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Acta Cryst. (2009). E65, o1524    [ doi:10.1107/S1600536809021266 ]

3-Hydroxy-1,2-dimethoxyanthraquinone

Y.-J. Xu, X.-X. Yang and H.-B. Zhao

Abstract top

The title compound, C16H12O5, was isolated from Morinda officinalis How. The anthraquinone ring system is almost planar, the dihedral angle between the two benzene rings being 1.12 (4)°. In the crystal structure, O-H...O and C-H...O hydrogen bonds link the moleculesin the crystallographic a-axis direction. Weak [pi]-[pi] stacking interactions [centroid-centroid distance between symmetry-related benzene rings of 3.699 (4) Å] are also present.

Comment top

Anthraquinone derivatives extracted from the roots of Morinda officinalis How. (most common familiar name in China: Bajitian) have been used to support the entire body treating a wide range of symptoms, including poor digestion, high blood pressure and immune deficiencies in China since ancient times. Recent studies have demonstrated that they have multiple pharmacological actions such as anti-HIV, anti-inflammatory, antinociceptive, antimicrobial, antioxidant, antihepatotoxic and antimutagenic activities (Kim et al., 2005). One component found in Morinda officinalis How., 1,2-dimethoxy-3-hydroxyanthraquinone, exhibits a variety of potent biological effects such as antiviral and antimicrobial activities (Ali et al., 2000), antioxidant activity (Jia et al., 2007) and cyototoxic activity (Wu et al., 2003). We report here the structure of the title compound.

In the title compound (Fig. 1), the C-C bond lengths show normal values (Allen et al., 1987), and the C-O and C=O bond lengths are comparable to those observed in similar structures (Ng et al., 2005; Boonnak et al., 2005). The anthraquinone ring system is substantially planar, the dihedral angle between the two benzene rings being 1.12 (4)°. The molecules are self-assembled by C—H···O and O—H···.O hydrogen bonding interactions (Table 1) into a supramolecular network. The crystal structure is further stabilized by weak π-π interactions along the a axis (Fig. 2) between the anthraquinone ring systems of the stacked molecules. The centroid-to-centriod distances between related benzene rings of the stacked molecules is 3.699 (4)Å, thus indicating weak π-π contacts.

Related literature top

For the biological properties of anthraquinone derivatives, see: Kim et al. (2005) and of the title compound, see: Ali et al. (2000); Jia et al. (2007); Wu et al. (2003). For related structures, see: Ng et al. (2005); Boonnak et al. (2005). For the structure of another compound isolated from Morinda officinalis How., see: Liu et al. (2009). For reference structural data, see: Allen et al. (1987).

Experimental top

The roots of Morinda officinalis How. (1000 g) were shattered to powder (about 30 mesh) and extracted with 85% ethanol (4000 ml) for 2 h with stirring. The extraction procedure was repeated three times. The extracts were combined and evaporated to dryness under reduced pressure at 333 K, the residue was redissolved in water (800 ml). Then the enriched extracts were extracted with chloroform three times (800 ml each), the chlorofrom solutions were combined and evaporated to dryness under reduced pressure at 333 K, 6.80 g crude extracts were obtained. The crude extracts were separated with n-hexane-ethyl acetate-methanol-water (6 : 4 : 5 : 5, v/v) using high-speed counter-current chromatography (HSCCC) to obtain 1,2-dimethoxy-3-hydroxyanthraquinone (yield 20.3 mg). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement top

