6-Hydroxy-methyl-4-meth-oxy-2H-pyran-2-one (Opuntiol).

Abstract

The title compound, C(7)H(8)O(4), isolated from Opuntia dillenii Haw (Cacta-ceae), is almost planar [maximum deviation of 0.027 (2) Å] except for the H atoms of the methylene and methyl groups. The crystal packing is stabilized by C-H⋯O and O-H⋯O inter-molecular hydrogen bonds, resulting in the formation of a three-dimensional network.

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6-Hydroxymethyl-4-methoxy-2H-pyran-
2-one (Opuntiol)
Muhammad Athar Abbasi,a‡ Tayyaba Shahzadi,aMehmet
Akkurt,b* Aziz-ur-Rehmanaand Tauheeda Riaza
aDepartment of Chemistry, Center for Natural Product Drug Development,
Government College University, Lahore 54000, Pakistan, andbDepartment of
Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey
Correspondence e-mail: akkurt@erciyes.edu.tr
Received 9 December 2009; accepted 14 December 2009
Key indicators: single-crystal X-ray study; T = 296 K; mean ?(C–C) = 0.002 A ˚;
R factor = 0.037; wR factor = 0.094; data-to-parameter ratio = 12.1.
The title compound, C7H8O4, isolated from Opuntia dillenii
Haw (Cactaceae), is almost planar [maximum deviation of
0.027 (2) A˚] except for the H atoms of the methylene and
methyl groups. The crystal packing is stabilized by C—H???O
and O—H???O intermolecular hydrogen bonds, resulting in
the formation of a three-dimensional network.
Related literature
For the use of the stem and fruit of Opuntia dillenii Haw
(Cactaceae) in folk medicine, see: Chang et al. (2008). For
phytochemical investigations of this plant, see: Qiu et al.
(2002). For comparitive bond lengths, see: Allen et al. (1987).
Experimental
Crystal data
C7H8O4
Mr= 156.13
Monoclinic, P21=c
a = 4.0499 (5) A˚
b = 18.101 (2) A˚
c = 9.4743 (13) A˚
? = 96.720 (7)?
V = 689.76 (15) A˚3
Z = 4
Mo K? radiation
? = 0.13 mm?1
T = 296 K
0.34 ? 0.25 ? 0.19 mm
Data collection
Bruker Kappa APEXII CCD area-
detector diffractometer
6516 measured reflections
1268 independent reflections
882 reflections with I > 2?(I)
Rint= 0.046
Refinement
R[F2> 2?(F2)] = 0.037
wR(F2) = 0.094
S = 1.02
1268 reflections
105 parameters
1 restraint
H atoms treated by a mixture of
independent and constrained
refinement
??max= 0.16 e A˚?3
??min= ?0.16 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O4—H1???O1i
O4—H1???O2i
C7—H7B???O4ii
C7—H7C???O2iii
Symmetry codes: (i) x ? 1;?y þ1
D—HH???AD???AD—H???A
0.836 (14)
0.836 (14)
0.96
0.96
2.47 (2)
2.073 (13)
2.58
2.57
3.1840 (19)
2.8678 (18)
3.494 (2)
3.504 (2)
144.2 (17)
158.6 (18)
159
164
2;z ?1
2; (ii) ?x;?y;?z; (iii) ?x þ 1;?y;?z þ 1.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SIR97 (Altomare et al., 1999); program(s) used to refine
structure:SHELXL97(Sheldrick,
ORTEP-3 (Farrugia, 1997); software used to prepare material for
publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
2008);moleculargraphics:
The authors are grateful to the Higher Education
Commission for providing financial support. Professor Islam
Ullah Khan and Mr Shahzad Sharif are also gratefully
acknowledged for providing single-crystal X-ray diffraction
facilities at the Materials Chemistry Laboratory, GC Univer-
sity Lahore.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: RK2184).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C.,
Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.
Appl. Cryst. 32, 115–119.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Chang, S. F., Hsieh, C. L. & Yen, G. C. (2008). Food Chem. 106, 569–575.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Qiu, Y., Chen, Y., Pei, Y., Matsuda, H. & Yoshikawa, M. (2002). Chem. Pharm.
Bull. 50, 1507–1510.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
organic compounds
Acta Cryst. (2010). E66, o199doi:10.1107/S1600536809053860Abbasia et al.
o199
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
‡ Additional corresponding author, e-mail: atrabbasi@yahoo.com.

