3-O-Methyl-1-isomangostin

Boonnak, N.; Chantrapromma, S.; Fun, H.-K.

doi:10.1107/S1600536812023409

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1950-o1951

doi:10.1107/S1600536812023409

Open

access

3-O-Methyl-1-isomangostin

Nawong Boonnak,^a Suchada Chantrapromma ^a ^*‡ and Hoong-Kun Fun ^b §

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 15 May 2012; accepted 22 May 2012; online 31 May 2012)

In the title xanthone derivative [systematic name: 9-hydroxy-5,10-dimethoxy-2,2-dimethyl-11-(3-methylbut-2-en-1-yl)-2,3,4,12-tetrahydro-1,7-dioxatetraphen-12-one], C₂₅H₂₈O₆, the xanthone ring system is roughly planar, with an r.m.s. deviation of 0.1038 (1) Å. The chromane ring is in a half-chair conformation and the 3-methylbut-2-enyl substituent is axially attached with an (+)-anticlinal conformation. Two weak intramolecular C—H⋯O interactions generate two S(6) ring motifs. In the crystal, molecules are linked into ribbons along the c axis by O—H⋯O and weak C—H⋯O hydrogen bonds. A π–π interaction, with a centroid–centroid distance of 3.5413 (8) Å, is also observed.

Related literature

For background to xanthones and their biological activity, see: Bennett & Lee (1989 ); Boonnak et al. (2010 ); Gopalakrishnan et al. (1997 ); Ho et al. (2002 ); Mahabusarakam et al. (1987 ); Obolskiy et al. (2009 ); Phongpaichit et al. (1994 ); Shankaranarayan et al. (1979 ); Yoshikawa et al. (1994 ). For related structures, see: Chantrapromma et al. (2005 ). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring conformations, see: Cremer & Pople (1975 ). For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₅H₂₈O₆
M_r = 424.47
Monoclinic, P 2₁ /c
a = 10.8635 (9) Å
b = 16.6117 (13) Å
c = 13.4146 (8) Å
β = 118.843 (5)°
V = 2120.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.33 × 0.23 × 0.17 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.970, T_max = 0.984
21681 measured reflections
5630 independent reflections
4344 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.134
S = 1.05
5630 reflections
286 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1O5⋯O2ⁱ	0.90	1.77	2.6082 (17)	155
C15—H15A⋯O1ⁱⁱ	0.99	2.55	3.3820 (18)	141
C20—H20C⋯O5	0.98	2.57	3.104 (2)	115
C21—H21A⋯O2	0.99	2.29	2.807 (2)	111
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812023409/rz2760sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023409/rz2760Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023409/rz2760Isup3.cml

checkCIF report

Comment top

Garcinia genus plants are commonly known as a good providing source of bioactive xanthones (Bennett & Lee, 1989). The α-, β- and γ-mangostins are well known bioactive xanthones that were isolated from G. mangostana as major constituents (Mahabusarakam et al., 1987) and they exhibit various biological and pharmacological properties (Obolskiy et al., 2009; Phongpaichit et al., 1994) such as antibacterial (Boonnak et al., 2010), antifungal (Gopalakrishnan et al., 1997), anti-inflammatory (Shankaranarayan et al., 1979), antioxidant (Yoshikawa et al., 1994) and anti-cancer (Ho et al., 2002) activities. These interesting biological properties of xanthones have led us to synthesize the title compound (I) by modification of an isoprenyl side chain of β-mangostin to the chromane ring via acid catalysis (Gopalakrishnan et al., 1997) with the hope to enhance its bioactivity. However our antibacterial testing has found that (I) is less active than its precusor (β-mangostin). Herein the crystal structure of (I) is reported.

