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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1433–o1434.
Published online 2009 May 29. doi:  10.1107/S1600536809017607
PMCID: PMC2969543

1,3-Dihydr­oxy-2-methoxy­methyl-9,10-anthraquinone from Rennellia elliptica Korth.

Abstract

The title compound, C16H12O5, common name: lucidin ω-methyl ether, exists as a planar mol­ecule (r.m.s. deviation = 0.04 Å). Within the mol­ecule, the 1-hydr­oxy group forms a hydrogen bond to the adjacent carbonyl O atom, and the 3-hydr­oxy group forms a hydrogen bond to the adjacent meth­oxy O atom. The meth­oxy O atom is disordered over two positions of equal occupancy.

Related literature

The title compound has been isolated from several plants: Rubia tinctorum L. (Boldizsar et al., 2004 [triangle]), taurina subsp. caucasica (Ozgen et al., 2006 [triangle]), Prismatomeris fragrans (Kanokmedhakul et al., 2005 [triangle]), Crucianella maritima L. (El-Lakany et al., 2004 [triangle]), Rubia wallichiana Decne (Wu et al., 2003 [triangle]), Morinda elliptica (Ali et al., 2000 [triangle]; Ismail et al., 1997 [triangle]; Ismail et al., 2002 [triangle]), Ophiorrhiza pumila (Kitajima et al., 1998 [triangle]), Morinda officinalis How. (Yoshikawa et al., 1995 [triangle]), Galiumspurium var. echinospermon (Koyama et al., 1993 [triangle]), Damnacanthus indicus (Koyama et al., 1992 [triangle]), Rubia cordifolia L. (Vidal-Tessier et al., 1987 [triangle]), Faramea cyanea (Ferrari et al., 1985 [triangle]), Morinda parvifolia (Chang & Lee, 1984 [triangle]) and Galium album (Kupier & Labadie, 1984 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1433-scheme1.jpg

Experimental

Crystal data

  • C16H12O5
  • M r = 284.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1433-efi1.jpg
  • a = 4.6725 (1) Å
  • b = 39.685 (1) Å
  • c = 6.9869 (2) Å
  • β = 107.654 (2)°
  • V = 1234.55 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 100 K
  • 0.30 × 0.07 × 0.02 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 10046 measured reflections
  • 2825 independent reflections
  • 1888 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.156
  • S = 1.01
  • 2825 reflections
  • 201 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017607/tk2447sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017607/tk2447Isup2.hkl

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

Acknowledgments

We thank Universiti Teknologi MARA and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

About 1 kg of the root of Rennelia elliptica Korth., which was collected from the Kuala Keniam National Park, Malaysia, was extracted with dichloromethane. The solvent was removed to give a crude material (approx. 10 g) that was fractionated on a chromatography column (60 x 5 cm) packed with silica. The silica had been previously immersed in 4% oxalic acid and then activated by heating to 363 K. The fractions were eluted with hexane–dichloromethane and dichloromethane–methanol in increasing polarity. The fraction eluted with hexane–dichloromethane (2:8 v/v) was purified by thin layer chromatography (2 mm). The product was recrystallized from dichloromethane to furnish yellow crystals. The formulation was established by 1H- and 13C-NMR spectroscopy.

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.95–0.99 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times Ueq(C). The hydroxy H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.84±0.01 Å; their temperature factors were refined.

The methoxy oxygen atom is disordered over two positions, but the occupancy could not be refined. The disorder was assumed to be 50:50. The C–O/C–O' bonds to the aryl group were restrained to within 0.01 Å of each other, as were those to the alkyl group. The anisotropic displacement factors of the primed atom were restrained to those of the umprimed one.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of the molecule of C16H12O5 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The disorder is not shown

Crystal data

C16H12O5F(000) = 592
Mr = 284.26Dx = 1.529 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1810 reflections
a = 4.6725 (1) Åθ = 3.1–27.9°
b = 39.685 (1) ŵ = 0.12 mm1
c = 6.9869 (2) ÅT = 100 K
β = 107.654 (2)°Plate, yellow
V = 1234.55 (6) Å30.30 × 0.07 × 0.02 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer1888 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.041
graphiteθmax = 27.5°, θmin = 1.0°
ω scansh = −5→6
10046 measured reflectionsk = −51→51
2825 independent reflectionsl = −9→8

