(25R) 5a Spiro­stane 3,12 dione

(25

R

)-5a-Spirostane-3,12-dione

Tie-Ying Zi,aZhi-He Zang,bMing-Yong Yuanaand Ling-Li Zhenga*

a

The First Affiliated Hospital, Chengdu Medical College, Xindu 610500, People’s Republic of China, andbDepartment of Pharmacy, Chengdu Medical College, Chengdu 610081, People’s Republic of China

Correspondence e-mail: [email protected]

Received 20 November 2008; accepted 23 December 2008

Key indicators: single-crystal X-ray study;T= 292 K; mean(C–C) = 0.011 A˚;

Rfactor = 0.078;wRfactor = 0.202; data-to-parameter ratio = 8.5.

The title compound, C27H40O4, was obtained from the oxidation of (25R)-3b-hydroxy-5a-spirostan-12-one (Heco-genin) by Jone’s reagent. The molecule contains six alicyclic and heterocyclic rings, alltrans-fused, among which four six-membered rings adopt similar chair conformations while two five-membered rings assume an envelope conformation.

Related literature

For general background, see: Chakravartiet al. (1953); Djer-assiet al.(1962); Huanget al.(2002).

Experimental

Crystal data

C27H40O4 Mr= 428.59

Monoclinic,C2 a= 12.660 (3) A˚ b= 6.443 (3) A˚ c= 30.167 (3) A˚ = 98.02 (3)

V= 2436.8 (14) A˚3

Z= 4

MoKradiation = 0.08 mm 1 T= 292 (2) K 0.440.400.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none 2837 measured reflections 2407 independent reflections

919 reflections withI> 2(I) Rint= 0.136

3 standard reflections every 150 reflections intensity decay: 2.6%

Refinement

R[F2_{> 2(F}2_{)] = 0.078}

wR(F2) = 0.202 S= 1.07 2407 reflections 284 parameters

2 restraints

H-atom parameters constrained max= 0.19 e A˚ 3

min= 0.23 e A˚ 3

Data collection:DIFRAC(Gabe & White, 1993); cell refinement:

DIFRAC; data reduction:NRCVAX(Gabeet al., 1989); 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); software used to prepare material for publication:WinGX(Farrugia, 1999).

This project was supported by the Scientific Research Fund of Chengdu Medical College, China (No. CYZ07–010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2465).

References

Chakravarti, C., Lemin, A. J., Martines, G. & Sondheimer, F. (1953).J. Am. Chem. Soc.75, 4885–4887.

Djerassi, C., Chakravarti, R. N. & Mitra, M. N. (1962).Nature (London),193, 1071–1072.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.

Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S (1989).J. Appl. Cryst.22, 384–387.

Gabe, E. J. & White, P. S. (1993). American Crystallographic Association Pittsburgh Meeting, Abstract PA104.

Huang, J. W., Jiang, S. H., Tan, C. H. & Zhu, D. Y. (2002).Chin. J. Org. Chem. 22, 917–921.

Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122. Acta Crystallographica Section E

Structure Reports

Online

supporting information

Acta Cryst. (2009). E65, o232 [doi:10.1107/S1600536808043687]

(25

R

)-5a-Spirostane-3,12-dione

Tie-Ying Zi, Zhi-He Zang, Ming-Yong Yuan and Ling-Li Zheng

S1. Comment

Steroid sapogenins are a class of important compounds, which present many significant bioactivities in platelet aggregation, arteriosclerosis and so on (Huang et al., 2002). The hecogenin (25R-5a-Spirostane-3b-ol-12-one) is an important steroid (Djerassi et al., 1962; Chakravarti et al., 1953), which has been isolated from Chinese traditional medicine Tribulus terrestris. The title compound was recently obtained by Jone's oxidation of hecogenin in our laboratory, and its crystal structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The molecule contains six alicylic and heterocyclic rings with trans-fused. Cyclohexane rings A (C1/C2/C3/C4/C5/C10), B (C5/C6/C7/C8/C9/C10), C

(C8/C9/C11/C12/C13/C14) and six-membered heterocyclic ring F (C22/C23/C24/C25/C26/O4) adopt chair conformation. Cyclopetane ring D (C13/C14/C15/C16/C17) and five-membered heterocyclic ring E (C16/C17/C20/C22/O3) have envelope conformation.

