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Acta Cryst. (2008). E64, o762    [ doi:10.1107/S1600536808007769 ]

6-Hydroxy-7-isopropyl-1,1,4a-trimethyl-2,3,4,4a,10,10a-hexahydrophenanthren-9(1H)-one

N. Rajouani, My. Y. Ait Itto, A. Benharref, A. Auhmani and J.-C. Daran

Abstract top

The title compound, C20H28O2, commonly named Sugiol, is a natural oxygenated diterpene that we have isolated for the first time from a hexane extract of the fruits of Juniperus Oxycedrus L. Its X-ray crystal structure determination confirms an abietane skeleton which was predicted by spectroscopic analysis, mainly by 1H and 13C NMR. The cyclohexane ring adopts a flattened chair conformation, while the cyclohexene ring adopts an envelope conformation. The molecules are linked through O-H...O hydrogen bonds to form a zigzag chain extending parallel to the c axis.

Comment top

Juniperus oxycedrus L. has been used in traditional folk medicine for the treatment of chronic eczema and other several skin diseases (Bouhlal et al., 1988). Diterpenes are among the identified chemical constituents of this plant. They are of great interest with respect to their biological activity including antitumor, antituberculous and antimalarial effects (Iwamato et al., 2003; Politi et al., 2003; Ulubelen et al., 1997).

The structure of the title compound is built up by three fused six-membered rings A, B and C (Fig. 1). B displays an envelope conformation with puckering parameters, Q=0.510 (4) Å, θ= 124.6 (4)° and φ= 227.1 (6)° (Cremer & Pople, 1975) whereas C has a flattened chair conformation with Q= 0.546 (4) Å, θ = 5.0 (4) and φ = 234 (5)°. A is an aromatic ring and it is perfectly planar. The molecules are linked through O—H···O hydrogen bonds involving the hydroxyl group as a donor and the ketone oxygen as an acceptor yielding a zig zag chain developing parallel to the c axis (Fig. 2, Table 1).

Related literature top

For related literature, see: Bai-Ping & Isao (1991); Bouhlal et al. (1988); Cremer & Pople (1975); Iwamato et al. (2003); Politi et al. (2003); Ulubelen et al. (1997).

Experimental top

In order to isolate similar compounds, we have studied the chemical composition of the fruits of Juniperus oxycedrus L. Thus, 203 g of pulverized cones was extracted with hexane. The solvent was evaporated under reduced pressure to give 14.3 g of the crude hexanic extract which was purified on silica gel column chromatography using hexane–AcOEt (97:3) as eluent, to give crystals of Sugiol (I). All 1H and 13C NMR spectroscopic data of the isolated product were in full accord with the litterature (Bai-Ping & Isao, 1991).

Refinement top

All H atoms attached to C and O atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.98 Å (methine), 0.97 Å (methylene), 0.96 Å (methyl) and O—H = 0.82 Å with Uiso(H) = 1.2Ueq or Uiso(H) = 1.5Ueq(methyl, OH).

