The title compound, C
18H
21FO
2, (I), is a steroid with a dienone structure and six stereogenic centers. These steroids are substrates for estradiol derivatives with an alkyl chain in the 7α-position [Krause & Thorand (1999).
Inorg. Chim. Acta.
296, 1–11; Uerdingen & Krause (2000).
Tetrahedron,
56, 2799–2804]. The configuration of the 11-position is
S. The diene is in conjugation with the carbonyl group and the latter is involved in a weak intermolecular C—H
O hydrogen bond.
Supporting information
CCDC reference: 159718
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.005 Å
- R factor = 0.042
- wR factor = 0.096
- Data-to-parameter ratio = 7.4
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
STRVAL_01
From the CIF: _refine_ls_abs_structure_Flack -0.800
From the CIF: _refine_ls_abs_structure_Flack_su 1.600
Alert C Flack parameter is too small
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 25.34
From the CIF: _reflns_number_total 1409
Count of symmetry unique reflns 1482
Completeness (_total/calc) 95.07%
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
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.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound, (I), was obtained with 80–90% yield through bromination and
dehydrobromination from 3-acetyl-11-fluoroandrosta-4,6-dien-17-one (Vettel,
1998). It was dissolved in a small amount of dichloromethane and cyclohexane,
and crystals were obtained by vapour diffusion.
H atoms were placed in calculated positions with Uiso constrained to be
1.5Ueq of the carrier atom for the methyl groups and 1.2Ueq
for the remaining positions. The absolute structure could not be determined
reliably and the Friedel reflections were merged before final refinement
because of the large s.u. for the Flack parameter [-0.8 (16)].
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).
Crystal data top
C18H21FO2 | F(000) = 308 |
Mr = 288.35 | Dx = 1.288 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4058 (5) Å | Cell parameters from 3898 reflections |
b = 7.7654 (4) Å | θ = 3.3–25.3° |
c = 10.2125 (6) Å | µ = 0.09 mm−1 |
β = 94.349 (3)° | T = 291 K |
V = 743.77 (7) Å3 | Plate, colourless |
Z = 2 | 0.35 × 0.30 × 0.05 mm |
Data collection top
Nonius KappaCCD diffractometer | 876 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 25.3°, θmin = 3.3° |
Detector resolution: 10 vertical, 18 horizontal pixels mm-1 | h = −11→11 |
206 frames via ω–rotation (Δω=1%) at different κ–angles and two
times 60 s per frame scans | k = 0→9 |
3898 measured reflections | l = 0→12 |
