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In the title compound, C23H34O4, which is an inter­mediate in the synthesis of pregnane derivatives with a modified skeleton that show potent abortion-inducing activity, the conformation of ring B is close to half-chair due to the presence of both the C=C double bond and the axial 5[beta]-methyl group. Rings A and C have conformations close to chair, while ring D has a twisted conformation around the bridgehead C-C bond. Mol­ecules are hydrogen bonded via the hydroxyl and acet­oxy groups into infinite chains. Quantum-mechanical ab initio Roothan Hartree-Fock calculations show that crystal packing might be responsible for the low values of the angles between rings A and B, and between ring A and rings C and D, as well as for a different steric position of the methyl ketone side chain compared to the geometry of the free mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109010233/sk3302sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109010233/sk3302Isup2.hkl
Contains datablock I

CCDC reference: 735124

Comment top

The Westphalen rearrangement is a well known reaction in steroid chemistry for the synthesis of olefinic 19-norsteroids. This classical transformation involves migration of the 10β-methyl group to the 5β-position with the formation of 5β-methyl-Δ9(10)-19-nor derivatives (Kamernitskii et al., 1987).

As part of our current interest on the application of bismuth(III) salts to the chemistry of epoxysteroids (Pinto et al., 2006, 2007; Pinto, Salvador, Le Roux et al., 2008), we have recently reported a catalytic process for the preparation of Westphalen-type compounds (Pinto, Salvador, Le Roux et al., 2008). Several 5β-methyl-Δ9(10)-19-norsteroids from the cholestane, androstane and pregnane series were prepared by reaction of the corresponding 5β,6β-epoxysteroids in 1,4-dioxane, using a catalytic amount of bismuth trifluoromethanesulfonate (Pinto, Salvador, Le Roux et al., 2008).

Of special interest was the preparation of the title 5β-methyl-Δ9(10)-19-norsteroid, (I). This compound is a pregnane derivative with a modified skeleton, structurally related to the endogenous hormone progesterone. In the last decade, extensive synthetic work developed by Polman and Kasal led to the preparation of analogues of progesterone possessing a 5β-methyl-Δ9(10)-19-nor structure, which have shown potent abortion-inducing activity (Polman & Kasal, 1990, 1991; Kasal et al., 1998). The title compound, (I), can then be seen as an intermediate in the synthesis of this family of compounds. In this communication, we report the molecular structure (I) and compare it with that of the free molecule as given by quantum mechanical ab initio calculation.

The structure of (I) with the corresponding atomic numbering scheme is shown in Fig. 1. This steroid compound is from the pregnane series with a double bond located in ring B at C9C10. The typical C19-methyl group is absent. The acetoxy group at C3 is axial to ring A. The 5β-methyl group on ring B is also in an axial position, whereas the hydroxyl group at C6 is equatorial. The side chain attached to ring D is equatorial.

The angle between the least-squares planes of rings A and B is 19.43 (10)°, while the angle between ring A and rings C and D is 60.37 (6)°. Rings C and D are almost coplanar, as shown by the low value of the angle between their least-squares planes of 7.53 (6)°.

Rings A and ring C have conformations close to chair, as shown by the Cremer & Pople (1975) parameters [for ring A: Q = 0.507 (2)Å, θ = 168.3 (2)° and ϕ = 242.7 (11)°; for ring C: Q = 0.5811 (19)Å, θ = 2.49 (19)° and ϕ = 274 (4)°]. Ring B has a conformation close to half-chair [Q = 0.494 (2)Å, θ = 128.1 (2)° and ϕ = 246.2 (3)°]. RingD has a twisted conformation around the C13—C14 bond, with puckering parameters q2 = 0.457 (2)Å and ϕ2 = 194.4 (3)°, and asymmetry parameters (Duax & Norton, 1975) ΔC2(16) = ΔC2(13,14) = 3.9 (3)°.

Molecules of (I) are hydrogen bonded via the hydroxyl and acetoxy groups into infinite chains running in the [100] direction. Two short intramolecular interactions are present in the molecule: (i) between the 5β-methyl group and the neighbouring O3A atom and (ii) between the C20 carbonyl O atom and one of the H atoms bound to C16.