Methyl H atoms were placed at calculated positions and treated as riding on the parent C atoms with C—H = 0.96 °H and Uiso(H) = 1.2Ueq(C). Coordinates of all other hydrogens were refined but their Uiso values were fixed at 0.105 Å2.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure showing the atomic-numbering scheme and displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular packing showing the hydrogen bonding interactions as broken lines.
3-Hydroxy-1,2-dimethoxyanthraquinone top
Crystal data top
C16H12O5Z = 2
Mr = 284.26F(000) = 296.0
Triclinic, P1Dx = 1.503 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4087 (17) ÅCell parameters from 1305 reflections
b = 8.0387 (18) Åθ = 3.1–27.3°
c = 11.802 (3) ŵ = 0.11 mm−1
α = 95.386 (3)°T = 293 K
β = 92.357 (3)°Block, yellow
γ = 115.712 (2)°0.30 × 0.20 × 0.20 mm
V = 627.9 (3) Å3
Data collection top
Bruker APEXII area-detector
diffractometer		2182 independent reflections
Radiation source: fine-focus sealed tube1639 reflections with I > 2σ(I)
graphiteRint = 0.013
φ and ω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→8
Tmin = 0.967, Tmax = 0.978k = −9→9
3200 measured reflectionsl = −14→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0736P)2 + 0.1017P]
where P = (Fo2 + 2Fc2)/3
2182 reflections(Δ/σ)max < 0.001
210 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.17 e Å−3
Crystal data top
C16H12O5γ = 115.712 (2)°
Mr = 284.26V = 627.9 (3) Å3
Triclinic, P1Z = 2
a = 7.4087 (17) ÅMo Kα radiation
b = 8.0387 (18) ŵ = 0.11 mm−1
c = 11.802 (3) ÅT = 293 K
α = 95.386 (3)°0.30 × 0.20 × 0.20 mm
β = 92.357 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer		2182 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1639 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.978Rint = 0.013
3200 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.136Δρmax = 0.25 e Å−3
S = 1.06Δρmin = −0.17 e Å−3
2182 reflectionsAbsolute structure: ?
210 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
O10.2605 (2)0.79647 (18)0.14638 (13)0.0605 (4)
O20.2359 (2)0.18299 (17)−0.09353 (11)0.0560 (4)
O60.2197 (2)0.3418 (2)0.43860 (11)0.0597 (4)
O70.2427 (2)0.64028 (18)0.34133 (12)0.0547 (4)
O80.1946 (2)0.03307 (19)0.30888 (12)0.0582 (4)
C150.2626 (3)0.4756 (3)−0.21242 (16)0.0463 (5)
C160.2985 (3)0.7870 (3)−0.20248 (19)0.0550 (5)
C170.2839 (3)0.6275 (3)−0.26601 (19)0.0546 (5)
C180.2898 (3)0.7953 (3)−0.08620 (19)0.0474 (5)
C190.2686 (2)0.6434 (2)−0.03041 (15)0.0379 (4)
C200.2551 (2)0.4817 (2)−0.09503 (15)0.0372 (4)
C210.2574 (3)0.6545 (2)0.09545 (16)0.0403 (4)
C220.2422 (2)0.4946 (2)0.15295 (15)0.0368 (4)
C230.2284 (2)0.3315 (2)0.08725 (14)0.0350 (4)
C240.2378 (2)0.3203 (2)−0.03826 (15)0.0377 (4)
C250.2095 (3)0.1777 (2)0.13812 (16)0.0399 (4)
C260.2058 (3)0.1783 (2)0.25489 (15)0.0425 (4)
