Hopeahainol C monohydrate

Hoong-Kun Fun; Kanokorn Sudto; Hui-Ming Ge; Ren-Xiang Tan; Supa Hannongbua; Suchada Chantrapromma

doi:10.1107/S1600536811017053

. 2011 May 14;67(Pt 6):o1392–o1393. doi: 10.1107/S1600536811017053

Hopeahainol C monohydrate

Hoong-Kun Fun ^a,^*,^‡, Kanokorn Sudto ^b, Hui-Ming Ge ^c, Ren-Xiang Tan ^c, Supa Hannongbua ^b, Suchada Chantrapromma ^d,^§

PMCID: PMC3120350 PMID: 21754780

Abstract

In the structure of the title compound, C₂₈H₁₆O₆·H₂O [systematic name 3,11-bis(4-hydroxyphenyl)-4,12-dioxapentacyclo[8.6.1.1^2,5.0^13,17.0^9,18]octadeca-1(16),2,5(18),6,8,10,13(17),14-octaene-7,15-diol monohydrate], the hopeahainol C molecule lies about an inversion center with the solvent water molecule located on a crystallographic twofold axis. Hopeahainol C is an oligostillbenoid compound and was isolated from the bark of Shorea roxburghii G. Don. The five central fused rings are essentially planar with an r.m.s. deviation of 0.0173 (3) Å. The 4-hydroxyphenyl ring is twisted with respect to this plane, with the dihedral angle between the phenyl ring and the fused-ring system being 41.70 (10)°. The crystal features intermolecular O—H⋯O hydrogen bonds. These interactions link the hopeahainol C molecules into chains along the b axis. Water molecules are located interstitially between the hopeahainol C molecules linked by O(water)—H⋯O(hydroxy) and O(hydroxy)—H⋯O(water) hydrogen bonds. π–π interactions are also observed with centroid–centroid distances of 3.6056 (17) and 3.5622 (17) Å. Short O⋯O contacts [2.703 (2)–2.720 (3) Å] are also present in the crystal.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to oligostillbenoids and their activities, see: Cai et al. (2003 ▶); Donnelly et al. (2004 ▶); Ge et al. (2009 ▶); Jang & Pezzuto (1999 ▶); Stivala et al. (2001 ▶). For details of Dipterocarpaceae plants, see: Gorham (1995 ▶); Hakim (2002 ▶); Sotheeswaran & Pasuphaty (1993 ▶); Symington (1974 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C₂₈H₁₆O₆·H₂O
M _r = 466.42
Monoclinic,
a = 21.225 (4) Å
b = 3.8500 (7) Å
c = 25.353 (5) Å
β = 108.933 (4)°
V = 1959.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.05 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.972, T _max = 0.994
7974 measured reflections
2171 independent reflections
1463 reflections with I > 2σ(I)
R _int = 0.082

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.161
S = 1.07
2171 reflections
163 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.35 e Å⁻³

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 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017053/sj5138sup1.cif

e-67-o1392-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017053/sj5138Isup2.hkl

e-67-o1392-Isup2.hkl^{(106.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017053/sj5138Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O2ⁱ	0.92 (3)	1.83 (3)	2.720 (2)	163 (3)
O3—H3A⋯O1Wⁱⁱ	0.82	1.89	2.703 (2)	169
O2—H2A⋯O3ⁱⁱⁱ	0.82	2.00	2.716 (3)	145

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This project was supported by the Thailand Research Fund (grant Nos. DBG5280018 and RTA5380010). The authors are also very grateful to Associate Professor Srunya Vajrodaya, Head of Department of Botany, Faculty of Science, Kasetsart University, Thailand, for identification of the plant specimens. The authors also thank the Malaysian government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

