organic compounds
Methyl 2-oxo-2H-chromene-3-carboxylate
aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, bChemistry Division, Directorate of Science, PINSTECH, Nilore, Islamabad, Pakistan, and cInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany.
*Correspondence e-mail: aamersaeed@yahoo.com
The title compound, C11H8O4, features an almost planar molecule (r.m.s. deviation = 0.033 Å for all non-H atoms). In the crystal, the molecules are linked via C—H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to (1-21).
Related literature
For details of the biological activity of et al. (2006); Kostova (2006); Reddy et al. (2002); Lacy & O'Kennedy (2004). For other applications of see: Flašík et al. (2009); Fonsecaa et al. (2010).
see: SuryaExperimental
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2001); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812040044/su2501sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040044/su2501Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812040044/su2501Isup3.mol
Supporting information file. DOI: https://doi.org/10.1107/S1600536812040044/su2501Isup4.cml
Salicylaldehyde (1.22 g, 0.01 mol) and diethylmalonate (1.6 g, 0.01 mol) were dissolved in ethanol to give a clear solution. Piperidine (2 ml) was added and the mixture was refluxed for 5 h. The content was concentrated to a small volume. The product (3) was poured onto crushed ice, filtered out and crystallized from ethanol to give colourless crystals, m.p. 393–395 K; Yield: 90%. Spectroscopic data for the title compound are available in the archived CIF.
All the H atoms were included in calculated positions and treated as riding atoms: Caromatic—H = 0.95 Å and Cmethyl—H = 0.98 Å, with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl).
Coumarins (2H-1-benzopyran-2-ones) are natural
and amongst the best known oxygen heterocycles, well represented as a structural motif in numerous natural products (Surya et al., 2006). Various coumarin derivatives are known to possess an array of biological activities, including anticancer, anti-HIV, anti acetylcholinesterase, antifungal, antioxidant, antihelmintic, anticoagulant, antibacterial, antiviral and anticlotting activities, and find extensive application in pharmaceuticals, fragrances, agrochemicals, additives in food and cosmetics and insecticides (Kostova, 2006; Reddy et al., 2002; Lacy & O'Kennedy, 2004). Moreover, find applications as dyes in laser technology, fluorescent indicators, optical brighteners and photosensitizers (Flašík et al., 2009). Ethyl 2-oxo-2H-chromene-3-carboxylate irreversibly inhibits phospholipase A2 (sPLA2) from Crotalus durissus ruruima venom with an IC50 of 3.1 ± 0.06 nmol (Fonsecaa et al., 2010).The title compound, Fig. 1, features an almost planar molecule (r.m.s. deviation = 0.033 Å for all non-H atoms). The maximum deviation from the mean plane being 0.0734 (12) Å for atom O2.
In the crystal, molecules are linked via C—H···O hydrogen bonds forming two-dimensional networks lying parallel to (121); Table 1 and Fig. 2.
For details of the biological activity of
