7-Hy­droxy-8-isopropyl-1,1,4a-trimethyl-4a,9,10,10a-tetra­hydro-phenanthren-2(1H)-one

Benharref, A.; Lassaba, E.; Mazoir, N.; Daran, J.-C.; Berraho, M.

doi:10.1107/S1600536811009561

7-Hydroxy-8-isopropyl-1,1,4a-trimethyl-4a,9,10,10a-tetrahydro-phenanthren-2(1H)-one

A. Benharref, E. Lassaba, N. Mazoir, J.-C. Daran and M. Berraho

The title compound, C₂₀H₂₆O₂, was isolated from a chloroform extract of Tetraclinis articulata wood. The molecule contains three fused rings which exhibit different conformations. The non-aromatic oxo-substituted ring has a screw-boat conformation, while the central ring has a half-chair conformation. In the crystal, molecules are linked to each other by intermolecular O—H

O hydrogen bonds involving the carbonyl and hydroxy groups.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811009561/fj2405sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811009561/fj2405Isup2.hkl Contains datablock I

CCDC reference: 820226

checkCIF report

Key indicators

Single-crystal X-ray study
T = 180 K
Mean (C-C) = 0.004 Å
R factor = 0.047
wR factor = 0.128
Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.21
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          7

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.37
           From the CIF: _reflns_number_total               1893
           Count of symmetry unique reflns         1899
           Completeness (_total/calc)             99.68%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT791_ALERT_4_G Note: The Model has Chirality at C4A    (Verify)          S
PLAT791_ALERT_4_G Note: The Model has Chirality at C10A   (Verify)          R

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Among the diterpenoids, the class with the phenantrene skeleton may have biological activities which have been recently reported (Atta-ur-Rahman et al.,1999; Azucena et al.,2001; Panter et al., 2002; Ulusu et al., 2002). These diterpenoids are often isolated from the medicinal plants. In our study, we were interested to the medicinal plant, Tetraclinis articulata which is used in Moroccan traditional medicine (Bellakhdar, 1997). Some of its oxygenated compounds are effective as an antifongic (Evidente et al., 1997), cytotoxic (Comte et al., 1995) and inhibit various human leukocyte functions(Barrero et al., 2003). In order to isolate similar compounds, we have studied the chloroform extract of Tetraclinis articulata wood. Thus, the extraction with chloroform using a soxhlet apparatus allow us isolate the totarolenone (7-hydroxy-8-isporpyl-1,1,4a-trimethyl- 4a,9,10,10a- tetrahydro-1H-phenanthren-3-one) a derivative of totarolone (7-hydroxy-8-isporpyl-1,1,4a-trimethyl-3,4,4a,9,10,10a- hexahydophenantren-2-one) (Zeroual et al., 2007). The structure of this new product was determined by NMR spectral analysis of 1H, 13 C and mass spectroscopy and confirmed by its single-crystal X-ray structure. The molecule (I) is built up from three fused six-membered rings. The non aromatic oxo-substituted ring has a screw boat conformation, as indicated by the total puckering amplitude QT = 0.490 (3)Å and spherical polar angle θ =67.1 (4)° with ϕ = 272.2 (3)°. While the central ring has a half chair conformation with QT = 0.545 (3) Å, θ =53.4 (3)°, ϕ = 278.5 (3)° (Cremer & Pople, 1975). Molecules are linked by intermolecular O—H···O hydrogen bonds (Table 1, Figure 2) involving the carbonyl and the hydroxy groups and propagate in chain parallel to the a axis.

Related literature top

For background to the biological activity of dierpenoids, see: Atta-ur-Rahman & Choudhary (1999); Azucena & Mobashery (2001); Panter et al. (2002); Ulusu et al. (2002). For their use in traditional medicine, see: Bellakhdar (1997) and for their medicinal properties, see: Barrero et al. (2003); Comte et al. (1995); Evidente et al. (1997). For the synthesis see: Zeroual et al. (2007). For conformational analysis, see: Cremer & Pople (1975).

