The synthesis and crystal structure analysis
via X-ray diffraction of the title compound, C
20H
24O
4, (I), are described. The title compound is an androstadione bearing a diene in the
A and
B rings [Krause & Thorand (1999).
Inorg. Chim. Acta,
296, 1-11]. The diene conjugates with the carbonyl group. Intermolecular H
O contacts (2.53 and 2.64 Å; C-H
O angles 161 and 158°) indicate hydrogen bonds.
Supporting information
CCDC reference: 150749
Data collection: Nonius KappaCCD software; 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); software used to prepare material for publication: SHELXL97.
Crystal data top
C20H24O4 | Dx = 1.266 Mg m−3 |
Mr = 328.39 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 10662 reflections |
a = 9.7567 (3) Å | θ = 3.1–27.5° |
b = 10.3440 (3) Å | µ = 0.09 mm−1 |
c = 17.0684 (6) Å | T = 291 K |
V = 1722.60 (9) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.12 × 0.12 mm |
F(000) = 704 | |
Data collection top
Nonius KappaCCD diffractometer | 1217 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 27.5°, θmin = 3.1° |
Detector resolution: 10 vertical, 18 horizontal pixels mm-1 | h = −12→12 |
Method: 208 frames via ω–rotation (Δω = 1°) at different κ
values and two times 30 s per frame scans | k = −13→13 |
10662 measured reflections | l = −22→22 |
2205 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.035 | Calculated w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max = 0.001 |
S = 0.93 | Δρmax = 0.10 e Å−3 |
2205 reflections | Δρmin = −0.11 e Å−3 |
220 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0064 (13) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.4 (14) |
Special details top
Experimental. The data collection covered almost the whole sphere of reciprocal space. The
crystal to detector distance was 2.8 cm. Crystal decay was monitored by
repeating the initial frames at the end of data collection. Analysing the
duplicate reflections there was no indication for any decay. |
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 | |
O1 | 0.0499 (2) | −0.1526 (2) | −0.28079 (11) | 0.0938 (6) | |
O2 | 0.25114 (13) | 0.03781 (12) | 0.05679 (8) | 0.0530 (4) | |
O3 | 0.0222 (2) | 0.0794 (2) | 0.33335 (11) | 0.1062 (7) | |
O4 | 0.30436 (16) | 0.24636 (16) | 0.03861 (11) | 0.0809 (6) | |
C1 | −0.0406 (2) | −0.1870 (2) | −0.15573 (15) | 0.0626 (6) | |
H1 | −0.0783 | −0.2659 | −0.1705 | 0.075* | |
C2 | 0.0377 (3) | −0.1165 (2) | −0.21280 (16) | 0.0659 (7) | |