see: Surya et al. (2006); Kostova (2006); Reddy et al. (2002); Lacy & O'Kennedy (2004). For other applications of see: Flašík et al. (2009); Fonsecaa et al. (2010). [Please revise scheme to show correct methyl derivative, not ethyl]Data collection: X-AREA (Stoe & Cie, 2001); cell
X-AREA (Stoe & Cie, 2001); data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C11H8O4 | Z = 2 |
Mr = 204.17 | F(000) = 212 |
Triclinic, P1 | Dx = 1.474 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8874 (10) Å | Cell parameters from 10306 reflections |
b = 9.782 (3) Å | θ = 3.3–26.0° |
c = 13.078 (3) Å | µ = 0.11 mm−1 |
α = 111.569 (19)° | T = 173 K |
β = 90.83 (2)° | Block, colourless |
γ = 95.01 (2)° | 0.30 × 0.27 × 0.20 mm |
V = 460.1 (2) Å3 |
Stoe IPDS II two-circle diffractometer | 1725 independent reflections |
Radiation source: Genix 3D IµS microfocus X-ray source | 1378 reflections with I > 2σ(I) |
Genix 3D multilayer optics monochromator | Rint = 0.054 |
ω scans | θmax = 25.7°, θmin = 4.2° |
Absorption correction: multi-scan (X-RED32; Stoe & Cie, 2001) | h = −4→4 |
Tmin = 0.967, Tmax = 0.978 | k = −11→11 |
4851 measured reflections | l = −15→15 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0591P)2 + 0.0733P] where P = (Fo2 + 2Fc2)/3 |
1725 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C11H8O4 | γ = 95.01 (2)° |
Mr = 204.17 | V = 460.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 3.8874 (10) Å | Mo Kα radiation |
b = 9.782 (3) Å | µ = 0.11 mm−1 |
c = 13.078 (3) Å | T = 173 K |
α = 111.569 (19)° | 0.30 × 0.27 × 0.20 mm |
β = 90.83 (2)° |
Stoe IPDS II two-circle diffractometer | 1725 independent reflections |
Absorption correction: multi-scan (X-RED32; Stoe & Cie, 2001) | 1378 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.978 | Rint = 0.054 |
4851 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.21 e Å−3 |
1725 reflections | Δρmin = −0.18 e Å−3 |
136 parameters |
Experimental. Spectroscopic data for the title compound: IR (KBr, cm-1) 1710 (C═O, coumarin), 1670 (C═O), 1750 (C═O, ester), 1200 (C—O); 1HNMR (DMSO-d6, 300MHz, δ p.p.m.): 7.5 (4H, m, Ar—H), 8.1 (1H, s, Ar—H, H-4), 1.83 (3H, t, CH3), 3.20 (2H, q, CH2). Mass m/z (%): 216 M+. |
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 | ||
O1 | 0.8969 (3) | 0.56201 (13) | 0.15727 (9) | 0.0371 (3) | |
O2 | 1.2039 (3) | 0.76399 (14) | 0.26510 (10) | 0.0472 (4) | |
O3 | 0.8489 (3) | 0.68616 (13) | 0.54600 (9) | 0.0469 (4) | |
O4 | 1.1674 (3) | 0.84024 (13) | 0.48731 (9) | 0.0394 (3) | |
C1 | 1.0100 (4) | 0.66021 (18) | 0.26166 (14) | 0.0352 (4) | |
C2 | 0.8796 (4) | 0.62198 (18) | 0.35402 (13) | 0.0328 (4) | |
C3 | 0.6775 (4) | 0.49482 (18) | 0.33393 (13) | 0.0329 (4) | |
H3 | 0.5978 | 0.4715 | 0.3945 | 0.039* | |
C4 | 0.5793 (4) | 0.39425 (18) | 0.22513 (13) | 0.0330 (4) | |
C5 | 0.3781 (4) | 0.25926 (18) | 0.20103 (14) | 0.0371 (4) | |
H5 | 0.2943 | 0.2314 | 0.2591 | 0.045* | |
C6 | 0.3016 (4) | 0.1670 (2) | 0.09335 (15) | 0.0408 (4) | |
H6 | 0.1695 | 0.0745 | 0.0773 | 0.049* | |
C7 | 0.4178 (4) | 0.2090 (2) | 0.00751 (14) | 0.0422 (4) | |
H7 | 0.3604 | 0.1452 | −0.0666 | 0.051* | |
C8 | 0.6144 (4) | 0.34155 (19) | 0.02878 (14) | 0.0385 (4) | |
H8 | 0.6927 | 0.3700 | −0.0296 | 0.046* | |
