1,3-Dihydr­oxy-9,10-dioxo-9,10-di­hydro­anthracene-2-carbaldehyde

Khalijah Awang; Nor Hadiani Ismail; Rohaya Ahmad; Nor Hafizoh Saidan; Pascal Retailleau

doi:10.1107/S1600536808004169

. 2008 Feb 15;64(Pt 3):o597. doi: 10.1107/S1600536808004169

1,3-Dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-carbaldehyde

Khalijah Awang ^a, Nor Hadiani Ismail ^b, Rohaya Ahmad ^b, Nor Hafizoh Saidan ^b, Pascal Retailleau ^c,^*

PMCID: PMC2960756 PMID: 21201935

Abstract

The title compound, C₁₅H₈O₅, also known as nordamnacanthal, was isolated from the Malaysian Morinda citrifolia L. The 20 non-H atoms are coplanar. The structure is stabilized by intramolecular O—H⋯O hydrogen bonds and intermolecular O—H⋯O and C—H⋯O hydrogen bonds, forming bilayers of molecular tapes with alternating stacking directions along the a axis.

Related literature

For related literature, see: Chan-Blanco et al. (2006 ▶); Ismail (1998 ▶); Ohsawa & Ohba (1993 ▶); Singh et al. (1984 ▶); Whistler (1985 ▶); Wijnsma & Verpoorte (1986 ▶); Zhu et al. (2008 ▶).

Experimental

Crystal data

C₁₅H₈O₅
M _r = 268.21
Monoclinic,
a = 10.547 (2) Å
b = 5.669 (1) Å
c = 20.231 (3) Å
β = 110.62 (4)°
V = 1132.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.60 × 0.39 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
14030 measured reflections
2298 independent reflections
1554 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.150
S = 1.06
2296 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT (Nonius, 1999 ▶); cell refinement: DENZO and COLLECT; data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004169/bg2162sup1.cif

e-64-0o597-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004169/bg2162Isup2.hkl

e-64-0o597-Isup2.hkl^{(113KB, hkl)}

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
O3—H3⋯O2	0.82	1.86	2.590 (3)	148
O1—H1⋯O5	0.82	1.86	2.577 (2)	146
O1—H1⋯O5ⁱ	0.82	2.34	2.933 (2)	130
C4—H4⋯O4ⁱⁱ	0.93	2.45	3.358 (2)	166
C10—H10⋯O2ⁱⁱⁱ	0.93	2.53	3.312 (3)	142

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

Acknowledgments

KA thanks the Universiti Teknologi MARA and the Ministry of Science and Technology for financial support, and the Institut de Chimie des Substances Naturelles for research facilities.

supplementary crystallographic information

Comment

Morinda citrifolia Linn. (Noni), has been one of the most used traditional folk medicinal plants in Polynesia for over 2000 years (Whistler,1985). It has been reported to have a broad range of therapeutic and nutritional properties (Chan-Blanco et al.,2006) including antibacterial, antiviral, antifungal, antitumor, analgesic, hypotensive, anti-inflammatory and immune enhancing effects (Singh et al., 1984). Nordamnacanthal, damnacanthal and morindone (Ismail, 1998; Wijnsma & Verpoorte, 1986) have been isolated from the Malaysian Morinda citrifolia Linn. The crystal structure of damnacanthal having been reported by Ohsawa & Ohba (1993), we present in this communication the crystal structure of nordamnacanthal (I). (Fig. 1) shows its molecular structure. The C—C bond lengths in the anthraquinone ring range from 1.377 (3) Å to 1.484 (3) Å, the carbonyl bond distances from 1.220 (2) Å to 1.237 (2) Å and the two hydroxyl bond distances are 1.326 (2) Å and 1.349 (2) Å; all are comparable to those observed in similar structures (Ohsawa & Ohba, 1993; Zhu et al., 2008). All 20 non-H atoms of (I) are essentially coplanar, their mean deviation from the least-squares molecular plane being 0.028 Å and the dihedral angle between the two benzene rings being 1.27 (10)°. The molecule features two intramolecular O—H···O hydrogen bonds, with O3···O2 distance of 2.590 (3) Å and O1···O5 distance of 2.577 (2) Å. Additionally, atom O1 is also engaged into an intermolecular hydrogen bond with atom O5, viz. O1—H1···O5ⁱ [symmetry code:(i) -x, 1 - y, -z] leading to the formation of a coplanar centrosymmetric dimer via the key {H—O1—C1—C14—C13—O5}2 synthon, R₂²(12). Adjacent dimers extend through synthon R₂²(10) of weak C4—H4···O4ⁱⁱ [symmetry code:(ii) 1 - x, 3 - y, -z] hydrogen bond to form molecular tapes running parallel to the [120] and [120] directions (Fig. 2). The dihedral angle between the two molecular tape orientations is 66.03° and an additional weak C10—H10···O4ⁱⁱⁱ [symmetry code:(ii) -1 + x, 3/2 - y, -1/2 + z] hydrogen bond links the tapes along the c axis. The tapes are stacked along the a axis, forming two kinds of layers in which molecules related by an inversion center stack with an interplanar spacing of 3.255 (4) Å and a centroid offset of ca 3.5 Å (Fig. 3).

Experimental

Morinda citrifolia used in this study was collected from kg. Tanjung Keramat, Langkap, Perak. The roots were harvested, washed, chopped into small pieces and then dried at room temperature for one week. The dried sample was then ground to small size using grinder. The ground roots (1.5 kg) were soaked at room temperature in dichloromethane for 48 h. The solvent was then removed by filtration and fresh solvent added to the plant material. The extraction was repeated three times. The combined filtrate was evaporated under reduced pressure to give brown coloured residue (35.6 g). The crude extract was fractionated using Medium Pressure Liquid Chromatography (MPLC) system fitted with Buchi Pump Module C-601. The sample (10 g) was introduced dry after being pre-absorbed onto acid-washed silica gel (10 g) in two portions. The column (150 mm x 40 mm) was packed with 90 g acid-washed silica gel (Merck 7734) and eluted gradiently with petroleum ether, chloroform and chloroform enriched with increasing percentages of methanol (1%, 2% and 5%). Seven combined fractions were collected based on thin layer chromatography (TLC) pattern (labeled A, B, C, D, E, F, and G).

Nordamnacanthal (1.65 g) were isolated from fraction A after column chromatography. The fraction was re-chromatographed using small column (400 mm x 20 mm) packed with 2% acid-washed silica gel (Merck 9385) eluted gradiently with petroleum ether and chloroform. The first orange band eluted out from the column was collected in small vials and inspected using analytical TLC developed in PE:CHCl3 (4:6) showing a single spot of a purified compound. Recrystallization from hot CHCl3 gave bright orange crystals.