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Acta Cryst. (2009). E65, o1486    [ doi:10.1107/S1600536809020674 ]

(20S)-22-Acetoxymethyl-6[beta]-methoxy-3[alpha],5-dihydro-3'H-cyclopropa[3[alpha],5]-5[alpha]-pregnane

K. A. Ketuly, A. H. A. Hadi and S. W. Ng

Abstract top

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

Related literature top

For the synthesis and crystal structure of the iodo-substituted steroid, see: Ketuly et al. (2009).

Experimental top

(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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C25H40O3 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
\ (20S)-22-Acetoxymethyl-6β-methoxy-3α,5-dihydro-\ 3'H-cyclopropa[3α,5]-5α-pregnane top
Crystal data top
C25H40O3F(000) = 428
Mr = 388.57Dx = 1.189 Mg m−3
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 mm−1
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 top
Bruker SMART APEX
diffractometer		2550 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 top
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 = 1.05 w = 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 Å−3
1 restraintΔρmin = −0.18 e Å−3
Crystal data top
C25H40O3V = 1085.55 (2) Å3
Mr = 388.57Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.8222 (1) ŵ = 0.08 mm−1
b = 7.6128 (1) ÅT = 100 K
c = 15.2309 (2) Å0.30 × 0.10 × 0.02 mm
β = 107.604 (1)°
Data collection top
Bruker SMART APEX
diffractometer		2550 reflections with I > 2σ(I)
10411 measured reflectionsRint = 0.023
2674 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.092Δρmax = 0.30 e Å−3
S = 1.05Δρmin = −0.18 e Å−3
2674 reflectionsAbsolute structure: ?
258 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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)
Acknowledgements top

We thank the University of Malaya for supporting this study.

references
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