Experimental top

50 g of wood powder Tetraclinis articulata was extracted with chloroform in Soxhlet apparatus during 24 h. After evaporating the solvent under reduced pressure, a residue of 3.2 g was obtained. Chromatography on a column of silica gel of this residue eluting with hexan - ethyl acetate (94 / 4), allowed us to isolate in pure form 640 mg of 7-hydroxy-8-isporpyl- 1, 1,4 a-trimethyl-4a, 9,10,10 a-tetrahydro-1H-phenanthrene-3-one. Crystallization of this product was performed at room temperature in a solution of ethyl acetate.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. : Molecular structure 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.
	Fig. 2. : Partial packing view showing the O—H···O interactions (dashed lines) and the formation of a chain parallel to the b axis. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry code:(i) x + 1, y, z]

7-Hydroxy-8-isopropyl-1,1,4a-trimethyl-4a,9,10,10a-tetrahydro- phenanthren-2(1H)-one top

Crystal data top

C₂₀H₂₆O₂	F(000) = 324
M_r = 298.41	D_x = 1.169 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3905 reflections
a = 11.6731 (8) Å	θ = 3.6–29.2°
b = 6.4314 (4) Å	µ = 0.07 mm⁻¹
c = 12.1488 (10) Å	T = 180 K
β = 111.592 (9)°	Prism, colourless
V = 848.06 (11) Å³	0.48 × 0.36 × 0.29 mm
Z = 2

Data collection top

Agilent Xcalibur Eos Gemini ultra diffractometer	1591 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.066
Graphite monochromator	θ_max = 26.4°, θ_min = 3.7°
Detector resolution: 16.1978 pixels mm^-1	h = −14→14
ω scans	k = −8→8
9252 measured reflections	l = −15→15
1893 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0659P)² + 0.2266P] where P = (F_o² + 2F_c²)/3
1893 reflections	(Δ/σ)_max < 0.001
207 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₂₆O₂	V = 848.06 (11) Å³
M_r = 298.41	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 11.6731 (8) Å	µ = 0.07 mm⁻¹
b = 6.4314 (4) Å	T = 180 K
c = 12.1488 (10) Å	0.48 × 0.36 × 0.29 mm
β = 111.592 (9)°

Data collection top

Agilent Xcalibur Eos Gemini ultra diffractometer	1591 reflections with I > 2σ(I)
9252 measured reflections	R_int = 0.066
1893 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.128	H-atom parameters constrained
S = 1.03	Δρ_max = 0.18 e Å⁻³
1893 reflections	Δρ_min = −0.22 e Å⁻³
207 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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