Compound (I) has a xanthone nucleus with a fused angular fashion chromane ring (Fig. 1). The three-ring system [C1–C13/O1] of the xanthone nucleus is roughly planar with an r.m.s. deviation of 0.1038 (1) Å from the plane through all the fourteen non-hydrogen atoms (maximum deviation of -0.192 (1) Å for atom O1). The chromane ring (C1–C2/C14–C16/O3) is in a half-chair conformation with puckering parameter Q = 0.4631 (17) Å, θ = 49.7 (2)° and ϕ = 272.7 (2)° (Cremer & Pople, 1975), with the puckered C14 and C15 atoms having deviations of -0.306 (1) and 0.293 (2) Å, respectively. The hydroxyl group is planarly attached at atom C8. The two methoxy groups have different orientations in which one methoxy group at atom C3 lies close to the plane of its bound benzene ring with the torsion angle C19–O4–C3–C4 = 1.79 (19)° whereas the other is axially attached at atom C9 with the torsion angle C20–O6–C9–C8 = 80.63 (15)°, indicating an (+)-anti-clinal conformation. The 3-methyl-2-butenyl substituent is attached at atom C10 with the torsion angle C9–C10–C21–C22 = 87.47 (16) °, indicating an (+)-anti-clinal conformation (Fig. 1). Intramolecular C20—H20C···O5 and C21—H21A···O2 weak interactions (Table 1) generate two S(6) ring motifs (Bernstein et al., 1995). The bond distances in (I) are within normal ranges (Allen et al., 1987) and comparable to those found in a related structure (Chantrapromma et al., 2005).

In the crystal packing, the molecules are linked into ribbons along [0 0 1] by O—H···O hydrogen bonds and the adjacent ribbons are further linked by weak C—H···O interactions (Fig. 2 and Table 1). A π–π interaction with the distance of Cg₂···Cg₂ⁱⁱ = 3.5413 (8) Å is observed; Cg₂ is the centroid of C1–C5/C13 ring; symmetry code: (ii) 1-x, 2-y, 2-z.

Related literature top

For background to xanthones and their biological activity, see: Bennett & Lee (1989); Boonnak et al. (2010); Gopalakrishnan et al. (1997); Ho et al. (2002); Mahabusarakam et al. (1987); Obolskiy et al. (2009); Phongpaichit et al. (1994); Shankaranarayan et al. (1979); Yoshikawa et al. (1994). For related structures, see: Chantrapromma et al. (2005). For details of hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986).

Experimental top

A solution of β-mangostin (30 mg, 0.707 mmol) and p-toluenesulfonic acid (75 mg, 0.436 mmol) in dry acetic acid (1.30 ml) was stirred at room temperature for 24 h. The mixture was extracted with ethylacetate. The combined ethylacetate extract was further washed with a saturated aqueous NaHCO₃ solution and dried over anhydrous MgSO₄. The solvent was evaporated under reduced pressure to give a yellow residue, which was further purified by column chromatography (hexane/ethylacetate, 9:1 v/v) to yield the title compound (I). Yellow block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from a solution of CHCl₃/CH₃OH (9:1 v)/v by slow evaporation of the solvent at room temperature after several days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids. Hydrogen bonds were drawn as dashed lines.
	Fig. 2. The crystal packing of the title compound viewed approximately along the a axis. Only H atoms involved in hydrogen bonds (dashed lines) are shown for clarity.

3-O-methyl-1-isomangostin top

Crystal data top

C₂₅H₂₈O₆	F(000) = 904
M_r = 424.47	D_x = 1.330 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5630 reflections
a = 10.8635 (9) Å	θ = 2.1–29.0°
b = 16.6117 (13) Å	µ = 0.09 mm⁻¹
c = 13.4146 (8) Å	T = 100 K
β = 118.843 (5)°	Block, yellow
V = 2120.5 (3) Å³	0.33 × 0.23 × 0.17 mm
Z = 4