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0691P)2 + 1.3159P] where P = (Fo2 + 2Fc2)/3
2825 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 0.43 e Å3
4 restraintsΔρmin = −0.46 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
O10.5327 (4)0.35893 (4)0.3196 (2)0.0173 (4)
H1o0.476 (7)0.3392 (4)0.338 (5)0.039 (9)*
O20.2892 (4)0.31121 (4)0.4610 (3)0.0200 (4)
O30.0049 (4)0.39767 (4)0.9709 (2)0.0189 (4)
O40.5244 (4)0.46858 (4)0.5956 (3)0.0202 (4)
H4o0.601 (8)0.4724 (9)0.503 (4)0.051 (11)*
O50.777 (3)0.45857 (15)0.3246 (15)0.027 (2)0.50
O5'0.694 (3)0.46028 (15)0.2862 (15)0.027 (2)0.50
C10.4569 (5)0.43535 (6)0.5813 (3)0.0144 (5)
C20.3075 (5)0.42345 (6)0.7145 (3)0.0137 (5)
H20.25850.43860.80520.016*
C30.2318 (5)0.38992 (6)0.7142 (3)0.0129 (5)
C40.0737 (5)0.37804 (6)0.8575 (3)0.0135 (5)
C50.0051 (5)0.34142 (6)0.8590 (3)0.0139 (5)
C6−0.1291 (5)0.32923 (6)0.9985 (4)0.0183 (5)
H6−0.17740.34431.09000.022*
C7−0.1917 (6)0.29523 (6)1.0034 (4)0.0217 (5)
H7−0.27980.28691.10010.026*
C8−0.1268 (6)0.27307 (6)0.8677 (4)0.0229 (6)
H8−0.17280.24980.87070.028*
C90.0054 (6)0.28509 (6)0.7283 (4)0.0203 (5)
H90.04900.27000.63520.024*
C100.0745 (5)0.31922 (6)0.7240 (3)0.0146 (5)
C110.2280 (5)0.33153 (6)0.5794 (3)0.0141 (5)
C120.3044 (5)0.36698 (6)0.5816 (3)0.0132 (5)
C130.4545 (5)0.37961 (6)0.4486 (3)0.0129 (5)
C140.5296 (5)0.41375 (6)0.4458 (3)0.0131 (5)
C150.6804 (5)0.42442 (6)0.2919 (3)0.0153 (5)
H15A0.85550.40970.30220.018*0.50
H15B0.53780.42200.15510.018*0.50
H15C0.88580.41490.32770.018*0.50
H15D0.56540.41570.15780.018*0.50
C160.8677 (6)0.47240 (6)0.1631 (4)0.0221 (6)
H16A0.93080.49580.19380.033*0.50
H16B0.69890.47160.03900.033*0.50
H16C1.03570.45920.14590.033*0.50
H16D0.92620.49580.19840.033*0.50
H16E0.74740.47110.02150.033*0.50
H16F1.04820.45850.18530.033*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0221 (9)0.0145 (9)0.0194 (9)−0.0005 (7)0.0124 (7)−0.0022 (7)
O20.0264 (9)0.0162 (8)0.0209 (9)−0.0008 (7)0.0122 (8)−0.0020 (7)
O30.0220 (9)0.0190 (9)0.0184 (9)0.0000 (7)0.0102 (7)−0.0021 (7)
O40.0303 (10)0.0136 (8)0.0205 (9)−0.0041 (7)0.0134 (8)−0.0010 (7)
O50.036 (6)0.0142 (10)0.043 (3)0.0027 (18)0.033 (4)0.0050 (14)
O5'0.036 (6)0.0142 (10)0.043 (3)0.0027 (18)0.033 (4)0.0050 (14)
C10.0138 (11)0.0130 (11)0.0156 (11)−0.0001 (9)0.0032 (9)0.0012 (8)
C20.0135 (11)0.0143 (11)0.0138 (11)0.0003 (8)0.0050 (9)−0.0016 (8)
C30.0099 (11)0.0171 (12)0.0121 (11)0.0005 (9)0.0038 (9)0.0006 (8)
C40.0122 (11)0.0151 (11)0.0131 (11)0.0003 (9)0.0040 (9)0.0008 (9)
C50.0103 (11)0.0164 (11)0.0147 (11)−0.0009 (8)0.0032 (9)0.0023 (9)
C60.0180 (12)0.0196 (12)0.0189 (12)0.0006 (10)0.0082 (10)0.0024 (9)
C70.0217 (13)0.0231 (13)0.0230 (13)−0.0038 (10)0.0110 (10)0.0064 (10)
C80.0245 (13)0.0147 (12)0.0308 (14)−0.0030 (10)0.0102 (11)0.0037 (10)
C90.0217 (13)0.0151 (12)0.0248 (13)−0.0005 (9)0.0083 (11)−0.0011 (10)
C100.0135 (11)0.0144 (11)0.0154 (12)0.0015 (9)0.0038 (9)0.0023 (9)
C110.0116 (11)0.0166 (11)0.0137 (11)0.0035 (9)0.0031 (9)0.0007 (9)
C120.0128 (11)0.0136 (11)0.0124 (11)0.0008 (8)0.0027 (9)0.0002 (8)
C130.0098 (11)0.0163 (11)0.0114 (11)0.0022 (8)0.0015 (8)−0.0008 (8)
C140.0104 (11)0.0147 (11)0.0143 (11)0.0003 (8)0.0036 (9)0.0025 (9)
C150.0168 (12)0.0146 (11)0.0157 (11)−0.0002 (9)0.0068 (9)0.0001 (9)
C160.0273 (14)0.0184 (12)0.0257 (14)−0.0043 (10)0.0156 (11)0.0049 (10)

