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Acta Cryst. (2012). E68, o3413-o3414    [ doi:10.1107/S1600536812046600 ]

(25R)-6[alpha]-Hydroxy-5[alpha]-spirostan-3[beta]-yl tosylate

M. A. Fernández-Herrera, J. Sandoval-Ramírez, S. Bernès, M. Rodríguez-Acosta and M.-G. Hernández Linares

Abstract top

The title steroid, C34H50O6S, is an intermediate on the synthetic route between diosgenin and brassinosteroids, which possess the A ring modified with the 2[alpha],3[alpha]-diol functionality. The polycyclic spirostan system has the expected conformation, with six-membered rings adopting chair forms and the five-membered rings envelope forms (flap atoms are the methine C atom in the C/D-ring junction and the spiro C atom connecting rings E and F). The 3[beta]-tosylate group is oriented in such a way that S=O bonds are engaged in intermolecular hydrogen bonds with O-H and C-H donors. Chains of molecules are formed along [100] via O-H...O hydrogen bonds, and secondary weak C-H...O interactions connect two neighbouring chains in the [001] direction.

Comment top

Brassinosteroids (BS) are endogenous plant hormones essential for the regulation of multiple physiological processes required for normal plant growth and development (Asami et al., 2005). Since their discovery, more than 30 years ago, the synthetic chemistry has been extensively developed for obtaining BS and analogs (Zullo & Adam, 2002; Kang & Guo, 2011). The most active BS and analogs possess a 2α,3α-diol in ring A and a ketone at C-6 (or a lactone) in ring B. The introduction of the required 6-keto-2α,3α-diol functionality has been satisfactorily achieved from the 6-hydroxy-3β-tosylate framework. The title compound belongs to this line of synthetic approaches to BS analogs. It was synthesized from diosgenin, through a tosylation followed by hydroboration-oxidation (Smith & Pelter, 1991; Brown, 1962). Commonly, the crude product after the hydroboration-oxidation procedure is immediately oxidized in order to obtain the 6-keto derivative; we decided instead, to isolate and properly characterize the 6-hydroxy intermediate.

The compound crystallizes with one molecule in the asymmetric unit (Fig. 1) and the conformation of the A-F ring system is as expected for a spirostan nucleus. All 6-membered rings have a chair conformation, while 5-membered rings D and E are envelopes on C14 and C22, respectively. The tosylate group in equatorial position at C3 is oriented in such a way that a potential intramolecular stabilizing O—H···π contact could be formed between the hydroxyl group at C6 and the benzene ring of the tosylate. However, this interaction should have an energy approaching zero, because of the too long H···π separation, ca. 4.4 Å. On the other hand, the tosylate orientation in the title compound is similar to that observed in cholesteryl tosylate (Cox et al., 1996), which has C-6 engaged in a double bond. This suggests that the tosylate orientation results from packing restraints or intermolecular interactions rather than intramolecular contacts.

Regarding the crystal structure, the single feature of interest is the intermolecular hydrogen bond formed between the hydroxyl group and one S═O group in the tosylate. These contacts link molecules in chains oriented in the [100] direction in the crystal. A weak hydrogen bond involving the other S═O group is observed between chains, C40—H40A···O34, characterized by a small C—H···O angle of 133° (Fig. 2).

Related literature top

For background to brassinosteroids, see: Asami et al. (2005); Kang & Guo (2011); Zullo & Adam (2002). For the hydroboration-oxidation synthetic step used for the preparation of the title compound, see: Smith & Pelter (1991); Brown (1962). For the structure of another steroid functionalized at C-3 with a tosylate group, see: Cox et al. (1996).

Experimental top

Diosgenin (750 mg, 1.8 mmol) was tosylated by means of p-TsCl/py/DCM, following the standard procedure, affording diosgenin tosylate quantitatively; the crude was properly washed, dried and immediately submitted to the next reaction. Diosgenin tosylate (1 g, 1.76 mmol) was dissolved in THF (30 ml) and NaBH4 (0.4 g, 10.8 mmol) was added. The system was sealed under Ar atmosphere and then, BF3.Et2O (0.7 ml, 5.6 mmol) was carefully added. The reaction mixture was kept for 2 h at room temperature, concentrated under reduced pressure, and re-dissolved in a solution of KOH/MeOH (2%, 50 ml), followed by 5 ml of 35% H2O2. The reaction mixture was stirred for 1 h; then the addition of water produced a precipitate, which was filtered off, washed with cold water, and dried under high vacuum. The resulting white powder was purified by column chromatography with hexanes/EtOAc 7:3 to afford the title compound as a white powder. It was recrystallized from hexanes/EtOAc 8:2 to obtain 0.72 g (70%) of colourless crystals. M.p. 149–150 °C, [α]D -39° (c 1.0, CHCl3). Spectroscopic characterization may be found in the archived CIF.