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	5630 independent reflections
Radiation source: sealed tube	4344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 29.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.970, T_max = 0.984	k = −22→16
21681 measured reflections	l = −18→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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0637P)² + 0.7665P] where P = (F_o² + 2F_c²)/3
5630 reflections	(Δ/σ)_max = 0.001
286 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₅H₂₈O₆	V = 2120.5 (3) Å³
M_r = 424.47	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.8635 (9) Å	µ = 0.09 mm⁻¹
b = 16.6117 (13) Å	T = 100 K
c = 13.4146 (8) Å	0.33 × 0.23 × 0.17 mm
β = 118.843 (5)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	5630 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4344 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.984	R_int = 0.031
21681 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.05	Δρ_max = 0.42 e Å⁻³
5630 reflections	Δρ_min = −0.22 e Å⁻³
286 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.47611 (10)	0.79136 (6)	1.00159 (8)	0.0224 (2)
O2	0.72643 (12)	0.86788 (7)	0.87266 (9)	0.0303 (2)
O3	0.56536 (10)	0.99916 (6)	0.79679 (8)	0.0246 (2)
O4	0.17200 (10)	1.01564 (6)	0.85893 (9)	0.0254 (2)
O5	0.79450 (11)	0.58712 (6)	1.21935 (9)	0.0269 (2)
H1O5	0.7523	0.5913	1.2623	0.040*
O6	0.99052 (11)	0.64398 (6)	1.16684 (9)	0.0271 (2)
C1	0.48227 (14)	0.96827 (8)	0.83776 (11)	0.0208 (3)
C2	0.36202 (14)	1.00707 (8)	0.82405 (11)	0.0215 (3)
C3	0.28457 (14)	0.97195 (8)	0.87218 (11)	0.0214 (3)
C4	0.32266 (14)	0.89900 (8)	0.92935 (11)	0.0218 (3)
H4A	0.2671	0.8747	0.9582	0.026*
C5	0.44460 (14)	0.86281 (8)	0.94284 (11)	0.0199 (3)
C6	0.60528 (14)	0.75690 (8)	1.03800 (11)	0.0202 (3)
C7	0.63295 (15)	0.69158 (8)	1.11039 (12)	0.0219 (3)
H7A	0.5658	0.6742	1.1319	0.026*
C8	0.76041 (15)	0.65239 (8)	1.15050 (11)	0.0224 (3)
C9	0.86042 (14)	0.68063 (8)	1.11974 (12)	0.0228 (3)
C10	0.83498 (15)	0.74805 (8)	1.05092 (12)	0.0227 (3)
C11	0.70074 (14)	0.78588 (8)	1.00440 (11)	0.0209 (3)
C12	0.65700 (15)	0.85193 (8)	0.92089 (11)	0.0215 (3)
C13	0.52913 (14)	0.89451 (8)	0.90017 (11)	0.0199 (3)
C14	0.50491 (16)	1.06108 (9)	0.70826 (12)	0.0262 (3)
C15	0.42974 (16)	1.12362 (9)	0.74250 (13)	0.0275 (3)
H15A	0.4988	1.1504	0.8135	0.033*
H15B	0.3881	1.1651	0.6823	0.033*
C16	0.31443 (15)	1.08605 (8)	0.76085 (12)	0.0249 (3)
H16A	0.2884	1.1237	0.8048	0.030*
H16B	0.2301	1.0768	0.6862	0.030*
C17	0.63073 (18)	1.09726 (10)	0.70456 (15)	0.0350 (4)
H17A	0.6948	1.1207	0.7789	0.052*
H17B	0.5989	1.1393	0.6461	0.052*
H17C	0.6798	1.0551	0.6863	0.052*
C18	0.40695 (18)	1.01862 (10)	0.59661 (13)	0.0319 (3)
H18A	0.4595	0.9774	0.5806	0.048*
H18B	0.3689	1.0580	0.5346	0.048*
H18C	0.3296	0.9933	0.6030	0.048*
C19	0.09221 (16)	0.98457 (9)	0.91024 (14)	0.0287 (3)
H19A	0.0136	1.0209	0.8939	0.043*
H19B	0.1529	0.9805	0.9928	0.043*
H19C	0.0557	0.9311	0.8790	0.043*
