organic compounds
5-Hydroxy-7-methoxy-4H-chromen-4-one
aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, and bInstituto de Bio-Orgánica `Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez No. 2, La Laguna, Tenerife, Spain
*Correspondence e-mail: ivanbritob@yahoo.com
The molecular conformation of the title compound, C10H8O4, isolated from Laretia acualis, is stabilized by a strong intramolecular hydrogen bond between the hydroxyl and carbonyl groups. The crystal packing shows π–π stacking interactions. The chromene (4H-1-benzopyran-4-one) unit is essentially planar.
Related literature
For related literature, see: Gabor (1988); Valenti et al. (1993, 1998); Vasconcelos et al. (1998); Bernstein et al. (1995); Wickens (1995); Wallet & Cody (1995).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: COLLECT (Nonius, 1998); cell DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536807066494/bt2661sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066494/bt2661Isup2.hkl
Dried and finely powdered tissues from the aerial parts of Laretia acualis (535 g) were extracted with petrol ether at room temperature. The solvent was evaporated to dryness by vacuum distillation and low temperature, yielding a gum (15 g). The concentrated petrol ether extract was fractionated on silica gel column with hexane-ethyl acetate mixtures of increasing polarity as elution solvents. The fraction hexane-ethyl acetate 10% (2.45 g) was separated on silica gel using the same elution solvents yielding 45.5 mg of (I)(m.p. 374 K). The title compound was identified by comparing the spectroscopic data with the previously published data (Vasconcelos et al., 1998). Recrystallization from hexane/ethyl acetate (8:2) at room temperature afforded colourless crystals suitable for X-ray diffraction analysis.
H atom attached to O3 atom was located in a difference Fourier map and refined isotropically. All other H atoms were positioned geometrically and then treated as riding, with C—H distances of 0.93 (CH) and 0.96 Å (CH3), and Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl).
The title compound was originally isolated from Artemisia campestris (maritima) (Vasconcelos et al., 1998) and later from Laretia acualis (Cav.) which is known in Chile as "Llareta de la zona central", is a yellowish-green, compact resinous cushion shrub, which grows in the high Andes of Chile. Whole plant infusions are widely used as diabetes treatment in folk medicine (Wickens, 1995). Chromene derivatives exhibits a wide spectrum of biological activity, including spasmolytic, anti-arrhytmic, cardionthonic, antiviral, anticancer and alkylating properties (Gabor, 1988; Valenti et al., 1993, 1998).
The title structure (Fig.1), consists of a chromene moiety substituted in position 5 and 7 with a hydroxy and methoxy group, respectively. The chromene ring system is essentially planar with maximum deviation of -0.007 (2) Å for C2. The geometrical parameters of the chromene group are comparable to those of related structures reported earlier (Wallet & Cody, 1995). The mean bond distances are: O-Csp2 1.3552 (17) Å, and aromatic C—C 1.391 (2) Å, while C4=O2 is 1.2531 (18)Å and C2=C3 is essentially a double bond with a distance of 1.330 (2) Å Å. In the π- π stacking interactions (Table 2).
the molecular packing is stabilized by intramolecular O—H···O hydrogen bond generating a graph-set motif S(6) (Bernstein et al., 1995) as well asFor related literature, see: Gabor (1988); Valenti et al. (1993, 1998); Vasconcelos et al. (1998); Bernstein et al. (1995); Wickens (1995); Wallet & Cody (1995).
