) |
C2—C3—C4—C6 | −179.4 (2) | O3—C8—C9—O4 | 3.0 (3) |
C2—C3—C4—C5 | −0.1 (3) | C7—C8—C9—O4 | −176.09 (19) |
N1—C5—C4—C6 | −178.29 (18) | O3—C8—C9—C5 | 178.85 (17) |
C9—C5—C4—C6 | 2.2 (3) | C7—C8—C9—C5 | −0.3 (3) |
N1—C5—C4—C3 | 2.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.90 (3) | 2.07 (3) | 2.938 (2) | 161 (2) |
O2—H2···O1 | 0.82 | 2.33 | 2.756 (2) | 113 |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H11NO4 |
Mr | 221.21 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 4.9655 (16), 14.084 (5), 14.888 (5) |
β (°) | 96.208 (6) |
V (Å3) | 1035.1 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.60 × 0.37 × 0.31 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.937, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6788, 2228, 1761 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.174, 1.08 |
No. of reflections | 2228 |
No. of parameters | 150 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.50, −0.25 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.90 (3) | 2.07 (3) | 2.938 (2) | 161 (2) |
O2—H2···O1 | 0.82 | 2.33 | 2.756 (2) | 112.8 |
Symmetry code: (i) −x, −y+1, −z+2. |
Acknowledgements
Financial support from the National Science Foundation of China (grant No. 20072058), the 863 Foundation of China (grant No. 2003 A A624010) and Guangdong Pharmaceutical University is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Quinolin-2(1H)-ones can exist in both the lactam and lactim forms (Beak, 1977; Nimlos et al., 1987; Rajnikant et al., 2002). The tautomeric equilibrium of lactam-lactim attracts attention owing to its chemical, biological and theoretical importantce (Johnson, 1996). The title compound, (I), which is a part of the marine natural compound penicilliazine (Lin et al., 2000), was synthesized and characterized by our research group toward the natural product total synthesis. As part of our ongoing studies, we report herein the crystal structure of (I).
The molecule of the title compound, (I), (Fig. 1) adopts a bicyclic lactam-form with one hydroxy and two methoxy groups attached to atoms C2, C8 and C9, respectively. Rings A (N1/C1-C5) and B (C4-C9) are, of course, planar and the dihedral angle between them is A/B = 2.18 (3)°. The intramolecular O-H···O hydrogen bond (Table 1) results in the formation of a planar five-membered ring C (O1/O2/H2/C1/C2). Ring C is oriented with respect to the adjacent rings A and B at dihedral angles of A/C = 1.99 (3)° and B/C = 3.96 (3)°. So, rings A, B and C are nearly coplanar.
In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.