C20	0.98891 (17)	0.57034 (9)	1.11071 (13)	0.0294 (3)
H20A	1.0844	0.5485	1.1443	0.044*
H20B	0.9538	0.5807	1.0295	0.044*
H20C	0.9274	0.5314	1.1199	0.044*
C21	0.95680 (15)	0.78156 (9)	1.03784 (13)	0.0269 (3)
H21A	0.9428	0.8402	1.0236	0.032*
H21B	1.0449	0.7738	1.1104	0.032*
C22	0.97349 (17)	0.74360 (9)	0.94364 (14)	0.0291 (3)
H22A	0.8942	0.7445	0.8697	0.035*
C23	1.09098 (19)	0.70835 (9)	0.95472 (17)	0.0364 (4)
C24	1.22440 (18)	0.69855 (11)	1.06549 (19)	0.0455 (5)
H24A	1.2082	0.7148	1.1284	0.068*
H24B	1.2981	0.7324	1.0651	0.068*
H24C	1.2540	0.6421	1.0752	0.068*
C25	1.0935 (2)	0.67564 (13)	0.8511 (2)	0.0533 (5)
H25A	1.0008	0.6827	0.7843	0.080*
H25B	1.1172	0.6183	0.8620	0.080*
H25C	1.1641	0.7047	0.8395	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0212 (5)	0.0229 (5)	0.0282 (5)	0.0027 (4)	0.0158 (4)	0.0046 (4)
O2	0.0344 (6)	0.0341 (6)	0.0357 (6)	0.0082 (4)	0.0275 (5)	0.0088 (4)
O3	0.0271 (5)	0.0253 (5)	0.0274 (5)	0.0018 (4)	0.0179 (4)	0.0058 (4)
O4	0.0235 (5)	0.0275 (5)	0.0287 (5)	0.0051 (4)	0.0154 (4)	0.0024 (4)
O5	0.0339 (6)	0.0277 (5)	0.0280 (5)	0.0090 (4)	0.0219 (5)	0.0073 (4)
O6	0.0252 (5)	0.0314 (5)	0.0277 (5)	0.0079 (4)	0.0152 (4)	0.0027 (4)
C1	0.0233 (7)	0.0225 (6)	0.0189 (6)	−0.0020 (5)	0.0120 (5)	−0.0008 (5)
C2	0.0233 (7)	0.0220 (6)	0.0194 (6)	0.0001 (5)	0.0105 (5)	−0.0007 (5)
C3	0.0198 (6)	0.0252 (6)	0.0194 (6)	0.0011 (5)	0.0098 (5)	−0.0024 (5)
C4	0.0209 (7)	0.0257 (6)	0.0230 (6)	−0.0002 (5)	0.0138 (6)	0.0011 (5)
C5	0.0220 (6)	0.0203 (6)	0.0192 (6)	0.0000 (5)	0.0114 (5)	0.0005 (5)
C6	0.0197 (6)	0.0230 (6)	0.0208 (6)	0.0010 (5)	0.0121 (5)	−0.0016 (5)
C7	0.0248 (7)	0.0236 (6)	0.0235 (6)	0.0012 (5)	0.0165 (6)	0.0003 (5)
C8	0.0273 (7)	0.0234 (6)	0.0198 (6)	0.0034 (5)	0.0139 (6)	0.0003 (5)
C9	0.0220 (7)	0.0270 (7)	0.0224 (6)	0.0040 (5)	0.0132 (6)	−0.0007 (5)
C10	0.0243 (7)	0.0256 (6)	0.0232 (6)	0.0008 (5)	0.0156 (6)	−0.0016 (5)
C11	0.0225 (7)	0.0230 (6)	0.0218 (6)	0.0016 (5)	0.0143 (5)	−0.0002 (5)
C12	0.0241 (7)	0.0230 (6)	0.0217 (6)	0.0002 (5)	0.0144 (6)	−0.0010 (5)
C13	0.0215 (6)	0.0220 (6)	0.0189 (6)	−0.0003 (5)	0.0119 (5)	−0.0006 (5)
C14	0.0329 (8)	0.0239 (6)	0.0272 (7)	0.0023 (6)	0.0189 (6)	0.0062 (5)
C15	0.0338 (8)	0.0227 (6)	0.0309 (7)	0.0005 (6)	0.0193 (7)	0.0027 (5)
C16	0.0275 (7)	0.0225 (6)	0.0263 (7)	0.0023 (5)	0.0143 (6)	0.0021 (5)
C17	0.0399 (9)	0.0293 (8)	0.0465 (9)	0.0022 (6)	0.0294 (8)	0.0102 (7)
C18	0.0431 (9)	0.0314 (7)	0.0257 (7)	0.0027 (7)	0.0203 (7)	0.0034 (6)
C19	0.0239 (7)	0.0328 (7)	0.0347 (8)	0.0028 (6)	0.0184 (7)	−0.0002 (6)
C20	0.0323 (8)	0.0290 (7)	0.0301 (7)	0.0092 (6)	0.0176 (7)	0.0043 (6)
C21	0.0256 (7)	0.0284 (7)	0.0322 (7)	0.0002 (6)	0.0182 (6)	0.0013 (6)
C22	0.0312 (8)	0.0305 (7)	0.0353 (8)	0.0045 (6)	0.0237 (7)	0.0056 (6)
C23	0.0428 (9)	0.0264 (7)	0.0596 (11)	0.0074 (6)	0.0403 (9)	0.0122 (7)
C24	0.0344 (9)	0.0391 (9)	0.0749 (14)	0.0098 (7)	0.0358 (10)	0.0170 (9)
C25	0.0694 (14)	0.0468 (11)	0.0768 (14)	0.0169 (10)	0.0616 (13)	0.0112 (10)