Data collection: COLLECT (Nonius, 1998); cell
DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are draw at the 30% probability level. The dashed line indicates the intramolecular O–H···O hydrogen bond. H atoms are shown as small spheres of arbitrary radii. |
C10H8O4 | F(000) = 400 |
Mr = 192.16 | Dx = 1.486 Mg m−3 |
Monoclinic, P21/c | Melting point: 374 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7551 (3) Å | Cell parameters from 1504 reflections |
b = 11.7512 (9) Å | θ = 3.0–25.0° |
c = 7.5211 (7) Å | µ = 0.12 mm−1 |
β = 95.094 (4)° | T = 298 K |
V = 858.77 (11) Å3 | Prismatic, colourless |
Z = 4 | 0.19 × 0.10 × 0.08 mm |
Nonius KappaCCD area-detector diffractometer | 1393 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0 |
Graphite monochromator | θmax = 25.3°, θmin = 3.2° |
φ scans, and ω scans with κ offsets | h = −11→11 |
1504 measured reflections | k = −14→0 |
1504 independent reflections | l = 0→9 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.1521P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.115 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.15 e Å−3 |
1504 reflections | Δρmin = −0.17 e Å−3 |
131 parameters |
C10H8O4 | V = 858.77 (11) Å3 |
Mr = 192.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.7551 (3) Å | µ = 0.12 mm−1 |
b = 11.7512 (9) Å | T = 298 K |
c = 7.5211 (7) Å | 0.19 × 0.10 × 0.08 mm |
β = 95.094 (4)° |
Nonius KappaCCD area-detector diffractometer | 1393 reflections with I > 2σ(I) |
1504 measured reflections | Rint = 0 |
1504 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.15 e Å−3 |
1504 reflections | Δρmin = −0.17 e Å−3 |
131 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 > 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 | 0.70907 (10) | 0.05272 (8) | 0.30079 (14) | 0.0533 (3) | |
O2 | 0.96609 (11) | 0.31131 (10) | 0.18700 (17) | 0.0649 (4) | |
O3 | 0.77689 (13) | 0.45485 (9) | 0.25771 (16) | 0.0629 (4) | |
H9 | 0.855 (3) | 0.422 (2) | 0.219 (3) | 0.098 (7)* | |
O4 | 0.36201 (10) | 0.31332 (9) | 0.43512 (14) | 0.0558 (3) | |
C1 | 0.27108 (16) | 0.22189 (16) | 0.4674 (2) | 0.0633 (5) | |
H1A | 0.1856 | 0.2521 | 0.5006 | 0.095* | |
H1B | 0.3121 | 0.175 | 0.5622 | 0.095* | |
H1C | 0.2544 | 0.177 | 0.3609 | 0.095* | |
C2 | 0.83521 (16) | 0.03322 (13) | 0.2464 (2) | 0.0586 (4) | |
H2 | 0.8626 | −0.042 | 0.235 | 0.07* | |
C3 | 0.92292 (15) | 0.11442 (14) | 0.2080 (2) | 0.0568 (4) | |
H3 | 1.0084 | 0.0946 | 0.1715 | 0.068* | |
C4 | 0.88700 (14) | 0.23206 (12) | 0.22245 (19) | 0.0460 (4) | |
C4A | 0.75193 (13) | 0.25315 (10) | 0.27872 (16) | 0.0384 (3) | |
C5 | 0.69920 (14) | 0.36468 (11) | 0.29717 (17) | 0.0427 (3) | |
C6 | 0.57034 (15) | 0.38106 (12) | 0.35134 (17) | 0.0460 (4) | |
H6 | 0.5372 | 0.4545 | 0.3645 | 0.055* | |
C7 | 0.48861 (13) | 0.28748 (12) | 0.38688 (16) | 0.0419 (3) | |
C8 | 0.53533 (13) | 0.17729 (11) | 0.37016 (17) | 0.0419 (3) | |
H8 | 0.4808 | 0.1152 | 0.394 | 0.05* | |
C8A | 0.66641 (13) | 0.16281 (11) | 0.31662 (17) | 0.0391 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0439 (6) | 0.0339 (5) | 0.0831 (7) | 0.0016 (4) | 0.0111 (5) | −0.0009 (4) |
