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Acta Cryst. (2009). E65, o1195    [ doi:10.1107/S1600536809014603 ]

3-Iodo-8[beta],9[alpha],14[alpha]-estra-1,3,5(10)-trien-17-one

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

Abstract top

In the title compound, C18H21IO, the cyclohexane ring adopts a chair conformation, whereas the cyclopentane ring and the ten-membered tetraline portions each adopt an envelope conformation. For the five-membered ring, the methine C atom deviates by 0.638 (4) Å (r.m.s. of the four other atoms is 0.005 Å) and for the ten-membered ring, the methine C atom constituting the flap deviates by 0.671 (3) Å (r.m.s. of the other nine atoms is 0.066 Å).

Related literature top

There are only few crystal structure reports of similar compounds; for the methoxyl-substituted derivative, see: Herrmann et al. (2006). For the synthesis of the 3-amino-substituted reagent, see: Conrow & Bernstein (1968).

Experimental top

The reactant, 3-amino-estra-1,3,5(1)-trien-17-one, was synthesized by using a literature procedure (Conrow & Bernstein, 1968). The compound (390 mg) was dissolved in hydrobromic acid (54% w/v). Concentrated sulfuric acid (2 ml) and water (4 ml) were added. The solution was cooled in an ice-bath. Sodium nitrite (147 mg) in water (2 ml) was added followed by the addition of excess potassium iodide (1.02 g) dissolved in water (4 ml).

The solution was filtered and the gummy product collected and dissolved in ether–ethyl acetate. The solvent was removed and the crude product (537 mg) chromatographed on a silica-gel (40 g) column. The compound was eluted by chloroform–ethyl acetate (3:1 v/v). The second fraction (465 mg) was a tan glassy material. This was recrystallized from chloroform, methanol and ethyl acetate to give single crystals.

Refinement top

Hydrogen atoms were placed at calculated positions (C–H 0.95–1.00 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times Ueq(C).