	x	y	z	U_iso*/U_eq
C1	−0.3286 (2)	0.3531 (5)	0.7146 (2)	0.0290 (6)
C2	−0.4104 (2)	0.3898 (5)	0.5849 (3)	0.0314 (7)
C3	−0.3525 (3)	0.4063 (6)	0.4963 (3)	0.0364 (7)
H3	−0.4016	0.3822	0.4154	0.045 (10)*
C4	−0.2337 (3)	0.4540 (5)	0.5251 (3)	0.0324 (7)
H4	−0.2019	0.4667	0.4638	0.047 (10)*
C4A	−0.1473 (2)	0.4886 (5)	0.6526 (2)	0.0283 (6)
C4B	−0.0133 (2)	0.4386 (4)	0.6696 (2)	0.0274 (6)
C5	0.0337 (2)	0.5177 (5)	0.5876 (3)	0.0296 (6)
H5	−0.0179	0.6000	0.5237	0.036*
C6	0.1537 (2)	0.4788 (5)	0.5974 (3)	0.0303 (7)
H6	0.1846	0.5371	0.5420	0.036*
C7	0.2287 (2)	0.3544 (5)	0.6887 (2)	0.0299 (6)
C8	0.1866 (2)	0.2729 (5)	0.7742 (2)	0.0287 (6)
C8A	0.0651 (2)	0.3211 (5)	0.7647 (2)	0.0273 (6)
C9	0.0224 (2)	0.2470 (6)	0.8626 (3)	0.0351 (7)
H9A	0.0867	0.2814	0.9402	0.042*
H9B	0.0136	0.0938	0.8579	0.042*
C10	−0.0995 (2)	0.3422 (6)	0.8568 (2)	0.0336 (7)
H10A	−0.1329	0.2626	0.9079	0.040*
H10B	−0.0861	0.4875	0.8856	0.040*
C10A	−0.1905 (2)	0.3373 (5)	0.7292 (2)	0.0282 (6)
H10	−0.1817	0.1953	0.6997	0.034*
C11	0.2702 (3)	0.1345 (6)	0.8719 (3)	0.0383 (8)
H11	0.2229	0.0978	0.9231	0.046*
C12	0.3000 (3)	−0.0718 (6)	0.8246 (4)	0.0526 (9)
H12A	0.3534	−0.0452	0.7800	0.079*
H12B	0.2233	−0.1371	0.7725	0.079*
H21A	0.3421	−0.1649	0.8911	0.079*
C13	0.3870 (3)	0.2455 (7)	0.9521 (3)	0.0474 (9)
H13A	0.4396	0.2761	0.9071	0.071*
H13B	0.4317	0.1559	1.0195	0.071*
H13C	0.3646	0.3757	0.9810	0.071*
C15	−0.3538 (3)	0.5228 (6)	0.7922 (3)	0.0422 (8)
H15A	−0.4422	0.5272	0.7773	0.063*
H15B	−0.3274	0.6580	0.7727	0.063*
H15C	−0.3079	0.4913	0.8758	0.063*
C16	−0.3680 (3)	0.1419 (5)	0.7484 (3)	0.0371 (7)
H16A	−0.3634	0.0355	0.6925	0.056*
H16B	−0.4528	0.1515	0.7457	0.056*
H16C	−0.3130	0.1042	0.8286	0.056*
C18	−0.1553 (3)	0.7207 (5)	0.6809 (3)	0.0427 (8)
H18A	−0.1174	0.8047	0.6362	0.064*
H18B	−0.1117	0.7442	0.7658	0.064*
H18C	−0.2419	0.7606	0.6587	0.064*
O1	−0.52293 (18)	0.4045 (4)	0.5543 (2)	0.0440 (6)
O2	0.34674 (17)	0.3068 (4)	0.69940 (18)	0.0396 (6)
H2	0.3623	0.3635	0.6442	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0193 (12)	0.0352 (16)	0.0359 (15)	0.0034 (12)	0.0140 (11)	0.0023 (13)
C2	0.0210 (13)	0.0368 (17)	0.0389 (15)	0.0037 (12)	0.0138 (11)	0.0033 (13)
C3	0.0240 (14)	0.056 (2)	0.0299 (14)	0.0060 (14)	0.0106 (11)	0.0032 (14)
C4	0.0247 (14)	0.0416 (18)	0.0355 (15)	0.0089 (12)	0.0165 (12)	0.0062 (13)
C4A	0.0213 (13)	0.0343 (16)	0.0338 (14)	0.0029 (12)	0.0153 (11)	0.0026 (13)
C4B	0.0208 (13)	0.0313 (16)	0.0338 (14)	−0.0026 (11)	0.0145 (11)	−0.0017 (12)
C5	0.0245 (14)	0.0317 (15)	0.0345 (14)	0.0003 (12)	0.0129 (11)	0.0013 (12)
C6	0.0258 (14)	0.0365 (17)	0.0346 (14)	−0.0068 (13)	0.0182 (12)	−0.0015 (13)
C7	0.0166 (12)	0.0403 (17)	0.0354 (15)	−0.0036 (13)	0.0126 (11)	−0.0034 (14)
C8	0.0204 (13)	0.0335 (15)	0.0335 (14)	−0.0016 (12)	0.0115 (11)	0.0003 (12)
C8A	0.0180 (12)	0.0329 (15)	0.0334 (14)	−0.0017 (11)	0.0125 (11)	0.0000 (12)
C9	0.0195 (14)	0.0533 (19)	0.0340 (15)	−0.0013 (13)	0.0117 (11)	0.0041 (14)
C10	0.0235 (13)	0.0494 (19)	0.0310 (14)	−0.0024 (14)	0.0136 (11)	0.0025 (14)
C10A	0.0171 (12)	0.0396 (16)	0.0309 (14)	0.0030 (12)	0.0124 (10)	0.0005 (13)
C11	0.0193 (13)	0.055 (2)	0.0408 (16)	0.0001 (14)	0.0119 (12)	0.0067 (15)
C12	0.0414 (19)	0.049 (2)	0.061 (2)	0.0066 (16)	0.0101 (17)	0.0116 (18)
C13	0.0300 (17)	0.069 (3)	0.0414 (18)	−0.0075 (16)	0.0115 (14)	0.0022 (18)
C15	0.0279 (16)	0.053 (2)	0.054 (2)	−0.0006 (15)	0.0258 (15)	−0.0119 (17)
C16	0.0241 (14)	0.0423 (18)	0.0495 (18)	0.0017 (13)	0.0187 (13)	0.0097 (15)
C18	0.0426 (19)	0.0361 (19)	0.061 (2)	0.0025 (14)	0.0327 (17)	0.0003 (16)
O1	0.0197 (10)	0.0687 (17)	0.0459 (12)	0.0077 (10)	0.0146 (9)	0.0109 (12)
O2	0.0212 (10)	0.0626 (16)	0.0409 (12)	0.0021 (10)	0.0184 (9)	0.0044 (11)