C9 | 0.6949 (4) | 0.43218 (18) | 0.13747 (13) | 0.0338 (4) | |
C10 | 0.9625 (4) | 0.71847 (18) | 0.47158 (13) | 0.0338 (4) | |
C11 | 1.2460 (4) | 0.9364 (2) | 0.60135 (14) | 0.0415 (4) | |
H11A | 1.3986 | 1.0231 | 0.6043 | 0.062* | |
H11B | 1.3614 | 0.8827 | 0.6399 | 0.062* | |
H11C | 1.0311 | 0.9682 | 0.6368 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0401 (6) | 0.0439 (7) | 0.0297 (6) | −0.0047 (5) | 0.0051 (5) | 0.0184 (5) |
O2 | 0.0525 (7) | 0.0500 (7) | 0.0411 (7) | −0.0127 (6) | 0.0077 (6) | 0.0228 (6) |
O3 | 0.0582 (7) | 0.0504 (8) | 0.0306 (7) | −0.0130 (6) | 0.0077 (5) | 0.0171 (6) |
O4 | 0.0420 (6) | 0.0437 (7) | 0.0321 (6) | −0.0096 (5) | −0.0006 (5) | 0.0167 (5) |
C1 | 0.0333 (8) | 0.0419 (9) | 0.0325 (9) | −0.0004 (7) | 0.0049 (6) | 0.0171 (7) |
C2 | 0.0294 (7) | 0.0411 (9) | 0.0312 (9) | 0.0011 (6) | 0.0042 (6) | 0.0178 (7) |
C3 | 0.0309 (8) | 0.0423 (9) | 0.0301 (8) | 0.0021 (7) | 0.0053 (6) | 0.0191 (7) |
C4 | 0.0304 (7) | 0.0400 (9) | 0.0313 (9) | 0.0015 (6) | 0.0033 (6) | 0.0165 (7) |
C5 | 0.0349 (8) | 0.0450 (9) | 0.0348 (9) | −0.0009 (7) | 0.0024 (7) | 0.0198 (8) |
C6 | 0.0395 (8) | 0.0422 (9) | 0.0401 (10) | −0.0031 (7) | −0.0016 (7) | 0.0161 (8) |
C7 | 0.0407 (9) | 0.0506 (10) | 0.0318 (9) | 0.0017 (8) | −0.0016 (7) | 0.0120 (8) |
C8 | 0.0372 (8) | 0.0505 (10) | 0.0318 (9) | 0.0043 (7) | 0.0044 (7) | 0.0199 (8) |
C9 | 0.0300 (7) | 0.0407 (9) | 0.0339 (9) | 0.0018 (6) | 0.0034 (6) | 0.0179 (7) |
C10 | 0.0319 (8) | 0.0390 (9) | 0.0333 (9) | −0.0003 (6) | 0.0032 (6) | 0.0173 (7) |
C11 | 0.0417 (9) | 0.0456 (10) | 0.0356 (9) | −0.0061 (7) | −0.0029 (7) | 0.0158 (8) |
O1—C9 | 1.3691 (19) | C4—C5 | 1.400 (2) |
O1—C1 | 1.387 (2) | C5—C6 | 1.376 (2) |
O2—C1 | 1.1970 (19) | C5—H5 | 0.9500 |
O3—C10 | 1.2069 (19) | C6—C7 | 1.398 (3) |
O4—C10 | 1.3209 (19) | C6—H6 | 0.9500 |
O4—C11 | 1.452 (2) | C7—C8 | 1.378 (2) |
C1—C2 | 1.474 (2) | C7—H7 | 0.9500 |
C2—C3 | 1.348 (2) | C8—C9 | 1.384 (2) |
C2—C10 | 1.491 (2) | C8—H8 | 0.9500 |
C3—C4 | 1.424 (2) | C11—H11A | 0.9800 |
C3—H3 | 0.9500 | C11—H11B | 0.9800 |
C4—C9 | 1.397 (2) | C11—H11C | 0.9800 |
C9—O1—C1 | 123.86 (12) | C7—C6—H6 | 119.9 |
C10—O4—C11 | 115.67 (12) | C8—C7—C6 | 120.97 (17) |
O2—C1—O1 | 115.90 (14) | C8—C7—H7 | 119.5 |
O2—C1—C2 | 128.38 (16) | C6—C7—H7 | 119.5 |
O1—C1—C2 | 115.71 (14) | C7—C8—C9 | 118.30 (15) |
C3—C2—C1 | 120.00 (16) | C7—C8—H8 | 120.9 |
C3—C2—C10 | 117.20 (14) | C9—C8—H8 | 120.9 |
C1—C2—C10 | 122.80 (15) | O1—C9—C8 | 117.63 (13) |
C2—C3—C4 | 122.29 (14) | O1—C9—C4 | 120.23 (15) |
C2—C3—H3 | 118.9 | C8—C9—C4 | 122.14 (15) |
C4—C3—H3 | 118.9 | O3—C10—O4 | 123.18 (16) |
C9—C4—C5 | 118.29 (15) | O3—C10—C2 | 121.75 (15) |
C9—C4—C3 | 117.80 (15) | O4—C10—C2 | 115.07 (13) |
C5—C4—C3 | 123.90 (14) | O4—C11—H11A | 109.5 |
C6—C5—C4 | 120.13 (15) | O4—C11—H11B | 109.5 |
C6—C5—H5 | 119.9 | H11A—C11—H11B | 109.5 |
C4—C5—H5 | 119.9 | O4—C11—H11C | 109.5 |
C5—C6—C7 | 120.15 (16) | H11A—C11—H11C | 109.5 |
C5—C6—H6 | 119.9 | H11B—C11—H11C | 109.5 |
C9—O1—C1—O2 | 175.14 (13) | C1—O1—C9—C8 | −177.09 (13) |
C9—O1—C1—C2 | −4.0 (2) | C1—O1—C9—C4 | 2.4 (2) |
O2—C1—C2—C3 | −175.95 (16) | C7—C8—C9—O1 | 178.57 (13) |
O1—C1—C2—C3 | 3.1 (2) | C7—C8—C9—C4 | −0.9 (2) |