O2 | 0.0439 (6) | 0.0602 (7) | 0.0922 (8) | −0.0118 (5) | 0.0150 (5) | 0.0044 (6) |
O3 | 0.0628 (8) | 0.0378 (6) | 0.0895 (8) | −0.0086 (5) | 0.0146 (6) | 0.0063 (5) |
O4 | 0.0431 (6) | 0.0615 (7) | 0.0646 (6) | 0.0096 (5) | 0.0145 (5) | −0.0015 (5) |
C1 | 0.0409 (8) | 0.0829 (12) | 0.0677 (10) | −0.0004 (8) | 0.0138 (7) | 0.0061 (8) |
C2 | 0.0456 (8) | 0.0432 (8) | 0.0876 (11) | 0.0098 (6) | 0.0105 (7) | −0.0038 (7) |
C3 | 0.0376 (8) | 0.0554 (9) | 0.0779 (10) | 0.0068 (7) | 0.0087 (7) | −0.0033 (7) |
C4 | 0.0357 (7) | 0.0483 (8) | 0.0536 (8) | −0.0036 (6) | 0.0015 (5) | 0.0015 (6) |
C4A | 0.0353 (7) | 0.0387 (7) | 0.0405 (6) | −0.0017 (5) | −0.0012 (5) | 0.0006 (5) |
C5 | 0.0458 (8) | 0.0357 (7) | 0.0458 (7) | −0.0036 (6) | 0.0001 (5) | 0.0023 (5) |
C6 | 0.0501 (8) | 0.0372 (7) | 0.0502 (7) | 0.0085 (6) | 0.0026 (6) | −0.0011 (5) |
C7 | 0.0376 (7) | 0.0504 (8) | 0.0374 (6) | 0.0040 (6) | 0.0020 (5) | −0.0012 (5) |
C8 | 0.0380 (7) | 0.0408 (7) | 0.0470 (7) | −0.0039 (5) | 0.0043 (5) | 0.0015 (5) |
C8A | 0.0377 (7) | 0.0347 (7) | 0.0443 (7) | 0.0007 (5) | 0.0002 (5) | −0.0007 (5) |
O1—C2 | 1.3503 (18) | C3—C4 | 1.433 (2) |
O1—C8A | 1.3674 (15) | C3—H3 | 0.93 |
O2—C4 | 1.2531 (17) | C4—C4A | 1.4407 (19) |
O3—C5 | 1.3510 (16) | C4A—C8A | 1.3952 (18) |
O3—H9 | 0.92 (2) | C4A—C5 | 1.4192 (18) |
O4—C7 | 1.3522 (16) | C5—C6 | 1.369 (2) |
O4—C1 | 1.428 (2) | C6—C7 | 1.398 (2) |
C1—H1A | 0.96 | C6—H6 | 0.93 |
C1—H1B | 0.96 | C7—C8 | 1.3821 (19) |
C1—H1C | 0.96 | C8—C8A | 1.3848 (18) |
C2—C3 | 1.330 (2) | C8—H8 | 0.93 |
C2—H2 | 0.93 | ||
C2—O1—C8A | 118.65 (11) | C8A—C4A—C5 | 117.02 (12) |
C5—O3—H9 | 103.8 (15) | C8A—C4A—C4 | 120.54 (12) |
C7—O4—C1 | 118.20 (12) | C5—C4A—C4 | 122.44 (12) |
O4—C1—H1A | 109.5 | O3—C5—C6 | 120.20 (12) |
O4—C1—H1B | 109.5 | O3—C5—C4A | 119.18 (13) |
H1A—C1—H1B | 109.5 | C6—C5—C4A | 120.62 (12) |
O4—C1—H1C | 109.5 | C5—C6—C7 | 120.04 (12) |
H1A—C1—H1C | 109.5 | C5—C6—H6 | 120 |
H1B—C1—H1C | 109.5 | C7—C6—H6 | 120 |
C3—C2—O1 | 124.40 (14) | O4—C7—C8 | 123.45 (13) |
C3—C2—H2 | 117.8 | O4—C7—C6 | 115.13 (12) |
O1—C2—H2 | 117.8 | C8—C7—C6 | 121.42 (12) |
C2—C3—C4 | 120.62 (14) | C7—C8—C8A | 117.52 (12) |
C2—C3—H3 | 119.7 | C7—C8—H8 | 121.2 |
C4—C3—H3 | 119.7 | C8A—C8—H8 | 121.2 |
O2—C4—C3 | 122.79 (13) | O1—C8A—C8 | 115.95 (11) |
O2—C4—C4A | 122.08 (13) | O1—C8A—C4A | 120.66 (12) |
C3—C4—C4A | 115.12 (12) | C8—C8A—C4A | 123.38 (12) |
C8A—O1—C2—C3 | 0.7 (2) | C1—O4—C7—C8 | −1.15 (18) |
O1—C2—C3—C4 | −0.1 (3) | C1—O4—C7—C6 | 177.84 (12) |
C2—C3—C4—O2 | −179.70 (15) | C5—C6—C7—O4 | −178.42 (11) |
C2—C3—C4—C4A | −0.5 (2) | C5—C6—C7—C8 | 0.6 (2) |
O2—C4—C4A—C8A | 179.81 (12) | O4—C7—C8—C8A | 178.87 (11) |
C3—C4—C4A—C8A | 0.59 (19) | C6—C7—C8—C8A | −0.05 (19) |
O2—C4—C4A—C5 | 0.2 (2) | C2—O1—C8A—C8 | 179.00 (12) |
C3—C4—C4A—C5 | −178.99 (12) | C2—O1—C8A—C4A | −0.52 (19) |
C8A—C4A—C5—O3 | −178.38 (11) | C7—C8—C8A—O1 | −179.75 (11) |
C4—C4A—C5—O3 | 1.2 (2) | C7—C8—C8A—C4A | −0.24 (19) |
C8A—C4A—C5—C6 | 0.52 (19) | C5—C4A—C8A—O1 | 179.50 (10) |