In order to gain some insight how the crystal packing of (I) might affect the molecular geometry, we have performed a quantum chemical calculation on the equilibrium geometry of the free molecule. These calculations were performed with the computer program GAMESS (Schmidt et al., 1993). A molecular orbital Roothan Hartree–Fock method was used with an extended 6–31 G(d,p) basis set. Tight conditions for convergence of both the self-consistent field cycles and maximum density and energy gradient variations were imposed (10-5 atomic units). The program was run on the Milipeia cluster of UC–LCA (using 16 Opteron cores, 2.2 GHz runing Linux).

The ab initio calculations reproduce well the observed experimental bond length and valency angles of the molecule. All valency angles match the experimental values within 2°. Calculated and experimental bond distances agree within 0.025Å, with the exception of the following bonds: C3–O3A [calculated (calc) = 1.436Å and experimental (exp) = 1.467 (2)Å], C6–O6 [calc = 1.406Å and exp = 1.432 (2)Å] and C20–C21 [calc = 1.514Å and exp = 1.487 (4)Å].

The calculations reproduce well the small angle between the least-squares planes of rings C and D [calc = 8.3° and exp = 7.53 (6)°]. However, the calculated angles between the least-squares planes of the free molecule between rings A and B [calc = 24° and exp = 19.43 (10)°] and between ring A and rings C and D [calc = 71.4° and exp = 60.37 (6)°] differ significantly from those of the molecule in the crystal. These results might be interpreted as a result of a small induced defolding of the molecule due to crystal packing. In addition, the acetoxy side chain is almost perpendicular to ring D in the calculations, but a large tilt is observed in the crystal, as shown by the C13—C17—C20—C21 torsion angle [calc = -92.6° and exp = -70.5 (3)°].

One of the aims of the present study was to gain some insight on the structural differences between the (I) and 5β,6β-epoxy-20-oxopregnan-3β-yl acetate, the starting compound for its preparation, whose structure we have recently reported recently (Pinto, Salvador & Paixão, 2008). This 5β,6β-epoxysteroid possesses a large C19–C10···C13–C18 pseudo-torsion angle of 15.74 (17)°, which indicates a significantly twisted steroid nucleus (Pinto, Salvador & Paixão, 2008).

Interestingly, the similar C5A–C5···C13—C18 pseudo-torsion abgle for the title Westphalen-type compound is much lower, with a value of -0.94 (19)°. Calculated ab initio values also reproduce these findings [22.2° for 5β,6β-epoxy-20-oxopregnan-3β-yl acetate (Pinto, Salvador & Paixão, 2008) and 5.0° for (I)]. Thus, when the 5β,6β-epoxysteroid is converted into 5β-methyl-Δ9(10)-19-norsteroid (I), a strong relief in the twist of steroid nucleus is observed. On other hand, low values for the C19–C10···C13–C18 pseudo-torsion angle are found in the literature for several 5α,6α-epoxysteroids (Hanson, Hitchcock & Nagaratnam, 1999; Hanson, Hitchcock & Kiran, 1999; Litvinovskaya et al., 1995).

These data suggest that important steric factors, such as the above-mentioned change in the torsion of the steroid nucleus, may contribute to explain the differential reactivity observed between 5β,6β-epoxy- and 5α,6α-epoxysteroids, which do not react under the same reaction conditions (Pinto, Salvador, Le Roux et al., 2008), although similar electronic factors are present in both diastereomeric epoxides.

Related literature top

For related literature, see: Cremer & Pople (1975); Duax & Norton (1975); Hanson, Hitchcock & Kiran (1999); Hanson, Hitchcock & Nagaratnam (1999); Kamernitskii et al. (1987); Kasal et al. (1998); Litvinovskaya et al. (1995); Pinto et al. (2006, 2007, 2008a, 2008b); Polman & Kasal (1990, 1991); Schmidt et al. (1993).

