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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1486.
Published online 2009 June 6. doi:  10.1107/S1600536809020674
PMCID: PMC2969319

(20S)-22-Acetoxymethyl-6β-meth­oxy-3α,5-dihydro-3′H-cyclo­propa[3α,5]-5α-pregnane

Abstract

In the title steroid derivative, C25H40O3, the fused cyclo­propane unit that corresponds to a part of the A ring has a β-configuration and the associated cyclo­pentane ring an envelope-shaped conformation.

Related literature

For the synthesis and crystal structure of the iodo-substituted compound, see: Ketuly et al. (2009 [triangle]). The absolute configuration of the acetoxymethyl title compound is that of the iodo-substituted compound.

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Object name is e-65-o1486-scheme1.jpg

Experimental

Crystal data

  • C25H40O3
  • M r = 388.57
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1486-efi1.jpg
  • a = 9.8222 (1) Å
  • b = 7.6128 (1) Å
  • c = 15.2309 (2) Å
  • β = 107.604 (1)°
  • V = 1085.55 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 100 K
  • 0.30 × 0.10 × 0.02 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 10411 measured reflections
  • 2674 independent reflections
  • 2550 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.092
  • S = 1.05
  • 2674 reflections
  • 258 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.18 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]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020674/xu2534sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020674/xu2534Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

(20S)-22-Iodomethyl-6-methoxy-3,5-dihydro-3'H-cyclopropa[3α,5]-5-pregnane (Ketuly et al., 2009) (250 mg) was dissolved in pyridine (2 ml) and acetic anhydride (2 ml). The solution was heated at 353 K for an hour. The solvent was evaporated to give a product (280 mg), which was purified by recrystallization from ethanol (140 mg); m.p. 395–396 K. Mass spectrum: M+ 338. C&H elemental analysis: calc. C 77.27, H 10.38% (found: C 77.06, H 10.44%).

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). 2271 Friedel pairs were merged.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C25H40O3 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C25H40O3F(000) = 428
Mr = 388.57Dx = 1.189 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 5999 reflections
a = 9.8222 (1) Åθ = 2.2–28.3°
b = 7.6128 (1) ŵ = 0.08 mm1
c = 15.2309 (2) ÅT = 100 K
β = 107.604 (1)°Plate, colorless
V = 1085.55 (2) Å30.30 × 0.10 × 0.02 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer2550 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
graphiteθmax = 27.5°, θmin = 2.2°
ω scansh = −12→12
10411 measured reflectionsk = −9→9
2674 independent reflectionsl = −19→19

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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0668P)2 + 0.103P] where P = (Fo2 + 2Fc2)/3
2674 reflections(Δ/σ)max = 0.001
258 parametersΔρmax = 0.30 e Å3
1 restraintΔρmin = −0.18 e Å3