Geometric parameters (Å, º) top

O1—C6	1.3689 (16)	C14—C18	1.528 (2)
O1—C5	1.3737 (15)	C15—C16	1.522 (2)
O2—C12	1.2363 (16)	C15—H15A	0.9900
O3—C1	1.3635 (16)	C15—H15B	0.9900
O3—C14	1.4653 (16)	C16—H16A	0.9900
O4—C3	1.3579 (16)	C16—H16B	0.9900
O4—C19	1.4377 (18)	C17—H17A	0.9800
O5—C8	1.3549 (16)	C17—H17B	0.9800
O5—H1O5	0.8949	C17—H17C	0.9800
O6—C9	1.3805 (17)	C18—H18A	0.9800
O6—C20	1.4322 (18)	C18—H18B	0.9800
C1—C2	1.3871 (19)	C18—H18C	0.9800
C1—C13	1.4318 (18)	C19—H19A	0.9800
C2—C3	1.411 (2)	C19—H19B	0.9800
C2—C16	1.5114 (19)	C19—H19C	0.9800
C3—C4	1.3863 (19)	C20—H20A	0.9800
C4—C5	1.3848 (18)	C20—H20B	0.9800
C4—H4A	0.9500	C20—H20C	0.9800
C5—C13	1.3982 (18)	C21—C22	1.499 (2)
C6—C7	1.3890 (19)	C21—H21A	0.9900
C6—C11	1.4005 (19)	C21—H21B	0.9900
C7—C8	1.3826 (19)	C22—C23	1.346 (2)
C7—H7A	0.9500	C22—H22A	0.9500
C8—C9	1.415 (2)	C23—C24	1.502 (3)
C9—C10	1.3917 (19)	C23—C25	1.505 (3)
C10—C11	1.4258 (19)	C24—H24A	0.9800
C10—C21	1.522 (2)	C24—H24B	0.9800
C11—C12	1.4734 (19)	C24—H24C	0.9800
C12—C13	1.4611 (19)	C25—H25A	0.9800
C14—C17	1.516 (2)	C25—H25B	0.9800
C14—C15	1.523 (2)	C25—H25C	0.9800