In the absence of significant anomalous scattering, the absolute configuration could not be reliably determined and then the Friedel pairs were merged and any references to the Flack parameter were removed.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular view of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Partial packing view of the compound, showing the formation of the zig zag chain parallel to the c axis and built from O—H···O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity. [symmetry codes: (i) -x + 1/2,-y + 1, z + 1/2].
6-Hydroxy-7-isopropyl-1,1,4a-trimethyl-2,3,4,4a,10,10a-hexahydrophenanthren- 9(1H)-one top
Crystal data top
C20H28O2F000 = 656
Mr = 300.42Dx = 1.164 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3571 reflections
a = 9.6060 (4) Åθ = 2.7–32.1º
b = 12.6617 (6) ŵ = 0.07 mm−1
c = 14.0920 (7) ÅT = 180 (2) K
V = 1713.99 (14) Å3Flattened box, colorless
Z = 40.31 × 0.16 × 0.07 mm
Data collection top
Oxford Diffraction Xcalibur
diffractometer		2003 independent reflections
Radiation source: fine-focus sealed tube1212 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.068
Detector resolution: 8.2632 pixels mm-1θmax = 26.4º
T = 180(2) Kθmin = 2.7º
ω and φ scansh = −12→12
Absorption correction: nonek = −15→15
13398 measured reflectionsl = −14→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.154  w = 1/[σ2(Fo2) + (0.0842P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2003 reflectionsΔρmax = 0.36 e Å−3
205 parametersΔρmin = −0.38 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C20H28O2V = 1713.99 (14) Å3
Mr = 300.42Z = 4
Orthorhombic, P212121Mo Kα
a = 9.6060 (4) ŵ = 0.07 mm−1
b = 12.6617 (6) ÅT = 180 (2) K
c = 14.0920 (7) Å0.31 × 0.16 × 0.07 mm
Data collection top
Oxford Diffraction Xcalibur
diffractometer		2003 independent reflections
Absorption correction: none1212 reflections with I > 2σ(I)
13398 measured reflectionsRint = 0.068
Refinement top
R[F2 > 2σ(F2)] = 0.046Δρmax = 0.36 e Å−3
wR(F2) = 0.154Δρmin = −0.38 e Å−3
S = 1.05Absolute structure: ?
2003 reflectionsFlack parameter: ?
205 parametersRogers parameter: ?
H-atom parameters constrained
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 > 2σ(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
C10.0789 (4)0.8588 (3)0.0839 (3)0.0291 (10)
C20.1754 (4)0.9176 (3)0.1515 (3)0.0339 (11)
H2A0.26740.92110.12340.041*
H2B0.14180.98940.15880.041*
C30.1869 (5)0.8673 (3)0.2486 (3)0.0366 (11)
H3A0.09660.86810.27940.044*
H3B0.25110.90770.28740.044*
C40.2389 (4)0.7525 (3)0.2400 (3)0.0296 (10)
H4A0.24300.72150.30290.036*
H4B0.33270.75310.21450.036*
C4A0.1464 (4)0.6828 (3)0.1762 (3)0.0217 (9)
C4B0.2182 (4)0.5776 (3)0.1555 (3)0.0202 (9)
C50.3090 (4)0.5314 (3)0.2203 (3)0.0252 (9)
H50.32860.56610.27680.030*
C60.3699 (4)0.4356 (3)0.2023 (3)0.0255 (9)