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

xyzUiso*/Ueq
O10.10395 (12)0.50018 (19)0.12290 (8)0.0237 (3)
O20.24166 (13)0.5963 (2)0.03933 (8)0.0286 (3)
O30.25451 (12)0.95997 (17)0.77203 (8)0.0214 (3)
C10.49210 (17)0.7214 (2)0.92678 (10)0.0213 (3)
H1C0.50640.83530.95970.026*
H1D0.46180.62390.95960.026*
C20.58913 (18)0.6782 (2)0.87028 (11)0.0206 (3)
H20.66540.76380.86830.025*
C30.6102 (2)0.4859 (3)0.85413 (12)0.0307 (4)
H3C0.67010.42880.91120.037*
H3D0.65610.47010.80500.037*
C40.4587 (2)0.4096 (2)0.82473 (12)0.0308 (4)
H4C0.43230.36960.87930.037*
H4D0.45240.30840.78290.037*
C50.35775 (17)0.5589 (2)0.77468 (10)0.0193 (3)
C60.2085 (2)0.5381 (3)0.78560 (12)0.0312 (4)
H6D0.21400.55440.85040.047*
H6E0.17190.42030.76550.047*
H6F0.14430.62630.74790.047*
C70.43341 (16)0.7250 (2)0.82255 (10)0.0158 (3)
C80.39518 (15)0.9004 (2)0.77576 (10)0.0153 (3)
H80.46690.98970.80920.018*
C90.23898 (18)0.9981 (3)0.86009 (12)0.0258 (4)
H9D0.14841.05960.85220.039*
H9E0.31831.07260.89490.039*
H9F0.23950.88820.89370.039*
C100.39576 (16)0.8908 (2)0.67622 (10)0.0158 (3)
H10C0.49510.87460.67490.019*
H10D0.36001.00320.64510.019*
C110.30351 (15)0.7405 (2)0.62360 (10)0.0133 (3)
H110.20210.76090.62170.016*
C120.35449 (16)0.5638 (2)0.67192 (10)0.0163 (3)
H120.45530.54750.67150.020*
C130.2681 (2)0.4112 (2)0.61596 (12)0.0254 (4)
H13C0.16740.42180.61550.030*
H13D0.30590.29900.64660.030*
C140.27319 (19)0.4064 (2)0.51608 (11)0.0221 (3)
H14C0.37250.38480.51590.027*
H14D0.21290.30870.48270.027*
C150.21989 (15)0.5799 (2)0.46676 (10)0.0149 (3)
C160.05902 (15)0.6053 (3)0.45320 (11)0.0224 (3)
H16D0.04260.61240.51350.034*
H16E0.00580.50560.41860.034*
H16F0.02640.71410.41890.034*
C170.31116 (15)0.7284 (2)0.52507 (10)0.0136 (3)
H170.41270.69960.53040.016*
C180.27348 (18)0.8908 (2)0.46325 (11)0.0190 (3)
H18E0.35260.97710.47910.023*
H18F0.18570.94790.46850.023*
C190.24985 (18)0.8151 (2)0.36523 (10)0.0212 (3)
H19C0.32680.85470.34030.025*
H19D0.15710.85520.32330.025*
C200.25155 (15)0.6111 (2)0.37410 (10)0.0155 (3)
H200.35160.57090.38230.019*
C210.15462 (16)0.5210 (2)0.28707 (10)0.0188 (3)
H210.05460.56330.27670.023*
C220.1550 (2)0.3196 (3)0.29402 (12)0.0285 (4)
H22A0.10660.26950.23330.043*
H22B0.10500.28380.33790.043*