1409 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0429P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
1409 reflections | Δρmax = 0.11 e Å−3 |
190 parameters | Δρmin = −0.14 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.8 (16) |
Crystal data top
C18H21FO2 | V = 743.77 (7) Å3 |
Mr = 288.35 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.4058 (5) Å | µ = 0.09 mm−1 |
b = 7.7654 (4) Å | T = 291 K |
c = 10.2125 (6) Å | 0.35 × 0.30 × 0.05 mm |
β = 94.349 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 876 reflections with I > 2σ(I) |
3898 measured reflections | Rint = 0.042 |
1409 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.096 | Δρmax = 0.11 e Å−3 |
S = 0.99 | Δρmin = −0.14 e Å−3 |
1409 reflections | Absolute structure: Flack (1983) |
190 parameters | Absolute structure parameter: −0.8 (16) |
1 restraint | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'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 | Uiso*/Ueq | |
F1 | 0.5391 (2) | 0.2418 (4) | 0.6004 (2) | 0.0947 (9) | |
O1 | 0.0109 (4) | 0.3391 (5) | 0.9978 (4) | 0.1056 (11) | |
O2 | 1.0462 (2) | 0.4745 (4) | 0.6286 (2) | 0.0814 (10) | |
C1 | 0.3359 (3) | 0.2215 (6) | 0.8491 (3) | 0.0584 (10) | |
H1A | 0.3892 | 0.2069 | 0.9334 | 0.070* | |
H1B | 0.3643 | 0.1306 | 0.7914 | 0.070* | |
C2 | 0.1765 (3) | 0.2049 (5) | 0.8670 (4) | 0.0642 (11) | |
H2A | 0.1245 | 0.1988 | 0.7814 | 0.077* | |
H2B | 0.1596 | 0.0987 | 0.9133 | 0.077* | |
C3 | 0.1217 (4) | 0.3532 (6) | 0.9420 (3) | 0.0683 (12) | |
C4 | 0.1963 (4) | 0.5148 (6) | 0.9382 (3) | 0.0588 (10) | |
H4A | 0.1649 | 0.6061 | 0.9874 | 0.071* | |
C5 | 0.3089 (3) | 0.5403 (5) | 0.8671 (3) | 0.0489 (9) | |
C6 | 0.3690 (3) | 0.7099 (5) | 0.8550 (3) | 0.0586 (11) | |
H6A | 0.3278 | 0.8013 | 0.8971 | 0.070* | |
C7 | 0.4800 (4) | 0.7414 (5) | 0.7867 (3) | 0.0595 (10) | |
H7A | 0.5108 | 0.8547 | 0.7801 | 0.071* | |
C8 | 0.5585 (3) | 0.6031 (5) | 0.7197 (3) | 0.0489 (9) | |
H8A | 0.5194 | 0.5973 | 0.6281 | 0.059* | |
C9 | 0.5331 (3) | 0.4285 (5) | 0.7837 (3) | 0.0450 (9) | |
H9A | 0.5741 | 0.4373 | 0.8746 | 0.054* | |
C10 | 0.3730 (3) | 0.3956 (5) | 0.7914 (3) | 0.0460 (9) | |
H10A | 0.3286 | 0.3997 | 0.7015 | 0.055* | |
C11 | 0.6114 (3) | 0.2810 (5) | 0.7214 (4) | 0.0603 (10) | |
H11A | 0.6079 | 0.1798 | 0.7785 | 0.072* | |
C12 | 0.7677 (4) | 0.3185 (5) | 0.6999 (4) | 0.0617 (10) | |
H12A | 0.8236 | 0.3121 | 0.7835 | 0.074* | |
H12B | 0.8027 | 0.2306 | 0.6430 | 0.074* | |
C13 | 0.7888 (3) | 0.4934 (5) | 0.6394 (3) | 0.0504 (10) | |
C14 | 0.7183 (3) | 0.6309 (5) | 0.7200 (3) | 0.0496 (9) | |
H14A | 0.7564 | 0.6139 | 0.8110 | 0.060* | |
C15 | 0.7808 (4) | 0.8016 (6) | 0.6759 (4) | 0.0777 (13) | |