O2—C1—C2—C10 | 3.8 (3) | C5—C4—C9—O1 | −178.95 (13) |
O1—C1—C2—C10 | −177.24 (12) | C3—C4—C9—O1 | 0.3 (2) |
C1—C2—C3—C4 | −0.7 (2) | C5—C4—C9—C8 | 0.6 (2) |
C10—C2—C3—C4 | 179.63 (13) | C3—C4—C9—C8 | 179.76 (13) |
C2—C3—C4—C9 | −1.1 (2) | C11—O4—C10—O3 | −0.9 (2) |
C2—C3—C4—C5 | 178.10 (14) | C11—O4—C10—C2 | 179.09 (12) |
C9—C4—C5—C6 | 0.7 (2) | C3—C2—C10—O3 | −1.4 (2) |
C3—C4—C5—C6 | −178.50 (14) | C1—C2—C10—O3 | 178.88 (14) |
C4—C5—C6—C7 | −1.4 (2) | C3—C2—C10—O4 | 178.57 (13) |
C5—C6—C7—C8 | 1.0 (2) | C1—C2—C10—O4 | −1.1 (2) |
C6—C7—C8—C9 | 0.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.95 | 2.54 | 3.360 (2) | 145 |
C5—H5···O3i | 0.95 | 2.46 | 3.298 (2) | 147 |
C8—H8···O1ii | 0.95 | 2.55 | 3.454 (2) | 160 |
C11—H11A···O2iii | 0.98 | 2.53 | 3.354 (2) | 142 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+3, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H8O4 |
Mr | 204.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 3.8874 (10), 9.782 (3), 13.078 (3) |
α, β, γ (°) | 111.569 (19), 90.83 (2), 95.01 (2) |
V (Å3) | 460.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.30 × 0.27 × 0.20 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle |
Absorption correction | Multi-scan (X-RED32; Stoe & Cie, 2001) |
Tmin, Tmax | 0.967, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4851, 1725, 1378 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.123, 1.09 |
No. of reflections | 1725 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.18 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-RED32 (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.95 | 2.54 | 3.360 (2) | 145 |
C5—H5···O3i | 0.95 | 2.46 | 3.298 (2) | 147 |
C8—H8···O1ii | 0.95 | 2.55 | 3.454 (2) | 160 |
C11—H11A···O2iii | 0.98 | 2.53 | 3.354 (2) | 142 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+3, −y+2, −z+1. |
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.
Coumarins (2H-1-benzopyran-2-ones) are natural lactones and amongst the best known oxygen heterocycles, well represented as a structural motif in numerous natural products (Surya et al., 2006). Various coumarin derivatives are known to possess an array of biological activities, including anticancer, anti-HIV, anti acetylcholinesterase, antifungal, antioxidant, antihelmintic, anticoagulant, antibacterial, antiviral and anticlotting activities, and find extensive application in pharmaceuticals, fragrances, agrochemicals, additives in food and cosmetics and insecticides (Kostova, 2006; Reddy et al., 2002; Lacy & O'Kennedy, 2004). Moreover, coumarins find applications as dyes in laser technology, fluorescent indicators, optical brighteners and photosensitizers (Flašík et al., 2009). Ethyl 2-oxo-2H-chromene-3-carboxylate irreversibly inhibits phospholipase A2 (sPLA2) from Crotalus durissus ruruima venom with an IC50 of 3.1 ± 0.06 nmol (Fonsecaa et al., 2010).
The title compound, Fig. 1, features an almost planar molecule (r.m.s. deviation = 0.033 Å for all non-H atoms). The maximum deviation from the mean plane being 0.0734 (12) Å for atom O2.
In the crystal, molecules are linked via C—H···O hydrogen bonds forming two-dimensional networks lying parallel to (121); Table 1 and Fig. 2.