Experimental top

The synthesis of 6β-hydroxy-5β-methyl-20-oxo-19-norpregn-9(10)-en-3β-yl acetate, (I), was efficiently accomplished according to the previously reported method of Pinto, Salvador, Le Roux et al. (2008). The product of this reaction was isolated in 52% yield and identified as (I) from MS, IR, one-dimensional and two-dimensional NMR (Pinto, Salvador, Le Roux et al., 2008). Recrystallization from acetone/n-hexane at room temperature gave colourless single crystals suitable for X-ray diffraction analysis.

Refinement top

All H atoms were refined as riding on their parent atoms using SHELXL97 defaults, except for that of the hydroxyl group which had its coordinates freely refined with Uiso(H) = 1.5Ueq(O). The absolute configuration was not determined from the X-ray data but was known from the synthetic route.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the molecule of the title compound, with displacement ellipsoids drawn at the 50% probability level.
6β-Hydroxy-5β-methyl-20-oxo-19-norpregn-9(10)-en-3β-yl acetate top
Crystal data top
C23H34O4Dx = 1.178 Mg m3
Mr = 374.50Melting point: 411 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6566 reflections
a = 5.8903 (2) Åθ = 2.4–26.3°
b = 9.6929 (2) ŵ = 0.08 mm1
c = 36.9988 (8) ÅT = 293 K
V = 2112.41 (10) Å3Flat hexagonal prism, clear colourless
Z = 40.36 × 0.23 × 0.11 mm
F(000) = 816
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3729 independent reflections
Radiation source: fine-focus sealed tube2885 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ϕ and ω scansθmax = 30.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 88
Tmin = 0.882, Tmax = 0.991k = 1313
59317 measured reflectionsl = 5252
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0779P)2 + 0.1174P]
where P = (Fo2 + 2Fc2)/3
3729 reflections(Δ/σ)max < 0.001
249 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C23H34O4V = 2112.41 (10) Å3
Mr = 374.50Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.8903 (2) ŵ = 0.08 mm1
b = 9.6929 (2) ÅT = 293 K
c = 36.9988 (8) Å0.36 × 0.23 × 0.11 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3729 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
2885 reflections with I > 2σ(I)
Tmin = 0.882, Tmax = 0.991Rint = 0.041
59317 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.05Δρmax = 0.18 e Å3
3729 reflectionsΔρmin = 0.17 e Å3
249 parameters
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
xyzUiso*/Ueq
C10.4722 (4)0.12481 (19)0.12583 (5)0.0490 (5)
