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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1135.
Published online 2008 May 21. doi:  10.1107/S1600536808014451
PMCID: PMC2961515

2,7-Dihydr­oxy-3,6-dimethoxy­phenanthrene from Dehaasia longipedicellata

Abstract

The hydr­oxy groups in the title compound, C16H14O4, are each hydrogen bonded to the adjacent meth­oxy O atom; one of the two hydr­oxy groups is additionally linked to the O atom of the meth­oxy group of another mol­ecule, forming a linear chain.

Related literature

For related compounds isolated from other plants, see: Bhandari et al. (1985 [triangle]); Mujumder et al. (1985 [triangle]); Theuns et al. (1985 [triangle]); Zurinah Mahmud et al. (1992 [triangle]). For the crystal structure of 2,3-dimeth­oxy-6,7-methyl­enedioxy­phenanthrene, see: Wang et al. (2007 [triangle]).

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Object name is e-64-o1135-scheme1.jpg

Experimental

Crystal data

  • C16H14O4
  • M r = 270.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1135-efi1.jpg
  • a = 11.6268 (2) Å
  • b = 7.2207 (1) Å
  • c = 16.5351 (2) Å
  • β = 109.196 (1)°
  • V = 1311.00 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 100 (2) K
  • 0.30 × 0.25 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 15710 measured reflections
  • 2991 independent reflections
  • 2671 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.150
  • S = 1.10
  • 2991 reflections
  • 237 parameters
  • 14 restraints
  • All H-atom parameters refined
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [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, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014451/bt2712sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014451/bt2712Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for supporting this study (grants PPF/FP092/2005 C and 02–01-03-SF0370).

supplementary crystallographic information

Comment

2,7-Dihydroxy-3,6-dimethoxylphenanthrene (Scheme I, Fig. 1) is a new compound isolated from Dehaasia longipedicellata (Ridl.) Kosterm. The hydroxy groups are each hydrogen-bonded to the adjacent methoxy oxygen; one of the two hydroxy groups is additionally linked to the oxygen atom of the methoxy group of another molecule to form a linear chain.

Experimental

Dehaasia longipedicellata (Ridl.) Kosterm. was collected in Raub Forest Reserve, Pahang, Malaysia, in 1997. Specimens (KL4719) were deposited at the herbarium, Department of Chemistry, University of Malaya and the herbarium of the Forest Research Institute of Malaysia.

Some 1.4 kg of dried and ground leaves of D. longipedicellata was extracted with dichloromethane. The dichloromethane extract was concentrated under reduced pressure to a volume of 500 ml. This was repeatedly extracted with a solution of 5% hydrochloric acid. The combined extracts were then basified with 10% ammonium hydroxide to pH 11 and then re-extracted with dichloromethane. The brown alkaloid fraction amounted to (8.83 g). A portion (3 g) was subjected to column chromatography on silica gel 60 GF254 by using a step gradient of dichloromethane and methanol. The separation afforded 15 fractions, the first (100% dichloromethane) gave 2,7-dihydroxy-3,6-dimethoxyphenanthrene (8 mg), whose formulation was established by spectroscopic analysis. Light brown prisms were obtained upon recrystallization from dichloromethane.

Refinement

Hydrogen atoms were located in a difference Fourier map. They were refined isotropically with distance restraints of C–H 0.95±0.01 Å and O–H 0.85±0.01 Å.

Figures

Fig. 1.
Displacement ellipsoid plot (Barbour, 2001) of the molecule of C16H16O4 drawn at the 70% probability level. Hydrogen atoms are shown as spheres of arbitrary radii.
Fig. 2.
Hydrogen-bonded chain structure.