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supplementary materials

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supplementary materials
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Acta Cryst. (2010). E66, o199 [ doi:10.1107/S1600536809053860 ]
6-Hydroxymethyl-4-methoxy-2H-pyran-2-one (Opuntiol)
M. A. Abbasi, T. Shahzadi, M. Akkurt, Aziz-ur-Rehman and T. Riaz
Comment
Opuntia dillenii Haw (Cactaceae) usually grows in semi-desert regions in the tropics and subtropics. The stem and fruit
of this plant are used in a folk medicine for reducing cholesterol levels, treatment of gastric ulcers, inflammation, diabetes
and several other diseases (Chang et al., 2008). The phytochemical investigations on this plant have led to the isolation
of various oxygenated constituents namely opuntiol, opuntioside-I, p-hydroxybenzoic acid, ethyl 3,4-dihydroxybenzoate,
3,4-dihydroxybenzoic acid, L-(-)-malic acid, (E)-ferulic acid, 4-ethoxy-6-hydroxymethyl-α-pyrone, 1-heptanecanol, vanil-
lic acid, isorhamnetin, isorhamnetin-3-O-rutinoside, rutin, quercetin, 3,3'-dimethyl quercetin, 3-O-methyl quercetin, 3-O-
methyl quercetin 7-O-β-D-glucopyranoside, kaempferol, kaempferol 7-O-β-D-glucopyranoside, kaempferol 7-O-β-D-gluc-
opyranosyl-(1→4)- β-D-glucopyranoside, kaempferide, β-sitosterol, and manghaslin (Qiu et al., 2002). In the present study
we first time report the crystal structure of opuntiol using single-crystal XRD.
In the title molecule, I, shown in Fig. 1, bond lengths and angles display normal values (Allen et al., 1987). Except the
H atoms of the methlene and methyl groups, the molecule of I is almost planar, with maximum deviations of 0.027 (2)Å for
O4, 0.023 (2)Å for C7, 0.020 (1)Å for O2 and -0.019 (2)Å for C2. For the methoxy and hydroxy methyl groups at the C3 and
C5 positions in I, the C2–C3–O3–C7 and C4–C3–O3–C7 torsion angles are 0.9 (2)° and -178.94 (15)°, the O1–C5–C6–O4
and C4–C5–C6–O4 torsion angles are 177.77 (14)° and -2.9 (3)°, respectively.
In the crystal structure of I, there are non-classical C–H···O and classical O–H···O intermolecular hydrogen bonds (Table
1), forming a three-dimensional network (Figs. 2 and 3).
Experimental
Plant Material: Opuntia dillenii Haw (whole plant) was collected from the areas of Mar Balochan, Sangla Hill, Distt.
Nankana, Pakistan, in April 2008, and identified by Muhammad Ajaib (Taxonomist), Department of Botany, Government
College University, Lahore.
Extraction and isolation: The shade-dried ground whole plant (7 kg) of Opuntia dillenii Haw was exhaustively extracted
with methanol (10L ×4) at room temperature. The extract was evaporated to yield the residue (1.1 kg), which was dissolved
in distilled water (2.0 L) and partitioned with n-hexane (2L ×4), chloroform (2L × 4), ethyl acetate (2L × 4) and n-butanol
(2L × 4) respectively. The chloroform soluble extract (157 g) was subjected to column chromatography using hexane with
gradient of CHCl3 and followed by methanol up to 100%. Fifteen fractions (Fr. 1-15) were collected. The Fr. 14 was loaded
on flash silica gel and eluted with MeOH : CHCl3 (2 : 98) to get purified crystals of opuntiol (84.7 mg).

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supplementary materials
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Refinement
The H atom of the OH group was located in difference Fourier maps and were refined with a O–H distance restrained
to 0.83 (1)Å, with displacement parameters fixed at 1.5 times Ueq of the parent O atom. The rest H atoms were placed
geometrically, with C–H = 0.93-0.97 Å, and treated using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(parent atom).
Figures
Fig. 1. Molecular structure of the title compound with the atom numbering scheme. Displace-
ment ellipsoids for non-H atoms are drawn at the 50% probability level. H atoms are presen-
ted as a small spheres of arbitrary radius.
Fig. 2. The packing and hydrogen bonding of the title compound viewed down a axis. Hydro-
gen atoms not involved in hydrogen bonding have been omitted for clarity.
Fig. 3. The packing and hydrogen bonding of the title compound viewed down b axis. Hydro-
gen atoms not involved in hydrogen bonding have been omitted for clarity.
6-Hydroxymethyl-4-methoxy-2H-pyran-2-one
Crystal data
C7H8O4
F(000) = 328
Dx = 1.503 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1306 reflections
θ = 2.3–23.4°
µ = 0.13 mm−1
T = 296 K
Needle, colourless
Mr = 156.13
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 4.0499 (5) Å
b = 18.101 (2) Å
c = 9.4743 (13) Å
β = 96.720 (7)°
V = 689.76 (15) Å3
Z = 4
0.34 × 0.25 × 0.19 mm
Data collection
Bruker Kappa APEXII CCD area-detector
diffractometer
882 reflections with I > 2σ(I)

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supplementary materials
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Radiation source: sealed tube
graphite
φ– and ω–scans
6516 measured reflections
1268 independent reflections
Rint = 0.046
θmax = 25.5°, θmin = 2.4°
h = −4→4
k = −21→21
l = −11→11
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
H atoms treated by a mixture of independent and
constrained refinement
w = 1/[σ2(Fo2) + (0.0406P)2 + 0.1053P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.16 e Å−3
Δρmin = −0.16 e Å−3
Extinction correction: SHELXL97 (Sheldrick, 2008),
FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
R[F2 > 2σ(F2)] = 0.037
wR(F2) = 0.094
S = 1.01
1268 reflections
105 parameters
1 restraint
Primary atom site location: structure-invariant direct
methods
Extinction coefficient: 0.0080 (19)
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between
s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is
used for estimating s.u.'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, convention-
al 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)
x
0.6125 (3)
0.9490 (3)
0.3187 (3)
0.0594 (4)
0.7497 (4)
0.6491 (4)
0.4283 (4)
0.2914 (4)
0.3878 (4)
0.2807 (5)
y
0.16542 (6)
0.11978 (7)
−0.03651 (6)
0.22405 (7)
0.10447 (9)
0.03392 (9)
0.02721 (9)
0.09149 (9)
0.15778 (9)
0.23160 (9)
z
0.30332 (12)
0.48000 (14)
0.14748 (13)
0.00555 (16)
0.3778 (2)
0.32627 (18)
0.20778 (18)
0.13544 (18)
0.18521 (18)
0.1300 (2)
Uiso*/Ueq
0.0376 (4)
0.0495 (5)
0.0392 (4)
0.0558 (5)
0.0362 (6)
0.0336 (6)
0.0303 (5)
0.0334 (6)
0.0325 (6)
0.0413 (6)
O1
O2
O3
O4
C1
C2
C3
C4
C5
C6