H1A0.53080.11630.15020.059*
H1B0.55980.06360.11050.059*
C20.2256 (4)0.0786 (2)0.12548 (5)0.0525 (5)
H2A0.21630.01710.13300.063*
H2B0.13910.13370.14250.063*
C30.1252 (4)0.0935 (2)0.08821 (5)0.0489 (4)
H30.03580.06800.08870.059*
O3A0.2516 (3)0.00496 (14)0.06584 (4)0.0515 (3)
C3A0.1608 (4)0.0463 (2)0.03472 (5)0.0527 (5)
O3B0.0239 (3)0.0109 (2)0.02454 (4)0.0742 (5)
C3B0.3192 (5)0.1385 (2)0.01506 (6)0.0689 (7)
H3B10.31340.22920.02540.103*
H3B20.47080.10290.01690.103*
H3B30.27580.14320.00990.103*
C40.1503 (3)0.2403 (2)0.07486 (5)0.0462 (4)
H4A0.04670.29790.08860.055*
H4B0.10140.24310.04980.055*
C50.3888 (3)0.30562 (18)0.07705 (4)0.0402 (4)
C5A0.5356 (3)0.2532 (2)0.04534 (4)0.0476 (4)
H5A10.45630.26780.02300.071*
H5A20.56500.15650.04840.071*
H5A30.67670.30260.04490.071*
C60.3567 (4)0.4633 (2)0.07496 (4)0.0443 (4)
H60.25930.48870.09540.053*
O60.2385 (3)0.50490 (16)0.04296 (3)0.0568 (4)
H6A0.32480.50080.02560.085*
C70.5771 (4)0.5393 (2)0.08019 (5)0.0499 (5)
H7A0.55020.63770.07800.060*
H7B0.68280.51260.06140.060*
C80.6829 (3)0.50866 (19)0.11734 (4)0.0417 (4)
H80.84770.51730.11460.050*
C90.6366 (3)0.36341 (18)0.13065 (4)0.0409 (4)
C100.5061 (3)0.27213 (18)0.11307 (4)0.0412 (4)
C110.7514 (4)0.3358 (2)0.16667 (5)0.0503 (5)
H11A0.91470.33790.16340.060*
H11B0.71020.24420.17490.060*
C120.6851 (4)0.44162 (18)0.19574 (5)0.0453 (4)
H12A0.52450.43320.20110.054*
H12B0.76900.42300.21780.054*
C130.7360 (3)0.58741 (19)0.18293 (4)0.0397 (4)
C140.6117 (3)0.61062 (17)0.14663 (4)0.0384 (3)
H140.45080.59240.15140.046*
C150.6307 (5)0.7650 (2)0.14027 (5)0.0604 (6)
H15A0.51010.79740.12460.073*
H15B0.77600.78830.12950.073*
C160.6084 (6)0.8276 (2)0.17831 (6)0.0710 (7)
H16A0.46280.87320.18090.085*
H16B0.72770.89470.18250.085*
C170.6286 (4)0.7076 (2)0.20541 (5)0.0492 (4)
H170.47430.67950.21200.059*
C180.9926 (4)0.6111 (3)0.18014 (7)0.0648 (6)
H18A1.06190.59400.20320.097*
H18B1.02110.70480.17300.097*
H18C1.05550.54950.16250.097*
C200.7519 (5)0.7448 (3)0.23992 (6)0.0668 (6)
O200.8547 (6)0.8505 (2)0.24285 (6)0.1158 (10)
C210.7429 (7)0.6458 (3)0.27057 (6)0.0921 (11)
H21A0.86920.58340.26900.138*
H21B0.60370.59440.26950.138*
H21C0.75010.69550.29300.138*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0626 (12)0.0410 (9)0.0433 (8)0.0061 (9)0.0129 (9)0.0002 (8)
C20.0628 (12)0.0486 (10)0.0462 (9)0.0035 (10)0.0044 (9)0.0007 (8)
C30.0395 (9)0.0570 (11)0.0502 (9)0.0048 (9)0.0001 (8)0.0065 (8)
O3A0.0494 (7)0.0536 (7)0.0516 (7)0.0060 (7)0.0065 (6)0.0118 (6)