H15A | 0.7726 | 0.8910 | 0.7413 | 0.093* | |
H15B | 0.7348 | 0.8398 | 0.5928 | 0.093* | |
C16 | 0.9378 (4) | 0.7524 (7) | 0.6625 (4) | 0.0852 (14) | |
H16A | 0.9740 | 0.8112 | 0.5882 | 0.102* | |
H16B | 0.9961 | 0.7840 | 0.7413 | 0.102* | |
C17 | 0.9409 (4) | 0.5606 (7) | 0.6425 (3) | 0.0639 (11) | |
C18 | 0.7380 (3) | 0.4975 (7) | 0.4917 (3) | 0.0828 (15) | |
H18A | 0.7525 | 0.6107 | 0.4573 | 0.124* | |
H18B | 0.6385 | 0.4690 | 0.4809 | 0.124* | |
H18C | 0.7916 | 0.4153 | 0.4452 | 0.124* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0588 (12) | 0.109 (2) | 0.1170 (17) | −0.0086 (14) | 0.0121 (11) | −0.0693 (17) |
O1 | 0.0908 (19) | 0.102 (3) | 0.132 (2) | −0.019 (2) | 0.0631 (16) | −0.009 (2) |
O2 | 0.0479 (14) | 0.114 (3) | 0.0829 (16) | 0.0106 (17) | 0.0068 (11) | 0.0023 (17) |
C1 | 0.055 (2) | 0.047 (3) | 0.074 (2) | −0.004 (2) | 0.0058 (17) | 0.000 (2) |
C2 | 0.057 (2) | 0.055 (3) | 0.082 (2) | −0.009 (2) | 0.0128 (18) | 0.008 (2) |
C3 | 0.063 (2) | 0.079 (4) | 0.064 (2) | 0.001 (3) | 0.0176 (18) | 0.000 (2) |
C4 | 0.059 (2) | 0.055 (3) | 0.063 (2) | −0.003 (2) | 0.0140 (17) | −0.0066 (19) |
C5 | 0.0477 (19) | 0.050 (3) | 0.0487 (18) | 0.0040 (19) | 0.0004 (15) | −0.0009 (17) |
C6 | 0.066 (2) | 0.042 (3) | 0.070 (2) | 0.006 (2) | 0.0178 (19) | −0.005 (2) |
C7 | 0.064 (2) | 0.034 (2) | 0.082 (3) | 0.004 (2) | 0.0132 (19) | 0.004 (2) |
C8 | 0.050 (2) | 0.046 (3) | 0.0508 (18) | 0.0034 (19) | 0.0040 (14) | 0.0039 (18) |
C9 | 0.0473 (19) | 0.039 (3) | 0.0487 (18) | 0.0021 (17) | 0.0029 (14) | −0.0032 (16) |
C10 | 0.0440 (19) | 0.042 (3) | 0.0517 (18) | 0.0012 (17) | 0.0055 (14) | −0.0015 (18) |
C11 | 0.049 (2) | 0.048 (3) | 0.084 (3) | 0.0005 (19) | 0.0055 (18) | −0.011 (2) |
C12 | 0.049 (2) | 0.049 (3) | 0.088 (3) | 0.0054 (19) | 0.0082 (17) | −0.008 (2) |
C13 | 0.0407 (18) | 0.061 (3) | 0.0488 (18) | 0.004 (2) | 0.0019 (14) | −0.0020 (19) |
C14 | 0.054 (2) | 0.043 (3) | 0.0530 (19) | −0.0043 (19) | 0.0057 (15) | 0.0074 (18) |
C15 | 0.073 (3) | 0.065 (3) | 0.098 (3) | −0.004 (2) | 0.019 (2) | 0.017 (2) |
C16 | 0.067 (3) | 0.087 (4) | 0.104 (3) | −0.015 (3) | 0.021 (2) | 0.024 (3) |
C17 | 0.053 (2) | 0.087 (4) | 0.051 (2) | 0.004 (2) | 0.0027 (16) | 0.013 (2) |
C18 | 0.057 (2) | 0.134 (5) | 0.057 (2) | 0.013 (3) | 0.0026 (16) | −0.008 (3) |
Geometric parameters (Å, º) top
F1—C11 | 1.399 (4) | C9—C10 | 1.535 (4) |
O1—C3 | 1.230 (4) | C9—H9A | 0.9800 |
O2—C17 | 1.212 (4) | C10—H10A | 0.9800 |
C1—C10 | 1.526 (5) | C11—C12 | 1.530 (4) |
C1—C2 | 1.529 (4) | C11—H11A | 0.9800 |
C1—H1A | 0.9700 | C12—C13 | 1.512 (5) |
C1—H1B | 0.9700 | C12—H12A | 0.9700 |