Refinement top

Hydroxyl H atom H30 was found in a difference map and refined with free coordinates and isotropic U parameter. Other H atoms were placed in idealized positions and refined with a riding model and fixed isotropic U parameters. C—H bond lengths were fixed to 0.96 (methyl), 0.97 (methylene), or 0.98 Å (methine). Displacement parameters were calculated as Uiso(H) = xUeq(parent C) where x = 1.5 (methyl) or 1.2 (methylene, methine). Anomalous dispersion of the tosylate S atom allowed to refine a Flack parameter (Flack, 1983), which is in agreement with the expected absolute configuration for the molecule.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title molecule, with displacement ellipsoids at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of the title compound, showing pairs of chains. On the left stack, intermolecular contacts are depicted with dashed bonds. Red: O—H···O hydrogen bonds; green: interchain C—H···O weak interactions.
(25R)-6α-Hydroxy-5α-spirostan-3β-yl tosylate top
Crystal data top
C34H50O6SDx = 1.236 Mg m−3
Mr = 586.80Melting point: 422 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 72 reflections
a = 6.7653 (8) Åθ = 4.6–12.5°
b = 12.2856 (11) ŵ = 0.15 mm−1
c = 37.943 (4) ÅT = 296 K
V = 3153.6 (6) Å3Prism, colourless
Z = 40.6 × 0.5 × 0.4 mm
F(000) = 1272
Data collection top
Bruker P4
diffractometer		5274 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4Rint = 0.023
Graphite monochromatorθmax = 26.3°, θmin = 2.0°
ω scansh = −8→6
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)		k = −15→15
Tmin = 0.905, Tmax = 0.943l = −46→47
9218 measured reflections3 standard reflections every 97 reflections
6167 independent reflections intensity decay: 1.5%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.036 w = 1/[σ2(Fo2) + (0.0359P)2 + 0.5535P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.090(Δ/σ)max = 0.002
S = 1.03Δρmax = 0.16 e Å−3
6167 reflectionsΔρmin = −0.16 e Å−3
380 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0058 (5)
0 constraintsAbsolute structure: Flack (1983), 2504 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.03 (7)
Secondary atom site location: difference Fourier map
Crystal data top
C34H50O6SV = 3153.6 (6) Å3
Mr = 586.80Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.7653 (8) ŵ = 0.15 mm−1
b = 12.2856 (11) ÅT = 296 K
c = 37.943 (4) Å0.6 × 0.5 × 0.4 mm
Data collection top
Bruker P4
diffractometer		5274 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)		Rint = 0.023
Tmin = 0.905, Tmax = 0.943θmax = 26.3°
9218 measured reflections3 standard reflections every 97 reflections