C6—O1—C5	119.66 (11)	H15A—C15—H15B	107.9
C1—O3—C14	117.77 (11)	C2—C16—C15	111.17 (12)
C3—O4—C19	117.28 (11)	C2—C16—H16A	109.4
C8—O5—H1O5	108.7	C15—C16—H16A	109.4
C9—O6—C20	112.70 (11)	C2—C16—H16B	109.4
O3—C1—C2	122.40 (12)	C15—C16—H16B	109.4
O3—C1—C13	116.11 (12)	H16A—C16—H16B	108.0
C2—C1—C13	121.44 (12)	C14—C17—H17A	109.5
C1—C2—C3	118.60 (12)	C14—C17—H17B	109.5
C1—C2—C16	121.55 (13)	H17A—C17—H17B	109.5
C3—C2—C16	119.85 (12)	C14—C17—H17C	109.5
O4—C3—C4	123.32 (12)	H17A—C17—H17C	109.5
O4—C3—C2	114.67 (12)	H17B—C17—H17C	109.5
C4—C3—C2	122.01 (12)	C14—C18—H18A	109.5
C5—C4—C3	117.60 (12)	C14—C18—H18B	109.5
C5—C4—H4A	121.2	H18A—C18—H18B	109.5
C3—C4—H4A	121.2	C14—C18—H18C	109.5
O1—C5—C4	114.08 (12)	H18A—C18—H18C	109.5
O1—C5—C13	121.95 (12)	H18B—C18—H18C	109.5
C4—C5—C13	123.97 (12)	O4—C19—H19A	109.5
O1—C6—C7	114.52 (12)	O4—C19—H19B	109.5
O1—C6—C11	122.16 (12)	H19A—C19—H19B	109.5
C7—C6—C11	123.33 (12)	O4—C19—H19C	109.5
C8—C7—C6	118.57 (13)	H19A—C19—H19C	109.5
C8—C7—H7A	120.7	H19B—C19—H19C	109.5
C6—C7—H7A	120.7	O6—C20—H20A	109.5
O5—C8—C7	122.36 (13)	O6—C20—H20B	109.5
O5—C8—C9	117.91 (12)	H20A—C20—H20B	109.5
C7—C8—C9	119.73 (12)	O6—C20—H20C	109.5
O6—C9—C10	119.36 (13)	H20A—C20—H20C	109.5
O6—C9—C8	118.73 (12)	H20B—C20—H20C	109.5
C10—C9—C8	121.70 (12)	C22—C21—C10	114.13 (13)
C9—C10—C11	118.61 (13)	C22—C21—H21A	108.7
C9—C10—C21	117.73 (12)	C10—C21—H21A	108.7
C11—C10—C21	123.44 (12)	C22—C21—H21B	108.7
C6—C11—C10	117.87 (12)	C10—C21—H21B	108.7
C6—C11—C12	118.90 (12)	H21A—C21—H21B	107.6
C10—C11—C12	123.20 (12)	C23—C22—C21	125.71 (16)
O2—C12—C13	124.11 (12)	C23—C22—H22A	117.1
O2—C12—C11	120.20 (12)	C21—C22—H22A	117.1
C13—C12—C11	115.69 (12)	C22—C23—C24	124.58 (17)
C5—C13—C1	116.31 (12)	C22—C23—C25	119.59 (18)
C5—C13—C12	119.45 (12)	C24—C23—C25	115.83 (15)
C1—C13—C12	124.24 (12)	C23—C24—H24A	109.5
O3—C14—C17	104.25 (12)	C23—C24—H24B	109.5
O3—C14—C15	109.29 (11)	H24A—C24—H24B	109.5
C17—C14—C15	111.26 (12)	C23—C24—H24C	109.5
O3—C14—C18	107.36 (11)	H24A—C24—H24C	109.5
C17—C14—C18	111.32 (13)	H24B—C24—H24C	109.5
C15—C14—C18	112.91 (13)	C23—C25—H25A	109.5
C16—C15—C14	111.83 (12)	C23—C25—H25B	109.5
C16—C15—H15A	109.3	H25A—C25—H25B	109.5
C14—C15—H15A	109.3	C23—C25—H25C	109.5
C16—C15—H15B	109.3	H25A—C25—H25C	109.5
C14—C15—H15B	109.3	H25B—C25—H25C	109.5