Crystal data

C16H14O4F000 = 568
Mr = 270.27Dx = 1.369 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8700 reflections
a = 11.6268 (2) Åθ = 2.6–28.3º
b = 7.2207 (1) ŵ = 0.10 mm1
c = 16.5351 (2) ÅT = 100 (2) K
β = 109.196 (1)ºPrism, pale brown
V = 1311.00 (3) Å30.30 × 0.25 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer2671 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 2.6º
ω scansh = −11→15
Absorption correction: Nonek = −9→9
15710 measured reflectionsl = −21→21
2991 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046All H-atom parameters refined
wR(F2) = 0.150  w = 1/[σ2(Fo2) + (0.07P)2 + 1.2422P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
2991 reflectionsΔρmax = 0.42 e Å3
237 parametersΔρmin = −0.23 e Å3
14 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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

xyzUiso*/Ueq
O10.71900 (10)0.23952 (17)0.51347 (7)0.0175 (3)
O20.85160 (11)0.40262 (19)0.65922 (8)0.0213 (3)
O3−0.02829 (12)0.2974 (2)0.54817 (9)0.0277 (3)
O40.05316 (11)0.19182 (19)0.42576 (8)0.0236 (3)
C10.47440 (14)0.3578 (2)0.60344 (10)0.0137 (3)
C20.53118 (14)0.2890 (2)0.54541 (10)0.0141 (3)
C30.65507 (14)0.3029 (2)0.56408 (10)0.0147 (3)
C40.72887 (14)0.3887 (2)0.64087 (10)0.0160 (3)
C50.67565 (15)0.4568 (2)0.69713 (10)0.0164 (3)
C60.54872 (14)0.4405 (2)0.68039 (10)0.0148 (3)
C70.49473 (15)0.5060 (2)0.74130 (10)0.0161 (3)
C80.37442 (15)0.4861 (2)0.72813 (10)0.0174 (3)
C90.29560 (15)0.4047 (2)0.65046 (10)0.0159 (3)
C100.16910 (16)0.3874 (2)0.63624 (11)0.0197 (4)
C110.09423 (15)0.3145 (2)0.56196 (11)0.0197 (4)
C120.14106 (15)0.2572 (2)0.49676 (11)0.0180 (3)
C130.26312 (15)0.2727 (2)0.50896 (10)0.0157 (3)
C140.34417 (14)0.3444 (2)0.58698 (10)0.0142 (3)
C150.64950 (15)0.1659 (2)0.43192 (10)0.0172 (3)
C160.09098 (17)0.1296 (3)0.35617 (11)0.0234 (4)
H2O0.870 (2)0.361 (4)0.6173 (12)0.042 (7)*
H3O−0.059 (3)0.257 (4)0.4974 (10)0.060 (9)*
H20.4840 (17)0.236 (3)0.4925 (9)0.019 (5)*
H50.7270 (16)0.513 (3)0.7485 (9)0.019 (5)*
H70.5458 (16)0.571 (3)0.7897 (10)0.019 (5)*
H80.3392 (18)0.525 (3)0.7698 (11)0.019 (5)*
H100.1355 (19)0.429 (3)0.6789 (11)0.027 (6)*
H130.2932 (18)0.230 (3)0.4656 (10)0.019 (5)*
H1510.7096 (16)0.132 (3)0.4069 (14)0.028 (6)*
H1520.5945 (16)0.259 (2)0.4015 (12)0.019 (5)*
H1530.6033 (16)0.058 (2)0.4361 (13)0.015 (5)*
H1610.0189 (14)0.090 (3)0.3123 (11)0.030 (6)*
H1620.1507 (18)0.034 (3)0.3737 (15)0.034 (6)*
H1630.128 (2)0.234 (2)0.3382 (15)0.032 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0127 (5)0.0242 (6)0.0160 (6)0.0004 (4)0.0053 (4)−0.0032 (4)
O20.0122 (6)0.0314 (7)0.0193 (6)−0.0021 (5)0.0038 (4)−0.0035 (5)
O30.0126 (6)0.0442 (8)0.0273 (7)−0.0017 (5)0.0079 (5)−0.0053 (6)
O40.0135 (6)0.0342 (7)0.0207 (6)−0.0026 (5)0.0025 (5)−0.0061 (5)
C10.0140 (7)0.0133 (7)0.0138 (7)0.0008 (6)0.0046 (6)0.0016 (5)
C20.0148 (7)0.0151 (7)0.0122 (7)0.0001 (6)0.0039 (6)0.0004 (5)
C30.0152 (7)0.0153 (7)0.0143 (7)0.0014 (6)0.0058 (6)0.0013 (6)
C40.0126 (7)0.0174 (7)0.0171 (7)−0.0008 (6)0.0037 (6)0.0023 (6)
C50.0164 (8)0.0169 (7)0.0137 (7)−0.0017 (6)0.0019 (6)−0.0004 (6)
C60.0163 (8)0.0145 (7)0.0132 (7)0.0009 (6)0.0043 (6)0.0023 (5)
C70.0199 (8)0.0154 (7)0.0111 (7)0.0007 (6)0.0027 (6)−0.0002 (5)
C80.0216 (8)0.0177 (7)0.0148 (7)0.0033 (6)0.0086 (6)0.0013 (6)
C90.0157 (8)0.0165 (7)0.0160 (7)0.0024 (6)0.0061 (6)0.0028 (6)
C100.0175 (8)0.0242 (8)0.0197 (8)0.0028 (6)0.0094 (6)0.0010 (6)
C110.0129 (8)0.0243 (8)0.0231 (8)0.0019 (6)0.0076 (6)0.0029 (7)
C120.0154 (8)0.0197 (8)0.0173 (8)0.0000 (6)0.0033 (6)−0.0002 (6)
C130.0156 (8)0.0176 (7)0.0146 (7)0.0011 (6)0.0059 (6)0.0013 (6)
C140.0136 (7)0.0138 (7)0.0152 (7)0.0017 (5)0.0048 (6)0.0026 (6)
C150.0181 (8)0.0198 (8)0.0142 (7)0.0003 (6)0.0061 (6)−0.0021 (6)
C160.0197 (8)0.0295 (9)0.0177 (8)−0.0019 (7)0.0016 (6)−0.0054 (7)

