5-Hydr­oxy-7-meth­oxy-4H-chromen-4-one

Brito, I.; Bórquez, J.; Loyola, L.A.; López-Rodríguez, M.

doi:10.1107/S1600536807066494

organic compounds

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Volume 64| Part 1| January 2008| Page o285

https://doi.org/10.1107/S1600536807066494

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5-Hydroxy-7-methoxy-4H-chromen-4-one

Iván Brito,^a ^* Jorge Bórquez,^a Luis Alberto Loyola ^a and Matías López-Rodríguez ^b

^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

(Received 30 November 2007; accepted 11 December 2007; online 18 December 2007)

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

C₁₀H₈O₄
M_r = 192.16
Monoclinic, P 2₁ /c
a = 9.7551 (3) Å
b = 11.7512 (9) Å
c = 7.5211 (7) Å
β = 95.094 (4)°
V = 858.77 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 (2) K
0.19 × 0.10 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: none
1504 measured reflections
1504 independent reflections
1393 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 1.08
1504 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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)

Table 2
π–π interactions (Å,°)

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.

CgI	CgJ	CgI⋯CgJ	Dihedral angle	Interplanar distance	Offset
Cg1	Cg2ⁱ	3.6661 (8)	1.39	3.51	1.13
Cg2	Cg1ⁱⁱ	3.6660 (8)	1.39	3.49	1.06
Cg2	Cg2ⁱ	3.7930 (8)	1.69	3.47	1.50
Cg2	Cg2ⁱⁱ	3.7931 (8)	1.69	3.49	1.53
Symmetry codes: (i) $[x, {\script{1\over 2}}-y, -{\script{1\over 2}}+z]$ ; (ii) $[x, {\script{1\over 2}}-y, {\script{1\over 2}}+z]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807066494/bt2661sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066494/bt2661Isup2.hkl

checkCIF report

Comment top

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-Csp²1.3552 (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).

Related literature top

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 top

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.

Structure description top

For related literature, see: Gabor (1988); Valenti et al. (1993, 1998); Vasconcelos et al. (1998); Bernstein et al. (1995); Wickens (1995); Wallet & Cody (1995).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: 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).

Figures top

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.

5-Hydroxy-7-methoxy-4H-chromen-4-one top

Crystal data top

C₁₀H₈O₄	F(000) = 400
M_r = 192.16	D_x = 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

Data collection top

Nonius KappaCCD area-detector diffractometer	1393 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0
Graphite monochromator	θ_max = 25.3°, θ_min = 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 top

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(F_o²) + (0.06P)² + 0.1521P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.115	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.15 e Å⁻³
1504 reflections	Δρ_min = −0.17 e Å⁻³
131 parameters

Crystal data top

C₁₀H₈O₄	V = 858.77 (11) Å³
M_r = 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)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1393 reflections with I > 2σ(I)
1504 measured reflections	R_int = 0
1504 independent reflections

Refinement top

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	Δρ_max = 0.15 e Å⁻³
1504 reflections	Δρ_min = −0.17 e Å⁻³
131 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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)

π–π interactions (Å,°) top

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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