The genus Shorea is the largest genus of the family Dipterocarpaceae and is mostly distributed in Southeast Asia (Symington, 1974). The Dipterocarpaceous plant has already proved to be a rich source of oligostilbene compounds that are derived from stilbene and resveratrol (3,5,4'-trihydroxystilbene) (Gorham, 1995; Hakim, 2002; Sotheeswaran & Pasuphaty, 1993). It also has been known that resveratrol possesses various biological activities including antioxidant (Cai et al., 2003), anti-cancer, chemo-preventive (Jang & Pezzuto, 1999; Stivala et al., 2001) and anti-inflammatory properties (Donnelly et al., 2004). During the course of our research on searching for novel bioactive compounds from Thai dipeterocarpaceous plants, the title compound (I), known as hopeahainol C, was obtained from Shorea roxburghii G. Don. Hopeahainol C is an oligostilbenoid, which is a highly unsaturated resveratrol dimer, and it possesses potent antioxidant activity (Ge et al., 2009). Herein we report its crystal structure.

The molecule of the title oligostilbenoid (I) (Fig. 1), C₂₈H₁₆O₆.H₂O, is a symmetrical dimer. Its asymmetric unit contains one half-molecule. The complete molecule of hopeahainol C is generated by a crystallographic center of symmetry 1/2-x, 3/2-y, -z whereas the other hydrogen atom of the water molecule is generated by a two-fold rotation axis -x, y, 1/2-z. The five central fused rings are essentially planar with the r.m.s. 0.0173 (3) Å for the eighteen non-hydrogen atoms. The 4-hydroxyphenyl ring is twisted which respect to the five central fused rings with the dihedral angle between the phenyl and the five central fused rings being 41.65 (10)°. The dihedral angle between the phenyl and the attached dihydrofuran (O1/C7–C9/C14) rings is 40.50 (15)°. The two hydroxy groups of the half molecule are co-planar with the attached benzene ring with the torsion angles O3–C4–C5–C6 = -178.1 (2)° and C10–C11–C12–O2 = -179.5 (2)°. The bond distances are of normal values (Allen et al., 1987).

In the crystal packing (Fig. 2), the molecules of hopeahainol C are linked into chains along the b axis by O(hydroxy)—H···O(hydroxy) hydrogen bonds which form between the two hydroxy groups (Table 1). The water molecules are located in the interstitials of hopeahainol C molecules and are linked to the molecules of hopehainol C by two types of hydrogen bond i.e. O(water)—H···O(hydroxy) and O(hydroxy)—H···O(water) hydrogens bond (Table 1). The crystal is consolidated by these O—H···O hydrogen bonds. π–π interaction with Cg₁···Cg₃ distance = 3.6055 (17) Å (symmetry code: x, 1+y, z) and Cg₂···Cg₃ distance = 3.5622 (17) Å (symmetry code: 1/2-x, 5/2-y, -z) were observed where Cg1, Cg2 and Cg3 are the centroids of the O1/C7–C9/C14, C8–C10/C8A–C10A and C9–C14 rings, respectively. In addition O···O short contacts [2.703 (2)-2.720 (3) Å] are also presented in the crystal.

Experimental

The dried powdered bark of Shorea roxburghii G. Don. (1 kg) which was collected during June-August 2010 from Sam Sung District, Khon Kaen province in the northeastern part of Thailand, was macerated in C₂H₅OH (2.5 L) for 7 days. The slurry was filtered and the ethanolic extract obtained was dried with a rotary evaporator under reduced pressure at 313 K. The dried extract (98 g) was ground, dissolved in CH₃OH, mixed with silica gel (118 g), and then dried in hot air oven at 333 K for one day. The sample was separated by using a wet column chromatographic technique. The column was packed with 1 kg of silica gel (200-300 mesh) and was eluted with gradient mixtures of CHCl₃ and CH₃OH (100:0 to 0:100), to give 8 major fractions (A–H). Fraction G was further isolated using sephadex column chromatography, eluted with 100% CH₃OH. Only the blue methanolic extract could be selectively collected and was pre-concentrated and heated for 5-10 minutes at 313-333 K before being left for 2-3 days at 298 K to allow crystallization of hopeahainol C. Colorless needle-shaped single crystals of the hopeahainol C suitable for X-ray structure determination were obtained from CH₃OH by slow evaporation at room temperature after a few days.