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. Displacement ellipsoid plot (Barbour, 2001) of C18H21IO at the 70% probability level. H atoms are drawn as spheres of arbitrary radius.
3-Iodo-8β,9α,14α-estra-1,3,5(10)-trien-17-one top
Crystal data top
C18H21IOF000 = 760
Mr = 380.25Dx = 1.678 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6954 reflections
a = 9.9636 (2) Åθ = 2.4–28.3º
b = 10.5246 (2) ŵ = 2.12 mm−1
c = 14.3535 (2) ÅT = 100 K
V = 1505.15 (5) Å3Irregular block, colorless
Z = 40.20 × 0.15 × 0.10 mm
Data collection top
Bruker SMART APEX
diffractometer		3452 independent reflections
Radiation source: fine-focus sealed tube3353 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 100 Kθmax = 27.5º
ω scansθmin = 2.4º
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.636, Tmax = 0.746k = −13→13
10547 measured reflectionsl = −18→18
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.018  w = 1/[σ2(Fo2) + (0.0262P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.045(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.47 e Å−3
3452 reflectionsΔρmin = −0.39 e Å−3
181 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1473 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.01 (2)
Crystal data top
C18H21IOV = 1505.15 (5) Å3
Mr = 380.25Z = 4
Orthorhombic, P212121Mo Kα
a = 9.9636 (2) ŵ = 2.12 mm−1
b = 10.5246 (2) ÅT = 100 K
c = 14.3535 (2) Å0.20 × 0.15 × 0.10 mm
Data collection top
Bruker SMART APEX
diffractometer		3452 independent reflections
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		3353 reflections with I > 2σ(I)
Tmin = 0.636, Tmax = 0.746Rint = 0.021
10547 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.045Δρmax = 0.47 e Å−3
S = 1.03Δρmin = −0.39 e Å−3
3452 reflectionsAbsolute structure: Flack (1983), 1473 Friedel pairs
181 parametersFlack parameter: 0.01 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.398911 (14)1.187407 (14)0.171916 (11)0.01746 (5)
O10.05863 (18)0.21965 (16)0.45415 (13)0.0230 (4)
C10.0408 (2)0.3314 (2)0.46921 (16)0.0164 (5)
C2−0.0646 (3)0.3860 (2)0.53518 (19)0.0192 (6)
H2A−0.04920.35570.59960.023*
H2B−0.15580.36040.51550.023*
C3−0.0483 (3)0.5320 (2)0.52963 (18)0.0185 (5)
H3A−0.13620.57550.53330.022*
H3B0.01080.56410.57980.022*
C40.0166 (2)0.5494 (2)0.43324 (16)0.0133 (5)
H4−0.05480.53000.38640.016*
C50.0771 (2)0.6760 (2)0.40501 (15)0.0117 (4)
H50.15660.69300.44560.014*
C6−0.0183 (2)0.7883 (2)0.41237 (16)0.0146 (5)
H6A−0.06060.78910.47480.018*
H6B−0.09030.77990.36520.018*
C70.0573 (2)0.9119 (2)0.39693 (17)0.0143 (5)
H7A0.10710.93380.45440.017*
H7B−0.00810.98080.38480.017*
C80.1562 (2)0.9044 (2)0.31532 (16)0.0126 (5)
C90.2161 (2)1.0179 (2)0.28663 (17)0.0139 (5)
H90.19501.09520.31750.017*
C100.3063 (2)1.0176 (2)0.21308 (17)0.0144 (5)
C110.3359 (2)0.9057 (2)0.16548 (19)0.0169 (5)