S2. Experimental

A solution of hecogenin (200 mg) in acetone (10 ml) was added by Jone's reagent drops by drops. The reaction solution was stirred for 20 min and quenched by water (10 ml). The mixture was extracted with CH2Cl2 (5 ml×3) and the organic

phase was concentrated to give the title compound. The crystals suitable for X-ray analysis were obtained by slow evaporation from acetone solution at room temperature. The absolute configuration was deduced not by the present experiment but by the synthetic path from Hecognin, whose absolute configuration is known.

S3. Refinement

H atoms were located geometrically with C—H = 0.93–0.98 Å and refined using a riding model with Uiso(H) = 1.2Ueq(C).

Friedel pairs were merged and the absolute configuration was not determined.

Figure 1

(25R)-5a-Spirostane-3,12-dione

Crystal data

C27H40O4

Mr = 428.59

Monoclinic, C2 Hall symbol: C 2y

a = 12.660 (3) Å

b = 6.443 (3) Å

c = 30.167 (3) Å

β = 98.02 (3)°

V = 2436.8 (14) Å3

Z = 4

F(000) = 936

Dx = 1.168 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 12 reflections

θ = 4.3–5.6°

µ = 0.08 mm−1

T = 292 K Block, colourless 0.44 × 0.40 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

2837 measured reflections 2407 independent reflections 919 reflections with I > 2σ(I)

Rint = 0.136

θmax = 25.5°, θmin = 1.4°

h = −15→15

k = −7→7

l = −35→36

3 standard reflections every 150 reflections intensity decay: 2.6%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.078}

wR(F2_{) = 0.202}

S = 1.07 2407 reflections 284 parameters 2 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0752P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.19 e Å−3

Δρmin = −0.23 e Å−3

Special details

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

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

H21A 0.7527 1.0474 0.8483 0.146* H21B 0.7190 0.8765 0.8805 0.146* H21C 0.6678 0.8796 0.8301 0.146* C22 0.9283 (7) 0.7917 (16) 0.8671 (3) 0.084 (3) C23 0.9441 (6) 0.6702 (13) 0.9110 (3) 0.078 (2) H23A 0.9425 0.5224 0.9048 0.093* H23B 0.8867 0.7017 0.9282 0.093* C24 1.0524 (8) 0.729 (2) 0.9385 (3) 0.118 (4) H24A 1.0583 0.6638 0.9678 0.141* H24B 1.1100 0.6768 0.9235 0.141* C25 1.0628 (8) 0.956 (2) 0.9439 (4) 0.123 (4) H25 1.0063 1.0032 0.9607 0.147* C26 1.0440 (8) 1.0586 (18) 0.8978 (3) 0.109 (3) H26A 1.0507 1.2080 0.9012 0.130* H26B 1.0977 1.0116 0.8801 0.130* C27 1.1729 (7) 1.030 (3) 0.9702 (3) 0.164 (5) H27A 1.2271 1.0205 0.9510 0.247* H27B 1.1917 0.9440 0.9960 0.247* H27C 1.1668 1.1718 0.9795 0.247*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C22 0.102 (7) 0.063 (6) 0.083 (6) 0.023 (6) 0.005 (6) −0.005 (6) C23 0.086 (6) 0.067 (6) 0.081 (5) 0.004 (5) 0.014 (5) 0.013 (5) C24 0.127 (9) 0.143 (13) 0.079 (7) 0.019 (8) −0.002 (6) 0.019 (7) C25 0.105 (8) 0.142 (13) 0.114 (8) 0.007 (8) −0.007 (7) −0.026 (7) C26 0.132 (9) 0.093 (9) 0.102 (6) 0.002 (7) 0.021 (7) −0.028 (6) C27 0.129 (9) 0.221 (16) 0.133 (8) −0.024 (11) −0.015 (7) −0.036 (11)

Geometric parameters (Å, º)

O1—C3 1.220 (8) C13—C18 1.530 (10) O2—C12 1.211 (9) C13—C17 1.579 (11) O3—C22 1.412 (9) C14—C15 1.547 (9)