C2—C3 | 1.496 (5) | C12—H12B | 0.9700 |
C2—H2A | 0.9700 | C13—C17 | 1.521 (5) |
C2—H2B | 0.9700 | C13—C14 | 1.530 (5) |
C3—C4 | 1.440 (6) | C13—C18 | 1.548 (4) |
C4—C5 | 1.344 (4) | C14—C15 | 1.532 (6) |
C4—H4A | 0.9300 | C14—H14A | 0.9800 |
C5—C6 | 1.442 (5) | C15—C16 | 1.541 (5) |
C5—C10 | 1.515 (5) | C15—H15A | 0.9700 |
C6—C7 | 1.321 (4) | C15—H15B | 0.9700 |
C6—H6A | 0.9300 | C16—C17 | 1.503 (7) |
C7—C8 | 1.498 (5) | C16—H16A | 0.9700 |
C7—H7A | 0.9300 | C16—H16B | 0.9700 |
C8—C14 | 1.518 (4) | C18—H18A | 0.9600 |
C8—C9 | 1.532 (5) | C18—H18B | 0.9600 |
C8—H8A | 0.9800 | C18—H18C | 0.9600 |
C9—C11 | 1.526 (5) | | |
| | | |
C10—C1—C2 | 112.1 (3) | F1—C11—C9 | 108.3 (3) |
C10—C1—H1A | 109.2 | F1—C11—C12 | 108.8 (3) |
C2—C1—H1A | 109.2 | C9—C11—C12 | 114.6 (3) |
C10—C1—H1B | 109.2 | F1—C11—H11A | 108.3 |
C2—C1—H1B | 109.2 | C9—C11—H11A | 108.3 |
H1A—C1—H1B | 107.9 | C12—C11—H11A | 108.3 |
C3—C2—C1 | 112.1 (3) | C13—C12—C11 | 112.8 (3) |
C3—C2—H2A | 109.2 | C13—C12—H12A | 109.0 |
C1—C2—H2A | 109.2 | C11—C12—H12A | 109.0 |
C3—C2—H2B | 109.2 | C13—C12—H12B | 109.0 |
C1—C2—H2B | 109.2 | C11—C12—H12B | 109.0 |
H2A—C2—H2B | 107.9 | H12A—C12—H12B | 107.8 |
O1—C3—C4 | 121.4 (4) | C12—C13—C17 | 116.9 (3) |
O1—C3—C2 | 120.4 (4) | C12—C13—C14 | 109.3 (2) |
C4—C3—C2 | 118.0 (3) | C17—C13—C14 | 101.3 (3) |
C5—C4—C3 | 123.3 (4) | C12—C13—C18 | 112.1 (3) |
C5—C4—H4A | 118.4 | C17—C13—C18 | 103.5 (2) |
C3—C4—H4A | 118.4 | C14—C13—C18 | 113.3 (3) |
C4—C5—C6 | 120.8 (3) | C8—C14—C13 | 111.7 (3) |
C4—C5—C10 | 121.8 (3) | C8—C14—C15 | 121.6 (3) |
C6—C5—C10 | 117.4 (3) | C13—C14—C15 | 104.7 (3) |
C7—C6—C5 | 123.0 (4) | C8—C14—H14A | 105.9 |
C7—C6—H6A | 118.5 | C13—C14—H14A | 105.9 |
C5—C6—H6A | 118.5 | C15—C14—H14A | 105.9 |
C6—C7—C8 | 123.0 (4) | C14—C15—C16 | 101.7 (3) |
C6—C7—H7A | 118.5 | C14—C15—H15A | 111.4 |
C8—C7—H7A | 118.5 | C16—C15—H15A | 111.4 |
C7—C8—C14 | 114.8 (3) | C14—C15—H15B | 111.4 |
C7—C8—C9 | 110.0 (2) | C16—C15—H15B | 111.4 |
C14—C8—C9 | 108.1 (3) | H15A—C15—H15B | 109.3 |
C7—C8—H8A | 107.9 | C17—C16—C15 | 106.7 (4) |
C14—C8—H8A | 107.9 | C17—C16—H16A | 110.4 |
C9—C8—H8A | 107.9 | C15—C16—H16A | 110.4 |
C11—C9—C8 | 113.0 (2) | C17—C16—H16B | 110.4 |
C11—C9—C10 | 113.7 (3) | C15—C16—H16B | 110.4 |
C8—C9—C10 | 110.7 (3) | H16A—C16—H16B | 108.6 |
C11—C9—H9A | 106.2 | O2—C17—C16 | 125.9 (4) |
C8—C9—H9A | 106.2 | O2—C17—C13 | 125.7 (5) |
C10—C9—H9A | 106.2 | C16—C17—C13 | 108.3 (3) |
C5—C10—C1 | 110.4 (2) | C13—C18—H18A | 109.5 |
C5—C10—C9 | 109.4 (3) | C13—C18—H18B | 109.5 |
C1—C10—C9 | 114.9 (3) | H18A—C18—H18B | 109.5 |
C5—C10—H10A | 107.3 | C13—C18—H18C | 109.5 |