C14—O3—C1—C2	−18.47 (18)	O1—C6—C11—C12	−4.4 (2)
C14—O3—C1—C13	163.92 (11)	C7—C6—C11—C12	175.70 (12)
O3—C1—C2—C3	−178.12 (12)	C9—C10—C11—C6	5.0 (2)
C13—C1—C2—C3	−0.63 (19)	C21—C10—C11—C6	−169.51 (13)
O3—C1—C2—C16	0.9 (2)	C9—C10—C11—C12	−173.19 (13)
C13—C1—C2—C16	178.37 (12)	C21—C10—C11—C12	12.3 (2)
C19—O4—C3—C4	1.79 (19)	C6—C11—C12—O2	−165.46 (13)
C19—O4—C3—C2	−177.51 (12)	C10—C11—C12—O2	12.8 (2)
C1—C2—C3—O4	177.28 (11)	C6—C11—C12—C13	13.96 (18)
C16—C2—C3—O4	−1.74 (18)	C10—C11—C12—C13	−167.83 (12)
C1—C2—C3—C4	−2.0 (2)	O1—C5—C13—C1	178.29 (12)
C16—C2—C3—C4	178.95 (12)	C4—C5—C13—C1	−1.0 (2)
O4—C3—C4—C5	−176.20 (12)	O1—C5—C13—C12	−1.69 (19)
C2—C3—C4—C5	3.0 (2)	C4—C5—C13—C12	179.04 (13)
C6—O1—C5—C4	−168.53 (12)	O3—C1—C13—C5	179.69 (11)
C6—O1—C5—C13	12.13 (19)	C2—C1—C13—C5	2.05 (19)
C3—C4—C5—O1	179.18 (12)	O3—C1—C13—C12	−0.32 (19)
C3—C4—C5—C13	−1.5 (2)	C2—C1—C13—C12	−177.96 (13)
C5—O1—C6—C7	170.98 (11)	O2—C12—C13—C5	168.33 (13)
C5—O1—C6—C11	−8.95 (19)	C11—C12—C13—C5	−11.06 (18)
O1—C6—C7—C8	179.30 (12)	O2—C12—C13—C1	−11.6 (2)
C11—C6—C7—C8	−0.8 (2)	C11—C12—C13—C1	168.96 (12)
C6—C7—C8—O5	−178.50 (12)	C1—O3—C14—C17	165.58 (12)
C6—C7—C8—C9	1.6 (2)	C1—O3—C14—C15	46.56 (16)
C20—O6—C9—C10	−104.50 (15)	C1—O3—C14—C18	−76.23 (15)
C20—O6—C9—C8	80.63 (15)	O3—C14—C15—C16	−58.35 (16)
O5—C8—C9—O6	−4.17 (19)	C17—C14—C15—C16	−172.94 (12)
C7—C8—C9—O6	175.69 (12)	C18—C14—C15—C16	61.06 (16)
O5—C8—C9—C10	−178.92 (12)	C1—C2—C16—C15	−13.47 (18)
C7—C8—C9—C10	0.9 (2)	C3—C2—C16—C15	165.52 (12)
O6—C9—C10—C11	−179.05 (12)	C14—C15—C16—C2	41.79 (16)
C8—C9—C10—C11	−4.3 (2)	C9—C10—C21—C22	87.47 (16)
O6—C9—C10—C21	−4.18 (19)	C11—C10—C21—C22	−97.93 (16)
C8—C9—C10—C21	170.53 (13)	C10—C21—C22—C23	−124.59 (16)
O1—C6—C11—C10	177.31 (12)	C21—C22—C23—C24	2.4 (3)
C7—C6—C11—C10	−2.6 (2)	C21—C22—C23—C25	−177.60 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O2ⁱ	0.90	1.77	2.6082 (17)	155
C15—H15A···O1ⁱⁱ	0.99	2.55	3.3820 (18)	141
C20—H20C···O5	0.98	2.57	3.104 (2)	115
C21—H21A···O2	0.99	2.29	2.807 (2)	111