C270.2176 (3)0.3354 (3)0.32218 (15)0.0440 (5)
C280.2364 (3)0.4919 (2)0.27130 (15)0.0405 (4)
C290.0304 (4)0.2459 (4)0.4794 (2)0.0804 (8)
H29A−0.04390.31800.47540.097*
H29B0.04830.22640.55730.097*
H29C−0.04220.12780.43330.097*
C340.4369 (4)0.7632 (3)0.3940 (2)0.0703 (7)
H34A0.48620.69690.44030.084*
H34B0.42950.86360.44120.084*
H34C0.52660.81210.33630.084*
H10.249 (4)0.360 (4)−0.255 (2)0.105*
H40.298 (5)0.897 (4)−0.044 (3)0.105*
H30.323 (4)0.897 (4)−0.239 (2)0.105*
H20.292 (4)0.616 (4)−0.345 (3)0.105*
H50.198 (4)0.069 (4)0.089 (3)0.105*
H60.199 (5)−0.044 (4)0.253 (3)0.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0852 (11)0.0373 (7)0.0687 (9)0.0365 (7)0.0148 (8)−0.0003 (6)
O20.0889 (11)0.0383 (7)0.0479 (8)0.0358 (7)0.0051 (7)−0.0014 (6)
O60.0681 (10)0.0683 (10)0.0419 (8)0.0301 (8)0.0044 (7)0.0023 (7)
O70.0608 (9)0.0478 (8)0.0564 (8)0.0291 (7)0.0023 (7)−0.0142 (6)
O80.0884 (11)0.0506 (9)0.0507 (8)0.0423 (8)0.0151 (7)0.0147 (6)
C150.0462 (11)0.0455 (11)0.0489 (11)0.0220 (9)0.0019 (8)0.0054 (8)
C160.0524 (12)0.0451 (12)0.0689 (14)0.0202 (10)0.0041 (10)0.0208 (10)
C170.0569 (13)0.0551 (12)0.0534 (12)0.0247 (10)0.0048 (10)0.0143 (10)
C180.0420 (11)0.0346 (10)0.0673 (13)0.0183 (9)0.0037 (9)0.0076 (9)
C190.0293 (9)0.0313 (9)0.0540 (11)0.0144 (7)0.0026 (7)0.0046 (8)
C200.0295 (9)0.0320 (9)0.0501 (11)0.0140 (7)0.0020 (7)0.0032 (7)
C210.0349 (9)0.0291 (9)0.0575 (11)0.0161 (8)0.0050 (8)−0.0014 (8)
C220.0312 (9)0.0307 (9)0.0491 (11)0.0152 (7)0.0045 (7)0.0000 (7)
C230.0310 (9)0.0276 (9)0.0460 (10)0.0135 (7)0.0034 (7)−0.0005 (7)
C240.0347 (9)0.0289 (9)0.0480 (10)0.0140 (7)0.0012 (7)−0.0004 (7)
C250.0419 (10)0.0316 (9)0.0476 (11)0.0179 (8)0.0055 (8)0.0020 (7)
C260.0451 (11)0.0388 (10)0.0472 (11)0.0213 (9)0.0067 (8)0.0071 (8)
C270.0439 (11)0.0496 (11)0.0400 (10)0.0228 (9)0.0043 (8)0.0008 (8)
C280.0363 (10)0.0386 (10)0.0470 (10)0.0191 (8)0.0027 (7)−0.0060 (8)
C290.0866 (18)0.102 (2)0.0514 (13)0.0379 (16)0.0221 (12)0.0158 (13)
C340.0775 (16)0.0484 (12)0.0745 (15)0.0243 (12)−0.0103 (12)−0.0172 (11)
Geometric parameters (Å, °) top
O1—C211.230 (2)C19—C211.488 (3)
O2—C241.222 (2)C20—C241.475 (2)
O6—C271.369 (2)C21—C221.473 (3)
O6—C291.407 (3)C22—C281.401 (3)
O7—C281.368 (2)C22—C231.421 (2)
O7—C341.418 (3)C23—C251.380 (3)
O8—C261.355 (2)C23—C241.482 (3)
O8—H60.88 (3)C25—C261.379 (3)
C15—C171.379 (3)C25—H50.97 (3)
C15—C201.386 (3)C26—C271.394 (3)
C15—H10.98 (3)C27—C281.400 (3)
C16—C181.373 (3)C29—H29A0.9600
C16—C171.382 (3)C29—H29B0.9600
C16—H30.97 (3)C29—H29C0.9600
C17—H20.94 (3)C34—H34A0.9600
C18—C191.394 (3)C34—H34B0.9600
C18—H40.90 (3)C34—H34C0.9600
C19—C201.405 (2)
C27—O6—C29114.93 (16)C22—C23—C24121.57 (16)
C28—O7—C34114.31 (15)O2—C24—C20120.49 (16)
C26—O8—H6102 (2)O2—C24—C23121.23 (16)
C17—C15—C20120.31 (19)C20—C24—C23118.26 (15)