C4—C4A—C5—C6 | −179.88 (11) | C4—C4A—C8A—O1 | −0.11 (19) |
O3—C5—C6—C7 | 178.07 (11) | C5—C4A—C8A—C8 | 0.02 (19) |
C4A—C5—C6—C7 | −0.8 (2) | C4—C4A—C8A—C8 | −179.59 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H9···O2 | 0.92 (3) | 1.72 (3) | 2.5901 (17) | 155 (2) |
Experimental details
Crystal data | |
Chemical formula | C10H8O4 |
Mr | 192.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.7551 (3), 11.7512 (9), 7.5211 (7) |
β (°) | 95.094 (4) |
V (Å3) | 858.77 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.19 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1504, 1504, 1393 |
Rint | 0 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.115, 1.08 |
No. of reflections | 1504 |
No. of parameters | 131 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.17 |
Computer programs: COLLECT (Nonius, 1998), DENZO–SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H9···O2 | 0.92 (3) | 1.72 (3) | 2.5901 (17) | 155 (2) |
CgI | CgJ | CgI···CgJ | Dihedral angle | Interplanar distance | Offset |
Cg1 | Cg2i | 3.6661 (8) | 1.39 | 3.508 | 1.13 |
Cg2 | Cg1ii | 3.6660 (8) | 1.39 | 3.487 | 1.06 |
Cg2 | Cg2i | 3.7930 (8) | 1.69 | 3.471 | 1.50 |
Cg2 | Cg2ii | 3.7931 (8) | 1.69 | 3.486 | 1.53 |
Symmetry codes: (i)x, 1/2-y, -1/2+z; (ii) x, 1/2-y, 1/2+z. Cg1 and Cg2 are the centroids of rings O1/C2-C4/C4A–C8A and C4A/C5–C8/C8A, respectively. The offset is defined as the distance between CgI and the perpendicular projection of CgJ on ring I. |
Acknowledgements
LAL thanks the Fondo Nacional de Desarrollo Científico y Tecnológico de Chile for grant 1060339. We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the Cambridge Structural Database.
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.
The title compound was originally isolated from Artemisia campestris (maritima) (Vasconcelos et al., 1998) and later from Laretia acualis (Cav.) which is known in Chile as "Llareta de la zona central", is a yellowish-green, compact resinous cushion shrub, which grows in the high Andes of Chile. Whole plant infusions are widely used as diabetes treatment in folk medicine (Wickens, 1995). Chromene derivatives exhibits a wide spectrum of biological activity, including spasmolytic, anti-arrhytmic, cardionthonic, antiviral, anticancer and alkylating properties (Gabor, 1988; Valenti et al., 1993, 1998).
The title structure (Fig.1), consists of a chromene moiety substituted in position 5 and 7 with a hydroxy and methoxy group, respectively. The chromene ring system is essentially planar with maximum deviation of -0.007 (2) Å for C2. The geometrical parameters of the chromene group are comparable to those of related structures reported earlier (Wallet & Cody, 1995). The mean bond distances are: O-Csp2 1.3552 (17) Å, and aromatic C—C 1.391 (2) Å, while C4=O2 is 1.2531 (18)Å and C2=C3 is essentially a double bond with a distance of 1.330 (2) Å Å. In the crystal structure, the molecular packing is stabilized by intramolecular O—H···O hydrogen bond generating a graph-set motif S(6) (Bernstein et al., 1995) as well as π- π stacking interactions (Table 2).