6167 independent reflections intensity decay: 1.5%
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090Δρmax = 0.16 e Å−3
S = 1.03Δρmin = −0.16 e Å−3
6167 reflectionsAbsolute structure: Flack (1983), 2504 Friedel pairs
380 parametersFlack parameter: −0.03 (7)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7277 (3)0.76613 (17)0.81367 (5)0.0487 (5)
H1A0.75490.70240.79940.058*
H1B0.80560.82590.80440.058*
C20.7923 (3)0.74351 (17)0.85158 (5)0.0535 (5)
H2A0.72460.67930.86030.064*
H2B0.93330.72930.85210.064*
C30.7455 (3)0.83933 (17)0.87512 (5)0.0501 (5)
H3A0.82910.90130.86860.060*
C40.5302 (3)0.87241 (18)0.87337 (5)0.0510 (5)
H4A0.50950.93740.88740.061*
H4B0.44850.81480.88300.061*
C50.4702 (3)0.89471 (15)0.83500 (4)0.0424 (4)
H5A0.55630.95320.82650.051*
C60.2580 (3)0.93700 (16)0.83213 (5)0.0478 (4)
H6A0.16640.88050.84020.057*
C70.2094 (3)0.96671 (16)0.79427 (5)0.0484 (5)
H7A0.29011.02820.78720.058*
H7B0.07200.98890.79290.058*
C80.2445 (3)0.87236 (14)0.76861 (4)0.0392 (4)
H8A0.15400.81300.77480.047*
C90.4581 (3)0.82992 (14)0.77203 (4)0.0397 (4)
H9A0.54430.89200.76680.048*
C100.5071 (3)0.79483 (14)0.81045 (4)0.0398 (4)
C110.5084 (3)0.74214 (17)0.74437 (5)0.0520 (5)
H11A0.64940.72800.74510.062*
H11B0.44100.67520.75070.062*
C120.4505 (3)0.77331 (17)0.70650 (5)0.0493 (5)
H12A0.53390.83260.69850.059*
H12B0.47230.71160.69100.059*
C130.2344 (3)0.80791 (14)0.70437 (4)0.0392 (4)
C140.2068 (3)0.90418 (14)0.73031 (4)0.0394 (4)
H14A0.30940.95730.72430.047*
C150.0107 (3)0.95550 (16)0.71905 (5)0.0487 (4)
H15A−0.00631.02750.72910.058*
H15B−0.10110.91020.72550.058*
C160.0397 (3)0.96013 (15)0.67900 (4)0.0444 (4)
H16A0.10651.02810.67260.053*
C170.1717 (3)0.86180 (14)0.66890 (4)0.0409 (4)
H17A0.29000.88850.65670.049*
C180.1006 (3)0.71110 (16)0.71335 (5)0.0555 (5)
H18A0.13500.68330.73620.083*
H18B0.11780.65500.69600.083*
H18C−0.03480.73440.71350.083*
C190.3831 (3)0.69510 (15)0.82133 (5)0.0517 (5)
H19A0.43380.63130.80990.078*
H19B0.24800.70620.81450.078*
H19C0.39020.68580.84640.078*
C200.0414 (3)0.79983 (16)0.64246 (5)0.0483 (5)
H20A−0.04000.74840.65580.058*
C210.1537 (4)0.7352 (2)0.61469 (6)0.0721 (7)
H21A0.06140.70070.59910.108*
H21B0.23330.68080.62600.108*
H21C0.23730.78340.60150.108*
C22−0.0941 (3)0.88812 (16)0.62844 (4)0.0471 (4)
C23−0.2867 (3)0.85149 (19)0.61189 (5)0.0588 (5)
H23A−0.36650.81510.62960.071*
H23B−0.25870.79950.59330.071*
C24−0.4025 (4)0.9461 (2)0.59666 (6)0.0648 (6)
H24A−0.51650.91850.58400.078*
H24B−0.44990.99180.61570.078*
C25−0.2772 (4)1.01361 (18)0.57190 (5)0.0593 (5)
H25A−0.24290.96860.55150.071*
C26−0.0883 (4)1.04441 (18)0.59073 (5)0.0599 (5)
H26A−0.00321.08340.57450.072*
H26B−0.11981.09320.61000.072*