H22C0.25380.27720.31530.043*
C230.20266 (16)0.5758 (2)0.20495 (10)0.0202 (3)
H23D0.20260.70540.19990.024*
H23E0.30070.53280.21260.024*
C240.13665 (17)0.5221 (2)0.04415 (11)0.0211 (3)
C250.0256 (2)0.4403 (4)−0.03584 (12)0.0402 (5)
H25D−0.00460.5256−0.08620.060*
H25E−0.05700.4052−0.01650.060*
H25F0.06590.3367−0.05700.060*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0205 (5)0.0370 (7)0.0136 (5)−0.0064 (5)0.0052 (4)−0.0046 (5)
O20.0325 (6)0.0348 (7)0.0209 (6)−0.0102 (6)0.0118 (5)−0.0031 (6)
O30.0187 (5)0.0283 (6)0.0156 (5)0.0068 (5)0.0027 (4)−0.0055 (5)
C10.0284 (8)0.0204 (8)0.0125 (7)0.0008 (7)0.0024 (6)0.0001 (6)
C20.0216 (8)0.0210 (8)0.0158 (7)0.0040 (6)0.0008 (6)0.0002 (6)
C30.0431 (11)0.0242 (9)0.0185 (8)0.0145 (8)0.0001 (7)0.0013 (7)
C40.0559 (12)0.0158 (8)0.0159 (8)0.0000 (9)0.0034 (7)0.0025 (7)
C50.0296 (8)0.0149 (7)0.0123 (7)−0.0046 (7)0.0046 (5)0.0008 (6)
C60.0381 (10)0.0397 (11)0.0187 (8)−0.0207 (9)0.0129 (7)−0.0035 (8)
C70.0185 (7)0.0160 (7)0.0123 (7)0.0002 (6)0.0037 (5)−0.0004 (6)
C80.0151 (6)0.0144 (7)0.0157 (7)0.0010 (6)0.0038 (5)−0.0010 (6)
C90.0210 (7)0.0358 (10)0.0205 (8)0.0039 (7)0.0063 (6)−0.0081 (7)
C100.0202 (7)0.0124 (7)0.0152 (7)−0.0004 (6)0.0059 (5)0.0006 (6)
C110.0148 (6)0.0127 (7)0.0126 (6)0.0004 (5)0.0045 (5)0.0000 (5)
C120.0230 (7)0.0125 (7)0.0123 (7)−0.0016 (6)0.0039 (5)0.0008 (6)
C130.0446 (10)0.0127 (7)0.0162 (8)−0.0077 (7)0.0053 (7)0.0005 (6)
C140.0337 (9)0.0132 (7)0.0169 (8)−0.0010 (7)0.0039 (6)−0.0014 (6)
C150.0177 (7)0.0150 (7)0.0128 (6)−0.0004 (6)0.0061 (5)−0.0010 (6)
C160.0165 (7)0.0333 (9)0.0187 (7)−0.0039 (7)0.0071 (5)−0.0034 (7)
C170.0151 (6)0.0130 (6)0.0129 (7)0.0003 (6)0.0046 (5)0.0003 (6)
C180.0274 (8)0.0150 (7)0.0144 (7)−0.0007 (6)0.0060 (6)0.0012 (6)
C190.0307 (8)0.0195 (8)0.0131 (7)−0.0020 (7)0.0064 (6)0.0019 (6)
C200.0154 (6)0.0182 (7)0.0132 (7)−0.0009 (6)0.0050 (5)−0.0014 (6)
C210.0183 (7)0.0250 (8)0.0133 (7)−0.0040 (6)0.0049 (6)−0.0035 (6)
C220.0410 (10)0.0262 (9)0.0179 (8)−0.0116 (8)0.0085 (7)−0.0057 (7)
C230.0201 (7)0.0265 (8)0.0134 (7)−0.0044 (7)0.0039 (5)−0.0033 (6)
C240.0239 (7)0.0236 (8)0.0167 (7)−0.0010 (6)0.0076 (6)−0.0023 (6)
C250.0399 (10)0.0626 (15)0.0185 (9)−0.0212 (11)0.0092 (7)−0.0084 (9)