H110.39580.90610.11400.020*
C120.2762 (2)0.7942 (2)0.19494 (15)0.0168 (5)
H120.29620.71760.16280.020*
C130.1868 (2)0.7901 (2)0.27081 (16)0.0129 (5)
C140.1260 (2)0.6646 (2)0.30264 (15)0.0128 (5)
H140.04430.65030.26360.015*
C150.2184 (3)0.5497 (2)0.28692 (18)0.0176 (5)
H15A0.23410.53990.21920.021*
H15B0.30610.56700.31670.021*
C160.1628 (2)0.4241 (2)0.32552 (19)0.0162 (5)
H16A0.08490.39670.28760.019*
H16B0.23260.35740.32150.019*
C170.1194 (2)0.4408 (2)0.42701 (15)0.0133 (5)
C180.2423 (2)0.4595 (2)0.49110 (18)0.0191 (5)
H18A0.29910.52740.46610.029*
H18B0.29390.38040.49410.029*
H18C0.21190.48270.55380.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01720 (7)0.01525 (7)0.01993 (8)−0.00127 (6)0.00318 (6)0.00288 (7)
O10.0296 (10)0.0126 (9)0.0269 (10)−0.0016 (7)0.0042 (8)−0.0013 (7)
C10.0185 (11)0.0152 (12)0.0155 (11)−0.0005 (10)−0.0024 (9)0.0012 (10)
C20.0233 (13)0.0143 (12)0.0199 (13)−0.0021 (10)0.0064 (10)0.0013 (10)
C30.0237 (12)0.0134 (12)0.0185 (12)−0.0014 (9)0.0064 (10)−0.0010 (10)
C40.0161 (11)0.0123 (11)0.0115 (11)−0.0015 (9)0.0001 (9)−0.0008 (9)
C50.0114 (10)0.0119 (10)0.0118 (10)0.0016 (9)−0.0003 (8)−0.0013 (9)
C60.0148 (11)0.0152 (12)0.0138 (11)0.0014 (9)0.0031 (9)−0.0015 (9)
C70.0186 (12)0.0119 (11)0.0124 (11)0.0014 (9)0.0029 (9)−0.0016 (9)
C80.0114 (9)0.0138 (11)0.0125 (12)0.0017 (8)−0.0034 (9)0.0005 (10)
C90.0148 (12)0.0131 (11)0.0137 (11)0.0008 (9)−0.0031 (9)−0.0006 (9)
C100.0124 (10)0.0152 (11)0.0158 (11)0.0009 (9)−0.0013 (9)0.0014 (9)
C110.0182 (11)0.0187 (11)0.0137 (11)0.0004 (9)0.0030 (10)−0.0012 (11)
C120.0221 (12)0.0153 (12)0.0131 (11)0.0011 (9)0.0023 (9)−0.0023 (9)
C130.0126 (10)0.0126 (12)0.0135 (11)−0.0009 (9)−0.0020 (8)0.0016 (9)
C140.0141 (11)0.0125 (11)0.0116 (11)−0.0012 (8)0.0010 (8)−0.0008 (8)
C150.0232 (13)0.0132 (12)0.0165 (12)0.0008 (10)0.0080 (10)−0.0022 (10)
C160.0210 (11)0.0095 (10)0.0181 (11)−0.0012 (9)0.0067 (11)−0.0038 (12)
C170.0161 (12)0.0115 (10)0.0124 (11)−0.0023 (10)0.0002 (9)−0.0016 (9)
C180.0185 (11)0.0137 (11)0.0250 (13)0.0014 (9)−0.0075 (10)0.0028 (11)
Geometric parameters (Å, °) top
I1—C102.097 (2)C8—C91.397 (3)
O1—C11.209 (3)C8—C131.396 (3)
C1—C21.526 (3)C9—C101.386 (3)
C1—C171.518 (3)C9—H90.9500
C2—C31.547 (3)C10—C111.393 (3)
C2—H2A0.9900C11—C121.382 (3)
C2—H2B0.9900C11—H110.9500
C3—C41.538 (3)C12—C131.407 (3)
C3—H3A0.9900C12—H120.9500
C3—H3B0.9900C13—C141.524 (3)
C4—C51.517 (3)C14—C151.537 (3)
C4—C171.539 (3)C14—H141.0000
C4—H41.0000C15—C161.537 (3)
C5—C61.520 (3)C15—H15A0.9900
C5—C141.553 (3)C15—H15B0.9900
C5—H51.0000C16—C171.529 (3)
C6—C71.520 (3)C16—H16A0.9900
C6—H6A0.9900C16—H16B0.9900
C6—H6B0.9900C17—C181.544 (3)
C7—C81.533 (3)C18—H18A0.9800
C7—H7A0.9900C18—H18B0.9800
C7—H7B0.9900C18—H18C0.9800
O1—C1—C2125.3 (2)C8—C9—H9120.0
O1—C1—C17126.2 (2)C9—C10—C11120.9 (2)
C2—C1—C17108.5 (2)C9—C10—I1119.85 (18)