C3 | 0.0980 (2) | 0.0097 (2) | −0.18597 (14) | 0.0661 (7) | |
H3A | 0.0337 | 0.0789 | −0.1971 | 0.079* | |
H3B | 0.1812 | 0.0267 | −0.2153 | 0.079* | |
C4 | 0.1307 (2) | 0.0097 (2) | −0.09894 (13) | 0.0550 (6) | |
H4A | 0.1641 | 0.0943 | −0.0836 | 0.066* | |
H4B | 0.2024 | −0.0529 | −0.0884 | 0.066* | |
C5 | −0.0624 (2) | −0.1452 (2) | −0.08219 (14) | 0.0526 (6) | |
C6 | −0.1586 (2) | −0.2105 (2) | −0.03095 (16) | 0.0690 (7) | |
H6 | −0.1987 | −0.2870 | −0.0481 | 0.083* | |
C7 | −0.1918 (2) | −0.1659 (2) | 0.03931 (16) | 0.0664 (7) | |
H7 | −0.2606 | −0.2074 | 0.0674 | 0.080* | |
C8 | −0.1225 (2) | −0.0512 (2) | 0.07488 (12) | 0.0495 (5) | |
H8 | −0.1756 | 0.0259 | 0.0611 | 0.059* | |
C9 | 0.02192 (19) | −0.03745 (18) | 0.03805 (12) | 0.0434 (5) | |
H9 | 0.0695 | −0.1196 | 0.0469 | 0.052* | |
C10 | 0.00343 (19) | −0.02388 (18) | −0.05079 (12) | 0.0468 (5) | |
H10 | −0.0624 | 0.0464 | −0.0590 | 0.056* | |
C11 | 0.10926 (19) | 0.0682 (2) | 0.07661 (12) | 0.0479 (5) | |
H11 | 0.0843 | 0.1531 | 0.0556 | 0.057* | |
C12 | 0.1037 (2) | 0.0705 (2) | 0.16567 (12) | 0.0536 (6) | |
H12A | 0.1465 | 0.1492 | 0.1845 | 0.064* | |
H12B | 0.1554 | −0.0022 | 0.1861 | 0.064* | |
C13 | −0.0416 (2) | 0.0639 (2) | 0.19599 (12) | 0.0516 (5) | |
C14 | −0.1107 (2) | −0.0569 (2) | 0.16349 (12) | 0.0516 (6) | |
H14 | −0.0491 | −0.1291 | 0.1752 | 0.062* | |
C15 | −0.2374 (2) | −0.0756 (2) | 0.21578 (14) | 0.0710 (7) | |
H15A | −0.2688 | −0.1645 | 0.2147 | 0.085* | |
H15B | −0.3118 | −0.0192 | 0.1998 | 0.085* | |
C16 | −0.1831 (3) | −0.0385 (3) | 0.29727 (14) | 0.0737 (7) | |
H16A | −0.2512 | 0.0110 | 0.3258 | 0.088* | |
H16B | −0.1609 | −0.1153 | 0.3273 | 0.088* | |
C17 | −0.0565 (3) | 0.0416 (3) | 0.28346 (16) | 0.0683 (7) | |
C18 | −0.1217 (3) | 0.1900 (2) | 0.17902 (14) | 0.0654 (7) | |
H18A | −0.2132 | 0.1824 | 0.1992 | 0.098* | |
H18B | −0.1253 | 0.2043 | 0.1235 | 0.098* | |
H18C | −0.0763 | 0.2614 | 0.2038 | 0.098* | |
C19 | 0.3388 (2) | 0.1352 (2) | 0.04178 (13) | 0.0564 (6) | |
C20 | 0.4796 (2) | 0.0836 (3) | 0.02874 (16) | 0.0764 (8) | |
H20A | 0.4824 | 0.0374 | −0.0200 | 0.115* | |
H20B | 0.5035 | 0.0262 | 0.0708 | 0.115* | |
H20C | 0.5437 | 0.1540 | 0.0271 | 0.115* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.1054 (15) | 0.1174 (15) | 0.0587 (13) | 0.0056 (13) | −0.0018 (11) | −0.0204 (12) |
O2 | 0.0382 (7) | 0.0515 (8) | 0.0695 (10) | −0.0067 (8) | 0.0041 (7) | 0.0025 (8) |