Geometric parameters (Å, °)

O1—C241.3425 (19)C12—C131.536 (2)
O1—C231.4491 (18)C12—H121.0000
O2—C241.198 (2)C13—C141.538 (2)
O3—C91.4247 (19)C13—H13C0.9900
O3—C81.4388 (18)C13—H13D0.9900
C1—C21.501 (2)C14—C151.532 (2)
C1—C71.516 (2)C14—H14C0.9900
C1—H1C0.9900C14—H14D0.9900
C1—H1D0.9900C15—C161.5425 (19)
C2—C31.509 (2)C15—C171.545 (2)
C2—C71.524 (2)C15—C201.5525 (19)
C2—H21.0000C16—H16D0.9800
C3—C41.533 (3)C16—H16E0.9800
C3—H3C0.9900C16—H16F0.9800
C3—H3D0.9900C17—C181.530 (2)
C4—C51.549 (2)C17—H171.0000
C4—H4C0.9900C18—C191.551 (2)
C4—H4D0.9900C18—H18E0.9900
C5—C61.532 (2)C18—H18F0.9900
C5—C71.535 (2)C19—C201.559 (2)
C5—C121.5562 (19)C19—H19C0.9900
C6—H6D0.9800C19—H19D0.9900
C6—H6E0.9800C20—C211.540 (2)
C6—H6F0.9800C20—H201.0000
C7—C81.507 (2)C21—C231.523 (2)
C8—C101.520 (2)C21—C221.536 (3)
C8—H81.0000C21—H211.0000
C9—H9D0.9800C22—H22A0.9800
C9—H9E0.9800C22—H22B0.9800
C9—H9F0.9800C22—H22C0.9800
C10—C111.527 (2)C23—H23D0.9900
C10—H10C0.9900C23—H23E0.9900
C10—H10D0.9900C24—C251.503 (2)
C11—C171.5279 (19)C25—H25D0.9800
C11—C121.542 (2)C25—H25E0.9800
C11—H111.0000C25—H25F0.9800
C24—O1—C23116.28 (12)C12—C13—H13C109.0
C9—O3—C8113.69 (12)C14—C13—H13C109.0
C2—C1—C760.67 (10)C12—C13—H13D109.0
C2—C1—H1C117.7C14—C13—H13D109.0
C7—C1—H1C117.7H13C—C13—H13D107.8
C2—C1—H1D117.7C15—C14—C13110.86 (13)
C7—C1—H1D117.7C15—C14—H14C109.5
H1C—C1—H1D114.8C13—C14—H14C109.5
C1—C2—C3116.65 (16)C15—C14—H14D109.5
C1—C2—C760.16 (10)C13—C14—H14D109.5
C3—C2—C7108.47 (15)H14C—C14—H14D108.1
C1—C2—H2119.1C14—C15—C16110.98 (14)
C3—C2—H2119.1C14—C15—C17107.23 (12)
C7—C2—H2119.1C16—C15—C17112.21 (13)
C2—C3—C4104.22 (16)C14—C15—C20116.41 (13)
C2—C3—H3C110.9C16—C15—C20109.75 (12)
C4—C3—H3C110.9C17—C15—C2099.78 (11)
C2—C3—H3D110.9C15—C16—H16D109.5
C4—C3—H3D110.9C15—C16—H16E109.5
H3C—C3—H3D108.9H16D—C16—H16E109.5
C3—C4—C5106.63 (14)C15—C16—H16F109.5
C3—C4—H4C110.4H16D—C16—H16F109.5
C5—C4—H4C110.4H16E—C16—H16F109.5
C3—C4—H4D110.4C11—C17—C18118.76 (13)
C5—C4—H4D110.4C11—C17—C15114.60 (12)
H4C—C4—H4D108.6C18—C17—C15104.30 (11)
C6—C5—C7112.04 (14)C11—C17—H17106.1
C6—C5—C4111.19 (15)C18—C17—H17106.1
C7—C5—C4103.00 (12)C15—C17—H17106.1
C6—C5—C12112.47 (13)C17—C18—C19103.31 (13)
C7—C5—C12108.54 (12)C17—C18—H18E111.1
C4—C5—C12109.15 (14)C19—C18—H18E111.1
C5—C6—H6D109.5C17—C18—H18F111.1
C5—C6—H6E109.5C19—C18—H18F111.1
H6D—C6—H6E109.5H18E—C18—H18F109.1
C5—C6—H6F109.5C18—C19—C20106.99 (13)
H6D—C6—H6F109.5C18—C19—H19C110.3
H6E—C6—H6F109.5C20—C19—H19C110.3
C8—C7—C1118.20 (14)C18—C19—H19D110.3
C8—C7—C2120.24 (14)C20—C19—H19D110.3
C1—C7—C259.17 (10)H19C—C19—H19D108.6
C8—C7—C5119.34 (12)C21—C20—C15118.22 (12)
C1—C7—C5117.30 (14)C21—C20—C19112.44 (13)
C2—C7—C5107.80 (13)C15—C20—C19103.36 (12)
O3—C8—C7113.39 (13)C21—C20—H20107.4
O3—C8—C10105.61 (12)C15—C20—H20107.4
C7—C8—C10110.70 (13)C19—C20—H20107.4
O3—C8—H8109.0C23—C21—C22109.58 (14)
C7—C8—H8109.0C23—C21—C20108.70 (12)
C10—C8—H8109.0C22—C21—C20113.40 (14)
O3—C9—H9D109.5C23—C21—H21108.3
O3—C9—H9E109.5C22—C21—H21108.3
H9D—C9—H9E109.5C20—C21—H21108.3
O3—C9—H9F109.5C21—C22—H22A109.5
H9D—C9—H9F109.5C21—C22—H22B109.5