C70.3444 (4)0.3792 (3)0.1186 (3)0.0296 (10)
C80.2533 (4)0.4252 (3)0.0564 (3)0.0244 (10)
H80.23350.38980.00020.029*
C8A0.1892 (4)0.5211 (3)0.0724 (3)0.0219 (9)
C90.0961 (4)0.5626 (3)0.0010 (3)0.0220 (9)
C100.0395 (4)0.6713 (3)0.0137 (3)0.0307 (10)
H10A−0.05450.66630.03840.037*
H10B0.03440.7054−0.04790.037*
C10A0.1257 (4)0.7408 (3)0.0804 (3)0.0227 (9)
H10C0.21860.74260.05180.027*
C110.0945 (5)0.9073 (3)−0.0143 (3)0.0455 (13)
H11A0.08470.9826−0.00990.068*
H11B0.02390.8795−0.05560.068*
H11C0.18470.8905−0.03930.068*
C12−0.0741 (4)0.8754 (3)0.1138 (3)0.0397 (12)
H12A−0.10130.94680.10060.060*
H12B−0.08360.86180.18050.060*
H12C−0.13280.82780.07900.060*
C130.0112 (4)0.6551 (3)0.2292 (3)0.0333 (11)
H13A−0.04940.61620.18790.050*
H13B−0.03430.71900.24900.050*
H13C0.03280.61300.28390.050*
C140.4133 (5)0.2730 (3)0.1025 (3)0.0322 (11)
H140.51000.27920.12400.039*
C150.4171 (6)0.2384 (4)0.0019 (4)0.0672 (18)
H15A0.32390.2261−0.02010.101*
H15B0.47010.1743−0.00320.101*
H15C0.45980.2923−0.03620.101*
C160.3443 (6)0.1868 (4)0.1627 (4)0.0614 (16)
H16A0.25160.17440.13990.092*
H16B0.34060.20930.22770.092*
H16C0.39760.12290.15820.092*
O60.4598 (3)0.3917 (2)0.2654 (2)0.0353 (8)
H60.46410.42870.31310.053*
O90.0639 (3)0.5113 (2)−0.06942 (18)0.0304 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.033 (2)0.018 (2)0.036 (2)0.0086 (18)−0.001 (2)0.0033 (19)
C20.033 (2)0.021 (2)0.048 (3)0.0042 (19)0.000 (2)−0.002 (2)
C30.032 (2)0.029 (2)0.048 (3)0.001 (2)−0.008 (2)−0.014 (2)
C40.032 (2)0.027 (2)0.029 (2)0.0046 (19)−0.0046 (19)−0.0085 (19)
C4A0.022 (2)0.021 (2)0.022 (2)−0.0028 (16)−0.0010 (18)0.0000 (17)
C4B0.0183 (18)0.0196 (19)0.023 (2)−0.0009 (16)0.0041 (18)0.0026 (17)
C50.028 (2)0.025 (2)0.023 (2)−0.0008 (18)0.000 (2)−0.0038 (18)
C60.029 (2)0.028 (2)0.019 (2)0.0069 (19)0.0023 (18)0.0033 (19)
C70.032 (3)0.025 (2)0.032 (2)0.0043 (19)0.007 (2)0.002 (2)
C80.028 (2)0.023 (2)0.022 (2)0.0025 (19)−0.0002 (18)0.0010 (18)
C8A0.026 (2)0.0196 (19)0.020 (2)−0.0039 (17)−0.0026 (19)0.0021 (18)
C90.024 (2)0.021 (2)0.020 (2)−0.0005 (17)0.0018 (18)0.0018 (18)
C100.033 (2)0.032 (2)0.027 (2)0.0024 (19)−0.006 (2)−0.0011 (19)
C10A0.021 (2)0.024 (2)0.023 (2)0.0048 (16)−0.0008 (18)−0.0035 (18)
C110.059 (3)0.029 (3)0.049 (3)0.008 (2)0.001 (3)0.011 (2)
C120.035 (3)0.035 (3)0.048 (3)0.013 (2)−0.009 (2)−0.010 (2)
C130.030 (2)0.033 (2)0.037 (3)0.0033 (19)0.003 (2)0.003 (2)
C140.036 (3)0.025 (2)0.035 (2)0.010 (2)−0.002 (2)0.0025 (18)
C150.093 (5)0.065 (4)0.044 (3)0.045 (4)0.001 (3)−0.011 (3)
C160.067 (4)0.036 (3)0.080 (4)0.006 (3)0.017 (3)0.006 (3)
O60.0436 (18)0.0353 (17)0.0271 (17)0.0196 (15)−0.0073 (15)−0.0031 (14)
O90.0393 (17)0.0288 (15)0.0231 (15)0.0002 (14)−0.0061 (14)−0.0076 (13)
Geometric parameters (Å, °) top
C1—C111.521 (6)C8A—C91.445 (5)
C1—C21.524 (6)C9—O91.226 (4)