C3A0.0621 (13)0.0501 (10)0.0457 (9)0.0041 (10)0.0046 (9)0.0001 (8)
O3B0.0676 (11)0.0944 (13)0.0605 (9)0.0082 (11)0.0198 (8)0.0072 (9)
C3B0.0915 (19)0.0569 (12)0.0583 (11)0.0061 (13)0.0018 (13)0.0095 (10)
C40.0378 (9)0.0558 (10)0.0450 (8)0.0128 (9)0.0026 (8)0.0034 (8)
C50.0416 (9)0.0471 (9)0.0318 (7)0.0124 (8)0.0028 (7)0.0031 (7)
C5A0.0426 (10)0.0597 (11)0.0406 (8)0.0121 (9)0.0005 (7)0.0080 (8)
C60.0528 (11)0.0494 (9)0.0308 (7)0.0165 (9)0.0023 (8)0.0037 (7)
O60.0662 (9)0.0660 (9)0.0383 (6)0.0236 (9)0.0079 (6)0.0083 (6)
C70.0660 (13)0.0475 (9)0.0362 (8)0.0050 (10)0.0003 (8)0.0054 (7)
C80.0429 (9)0.0447 (9)0.0377 (7)0.0037 (8)0.0006 (7)0.0004 (7)
C90.0457 (9)0.0413 (8)0.0356 (7)0.0127 (8)0.0053 (7)0.0002 (6)
C100.0473 (10)0.0411 (8)0.0351 (7)0.0107 (8)0.0047 (7)0.0005 (7)
C110.0616 (12)0.0435 (9)0.0458 (9)0.0106 (10)0.0189 (9)0.0019 (8)
C120.0552 (11)0.0440 (9)0.0366 (7)0.0028 (9)0.0109 (8)0.0012 (7)
C130.0336 (8)0.0443 (9)0.0412 (8)0.0011 (8)0.0046 (7)0.0032 (7)
C140.0388 (9)0.0379 (8)0.0385 (7)0.0026 (8)0.0014 (7)0.0001 (7)
C150.0906 (17)0.0416 (9)0.0492 (10)0.0010 (12)0.0061 (11)0.0034 (8)
C160.110 (2)0.0468 (11)0.0559 (11)0.0095 (14)0.0147 (14)0.0062 (9)
C170.0550 (11)0.0472 (10)0.0454 (9)0.0023 (10)0.0052 (8)0.0077 (8)
C180.0389 (10)0.0845 (17)0.0709 (13)0.0071 (12)0.0037 (10)0.0076 (13)
C200.0866 (17)0.0616 (12)0.0522 (11)0.0017 (14)0.0102 (12)0.0142 (10)
O200.163 (3)0.0923 (14)0.0918 (14)0.0498 (18)0.0469 (15)0.0115 (12)
C210.145 (3)0.0878 (19)0.0437 (11)0.007 (2)0.0139 (16)0.0065 (11)
Geometric parameters (Å, º) top
C1—C101.517 (3)C8—C91.516 (3)
C1—C21.520 (3)C8—C141.525 (2)
C1—H1A0.9700C8—H80.9800
C1—H1B0.9700C9—C101.341 (3)
C2—C31.507 (3)C9—C111.518 (2)
C2—H2A0.9700C11—C121.536 (3)
C2—H2B0.9700C11—H11A0.9700
C3—O3A1.467 (2)C11—H11B0.9700
C3—C41.513 (3)C12—C131.520 (3)
C3—H30.9800C12—H12A0.9700
O3A—C3A1.331 (2)C12—H12B0.9700
C3A—O3B1.201 (3)C13—C181.532 (3)
C3A—C3B1.483 (3)C13—C141.546 (2)
C3B—H3B10.9600C13—C171.565 (3)
C3B—H3B20.9600C14—C151.519 (3)
C3B—H3B30.9600C14—H140.9800
C4—C51.543 (3)C15—C161.538 (3)
C4—H4A0.9700C15—H15A0.9700
C4—H4B0.9700C15—H15B0.9700
C5—C101.536 (2)C16—C171.540 (3)
C5—C61.542 (3)C16—H16A0.9700
C5—C5A1.543 (2)C16—H16B0.9700
C5A—H5A10.9600C17—C201.513 (3)
C5A—H5A20.9600C17—H170.9800
C5A—H5A30.9600C18—H18A0.9600
C6—O61.432 (2)C18—H18B0.9600
C6—C71.506 (3)C18—H18C0.9600
C6—H60.9800C20—O201.195 (3)
O6—H6A0.8200C20—C211.487 (4)
C7—C81.538 (2)C21—H21A0.9600
C7—H7A0.9700C21—H21B0.9600
C7—H7B0.9700C21—H21C0.9600
C10—C1—C2113.60 (17)C7—C8—H8106.9