H9E—C9—H9F109.5H22A—C22—H22B109.5
C8—C10—C11112.28 (12)C21—C22—H22C109.5
C8—C10—H10C109.1H22A—C22—H22C109.5
C11—C10—H10C109.1H22B—C22—H22C109.5
C8—C10—H10D109.1O1—C23—C21107.87 (12)
C11—C10—H10D109.1O1—C23—H23D110.1
H10C—C10—H10D107.9C21—C23—H23D110.1
C10—C11—C17111.29 (12)O1—C23—H23E110.1
C10—C11—C12110.33 (11)C21—C23—H23E110.1
C17—C11—C12108.11 (12)H23D—C23—H23E108.4
C10—C11—H11109.0O2—C24—O1123.80 (15)
C17—C11—H11109.0O2—C24—C25124.99 (15)
C12—C11—H11109.0O1—C24—C25111.21 (14)
C13—C12—C11110.47 (12)C24—C25—H25D109.5
C13—C12—C5112.33 (13)C24—C25—H25E109.5
C11—C12—C5113.93 (13)H25D—C25—H25E109.5
C13—C12—H12106.5C24—C25—H25F109.5
C11—C12—H12106.5H25D—C25—H25F109.5
C5—C12—H12106.5H25E—C25—H25F109.5
C12—C13—C14112.90 (14)
C7—C1—C2—C3−96.93 (17)C4—C5—C12—C1373.88 (17)
C1—C2—C3—C447.2 (2)C6—C5—C12—C1176.57 (17)
C7—C2—C3—C4−18.01 (19)C7—C5—C12—C11−47.97 (17)
C2—C3—C4—C530.41 (18)C4—C5—C12—C11−159.54 (13)
C3—C4—C5—C6−150.84 (15)C11—C12—C13—C1455.86 (19)
C3—C4—C5—C7−30.67 (17)C5—C12—C13—C14−175.72 (14)
C3—C4—C5—C1284.52 (16)C12—C13—C14—C15−56.96 (19)
C2—C1—C7—C8−110.21 (16)C13—C14—C15—C16−67.31 (17)
C2—C1—C7—C595.32 (16)C13—C14—C15—C1755.57 (16)
C1—C2—C7—C8106.81 (16)C13—C14—C15—C20166.22 (13)
C3—C2—C7—C8−142.48 (15)C10—C11—C17—C18−55.54 (16)
C3—C2—C7—C1110.71 (16)C12—C11—C17—C18−176.85 (13)
C1—C2—C7—C5−111.68 (14)C10—C11—C17—C15−179.67 (12)
C3—C2—C7—C5−0.96 (18)C12—C11—C17—C1559.02 (15)
C6—C5—C7—C8−79.26 (17)C14—C15—C17—C11−59.41 (16)
C4—C5—C7—C8161.16 (15)C16—C15—C17—C1162.70 (17)
C12—C5—C7—C845.53 (18)C20—C15—C17—C11178.85 (12)
C6—C5—C7—C174.92 (18)C14—C15—C17—C18169.08 (12)
C4—C5—C7—C1−44.66 (17)C16—C15—C17—C18−68.81 (15)
C12—C5—C7—C1−160.29 (13)C20—C15—C17—C1847.34 (14)
C6—C5—C7—C2138.82 (14)C11—C17—C18—C19−163.91 (12)
C4—C5—C7—C219.24 (16)C15—C17—C18—C19−34.87 (15)
C12—C5—C7—C2−96.40 (14)C17—C18—C19—C208.70 (17)
C9—O3—C8—C765.98 (17)C14—C15—C20—C2179.65 (17)
C9—O3—C8—C10−172.64 (14)C16—C15—C20—C21−47.44 (19)
C1—C7—C8—O3−84.03 (16)C17—C15—C20—C21−165.44 (13)
C2—C7—C8—O3−152.90 (13)C14—C15—C20—C19−155.41 (14)
C5—C7—C8—O369.91 (17)C16—C15—C20—C1977.50 (16)
C1—C7—C8—C10157.49 (13)C17—C15—C20—C19−40.50 (14)
C2—C7—C8—C1088.62 (16)C18—C19—C20—C21148.82 (13)
C5—C7—C8—C10−48.57 (18)C18—C19—C20—C1520.22 (16)
O3—C8—C10—C11−70.54 (16)C15—C20—C21—C23177.98 (14)
C7—C8—C10—C1152.56 (16)C19—C20—C21—C2357.63 (17)
C8—C10—C11—C17−177.44 (12)C15—C20—C21—C22−59.89 (19)
C8—C10—C11—C12−57.44 (16)C19—C20—C21—C22179.76 (15)
C10—C11—C12—C13−176.47 (13)C24—O1—C23—C21−174.41 (14)
C17—C11—C12—C13−54.57 (16)C22—C21—C23—O159.70 (18)
C10—C11—C12—C555.99 (16)C20—C21—C23—O1−175.88 (13)
C17—C11—C12—C5177.89 (12)C23—O1—C24—O21.3 (3)
C6—C5—C12—C13−50.0 (2)C23—O1—C24—C25−179.22 (17)
C7—C5—C12—C13−174.54 (13)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2534).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–211.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ketuly, K. A. A., Hadi, A. H. & Ng, S. W. (2009). Acta Cryst. E65, o1125. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

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