3,5-Dihydr­oxy-2-methyl-4H-pyran-4-one

Dong, C.-M.; Pu, S.-C.; Gao, W.-Y.

doi:10.1107/S1600536808010957

organic compounds

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Volume 64| Part 6| June 2008| Page o1032

doi:10.1107/S1600536808010957

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3,5-Dihydroxy-2-methyl-4H-pyran-4-one

Cheng-Ming Dong,^a Shou-Cheng Pu ^b and Wen-Yuan Gao ^b ^*

^aDepartment of Pharmaceutical Science, Henan College of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China, and ^bSchool of Pharmaceutical Science & Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: pharmgao@tju.edu.cn

(Received 18 March 2008; accepted 19 April 2008; online 10 May 2008)

In the title compound, C₆H₆O₄, inter- and intramolecular hydrogen bonds are observed which help to establish the crystal structure. There are weak π–π interactions between pyran rings separated by 3.5692 (9) Å.

Related literature

For general background, see: Shinoda et al. (2004 ). For related structures, see: Yao et al. (2005 ); Gibbons et al. (2000 ).

Experimental

Crystal data

C₆H₆O₄
M_r = 142.11
Monoclinic, P 2₁ /n
a = 6.9400 (14) Å
b = 6.0648 (12) Å
c = 14.008 (3) Å
β = 92.77 (3)°
V = 588.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 113 (2) K
0.14 × 0.12 × 0.10 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.981, T_max = 0.986
3970 measured reflections
1381 independent reflections
1166 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.096
S = 1.10
1381 reflections
115 parameters
All H-ataom parameters refined
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H6⋯O3ⁱ	0.838 (18)	1.89 (2)	2.6902 (12)	159.6 (13)
O2—H5⋯O3ⁱⁱ	0.94 (2)	1.75 (2)	2.6596 (12)	162.6 (17)
O4—H6⋯O3	0.838 (18)	2.44 (2)	2.7820 (12)	105.4 (10)
C1—H3⋯O4	1.005 (15)	2.537 (14)	2.8957 (15)	100.5 (9)
C6—H4⋯O2ⁱⁱⁱ	0.936 (14)	2.412 (13)	3.3354 (14)	169.4 (12)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+3, -z+1.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010957/pv2074sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010957/pv2074Isup2.hkl

checkCIF report

Comment top

The title compound, 3,5-dihydroxy-2-methyl-pyran-4-one, (I) was identified as a decomposition product in the stored solution of orange juice (Shinoda, et al., 2004). We report here the crystal structure of the title compound (Fig. 1) which was isolated from Hydrocotyle sibthorpoioides Lam. The structure of (I) is stabilized by two strong intermolecular hydrogen bonds of the type O—H···O and a weak intermolecular interaction of the type C—H···O. Intramolecular interactions are also observed which result in five membered rings; details are given in Table 1. There is indication of π-π interactions between the pyran rings lying about inversion centers with minimum separation of 3.5692 (9) Å. The crystal structures of 2-hydroxymethyl analogue (Yao et al., 2005) and 5-hydroxy-3-methoxy-pyran-4-one (Gibbons et al., 2000) have been reported.

Related literature top

For general background, see:Shinoda et al. (2004). For related structures, see: Yao et al. (2005; Gibbons et al. (2000).

Experimental top

Dried powder of Hydrocotyle sibthorpoioides Lam was exacted with EtOH and the extract was concentrated in vacuo. The residue was subjected to silical-gel coloumn chromatography. Elution with chloroform-methanol (95:5 v/v) yielded the title compound. Crystals suitable for XRD study were grwon from a solution of methanol at room temperature by slow evaporation.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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).

Figures top

Fig. 1. A view of the molecule of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

3,5-Dihydroxy-2-methyl-4H-pyran-4-one top

Crystal data top

C₆H₆O₄	F(000) = 296
M_r = 142.11	D_x = 1.603 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1620 reflections
a = 6.9400 (14) Å	θ = 1.5–27.9°
b = 6.0648 (12) Å	µ = 0.14 mm⁻¹
c = 14.008 (3) Å	T = 113 K
β = 92.77 (3)°	Block, colorless
V = 588.9 (2) Å³	0.14 × 0.12 × 0.10 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	1381 independent reflections
Radiation source: rotating anode	1166 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.025
ω scans	θ_max = 27.9°, θ_min = 2.9°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −9→9
T_min = 0.981, T_max = 0.986	k = −7→7
3970 measured reflections	l = −10→18