O3 | 0.1049 (15) | 0.157 (2) | 0.0567 (12) | −0.0196 (15) | −0.0039 (12) | −0.0003 (13) |
O4 | 0.0693 (11) | 0.0572 (11) | 0.1162 (16) | −0.0161 (9) | −0.0030 (11) | 0.0193 (11) |
C1 | 0.0621 (14) | 0.0562 (14) | 0.0695 (17) | 0.0016 (12) | −0.0059 (14) | −0.0153 (14) |
C2 | 0.0632 (16) | 0.0779 (17) | 0.0567 (18) | 0.0220 (14) | −0.0069 (15) | −0.0073 (15) |
C3 | 0.0649 (14) | 0.0786 (18) | 0.0549 (16) | 0.0060 (14) | 0.0054 (12) | 0.0034 (12) |
C4 | 0.0528 (13) | 0.0560 (13) | 0.0563 (15) | 0.0011 (11) | 0.0018 (11) | 0.0000 (10) |
C5 | 0.0441 (13) | 0.0488 (12) | 0.0648 (16) | 0.0038 (11) | −0.0064 (12) | −0.0020 (12) |
C6 | 0.0671 (16) | 0.0586 (14) | 0.081 (2) | −0.0195 (14) | −0.0009 (16) | −0.0100 (14) |
C7 | 0.0533 (13) | 0.0662 (16) | 0.0799 (19) | −0.0216 (12) | 0.0087 (14) | −0.0007 (15) |
C8 | 0.0419 (11) | 0.0459 (12) | 0.0607 (15) | −0.0023 (11) | 0.0023 (10) | 0.0033 (11) |
C9 | 0.0393 (10) | 0.0369 (10) | 0.0539 (13) | 0.0014 (9) | −0.0002 (10) | 0.0012 (10) |
C10 | 0.0401 (11) | 0.0449 (11) | 0.0556 (14) | −0.0001 (10) | −0.0033 (10) | −0.0002 (11) |
C11 | 0.0377 (11) | 0.0471 (12) | 0.0588 (15) | −0.0001 (11) | 0.0022 (10) | 0.0024 (11) |
C12 | 0.0516 (13) | 0.0542 (13) | 0.0551 (15) | −0.0021 (12) | −0.0011 (11) | −0.0004 (12) |
C13 | 0.0507 (12) | 0.0525 (13) | 0.0517 (14) | 0.0001 (11) | 0.0041 (11) | 0.0010 (11) |
C14 | 0.0466 (12) | 0.0504 (13) | 0.0577 (15) | 0.0002 (11) | 0.0077 (11) | 0.0083 (12) |
C15 | 0.0634 (15) | 0.0712 (15) | 0.0785 (19) | −0.0028 (14) | 0.0195 (14) | 0.0089 (14) |
C16 | 0.0759 (16) | 0.0771 (16) | 0.0679 (18) | 0.0111 (15) | 0.0234 (14) | 0.0096 (15) |
C17 | 0.0724 (16) | 0.0751 (16) | 0.0573 (17) | 0.0046 (15) | 0.0036 (14) | 0.0012 (15) |
C18 | 0.0702 (15) | 0.0536 (13) | 0.0724 (17) | 0.0095 (12) | 0.0083 (13) | −0.0008 (12) |
C19 | 0.0506 (13) | 0.0657 (16) | 0.0527 (15) | −0.0149 (13) | −0.0002 (12) | 0.0069 (13) |
C20 | 0.0461 (13) | 0.1017 (19) | 0.0815 (18) | −0.0121 (15) | 0.0094 (12) | 0.0049 (16) |
Geometric parameters (Å, º) top
O1—C2 | 1.225 (3) | C9—H9 | 0.9800 |
O2—C19 | 1.346 (2) | C10—H10 | 0.9800 |
O2—C11 | 1.459 (2) | C11—C12 | 1.521 (3) |
O3—C17 | 1.211 (3) | C11—H11 | 0.9800 |
O4—C19 | 1.200 (3) | C12—C13 | 1.511 (3) |
C1—C5 | 1.344 (3) | C12—H12A | 0.9700 |
C1—C2 | 1.437 (3) | C12—H12B | 0.9700 |
C1—H1 | 0.9300 | C13—C17 | 1.518 (3) |
C2—C3 | 1.504 (3) | C13—C18 | 1.548 (3) |
C3—C4 | 1.519 (3) | C13—C14 | 1.524 (3) |