O3—C16 1.464 (8) C14—H14 0.9800

O4—C26 1.421 (9) C15—C16 1.523 (10) O4—C22 1.428 (12) C15—H15A 0.9700 C1—C2 1.509 (10) C15—H15B 0.9700 C1—C10 1.574 (9) C16—C17 1.569 (9)

C1—H1A 0.9700 C16—H16 0.9800

C1—H1B 0.9700 C17—C20 1.509 (10)

C2—C3 1.533 (11) C17—H17 0.9800

C2—H2A 0.9700 C18—H18A 0.9600

C2—H2B 0.9700 C18—H18B 0.9600

C3—C4 1.478 (10) C18—H18C 0.9600 C4—C5 1.488 (10) C19—H19A 0.9600

C4—H4A 0.9700 C19—H19B 0.9600

C4—H4B 0.9700 C19—H19C 0.9600

C5—C6 1.552 (9) C20—C21 1.504 (10) C5—C10 1.549 (9) C20—C22 1.524 (10)

C5—H5 0.9800 C20—H20 0.9800

C6—C7 1.543 (11) C21—H21A 0.9600

C6—H6A 0.9700 C21—H21B 0.9600

C6—H6B 0.9700 C21—H21C 0.9600

C7—C8 1.508 (9) C22—C23 1.529 (11)

C7—H7A 0.9700 C23—C24 1.546 (12)

C7—H7B 0.9700 C23—H23A 0.9700

C8—C14 1.500 (9) C23—H23B 0.9700 C8—C9 1.511 (8) C24—C25 1.478 (17)

C8—H8 0.9800 C24—H24A 0.9700

C9—C11 1.512 (9) C24—H24B 0.9700 C9—C10 1.521 (9) C25—C26 1.529 (14)

C9—H9 0.9800 C25—C27 1.579 (13)

C10—C19 1.546 (11) C25—H25 0.9800 C11—C12 1.510 (10) C26—H26A 0.9700

C11—H11A 0.9700 C26—H26B 0.9700

C11—H11B 0.9700 C27—H27A 0.9600

C8—C9—C10 114.2 (6) C20—C22—C23 115.3 (8) C11—C9—C10 115.2 (6) C22—C23—C24 109.8 (7) C8—C9—H9 103.9 C22—C23—H23A 109.7 C11—C9—H9 103.9 C24—C23—H23A 109.7 C10—C9—H9 103.9 C22—C23—H23B 109.7 C9—C10—C5 109.8 (5) C24—C23—H23B 109.7 C9—C10—C19 110.5 (6) H23A—C23—H23B 108.2 C5—C10—C19 112.9 (6) C25—C24—C23 111.1 (9) C9—C10—C1 111.2 (5) C25—C24—H24A 109.4 C5—C10—C1 104.8 (6) C23—C24—H24A 109.4 C19—C10—C1 107.6 (6) C25—C24—H24B 109.4 C9—C11—C12 114.7 (6) C23—C24—H24B 109.4 C9—C11—H11A 108.6 H24A—C24—H24B 108.0 C12—C11—H11A 108.6 C24—C25—C26 109.1 (10) C9—C11—H11B 108.6 C24—C25—C27 114.5 (12) C12—C11—H11B 108.6 C26—C25—C27 109.9 (10) H11A—C11—H11B 107.6 C24—C25—H25 107.7 O2—C12—C11 121.2 (8) C26—C25—H25 107.7 O2—C12—C13 123.7 (8) C27—C25—H25 107.7 C11—C12—C13 114.9 (7) O4—C26—C25 110.9 (9) C12—C13—C14 105.4 (5) O4—C26—H26A 109.5 C12—C13—C18 107.3 (6) C25—C26—H26A 109.5 C14—C13—C18 113.6 (6) O4—C26—H26B 109.5 C12—C13—C17 113.9 (6) C25—C26—H26B 109.5 C14—C13—C17 103.4 (6) H26A—C26—H26B 108.0 C18—C13—C17 113.2 (5) C25—C27—H27A 109.5 C8—C14—C13 117.2 (6) C25—C27—H27B 109.5 C8—C14—C15 122.1 (6) H27A—C27—H27B 109.5 C13—C14—C15 100.1 (5) C25—C27—H27C 109.5 C8—C14—H14 105.3 H27A—C27—H27C 109.5 C13—C14—H14 105.3 H27B—C27—H27C 109.5