O270.0167 (2)0.95231 (12)0.60433 (3)0.0537 (3)
C28−0.3833 (4)1.1154 (2)0.55875 (6)0.0824 (7)
H28A−0.29111.16130.54650.124*
H28B−0.43771.15430.57840.124*
H28C−0.48781.09480.54300.124*
O29−0.1410 (2)0.95014 (11)0.65939 (3)0.0510 (3)
O300.2301 (3)1.03360 (13)0.85290 (4)0.0693 (5)
H300.206 (5)1.017 (3)0.8723 (8)0.107 (12)*
O310.7980 (2)0.80181 (12)0.91112 (3)0.0565 (4)
S320.89495 (8)0.88025 (5)0.938758 (13)0.05819 (15)
O331.0188 (2)0.95749 (16)0.92101 (4)0.0753 (5)
O340.9767 (3)0.80926 (16)0.96460 (4)0.0825 (5)
C350.6942 (3)0.94918 (16)0.95735 (5)0.0506 (5)
C360.6646 (4)1.05871 (19)0.95077 (7)0.0735 (7)
H36A0.75371.09740.93690.088*
C370.5013 (5)1.1100 (2)0.96490 (8)0.0859 (8)
H37A0.48121.18340.96010.103*
C380.3682 (4)1.0562 (2)0.98576 (7)0.0763 (7)
C390.4014 (4)0.9468 (2)0.99195 (6)0.0749 (7)
H39A0.31250.90841.00590.090*
C400.5620 (3)0.89296 (19)0.97808 (5)0.0614 (6)
H40A0.58110.81930.98270.074*
C410.1927 (6)1.1145 (3)1.00114 (11)0.1337 (14)
H41A0.18861.18770.99230.201*
H41B0.20401.11601.02640.201*
H41C0.07371.07710.99460.201*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0473 (11)0.0556 (11)0.0431 (10)0.0123 (9)0.0071 (9)0.0001 (9)
C20.0517 (12)0.0623 (12)0.0465 (10)0.0189 (10)0.0007 (9)0.0011 (9)
C30.0565 (12)0.0576 (11)0.0362 (9)0.0088 (10)−0.0011 (9)0.0058 (8)
C40.0581 (12)0.0573 (11)0.0378 (9)0.0136 (10)0.0044 (8)0.0005 (9)
C50.0475 (10)0.0443 (9)0.0355 (8)0.0061 (9)0.0048 (8)0.0013 (7)
C60.0553 (11)0.0487 (10)0.0394 (9)0.0171 (9)0.0063 (9)−0.0048 (8)
C70.0552 (12)0.0494 (10)0.0407 (9)0.0202 (10)0.0017 (8)−0.0024 (8)
C80.0428 (10)0.0393 (9)0.0356 (8)0.0050 (8)0.0057 (7)−0.0007 (7)
C90.0406 (10)0.0420 (9)0.0367 (8)0.0025 (8)0.0077 (7)0.0027 (7)
C100.0411 (10)0.0416 (9)0.0369 (8)0.0078 (8)0.0084 (8)0.0022 (7)
C110.0537 (11)0.0586 (11)0.0436 (10)0.0190 (10)0.0077 (9)−0.0053 (9)
C120.0533 (12)0.0549 (11)0.0397 (9)0.0111 (10)0.0076 (8)−0.0040 (9)
C130.0441 (10)0.0369 (8)0.0366 (8)−0.0013 (8)0.0069 (8)−0.0022 (7)
C140.0446 (10)0.0357 (9)0.0380 (8)−0.0003 (8)0.0050 (8)−0.0008 (7)
C150.0578 (12)0.0491 (10)0.0393 (9)0.0138 (10)−0.0017 (9)−0.0074 (8)
C160.0529 (11)0.0416 (9)0.0387 (9)−0.0013 (9)−0.0036 (8)−0.0019 (8)
C170.0439 (10)0.0418 (9)0.0371 (8)−0.0051 (8)0.0046 (7)−0.0016 (7)
C180.0685 (13)0.0443 (10)0.0536 (11)−0.0121 (11)0.0078 (11)0.0016 (9)
C190.0589 (12)0.0464 (10)0.0498 (10)0.0020 (10)0.0090 (10)0.0082 (9)
C200.0554 (12)0.0471 (10)0.0424 (9)−0.0055 (9)0.0033 (8)−0.0089 (8)
C210.0797 (17)0.0773 (16)0.0594 (13)0.0107 (14)−0.0034 (12)−0.0307 (12)
C220.0501 (10)0.0540 (10)0.0373 (8)−0.0082 (10)0.0034 (8)−0.0058 (8)
C230.0579 (13)0.0719 (14)0.0468 (11)−0.0172 (12)−0.0006 (10)−0.0029 (10)