Geometric parameters (Å, °)

O1—C131.349 (3)C7—C81.392 (4)
O1—H1o0.848 (10)C7—H70.9500
O2—C111.249 (3)C8—C91.387 (3)
O3—C41.222 (3)C8—H80.9500
O4—C11.353 (3)C9—C101.395 (3)
O4—H4o0.842 (10)C9—H90.9500
O5—C151.425 (6)C10—C111.488 (3)
O5—C161.431 (6)C11—C121.450 (3)
O5'—C151.426 (6)C12—C131.415 (3)
O5'—C161.432 (6)C13—C141.401 (3)
C1—C141.393 (3)C14—C151.514 (3)
C1—C21.404 (3)C15—H15A0.9900
C2—C31.377 (3)C15—H15B0.9900
C2—H20.9500C15—H15C0.9900
C3—C121.412 (3)C15—H15D0.9900
C3—C41.490 (3)C16—H16A0.9800
C4—C51.489 (3)C16—H16B0.9800
C5—C61.396 (3)C16—H16C0.9800
C5—C101.399 (3)C16—H16D0.9800
C6—C71.383 (3)C16—H16E0.9800
C6—H60.9500C16—H16F0.9800
C13—O1—H1o107 (2)C3—C12—C13117.9 (2)
C1—O4—H4o105 (2)C3—C12—C11121.7 (2)
C15—O5—C16113.1 (5)C13—C12—C11120.4 (2)
C15—O5'—C16113.0 (5)O1—C13—C14117.32 (19)
O4—C1—C14123.4 (2)O1—C13—C12120.8 (2)
O4—C1—C2115.5 (2)C14—C13—C12121.9 (2)
C14—C1—C2121.1 (2)C1—C14—C13118.1 (2)
C3—C2—C1120.2 (2)C1—C14—C15124.9 (2)
C3—C2—H2119.9C13—C14—C15116.92 (19)
C1—C2—H2119.9O5—C15—C14110.1 (3)
C2—C3—C12120.8 (2)O5'—C15—C14109.5 (3)
C2—C3—C4119.0 (2)O5—C15—H15A109.6
C12—C3—C4120.3 (2)O5'—C15—H15A123.2
O3—C4—C5121.2 (2)C14—C15—H15A109.6
O3—C4—C3121.1 (2)O5—C15—H15B109.6
C5—C4—C3117.73 (19)C14—C15—H15B109.6
C6—C5—C10119.8 (2)H15A—C15—H15B108.2
C6—C5—C4119.1 (2)O5'—C15—H15C109.8
C10—C5—C4121.0 (2)C14—C15—H15C109.8
C7—C6—C5119.9 (2)O5'—C15—H15D109.8
C7—C6—H6120.0C14—C15—H15D109.8
C5—C6—H6120.0H15C—C15—H15D108.2
C6—C7—C8120.5 (2)O5—C16—H16A109.5
C6—C7—H7119.7O5—C16—H16B109.5
C8—C7—H7119.7H16A—C16—H16B109.5
C9—C8—C7119.8 (2)O5—C16—H16C109.5
C9—C8—H8120.1H16A—C16—H16C109.5
C7—C8—H8120.1H16B—C16—H16C109.5
C8—C9—C10120.3 (2)O5—C16—H16D107.0
C8—C9—H9119.9O5'—C16—H16D109.5
C10—C9—H9119.9H16B—C16—H16D110.0
C9—C10—C5119.7 (2)H16C—C16—H16D111.3