Geometric parameters (Å, °)

O1—C31.3679 (19)C7—C81.351 (2)
O1—C151.4273 (19)C7—H70.949 (10)
O2—C41.3615 (19)C8—C91.436 (2)
O2—H2O0.848 (10)C8—H80.951 (9)
O3—C111.372 (2)C9—C101.417 (2)
O3—H3O0.849 (10)C9—C141.414 (2)
O4—C121.363 (2)C10—C111.357 (2)
O4—C161.432 (2)C10—H100.959 (10)
C1—C61.414 (2)C11—C121.420 (2)
C1—C21.421 (2)C12—C131.371 (2)
C1—C141.451 (2)C13—C141.422 (2)
C2—C31.374 (2)C13—H130.946 (9)
C2—H20.947 (9)C15—H1510.954 (10)
C3—C41.420 (2)C15—H1520.948 (9)
C4—C51.367 (2)C15—H1530.959 (9)
C5—C61.414 (2)C16—H1610.955 (10)
C5—H50.954 (9)C16—H1620.952 (10)
C6—C71.431 (2)C16—H1630.959 (10)
C3—O1—C15116.73 (12)C10—C9—C8120.47 (15)
C4—O2—H2O108.9 (19)C14—C9—C8119.79 (14)
C11—O3—H3O105 (2)C11—C10—C9120.43 (15)
C12—O4—C16117.34 (13)C11—C10—H10119.4 (14)
C6—C1—C2118.23 (14)C9—C10—H10120.1 (14)
C6—C1—C14119.23 (14)C10—C11—O3120.48 (16)
C2—C1—C14122.54 (14)C10—C11—C12120.56 (15)
C3—C2—C1120.55 (14)O3—C11—C12118.95 (15)
C3—C2—H2118.9 (13)O4—C12—C13127.02 (15)
C1—C2—H2120.6 (13)O4—C12—C11112.88 (15)
O1—C3—C2125.36 (14)C13—C12—C11120.09 (15)
O1—C3—C4113.75 (14)C12—C13—C14120.56 (15)
C2—C3—C4120.89 (14)C12—C13—H13119.0 (13)
O2—C4—C5119.84 (15)C14—C13—H13120.4 (13)
O2—C4—C3120.83 (14)C9—C14—C13118.58 (14)
C5—C4—C3119.33 (15)C9—C14—C1119.15 (14)
C4—C5—C6120.91 (15)C13—C14—C1122.27 (14)
C4—C5—H5117.9 (13)O1—C15—H151103.7 (14)
C6—C5—H5121.1 (13)O1—C15—H152108.2 (13)
C5—C6—C1120.07 (14)H151—C15—H152114.5 (19)
C5—C6—C7120.38 (14)O1—C15—H153112.9 (12)
C1—C6—C7119.55 (14)H151—C15—H153109.3 (19)
C8—C7—C6121.47 (15)H152—C15—H153108.3 (18)
C8—C7—H7121.1 (13)O4—C16—H161106.3 (14)
C6—C7—H7117.4 (13)O4—C16—H162111.6 (15)
C7—C8—C9120.69 (15)H161—C16—H162112 (2)
C7—C8—H8121.4 (13)O4—C16—H163106.8 (15)
C9—C8—H8117.9 (13)H161—C16—H163112 (2)
C10—C9—C14119.73 (15)H162—C16—H163108 (2)
C6—C1—C2—C30.0 (2)C14—C9—C10—C11−0.4 (2)
C14—C1—C2—C3−179.27 (14)C8—C9—C10—C11178.42 (16)