C240.0556 (13)0.0872 (16)0.0516 (11)−0.0077 (14)−0.0082 (10)−0.0018 (11)
C250.0699 (14)0.0672 (13)0.0409 (10)−0.0005 (12)−0.0053 (10)−0.0072 (9)
C260.0707 (14)0.0584 (12)0.0506 (11)−0.0120 (12)−0.0046 (11)0.0041 (10)
O270.0522 (8)0.0616 (8)0.0472 (7)−0.0106 (7)0.0010 (6)0.0036 (7)
C280.0959 (19)0.0858 (17)0.0654 (14)0.0142 (17)−0.0129 (14)0.0027 (14)
O290.0533 (8)0.0609 (8)0.0387 (6)0.0071 (7)−0.0027 (6)−0.0085 (6)
O300.0981 (13)0.0661 (9)0.0435 (8)0.0378 (10)0.0019 (9)−0.0110 (7)
O310.0708 (10)0.0598 (8)0.0390 (6)0.0138 (8)−0.0043 (6)0.0051 (6)
S320.0559 (3)0.0777 (4)0.0410 (2)0.0079 (3)−0.0039 (2)0.0055 (2)
O330.0600 (9)0.1110 (13)0.0551 (9)−0.0139 (10)0.0071 (8)0.0017 (9)
O340.0882 (12)0.1071 (13)0.0521 (8)0.0312 (11)−0.0188 (9)0.0102 (9)
C350.0605 (12)0.0548 (11)0.0365 (9)−0.0038 (10)0.0006 (9)0.0038 (9)
C360.0881 (19)0.0585 (13)0.0740 (15)−0.0034 (13)0.0191 (13)0.0177 (12)
C370.108 (2)0.0530 (13)0.0968 (18)0.0096 (16)0.0092 (18)0.0002 (14)
C380.0751 (17)0.0809 (17)0.0730 (15)0.0027 (15)0.0090 (13)−0.0160 (14)
C390.0727 (16)0.0827 (17)0.0692 (14)−0.0126 (15)0.0197 (13)0.0031 (13)
C400.0720 (15)0.0563 (12)0.0559 (11)−0.0085 (12)0.0084 (11)0.0065 (10)
C410.117 (3)0.134 (3)0.150 (3)0.031 (3)0.041 (3)−0.040 (3)
Geometric parameters (Å, º) top
C1—C21.528 (3)C18—H18B0.9600
C1—C101.539 (3)C18—H18C0.9600
C1—H1A0.9700C19—H19A0.9600
C1—H1B0.9700C19—H19B0.9600
C2—C31.511 (3)C19—H19C0.9600
C2—H2A0.9700C20—C221.516 (3)
C2—H2B0.9700C20—C211.523 (3)
C3—O311.485 (2)C20—H20A0.9800
C3—C41.514 (3)C21—H21A0.9600
C3—H3A0.9800C21—H21B0.9600
C4—C51.536 (2)C21—H21C0.9600
C4—H4A0.9700C22—O271.422 (2)
C4—H4B0.9700C22—O291.435 (2)
C5—C61.530 (3)C22—C231.515 (3)
C5—C101.561 (2)C23—C241.516 (3)
C5—H5A0.9800C23—H23A0.9700
C6—O301.437 (2)C23—H23B0.9700
C6—C71.518 (2)C24—C251.513 (3)
C6—H6A0.9800C24—H24A0.9700
C7—C81.532 (2)C24—H24B0.9700
C7—H7A0.9700C25—C261.512 (3)
C7—H7B0.9700C25—C281.526 (3)
C8—C141.526 (2)C25—H25A0.9800
C8—C91.542 (2)C26—O271.432 (3)
C8—H8A0.9800C26—H26A0.9700
C9—C111.543 (2)C26—H26B0.9700
C9—C101.556 (2)C28—H28A0.9600
C9—H9A0.9800C28—H28B0.9600
C10—C191.541 (3)C28—H28C0.9600
C11—C121.538 (3)O30—H300.78 (3)
C11—H11A0.9700O31—S321.5680 (15)
C11—H11B0.9700S32—O341.4241 (16)
C12—C131.525 (3)S32—O331.4340 (18)
C12—H12A0.9700S32—C351.749 (2)
C12—H12B0.9700C35—C401.377 (3)
C13—C181.533 (3)C35—C361.383 (3)
C13—C141.550 (2)C36—C371.380 (4)
C13—C171.559 (2)C36—H36A0.9300
C14—C151.529 (3)C37—C381.369 (4)
C14—H14A0.9800C37—H37A0.9300
C15—C161.533 (2)C38—C391.383 (4)
C15—H15A0.9700C38—C411.504 (4)
C15—H15B0.9700C39—C401.377 (3)
C16—O291.436 (2)C39—H39A0.9300
C16—C171.550 (3)C40—H40A0.9300