Geometric parameters (Å, º) top

C1—C2	1.531 (4)	C9—H9A	0.9900
C1—C16	1.538 (4)	C9—H9B	0.9900
C1—C15	1.539 (4)	C10—C10A	1.523 (4)
C1—C10A	1.559 (3)	C10—H10A	0.9900
C2—O1	1.230 (3)	C10—H10B	0.9900
C2—C3	1.471 (4)	C10A—H10	1.0000
C3—C4	1.336 (4)	C11—C13	1.530 (5)
C3—H3	0.9500	C11—C12	1.536 (5)
C4—C4A	1.522 (4)	C11—H11	1.0000
C4—H4	0.9500	C12—H12A	0.9800
C4A—C4B	1.535 (4)	C12—H12B	0.9800
C4A—C18	1.542 (4)	C12—H21A	0.9800
C4A—C10A	1.554 (4)	C13—H13A	0.9800
C4B—C5	1.397 (4)	C13—H13B	0.9800
C4B—C8A	1.401 (4)	C13—H13C	0.9800
C5—C6	1.385 (4)	C15—H15A	0.9800
C5—H5	0.9500	C15—H15B	0.9800
C6—C7	1.386 (4)	C15—H15C	0.9800
C6—H6	0.9500	C16—H16A	0.9800
C7—O2	1.371 (3)	C16—H16B	0.9800
C7—C8	1.403 (4)	C16—H16C	0.9800
C8—C8A	1.414 (4)	C18—H18A	0.9800
C8—C11	1.517 (4)	C18—H18B	0.9800
C8A—C9	1.526 (4)	C18—H18C	0.9800
C9—C10	1.526 (4)	O2—H2	0.8400