C10—C1—H1A108.8C10—C9—C8123.94 (15)
C2—C1—H1A108.8C10—C9—C11124.41 (17)
C10—C1—H1B108.8C8—C9—C11111.64 (16)
C2—C1—H1B108.8C9—C10—C1123.06 (15)
H1A—C1—H1B107.7C9—C10—C5122.66 (16)
C3—C2—C1110.77 (17)C1—C10—C5114.20 (16)
C3—C2—H2A109.5C9—C11—C12112.56 (15)
C1—C2—H2A109.5C9—C11—H11A109.1
C3—C2—H2B109.5C12—C11—H11A109.1
C1—C2—H2B109.5C9—C11—H11B109.1
H2A—C2—H2B108.1C12—C11—H11B109.1
O3A—C3—C2104.73 (16)H11A—C11—H11B107.8
O3A—C3—C4112.22 (16)C13—C12—C11110.63 (15)
C2—C3—C4110.54 (17)C13—C12—H12A109.5
O3A—C3—H3109.8C11—C12—H12A109.5
C2—C3—H3109.8C13—C12—H12B109.5
C4—C3—H3109.8C11—C12—H12B109.5
C3A—O3A—C3118.69 (17)H12A—C12—H12B108.1
O3B—C3A—O3A123.3 (2)C12—C13—C18110.81 (19)
O3B—C3A—C3B126.0 (2)C12—C13—C14108.20 (14)
O3A—C3A—C3B110.7 (2)C18—C13—C14112.74 (17)
C3A—C3B—H3B1109.5C12—C13—C17116.53 (16)
C3A—C3B—H3B2109.5C18—C13—C17108.85 (18)
H3B1—C3B—H3B2109.5C14—C13—C1799.30 (14)
C3A—C3B—H3B3109.5C15—C14—C8120.53 (16)
H3B1—C3B—H3B3109.5C15—C14—C13104.06 (15)
H3B2—C3B—H3B3109.5C8—C14—C13113.12 (14)
C3—C4—C5117.24 (16)C15—C14—H14106.0
C3—C4—H4A108.0C8—C14—H14106.0
C5—C4—H4A108.0C13—C14—H14106.0
C3—C4—H4B108.0C14—C15—C16103.91 (16)
C5—C4—H4B108.0C14—C15—H15A111.0
H4A—C4—H4B107.2C16—C15—H15A111.0
C10—C5—C6107.94 (14)C14—C15—H15B111.0
C10—C5—C4111.61 (15)C16—C15—H15B111.0
C6—C5—C4107.01 (15)H15A—C15—H15B109.0
C10—C5—C5A109.75 (14)C15—C16—C17106.95 (17)
C6—C5—C5A110.92 (16)C15—C16—H16A110.3
C4—C5—C5A109.58 (14)C17—C16—H16A110.3
C5—C5A—H5A1109.5C15—C16—H16B110.3
C5—C5A—H5A2109.5C17—C16—H16B110.3
H5A1—C5A—H5A2109.5H16A—C16—H16B108.6
C5—C5A—H5A3109.5C20—C17—C16114.02 (18)
H5A1—C5A—H5A3109.5C20—C17—C13115.56 (18)
H5A2—C5A—H5A3109.5C16—C17—C13104.32 (16)
O6—C6—C7112.78 (16)C20—C17—H17107.5
O6—C6—C5112.36 (15)C16—C17—H17107.5
C7—C6—C5111.91 (16)C13—C17—H17107.5
O6—C6—H6106.4C13—C18—H18A109.5
C7—C6—H6106.4C13—C18—H18B109.5
C5—C6—H6106.4H18A—C18—H18B109.5
C6—O6—H6A109.5C13—C18—H18C109.5
C6—C7—C8111.68 (15)H18A—C18—H18C109.5
C6—C7—H7A109.3H18B—C18—H18C109.5
C8—C7—H7A109.3O20—C20—C21120.2 (2)
C6—C7—H7B109.3O20—C20—C17121.6 (2)
C8—C7—H7B109.3C21—C20—C17118.3 (2)
H7A—C7—H7B107.9C20—C21—H21A109.5
C9—C8—C14108.75 (14)C20—C21—H21B109.5
C9—C8—C7113.39 (16)H21A—C21—H21B109.5
C14—C8—C7113.47 (15)C20—C21—H21C109.5
C9—C8—H8106.9H21A—C21—H21C109.5
C14—C8—H8106.9H21B—C21—H21C109.5
C10—C1—C2—C357.1 (2)C4—C5—C10—C140.9 (2)
C1—C2—C3—O3A65.3 (2)C5A—C5—C10—C180.7 (2)
C1—C2—C3—C455.8 (2)C10—C9—C11—C12123.2 (2)
C2—C3—O3A—C3A160.07 (17)C8—C9—C11—C1255.3 (2)
C4—C3—O3A—C3A80.0 (2)C9—C11—C12—C1355.9 (2)