C3—H3A | 0.9700 | C14—C15 | 1.537 (3) |
C3—H3B | 0.9700 | C14—H14 | 0.9800 |
C4—C10 | 1.529 (3) | C15—C16 | 1.537 (3) |
C4—H4A | 0.9700 | C15—H15A | 0.9700 |
C4—H4B | 0.9700 | C15—H15B | 0.9700 |
C5—C6 | 1.449 (3) | C16—C17 | 1.506 (4) |
C5—C10 | 1.508 (3) | C16—H16A | 0.9700 |
C6—C7 | 1.325 (3) | C16—H16B | 0.9700 |
C6—H6 | 0.9300 | C18—H18A | 0.9600 |
C7—C8 | 1.494 (3) | C18—H18B | 0.9600 |
C7—H7 | 0.9300 | C18—H18C | 0.9600 |
C8—C14 | 1.518 (3) | C19—C20 | 1.491 (3) |
C8—C9 | 1.549 (3) | C20—H20A | 0.9600 |
C8—H8 | 0.9800 | C20—H20B | 0.9600 |
C9—C10 | 1.534 (3) | C20—H20C | 0.9600 |
C9—C11 | 1.534 (3) | | |
| | | |
C19—O2—C11 | 119.08 (16) | C12—C11—H11 | 110.1 |
C5—C1—C2 | 123.6 (2) | C9—C11—H11 | 110.1 |
C5—C1—H1 | 118.2 | C11—C12—C13 | 112.01 (17) |
C2—C1—H1 | 118.2 | C11—C12—H12A | 109.2 |
O1—C2—C1 | 122.7 (3) | C13—C12—H12A | 109.2 |
O1—C2—C3 | 121.0 (2) | C11—C12—H12B | 109.2 |
C1—C2—C3 | 116.2 (2) | C13—C12—H12B | 109.2 |
C2—C3—C4 | 112.3 (2) | H12A—C12—H12B | 107.9 |
C2—C3—H3A | 109.1 | C17—C13—C12 | 115.68 (19) |
C4—C3—H3A | 109.1 | C17—C13—C18 | 105.30 (18) |
C2—C3—H3B | 109.1 | C12—C13—C18 | 111.80 (19) |
C4—C3—H3B | 109.1 | C17—C13—C14 | 101.03 (19) |
H3A—C3—H3B | 107.9 | C12—C13—C14 | 109.15 (18) |
C3—C4—C10 | 110.78 (18) | C18—C13—C14 | 113.53 (17) |
C3—C4—H4A | 109.5 | C8—C14—C15 | 121.52 (19) |
C10—C4—H4A | 109.5 | C8—C14—C13 | 111.39 (17) |
C3—C4—H4B | 109.5 | C15—C14—C13 | 104.34 (18) |
C10—C4—H4B | 109.5 | C8—C14—H14 | 106.2 |
H4A—C4—H4B | 108.1 | C15—C14—H14 | 106.2 |
C1—C5—C6 | 121.1 (2) | C13—C14—H14 | 106.2 |
C1—C5—C10 | 122.1 (2) | C14—C15—C16 | 102.52 (18) |
C6—C5—C10 | 116.7 (2) | C14—C15—H15A | 111.3 |
C7—C6—C5 | 122.8 (2) | C16—C15—H15A | 111.3 |
C7—C6—H6 | 118.6 | C14—C15—H15B | 111.3 |
C5—C6—H6 | 118.6 | C16—C15—H15B | 111.3 |
C6—C7—C8 | 122.2 (2) | H15A—C15—H15B | 109.2 |
C6—C7—H7 | 118.9 | C17—C16—C15 | 106.16 (18) |
C8—C7—H7 | 118.9 | C17—C16—H16A | 110.5 |
C14—C8—C7 | 114.11 (18) | C15—C16—H16A | 110.5 |
C14—C8—C9 | 109.83 (17) | C17—C16—H16B | 110.5 |
C7—C8—C9 | 108.64 (17) | C15—C16—H16B | 110.5 |
C14—C8—H8 | 108.0 | H16A—C16—H16B | 108.7 |
C7—C8—H8 | 108.0 | O3—C17—C13 | 125.6 (2) |
C9—C8—H8 | 108.0 | O3—C17—C16 | 126.0 (2) |
C10—C9—C11 | 115.11 (16) | C13—C17—C16 | 108.4 (2) |
C10—C9—C8 | 107.62 (15) | C13—C18—H18A | 109.5 |
C11—C9—C8 | 113.37 (16) | C13—C18—H18B | 109.5 |
C10—C9—H9 | 106.7 | H18A—C18—H18B | 109.5 |
C11—C9—H9 | 106.7 | C13—C18—H18C | 109.5 |