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	All H-atom parameters refined
S = 1.11	w = 1/[σ²(F_o²) + (0.0654P)²] where P = (F_o² + 2F_c²)/3
1381 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₆O₄	V = 588.9 (2) Å³
M_r = 142.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9400 (14) Å	µ = 0.14 mm⁻¹
b = 6.0648 (12) Å	T = 113 K
c = 14.008 (3) Å	0.14 × 0.12 × 0.10 mm
β = 92.77 (3)°

Data collection top

Rigaku Saturn diffractometer	1381 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1166 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.986	R_int = 0.025
3970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.096	All H-atom parameters refined
S = 1.11	Δρ_max = 0.37 e Å⁻³
1381 reflections	Δρ_min = −0.24 e Å⁻³
115 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
O3	0.27997 (10)	1.01120 (11)	0.27250 (5)	0.0149 (2)
O1	0.76427 (10)	1.05517 (12)	0.44524 (5)	0.0157 (2)
O4	0.56909 (12)	0.69576 (12)	0.26153 (5)	0.0171 (2)
O2	0.32648 (11)	1.36372 (12)	0.40092 (5)	0.0173 (2)
C4	0.43152 (15)	1.02588 (15)	0.32615 (7)	0.0124 (2)
C5	0.46324 (15)	1.20540 (16)	0.39217 (7)	0.0132 (2)
C3	0.58183 (15)	0.86536 (16)	0.32479 (7)	0.0127 (2)
C2	0.74196 (15)	0.88197 (16)	0.38483 (7)	0.0139 (2)
C6	0.62774 (16)	1.21333 (17)	0.44749 (7)	0.0157 (2)
C1	0.90601 (15)	0.72547 (19)	0.39113 (8)	0.0174 (3)
H4	0.656 (2)	1.323 (2)	0.4929 (10)	0.021 (3)*
H3	0.871 (2)	0.582 (2)	0.3585 (10)	0.028 (3)*
H1	1.017 (2)	0.782 (2)	0.3616 (11)	0.037 (4)*
H2	0.940 (2)	0.689 (2)	0.4591 (10)	0.025 (3)*
H5	0.271 (3)	1.393 (3)	0.3397 (14)	0.054 (5)*
H6	0.454 (3)	0.669 (2)	0.2453 (11)	0.037 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0141 (4)	0.0150 (4)	0.0153 (4)	0.0004 (3)	−0.0022 (3)	−0.0013 (3)
O1	0.0155 (4)	0.0165 (4)	0.0148 (4)	−0.0005 (3)	−0.0020 (3)	−0.0020 (3)
O4	0.0136 (4)	0.0163 (4)	0.0211 (4)	0.0004 (3)	−0.0008 (3)	−0.0080 (3)
O2	0.0233 (4)	0.0142 (4)	0.0142 (4)	0.0058 (3)	−0.0018 (3)	−0.0018 (3)
C4	0.0142 (5)	0.0125 (5)	0.0105 (4)	−0.0022 (4)	0.0016 (4)	0.0017 (3)
C5	0.0177 (5)	0.0106 (5)	0.0116 (4)	0.0007 (4)	0.0021 (4)	0.0008 (3)
C3	0.0138 (5)	0.0118 (5)	0.0128 (5)	−0.0019 (4)	0.0023 (4)	−0.0011 (3)
C2	0.0145 (5)	0.0141 (5)	0.0132 (4)	−0.0017 (4)	0.0024 (4)	−0.0003 (3)
C6	0.0200 (6)	0.0133 (5)	0.0139 (5)	−0.0012 (4)	0.0006 (4)	−0.0020 (4)
C1	0.0126 (5)	0.0200 (6)	0.0195 (5)	0.0013 (4)	0.0001 (4)	−0.0010 (4)

Geometric parameters (Å, º) top

O3—C4	1.2659 (13)	C4—C5	1.4386 (13)
O1—C6	1.3497 (13)	C5—C6	1.3494 (16)
O1—C2	1.3531 (12)	C3—C2	1.3646 (15)
O4—C3	1.3577 (12)	C2—C1	1.4816 (15)
O4—H6	0.838 (18)	C6—H4	0.936 (14)
O2—C5	1.3598 (12)	C1—H3	1.005 (15)
O2—H5	0.94 (2)	C1—H1	0.956 (17)
C4—C3	1.4276 (14)	C1—H2	0.996 (15)