C3—O3A—C3A—O3B2.8 (3)C11—C12—C13—C1868.3 (2)
C3—O3A—C3A—C3B176.56 (18)C11—C12—C13—C1455.7 (2)
O3A—C3—C4—C565.7 (2)C11—C12—C13—C17166.49 (17)
C2—C3—C4—C550.8 (2)C9—C8—C14—C15177.80 (19)
C3—C4—C5—C1042.8 (2)C7—C8—C14—C1550.6 (3)
C3—C4—C5—C6160.68 (15)C9—C8—C14—C1358.2 (2)
C3—C4—C5—C5A78.98 (19)C7—C8—C14—C13174.57 (15)
C10—C5—C6—O6177.28 (15)C12—C13—C14—C15168.39 (18)
C4—C5—C6—O657.0 (2)C18—C13—C14—C1568.7 (2)
C5A—C5—C6—O662.5 (2)C17—C13—C14—C1546.4 (2)
C10—C5—C6—C754.64 (19)C12—C13—C14—C859.0 (2)
C4—C5—C6—C7174.89 (14)C18—C13—C14—C863.9 (2)
C5A—C5—C6—C765.63 (18)C17—C13—C14—C8178.92 (16)
O6—C6—C7—C8171.59 (15)C8—C14—C15—C16164.8 (2)
C5—C6—C7—C860.55 (19)C13—C14—C15—C1636.6 (3)
C6—C7—C8—C933.1 (2)C14—C15—C16—C1711.7 (3)
C6—C7—C8—C1491.64 (19)C15—C16—C17—C20144.0 (2)
C14—C8—C9—C10123.64 (19)C15—C16—C17—C1317.0 (3)
C7—C8—C9—C103.6 (3)C12—C13—C17—C2080.0 (2)
C14—C8—C9—C1154.9 (2)C18—C13—C17—C2046.1 (2)
C7—C8—C9—C11177.84 (16)C14—C13—C17—C20164.15 (18)
C8—C9—C10—C1176.61 (18)C12—C13—C17—C16153.96 (19)
C11—C9—C10—C15.0 (3)C18—C13—C17—C1679.9 (2)
C8—C9—C10—C50.2 (3)C14—C13—C17—C1638.1 (2)
C11—C9—C10—C5178.57 (18)C16—C17—C20—O2011.5 (4)
C2—C1—C10—C9133.5 (2)C13—C17—C20—O20109.4 (3)
C2—C1—C10—C549.8 (2)C16—C17—C20—C21168.6 (3)
C6—C5—C10—C925.0 (2)C13—C17—C20—C2170.5 (3)
C4—C5—C10—C9142.35 (18)C5A—C5—C13—C180.9 (2)
C5A—C5—C10—C996.0 (2)C1—C10—C9—C115.0 (3)
C6—C5—C10—C1158.26 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···O3Bi0.822.062.863 (2)166
C5A—H5A2···O3A0.962.503.104 (3)121
C16—H16B···O200.972.392.803 (3)105
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC23H34O4
Mr374.50
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)5.8903 (2), 9.6929 (2), 36.9988 (8)
V3)2112.41 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.36 × 0.23 × 0.11
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.882, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
59317, 3729, 2885
Rint0.041
(sin θ/λ)max1)0.715
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.133, 1.05
No. of reflections3729
No. of parameters249
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.17

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
C3A—O3B1.201 (3)C20—C211.487 (4)
C6—O61.432 (2)
C13—C17—C20—C2170.5 (3)C5A—C5—C13—C180.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···O3Bi0.822.062.863 (2)166
C5A—H5A2···O3A0.962.503.104 (3)121
C16—H16B···O200.972.392.803 (3)105
Symmetry code: (i) x+1/2, y+1/2, z.
 

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