C1—C10—H10A | 107.3 | H18A—C18—H18C | 109.5 |
C9—C10—H10A | 107.3 | H18B—C18—H18C | 109.5 |
| | | |
C10—C1—C2—C3 | −52.1 (4) | C8—C9—C11—C12 | 46.6 (4) |
C1—C2—C3—O1 | −158.9 (4) | C10—C9—C11—C12 | 174.0 (3) |
C1—C2—C3—C4 | 25.8 (5) | F1—C11—C12—C13 | 75.4 (4) |
O1—C3—C4—C5 | −172.8 (4) | C9—C11—C12—C13 | −46.0 (4) |
C2—C3—C4—C5 | 2.5 (5) | C11—C12—C13—C17 | 166.4 (3) |
C3—C4—C5—C6 | 172.8 (3) | C11—C12—C13—C14 | 52.2 (4) |
C3—C4—C5—C10 | −4.1 (5) | C11—C12—C13—C18 | −74.4 (3) |
C4—C5—C6—C7 | 179.7 (3) | C7—C8—C14—C13 | −174.9 (3) |
C10—C5—C6—C7 | −3.3 (5) | C9—C8—C14—C13 | 62.0 (3) |
C5—C6—C7—C8 | −2.6 (5) | C7—C8—C14—C15 | −50.4 (4) |
C6—C7—C8—C14 | −144.4 (3) | C9—C8—C14—C15 | −173.5 (3) |
C6—C7—C8—C9 | −22.2 (4) | C12—C13—C14—C8 | −62.1 (3) |
C7—C8—C9—C11 | −179.3 (3) | C17—C13—C14—C8 | 173.9 (3) |
C14—C8—C9—C11 | −53.3 (3) | C18—C13—C14—C8 | 63.7 (4) |
C7—C8—C9—C10 | 51.8 (3) | C12—C13—C14—C15 | 164.4 (3) |
C14—C8—C9—C10 | 177.8 (3) | C17—C13—C14—C15 | 40.4 (3) |
C4—C5—C10—C1 | −22.5 (4) | C18—C13—C14—C15 | −69.8 (4) |
C6—C5—C10—C1 | 160.5 (3) | C8—C14—C15—C16 | −167.2 (3) |
C4—C5—C10—C9 | −149.9 (3) | C13—C14—C15—C16 | −39.6 (4) |
C6—C5—C10—C9 | 33.1 (4) | C14—C15—C16—C17 | 23.0 (4) |
C2—C1—C10—C5 | 49.7 (4) | C15—C16—C17—O2 | −179.6 (3) |
C2—C1—C10—C9 | 174.1 (3) | C15—C16—C17—C13 | 1.7 (4) |
C11—C9—C10—C5 | 174.1 (3) | C12—C13—C17—O2 | 37.0 (5) |
C8—C9—C10—C5 | −57.4 (3) | C14—C13—C17—O2 | 155.7 (3) |
C11—C9—C10—C1 | 49.3 (4) | C18—C13—C17—O2 | −86.8 (4) |
C8—C9—C10—C1 | 177.8 (3) | C12—C13—C17—C16 | −144.3 (3) |
C8—C9—C11—F1 | −75.0 (3) | C14—C13—C17—C16 | −25.6 (4) |
C10—C9—C11—F1 | 52.4 (4) | C18—C13—C17—C16 | 91.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O1i | 0.93 | 2.46 | 3.280 (5) | 147 |
Symmetry code: (i) −x, y+1/2, −z+2. |
Experimental details
Crystal data |
Chemical formula | C18H21FO2 |
Mr | 288.35 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 291 |
a, b, c (Å) | 9.4058 (5), 7.7654 (4), 10.2125 (6) |
β (°) | 94.349 (3) |
V (Å3) | 743.77 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.30 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3898, 1409, 876 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.602 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.096, 0.99 |
No. of reflections | 1409 |
No. of parameters | 190 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.14 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.8 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O1i | 0.93 | 2.46 | 3.280 (5) | 147 |
Symmetry code: (i) −x, y+1/2, −z+2. |
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