C1—C121.543 (6)C9—C101.491 (5)
C1—C10A1.561 (5)C10—C10A1.530 (5)
C2—C31.514 (6)C10—H10A0.9700
C2—H2A0.9700C10—H10B0.9700
C2—H2B0.9700C10A—H10C0.9800
C3—C41.542 (5)C11—H11A0.9600
C3—H3A0.9700C11—H11B0.9600
C3—H3B0.9700C11—H11C0.9600
C4—C4A1.542 (5)C12—H12A0.9600
C4—H4A0.9700C12—H12B0.9600
C4—H4B0.9700C12—H12C0.9600
C4A—C4B1.528 (5)C13—H13A0.9600
C4A—C131.539 (5)C13—H13B0.9600
C4A—C10A1.550 (5)C13—H13C0.9600
C4B—C51.391 (5)C14—C151.485 (6)
C4B—C8A1.401 (5)C14—C161.532 (6)
C5—C61.370 (5)C14—H140.9800
C5—H50.9300C15—H15A0.9600
C6—O61.359 (4)C15—H15B0.9600
C6—C71.401 (5)C15—H15C0.9600
C7—C81.369 (5)C16—H16A0.9600
C7—C141.517 (5)C16—H16B0.9600
C8—C8A1.380 (5)C16—H16C0.9600
C8—H80.9300O6—H60.8200
C11—C1—C2108.1 (4)C8A—C9—C10118.6 (3)
C11—C1—C12106.7 (4)C9—C10—C10A114.0 (3)
C2—C1—C12110.0 (3)C9—C10—H10A108.7
C11—C1—C10A109.3 (3)C10A—C10—H10A108.7
C2—C1—C10A108.2 (3)C9—C10—H10B108.7
C12—C1—C10A114.4 (3)C10A—C10—H10B108.7
C3—C2—C1113.9 (3)H10A—C10—H10B107.6
C3—C2—H2A108.8C10—C10A—C4A109.4 (3)
C1—C2—H2A108.8C10—C10A—C1114.4 (3)
C3—C2—H2B108.8C4A—C10A—C1117.6 (3)
C1—C2—H2B108.8C10—C10A—H10C104.6
H2A—C2—H2B107.7C4A—C10A—H10C104.6
C2—C3—C4110.4 (3)C1—C10A—H10C104.6
C2—C3—H3A109.6C1—C11—H11A109.5
C4—C3—H3A109.6C1—C11—H11B109.5
C2—C3—H3B109.6H11A—C11—H11B109.5
C4—C3—H3B109.6C1—C11—H11C109.5
H3A—C3—H3B108.1H11A—C11—H11C109.5
C3—C4—C4A113.5 (3)H11B—C11—H11C109.5
C3—C4—H4A108.9C1—C12—H12A109.5
C4A—C4—H4A108.9C1—C12—H12B109.5
C3—C4—H4B108.9H12A—C12—H12B109.5
C4A—C4—H4B108.9C1—C12—H12C109.5
H4A—C4—H4B107.7H12A—C12—H12C109.5
C4B—C4A—C13106.0 (3)H12B—C12—H12C109.5
C4B—C4A—C4110.5 (3)C4A—C13—H13A109.5
C13—C4A—C4109.5 (3)C4A—C13—H13B109.5
C4B—C4A—C10A107.8 (3)H13A—C13—H13B109.5
C13—C4A—C10A115.0 (3)C4A—C13—H13C109.5
C4—C4A—C10A108.1 (3)H13A—C13—H13C109.5
C5—C4B—C8A117.3 (3)H13B—C13—H13C109.5
C5—C4B—C4A121.6 (3)C15—C14—C7114.6 (4)
C8A—C4B—C4A121.0 (3)C15—C14—C16109.2 (4)
C6—C5—C4B121.3 (4)C7—C14—C16111.0 (4)
C6—C5—H5119.4C15—C14—H14107.2
C4B—C5—H5119.4C7—C14—H14107.2
O6—C6—C5120.9 (4)C16—C14—H14107.2
O6—C6—C7117.0 (3)C14—C15—H15A109.5
C5—C6—C7122.2 (4)C14—C15—H15B109.5
C8—C7—C6115.8 (3)H15A—C15—H15B109.5
C8—C7—C14124.1 (4)C14—C15—H15C109.5
C6—C7—C14120.1 (4)H15A—C15—H15C109.5
C7—C8—C8A123.7 (4)H15B—C15—H15C109.5
C7—C8—H8118.2C14—C16—H16A109.5
C8A—C8—H8118.2C14—C16—H16B109.5
C8—C8A—C4B119.8 (4)H16A—C16—H16B109.5
C8—C8A—C9118.9 (3)C14—C16—H16C109.5
C4B—C8A—C9121.3 (3)H16A—C16—H16C109.5
O9—C9—C8A121.7 (3)H16B—C16—H16C109.5
O9—C9—C10119.6 (4)C6—O6—H6109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6···O9i0.821.842.642 (4)165
Symmetry codes: (i) −x+1/2, −y+1, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6···O9i0.821.842.642 (4)165
Symmetry codes: (i) −x+1/2, −y+1, z+1/2.
references
References top

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