C8—C9—H9 | 106.7 | H18A—C18—H18C | 109.5 |
C9—C10—C5 | 108.98 (16) | H18B—C18—H18C | 109.5 |
C9—C10—C4 | 117.18 (16) | O4—C19—O2 | 123.2 (2) |
C5—C10—C4 | 110.12 (18) | O4—C19—C20 | 126.5 (2) |
C9—C10—H10 | 106.7 | O2—C19—C20 | 110.3 (2) |
C5—C10—H10 | 106.7 | C19—C20—H20A | 109.5 |
C4—C10—H10 | 106.7 | C19—C20—H20B | 109.5 |
O2—C11—C12 | 105.59 (17) | H20A—C20—H20B | 109.5 |
O2—C11—C9 | 105.92 (15) | C19—C20—H20C | 109.5 |
C12—C11—C9 | 114.86 (17) | H20A—C20—H20C | 109.5 |
O2—C11—H11 | 110.1 | H20B—C20—H20C | 109.5 |
| | | |
C5—C1—C2—O1 | −175.7 (2) | C10—C9—C11—C12 | 168.14 (17) |
C5—C1—C2—C3 | 0.7 (3) | C8—C9—C11—C12 | 43.6 (2) |
O1—C2—C3—C4 | −153.6 (2) | O2—C11—C12—C13 | −164.17 (16) |
C1—C2—C3—C4 | 29.9 (3) | C9—C11—C12—C13 | −47.9 (3) |
C2—C3—C4—C10 | −55.8 (2) | C11—C12—C13—C17 | 169.51 (19) |
C2—C1—C5—C6 | 170.7 (2) | C11—C12—C13—C18 | −70.0 (2) |
C2—C1—C5—C10 | −4.9 (3) | C11—C12—C13—C14 | 56.5 (2) |
C1—C5—C6—C7 | −173.9 (2) | C7—C8—C14—C15 | −55.4 (3) |
C10—C5—C6—C7 | 1.9 (3) | C9—C8—C14—C15 | −177.68 (18) |
C5—C6—C7—C8 | −6.1 (4) | C7—C8—C14—C13 | −178.95 (17) |
C6—C7—C8—C14 | −147.6 (2) | C9—C8—C14—C13 | 58.8 (2) |
C6—C7—C8—C9 | −24.7 (3) | C17—C13—C14—C8 | 174.10 (19) |
C14—C8—C9—C10 | −176.59 (16) | C12—C13—C14—C8 | −63.6 (2) |
C7—C8—C9—C10 | 58.0 (2) | C18—C13—C14—C8 | 61.9 (2) |
C14—C8—C9—C11 | −48.1 (2) | C17—C13—C14—C15 | 41.3 (2) |
C7—C8—C9—C11 | −173.56 (17) | C12—C13—C14—C15 | 163.63 (18) |
C11—C9—C10—C5 | 170.16 (16) | C18—C13—C14—C15 | −70.9 (2) |
C8—C9—C10—C5 | −62.36 (19) | C8—C14—C15—C16 | −165.3 (2) |
C11—C9—C10—C4 | 44.3 (2) | C13—C14—C15—C16 | −38.5 (2) |
C8—C9—C10—C4 | 171.80 (16) | C14—C15—C16—C17 | 20.1 (2) |
C1—C5—C10—C9 | −151.3 (2) | C12—C13—C17—O3 | 32.1 (4) |
C6—C5—C10—C9 | 32.9 (2) | C18—C13—C17—O3 | −91.9 (3) |
C1—C5—C10—C4 | −21.4 (3) | C14—C13—C17—O3 | 149.8 (3) |
C6—C5—C10—C4 | 162.76 (18) | C12—C13—C17—C16 | −146.3 (2) |
C3—C4—C10—C9 | 175.74 (17) | C18—C13—C17—C16 | 89.7 (2) |
C3—C4—C10—C5 | 50.5 (2) | C14—C13—C17—C16 | −28.7 (2) |
C19—O2—C11—C12 | −94.8 (2) | C15—C16—C17—O3 | −173.1 (3) |
C19—O2—C11—C9 | 142.98 (17) | C15—C16—C17—C13 | 5.3 (3) |
C10—C9—C11—O2 | −75.75 (19) | C11—O2—C19—O4 | −5.2 (3) |
C8—C9—C11—O2 | 159.74 (16) | C11—O2—C19—C20 | 175.85 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2i | 0.93 | 2.64 | 3.526 (3) | 158 |
C10—H10···O4ii | 0.98 | 2.53 | 3.472 (2) | 161 |
Symmetry codes: (i) x−1/2, −y−1/2, −z; (ii) x−1/2, −y+1/2, −z. |