C15—O1—C3—C25.0 (2)C9—C10—C11—O3179.88 (15)
C15—O1—C3—C4−174.81 (13)C9—C10—C11—C12−1.0 (3)
C1—C2—C3—O1179.19 (14)C16—O4—C12—C130.9 (3)
C1—C2—C3—C4−1.0 (2)C16—O4—C12—C11−179.78 (15)
O1—C3—C4—O2−0.1 (2)C10—C11—C12—O4−178.39 (16)
C2—C3—C4—O2−179.89 (14)O3—C11—C12—O40.7 (2)
O1—C3—C4—C5−179.60 (14)C10—C11—C12—C131.0 (3)
C2—C3—C4—C50.6 (2)O3—C11—C12—C13−179.95 (15)
O2—C4—C5—C6−178.64 (14)O4—C12—C13—C14179.82 (16)
C3—C4—C5—C60.9 (2)C11—C12—C13—C140.6 (2)
C4—C5—C6—C1−1.9 (2)C10—C9—C14—C131.9 (2)
C4—C5—C6—C7177.63 (15)C8—C9—C14—C13−176.96 (14)
C2—C1—C6—C51.4 (2)C10—C9—C14—C1−178.18 (14)
C14—C1—C6—C5−179.26 (14)C8—C9—C14—C13.0 (2)
C2—C1—C6—C7−178.10 (14)C12—C13—C14—C9−1.9 (2)
C14—C1—C6—C71.2 (2)C12—C13—C14—C1178.09 (15)
C5—C6—C7—C8−177.65 (15)C6—C1—C14—C9−3.6 (2)
C1—C6—C7—C81.9 (2)C2—C1—C14—C9175.69 (14)
C6—C7—C8—C9−2.5 (2)C6—C1—C14—C13176.38 (14)
C7—C8—C9—C10−178.78 (15)C2—C1—C14—C13−4.3 (2)
C7—C8—C9—C140.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2o···O10.85 (1)2.20 (3)2.670 (2)115 (2)
O2—H2o···O3i0.85 (1)1.95 (1)2.754 (2)159 (3)
O3—H3o···O40.85 (1)2.08 (3)2.614 (2)121 (3)

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2712).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bhandari, S. R., Kapadi, A. H., Mujender, P. L., Joardar, M. & Shoolery, J. N. (1985). Phytochemistry, 24, 801–804.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Mujumder, P. L., Kar, A. & Shoolery, J. N. (1985). Phytochemistry, 24, 2083–2087.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Theuns, H. G., Janssen, R. H. A. M., Biessel, H. W. A. & Salemink, C. A. (1985). Phytochemistry, 24, 163–169.
  • Wang, Y.-X., Liu, C.-B., Fang, Z.-J., Wen, H.-L. & Xie, M.-Y. (2007). Acta Cryst. E63, o3905.
  • Westrip, S. P. (2008). publCIF In preparation.
  • Zurinah Mahmud, Z., Mohammad, N. K., Nordin, H. L. & Robert, F. T. (1992). J. Nat. Prod.55, 533–535.

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