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₈O₆
M_r	424.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.8635 (9), 16.6117 (13), 13.4146 (8)
β (°)	118.843 (5)
V (Å³)	2120.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.23 × 0.17

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.970, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	21681, 5630, 4344
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.134, 1.05
No. of reflections	5630
No. of parameters	286
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.22

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O2ⁱ	0.90	1.77	2.6082 (17)	155
C15—H15A···O1ⁱⁱ	0.99	2.55	3.3820 (18)	141
C20—H20C···O5	0.98	2.57	3.104 (2)	115
C21—H21A···O2	0.99	2.29	2.807 (2)	111

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

Footnotes

‡Thomson Reuters ResearcherID: A-5085-2009.

§Thomson Reuters ResearcherID: A-3561-2009. Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

NB thanks Prince of Songkla University for a postdoctoral fellowship. Financial support from Prince of Songkla University is gratefully acknowledged. The authors also thank Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

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. CrossRef Web of Science Google Scholar
Bennett, G. J. & Lee, H.-H. (1989). Phytochemistry, 28, 967–998. CrossRef CAS Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Boonnak, N., Karalai, C., Chantrapromma, S., Ponglimanont, C., Kanjana-Opas, A., Chantrapromma, K. & Kato, S. (2010). Chem. Pharm. Bull. 58, 386–389. CrossRef CAS PubMed Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chantrapromma, S., Boonnak, N., Fun, H.-K., Anjum, S. & Atta-ur-Rahman (2005). Acta Cryst. E61, o2136–o2138. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Gopalakrishnan, G., Banumathi, B. & Suresh, G. (1997). J. Nat. Prod. 60, 519–524. CrossRef CAS PubMed Web of Science Google Scholar
Ho, C. K., Huang, Y. L. & Chen, C. C. (2002). Planta Med. 68, 975–979. Web of Science CrossRef PubMed CAS Google Scholar
Mahabusarakam, W., Wiriyachitra, P. & Taylor, W. C. (1987). J. Nat. Prod. 50, 474–478. CrossRef CAS Web of Science Google Scholar
Obolskiy, D., Pischel, I., Siriwatanametanon, N. & Heinrich, M. (2009). Phytother. Res. 23, 1047–1065. Web of Science CrossRef PubMed CAS Google Scholar
Phongpaichit, S., Ongsakul, M., Nilrat, L., Tharavichitkul, P., Bunchoo, S., Chauprapaisilp, T. & Wiriyachitra, P. (1994). Songklanakarin J. Sci. Technol. 16, 399–405. Google Scholar
Shankaranarayan, D., Gopalakrishnan, C. & Kameswaran, L. (1979). Arch. Int. Pharmacodyn. Ther. 239, 257–269. CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yoshikawa, M., Harada, E., Miki, A., Tsukamoto, K., Si Quian, L., Yamahara, J. & Murakami, N. (1994). Yakugaku Zasshi, 114, 129–133. CAS Google Scholar