C6—O1—C2	120.47 (8)	O1—C2—C3	120.53 (9)
C3—O4—H6	110.7 (11)	O1—C2—C1	113.31 (9)
C5—O2—H5	107.9 (12)	C3—C2—C1	126.15 (9)
O3—C4—C3	122.06 (9)	C5—C6—O1	122.45 (9)
O3—C4—C5	122.13 (9)	C5—C6—H4	124.0 (8)
C3—C4—C5	115.82 (9)	O1—C6—H4	113.5 (8)
C6—C5—O2	119.86 (9)	C2—C1—H3	111.1 (8)
C6—C5—C4	119.68 (10)	C2—C1—H1	112.2 (9)
O2—C5—C4	120.44 (9)	H3—C1—H1	107.1 (13)
O4—C3—C2	118.92 (9)	C2—C1—H2	110.3 (8)
O4—C3—C4	120.04 (9)	H3—C1—H2	106.4 (12)
C2—C3—C4	121.01 (9)	H1—C1—H2	109.5 (13)

O3—C4—C5—C6	−179.79 (9)	C6—O1—C2—C1	179.47 (9)
C3—C4—C5—C6	0.12 (14)	O4—C3—C2—O1	176.47 (9)
O3—C4—C5—O2	1.94 (15)	C4—C3—C2—O1	−1.93 (15)
C3—C4—C5—O2	−178.15 (8)	O4—C3—C2—C1	−2.39 (16)
O3—C4—C3—O4	3.12 (15)	C4—C3—C2—C1	179.21 (9)
C5—C4—C3—O4	−176.78 (8)	O2—C5—C6—O1	176.71 (9)
O3—C4—C3—C2	−178.50 (9)	C4—C5—C6—O1	−1.58 (15)
C5—C4—C3—C2	1.59 (14)	C2—O1—C6—C5	1.32 (15)
C6—O1—C2—C3	0.47 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H6···O3ⁱ	0.838 (18)	1.89 (2)	2.6902 (12)	159.6 (13)
O2—H5···O3ⁱⁱ	0.94 (2)	1.75 (2)	2.6596 (12)	162.6 (17)
O4—H6···O3	0.838 (18)	2.44 (2)	2.7820 (12)	105.4 (10)
C1—H3···O4	1.005 (15)	2.537 (14)	2.8957 (15)	100.5 (9)
C6—H4···O2ⁱⁱⁱ	0.936 (14)	2.412 (13)	3.3354 (14)	169.4 (12)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+3, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₆O₄
M_r	142.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	6.9400 (14), 6.0648 (12), 14.008 (3)
β (°)	92.77 (3)
V (Å³)	588.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.981, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	3970, 1381, 1166
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.096, 1.11
No. of reflections	1381
No. of parameters	115
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.24

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H6···O3ⁱ	0.838 (18)	1.89 (2)	2.6902 (12)	159.6 (13)
O2—H5···O3ⁱⁱ	0.94 (2)	1.75 (2)	2.6596 (12)	162.6 (17)
O4—H6···O3	0.838 (18)	2.44 (2)	2.7820 (12)	105.4 (10)
C1—H3···O4	1.005 (15)	2.537 (14)	2.8957 (15)	100.5 (9)
C6—H4···O2ⁱⁱⁱ	0.936 (14)	2.412 (13)	3.3354 (14)	169.4 (12)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+3, −z+1.

References

Gibbons, S., Denny, B. J., Ali-Amine, S., Mathew, K. T., Skelton, B. W., White, A. H. & Gray, A. I. (2000). J. Nat. Prod. 63, 839–840. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku/MSC. (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shinoda, Y., Murata, M., Homma, S. & Komura, H. (2004). Biosci. Biotechnol. Biochem. 68, 529–536. Web of Science CrossRef PubMed CAS Google Scholar
Yao, G.-M., Wang, Y.-B., Wang, L.-Q. & Qin, G.-W. (2005). Acta Cryst. E61, o1403–o1405. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1032

doi:10.1107/S1600536808010957

Open

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