C17—C15—H1122.3 (18)C26—C25—C23120.99 (16)
C20—C15—H1117.3 (18)C26—C25—H5121.2 (18)
C18—C16—C17120.59 (19)C23—C25—H5117.8 (18)
C18—C16—H3119.1 (17)O8—C26—C25123.02 (16)
C17—C16—H3120.2 (17)O8—C26—C27117.56 (16)
C15—C17—C16120.0 (2)C25—C26—C27119.41 (17)
C15—C17—H2116.1 (19)O6—C27—C26120.69 (17)
C16—C17—H2123.9 (19)O6—C27—C28119.27 (16)
C16—C18—C19120.33 (19)C26—C27—C28119.98 (17)
C16—C18—H4122 (2)O7—C28—C27117.34 (16)
C19—C18—H4118 (2)O7—C28—C22121.20 (17)
C18—C19—C20119.00 (18)C27—C28—C22121.44 (15)
C18—C19—C21119.49 (16)O6—C29—H29A109.5
C20—C19—C21121.50 (16)O6—C29—H29B109.5
C15—C20—C19119.80 (16)H29A—C29—H29B109.5
C15—C20—C24119.84 (16)O6—C29—H29C109.5
C19—C20—C24120.34 (16)H29A—C29—H29C109.5
O1—C21—C22123.18 (18)H29B—C29—H29C109.5
O1—C21—C19118.37 (17)O7—C34—H34A109.5
C22—C21—C19118.45 (14)O7—C34—H34B109.5
C28—C22—C23116.89 (16)H34A—C34—H34B109.5
C28—C22—C21123.33 (15)O7—C34—H34C109.5
C23—C22—C21119.77 (16)H34A—C34—H34C109.5
C25—C23—C22121.27 (17)H34B—C34—H34C109.5
C25—C23—C24117.15 (15)
C20—C15—C17—C160.1 (3)C19—C20—C24—C232.0 (2)
C18—C16—C17—C15−0.6 (3)C25—C23—C24—O2−2.5 (3)
C17—C16—C18—C190.7 (3)C22—C23—C24—O2176.29 (16)
C16—C18—C19—C20−0.4 (3)C25—C23—C24—C20179.16 (14)
C16—C18—C19—C21−179.35 (16)C22—C23—C24—C20−2.1 (2)
C17—C15—C20—C190.2 (3)C22—C23—C25—C26−0.8 (3)
C17—C15—C20—C24−178.33 (16)C24—C23—C25—C26178.01 (15)
C18—C19—C20—C15−0.1 (3)C23—C25—C26—O8−177.61 (16)
C21—C19—C20—C15178.84 (15)C23—C25—C26—C271.2 (3)
C18—C19—C20—C24178.43 (15)C29—O6—C27—C26−78.9 (2)
C21—C19—C20—C24−2.6 (2)C29—O6—C27—C28103.9 (2)
C18—C19—C21—O12.4 (3)O8—C26—C27—O60.7 (3)
C20—C19—C21—O1−176.58 (15)C25—C26—C27—O6−178.22 (16)
C18—C19—C21—C22−177.85 (15)O8—C26—C27—C28177.81 (16)
C20—C19—C21—C223.2 (2)C25—C26—C27—C28−1.1 (3)
O1—C21—C22—C28−2.1 (3)C34—O7—C28—C2785.1 (2)
C19—C21—C22—C28178.18 (15)C34—O7—C28—C22−96.8 (2)
O1—C21—C22—C23176.54 (16)O6—C27—C28—O7−4.2 (3)
C19—C21—C22—C23−3.2 (2)C26—C27—C28—O7178.56 (15)
C28—C22—C23—C250.2 (3)O6—C27—C28—C22177.70 (15)
C21—C22—C23—C25−178.54 (15)C26—C27—C28—C220.5 (3)
C28—C22—C23—C24−178.54 (14)C23—C22—C28—O7−178.03 (14)
C21—C22—C23—C242.8 (2)C21—C22—C28—O70.6 (3)
C15—C20—C24—O22.2 (3)C23—C22—C28—C270.0 (3)
C19—C20—C24—O2−176.41 (16)C21—C22—C28—C27178.61 (15)
C15—C20—C24—C23−179.46 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C25—H5···O1i0.97 (3)2.57 (3)3.256 (2)128 (2)
O8—H6···O1i0.88 (3)1.91 (3)2.781 (2)168 (3)
Symmetry codes: (i) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C25—H5···O1i0.97 (3)2.57 (3)3.256 (2)128 (2)
O8—H6···O1i0.88 (3)1.91 (3)2.781 (2)168 (3)
Symmetry codes: (i) x, y−1, z.
Acknowledgements top

The authors gratefully acknowledge the Guangdong Province Natural Science Foundation (grant No. 7007735) for financial support.

references
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