C9—C10—C11119.7 (2)O5'—C16—H16E109.5
C5—C10—C11120.6 (2)H16D—C16—H16E109.5
O2—C11—C12121.9 (2)O5'—C16—H16F109.5
O2—C11—C10119.5 (2)H16D—C16—H16F109.5
C12—C11—C10118.62 (19)H16E—C16—H16F109.5
O4—C1—C2—C3−179.2 (2)C2—C3—C12—C11179.7 (2)
C14—C1—C2—C30.5 (3)C4—C3—C12—C110.2 (3)
C1—C2—C3—C120.4 (3)O2—C11—C12—C3179.3 (2)
C1—C2—C3—C4179.9 (2)C10—C11—C12—C3−1.2 (3)
C2—C3—C4—O31.7 (3)O2—C11—C12—C13−0.5 (3)
C12—C3—C4—O3−178.8 (2)C10—C11—C12—C13179.0 (2)
C2—C3—C4—C5−177.7 (2)C3—C12—C13—O1179.4 (2)
C12—C3—C4—C51.8 (3)C11—C12—C13—O1−0.9 (3)
O3—C4—C5—C6−2.7 (3)C3—C12—C13—C14−0.3 (3)
C3—C4—C5—C6176.8 (2)C11—C12—C13—C14179.5 (2)
O3—C4—C5—C10177.7 (2)O4—C1—C14—C13178.4 (2)
C3—C4—C5—C10−2.9 (3)C2—C1—C14—C13−1.2 (3)
C10—C5—C6—C70.3 (3)O4—C1—C14—C15−2.6 (4)
C4—C5—C6—C7−179.4 (2)C2—C1—C14—C15177.8 (2)
C5—C6—C7—C8−1.1 (4)O1—C13—C14—C1−178.5 (2)
C6—C7—C8—C90.8 (4)C12—C13—C14—C11.1 (3)
C7—C8—C9—C100.3 (4)O1—C13—C14—C152.4 (3)
C8—C9—C10—C5−1.1 (4)C12—C13—C14—C15−178.0 (2)
C8—C9—C10—C11177.4 (2)C16—O5—C15—O5'−77.9 (18)
C6—C5—C10—C90.8 (3)C16—O5—C15—C14−168.5 (6)
C4—C5—C10—C9−179.5 (2)C16—O5'—C15—O577.2 (17)
C6—C5—C10—C11−177.7 (2)C16—O5'—C15—C14172.5 (6)
C4—C5—C10—C112.0 (3)C1—C14—C15—O58.4 (6)
C9—C10—C11—O21.1 (3)C13—C14—C15—O5−172.6 (6)
C5—C10—C11—O2179.6 (2)C1—C14—C15—O5'−8.8 (6)
C9—C10—C11—C12−178.4 (2)C13—C14—C15—O5'170.2 (6)
C5—C10—C11—C120.1 (3)C15—O5—C16—O5'77.8 (18)
C2—C3—C12—C13−0.5 (3)C15—O5'—C16—O5−77.3 (17)
C4—C3—C12—C13179.98 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···O20.85 (1)1.79 (2)2.557 (2)150 (3)
O4—H4o···O50.84 (1)1.77 (2)2.546 (7)152 (4)
O4—H4o···O5'0.84 (1)1.77 (2)2.539 (7)152 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2447).

References

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