C1—C2—C3105.6 (2)C11—C10—I1119.26 (18)
C1—C2—H2A110.6C12—C11—C10118.4 (2)
C3—C2—H2A110.6C12—C11—H11120.8
C1—C2—H2B110.6C10—C11—H11120.8
C3—C2—H2B110.6C11—C12—C13122.3 (2)
H2A—C2—H2B108.7C11—C12—H12118.8
C4—C3—C2102.1 (2)C13—C12—H12118.8
C4—C3—H3A111.4C8—C13—C12117.8 (2)
C2—C3—H3A111.4C8—C13—C14121.5 (2)
C4—C3—H3B111.4C12—C13—C14120.7 (2)
C2—C3—H3B111.4C13—C14—C15113.55 (18)
H3A—C3—H3B109.2C13—C14—C5109.98 (19)
C5—C4—C3120.79 (19)C15—C14—C5112.83 (19)
C5—C4—C17111.87 (18)C13—C14—H14106.7
C3—C4—C17104.08 (19)C15—C14—H14106.7
C5—C4—H4106.4C5—C14—H14106.7
C3—C4—H4106.4C16—C15—C14114.06 (19)
C17—C4—H4106.4C16—C15—H15A108.7
C4—C5—C6114.57 (18)C14—C15—H15A108.7
C4—C5—C14108.02 (18)C16—C15—H15B108.7
C6—C5—C14108.79 (18)C14—C15—H15B108.7
C4—C5—H5108.4H15A—C15—H15B107.6
C6—C5—H5108.4C17—C16—C15110.27 (19)
C14—C5—H5108.4C17—C16—H16A109.6
C5—C6—C7110.23 (18)C15—C16—H16A109.6
C5—C6—H6A109.6C17—C16—H16B109.6
C7—C6—H6A109.6C15—C16—H16B109.6
C5—C6—H6B109.6H16A—C16—H16B108.1
C7—C6—H6B109.6C1—C17—C16116.02 (19)
H6A—C6—H6B108.1C1—C17—C4101.32 (18)
C6—C7—C8112.71 (19)C16—C17—C4109.19 (19)
C6—C7—H7A109.1C1—C17—C18105.57 (19)
C8—C7—H7A109.1C16—C17—C18111.01 (19)
C6—C7—H7B109.1C4—C17—C18113.48 (19)
C8—C7—H7B109.1C17—C18—H18A109.5
H7A—C7—H7B107.8C17—C18—H18B109.5
C9—C8—C13120.6 (2)H18A—C18—H18B109.5
C9—C8—C7117.1 (2)C17—C18—H18C109.5
C13—C8—C7122.3 (2)H18A—C18—H18C109.5
C10—C9—C8119.9 (2)H18B—C18—H18C109.5
C10—C9—H9120.0
O1—C1—C2—C3−179.5 (2)C8—C13—C14—C15−148.7 (2)
C17—C1—C2—C31.1 (3)C12—C13—C14—C1531.4 (3)
C1—C2—C3—C424.3 (3)C8—C13—C14—C5−21.2 (3)
C2—C3—C4—C5−167.6 (2)C12—C13—C14—C5158.9 (2)
C2—C3—C4—C17−41.0 (2)C4—C5—C14—C13179.61 (18)
C3—C4—C5—C6−55.3 (3)C6—C5—C14—C1354.7 (2)
C17—C4—C5—C6−178.27 (19)C4—C5—C14—C15−52.5 (2)
C3—C4—C5—C14−176.7 (2)C6—C5—C14—C15−177.42 (19)
C17—C4—C5—C1460.3 (2)C13—C14—C15—C16175.6 (2)
C4—C5—C6—C7171.42 (19)C5—C14—C15—C1649.6 (3)
C14—C5—C6—C7−67.6 (2)C14—C15—C16—C17−50.9 (3)
C5—C6—C7—C843.4 (3)O1—C1—C17—C1636.6 (3)
C6—C7—C8—C9170.8 (2)C2—C1—C17—C16−144.0 (2)
C6—C7—C8—C13−9.4 (3)O1—C1—C17—C4154.7 (2)
C13—C8—C9—C100.3 (3)C2—C1—C17—C4−25.9 (2)
C7—C8—C9—C10−179.9 (2)O1—C1—C17—C18−86.8 (3)
C8—C9—C10—C111.6 (4)C2—C1—C17—C1892.6 (2)
C8—C9—C10—I1−178.76 (17)C15—C16—C17—C1169.9 (2)
C9—C10—C11—C12−1.8 (4)C15—C16—C17—C456.3 (2)
I1—C10—C11—C12178.55 (18)C15—C16—C17—C18−69.6 (2)
C10—C11—C12—C130.2 (4)C5—C4—C17—C1173.37 (18)
C9—C8—C13—C12−1.9 (3)C3—C4—C17—C141.4 (2)
C7—C8—C13—C12178.3 (2)C5—C4—C17—C16−63.7 (2)
C9—C8—C13—C14178.2 (2)C3—C4—C17—C16164.26 (19)
C7—C8—C13—C14−1.6 (3)C5—C4—C17—C1860.7 (3)
C11—C12—C13—C81.7 (4)C3—C4—C17—C18−71.3 (2)
C11—C12—C13—C14−178.4 (2)
Acknowledgements top

We thank the University of Malaya for supporting this study.

references
References top

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

Westrip, S. P. (2009). publCIF. In preparation.