C2—C1—C16	106.1 (2)	C9—C10—H10A	109.8
C2—C1—C15	109.5 (2)	C10A—C10—H10B	109.8
C16—C1—C15	108.7 (2)	C9—C10—H10B	109.8
C2—C1—C10A	110.7 (2)	H10A—C10—H10B	108.3
C16—C1—C10A	108.1 (2)	C10—C10A—C4A	109.7 (2)
C15—C1—C10A	113.5 (2)	C10—C10A—C1	114.8 (2)
O1—C2—C3	120.0 (3)	C4A—C10A—C1	116.2 (2)
O1—C2—C1	121.0 (2)	C10—C10A—H10	104.9
C3—C2—C1	119.0 (2)	C4A—C10A—H10	104.9
C4—C3—C2	122.5 (3)	C1—C10A—H10	104.9
C4—C3—H3	118.8	C8—C11—C13	113.0 (3)
C2—C3—H3	118.8	C8—C11—C12	112.5 (3)
C3—C4—C4A	122.4 (2)	C13—C11—C12	111.7 (3)
C3—C4—H4	118.8	C8—C11—H11	106.3
C4A—C4—H4	118.8	C13—C11—H11	106.3
C4—C4A—C4B	111.5 (2)	C12—C11—H11	106.3
C4—C4A—C18	107.3 (3)	C11—C12—H12A	109.5
C4B—C4A—C18	108.4 (3)	C11—C12—H12B	109.5
C4—C4A—C10A	106.2 (2)	H12A—C12—H12B	109.5
C4B—C4A—C10A	109.2 (2)	C11—C12—H21A	109.5
C18—C4A—C10A	114.4 (2)	H12A—C12—H21A	109.5
C5—C4B—C8A	118.4 (2)	H12B—C12—H21A	109.5
C5—C4B—C4A	118.4 (2)	C11—C13—H13A	109.5
C8A—C4B—C4A	123.2 (2)	C11—C13—H13B	109.5
C6—C5—C4B	121.5 (3)	H13A—C13—H13B	109.5
C6—C5—H5	119.2	C11—C13—H13C	109.5
C4B—C5—H5	119.2	H13A—C13—H13C	109.5
C5—C6—C7	119.6 (2)	H13B—C13—H13C	109.5
C5—C6—H6	120.2	C1—C15—H15A	109.5
C7—C6—H6	120.2	C1—C15—H15B	109.5
O2—C7—C6	121.4 (2)	H15A—C15—H15B	109.5
O2—C7—C8	117.4 (2)	C1—C15—H15C	109.5
C6—C7—C8	121.2 (2)	H15A—C15—H15C	109.5
C7—C8—C8A	118.1 (3)	H15B—C15—H15C	109.5
C7—C8—C11	119.9 (2)	C1—C16—H16A	109.5
C8A—C8—C11	122.0 (2)	C1—C16—H16B	109.5
C4B—C8A—C8	121.1 (2)	H16A—C16—H16B	109.5
C4B—C8A—C9	120.7 (2)	C1—C16—H16C	109.5
C8—C8A—C9	118.2 (2)	H16A—C16—H16C	109.5
C8A—C9—C10	113.9 (3)	H16B—C16—H16C	109.5
C8A—C9—H9A	108.8	C4A—C18—H18A	109.5
C10—C9—H9A	108.8	C4A—C18—H18B	109.5
C8A—C9—H9B	108.8	H18A—C18—H18B	109.5
C10—C9—H9B	108.8	C4A—C18—H18C	109.5
H9A—C9—H9B	107.7	H18A—C18—H18C	109.5
C10A—C10—C9	109.2 (2)	H18B—C18—H18C	109.5
C10A—C10—H10A	109.8	C7—O2—H2	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.84	2.03	2.791 (3)	150

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₆O₂
M_r	298.41
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	180
a, b, c (Å)	11.6731 (8), 6.4314 (4), 12.1488 (10)
β (°)	111.592 (9)
V (Å³)	848.06 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.48 × 0.36 × 0.29

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini ultra diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9252, 1893, 1591
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.128, 1.03
No. of reflections	1893
No. of parameters	207
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.22

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999).