C16—H16A0.9800C41—H41A0.9600
C17—C201.537 (3)C41—H41B0.9600
C17—H17A0.9800C41—H41C0.9600
C18—H18A0.9600
C2—C1—C10113.18 (16)C16—C17—C13105.90 (13)
C2—C1—H1A108.9C20—C17—H17A109.1
C10—C1—H1A108.9C16—C17—H17A109.1
C2—C1—H1B108.9C13—C17—H17A109.1
C10—C1—H1B108.9C13—C18—H18A109.5
H1A—C1—H1B107.8C13—C18—H18B109.5
C3—C2—C1110.78 (16)H18A—C18—H18B109.5
C3—C2—H2A109.5C13—C18—H18C109.5
C1—C2—H2A109.5H18A—C18—H18C109.5
C3—C2—H2B109.5H18B—C18—H18C109.5
C1—C2—H2B109.5C10—C19—H19A109.5
H2A—C2—H2B108.1C10—C19—H19B109.5
O31—C3—C2104.59 (15)H19A—C19—H19B109.5
O31—C3—C4110.72 (16)C10—C19—H19C109.5
C2—C3—C4112.62 (18)H19A—C19—H19C109.5
O31—C3—H3A109.6H19B—C19—H19C109.5
C2—C3—H3A109.6C22—C20—C21115.60 (17)
C4—C3—H3A109.6C22—C20—C17102.79 (15)
C3—C4—C5110.11 (15)C21—C20—C17115.06 (18)
C3—C4—H4A109.6C22—C20—H20A107.6
C5—C4—H4A109.6C21—C20—H20A107.6
C3—C4—H4B109.6C17—C20—H20A107.6
C5—C4—H4B109.6C20—C21—H21A109.5
H4A—C4—H4B108.2C20—C21—H21B109.5
C6—C5—C4112.09 (15)H21A—C21—H21B109.5
C6—C5—C10112.00 (15)C20—C21—H21C109.5
C4—C5—C10112.53 (15)H21A—C21—H21C109.5
C6—C5—H5A106.6H21B—C21—H21C109.5
C4—C5—H5A106.6O27—C22—O29110.39 (15)
C10—C5—H5A106.6O27—C22—C23110.60 (16)
O30—C6—C7106.97 (15)O29—C22—C23107.87 (16)
O30—C6—C5111.38 (17)O27—C22—C20107.67 (16)
C7—C6—C5110.63 (15)O29—C22—C20103.08 (14)
O30—C6—H6A109.3C23—C22—C20116.93 (18)
C7—C6—H6A109.3C22—C23—C24111.99 (18)
C5—C6—H6A109.3C22—C23—H23A109.2
C6—C7—C8112.68 (15)C24—C23—H23A109.2
C6—C7—H7A109.1C22—C23—H23B109.2
C8—C7—H7A109.1C24—C23—H23B109.2
C6—C7—H7B109.1H23A—C23—H23B107.9
C8—C7—H7B109.1C25—C24—C23111.6 (2)
H7A—C7—H7B107.8C25—C24—H24A109.3
C14—C8—C7112.66 (14)C23—C24—H24A109.3
C14—C8—C9108.86 (14)C25—C24—H24B109.3
C7—C8—C9110.35 (15)C23—C24—H24B109.3
C14—C8—H8A108.3H24A—C24—H24B108.0
C7—C8—H8A108.3C26—C25—C24108.51 (17)
C9—C8—H8A108.3C26—C25—C28110.3 (2)
C8—C9—C11112.69 (16)C24—C25—C28112.9 (2)
C8—C9—C10111.83 (14)C26—C25—H25A108.3
C11—C9—C10113.38 (15)C24—C25—H25A108.3
C8—C9—H9A106.1C28—C25—H25A108.3
C11—C9—H9A106.1O27—C26—C25113.06 (17)
C10—C9—H9A106.1O27—C26—H26A109.0
C1—C10—C19108.94 (16)C25—C26—H26A109.0
C1—C10—C9110.15 (14)O27—C26—H26B109.0
C19—C10—C9110.82 (16)C25—C26—H26B109.0
C1—C10—C5106.74 (16)H26A—C26—H26B107.8
C19—C10—C5112.22 (14)C22—O27—C26114.12 (16)
C9—C10—C5107.90 (14)C25—C28—H28A109.5
C12—C11—C9113.93 (15)C25—C28—H28B109.5
C12—C11—H11A108.8H28A—C28—H28B109.5
C9—C11—H11A108.8C25—C28—H28C109.5
C12—C11—H11B108.8H28A—C28—H28C109.5
C9—C11—H11B108.8H28B—C28—H28C109.5
H11A—C11—H11B107.7C22—O29—C16106.34 (13)
C13—C12—C11111.28 (15)C6—O30—H30109 (2)
C13—C12—H12A109.4C3—O31—S32121.63 (13)
C11—C12—H12A109.4O34—S32—O33120.11 (12)
C13—C12—H12B109.4O34—S32—O31104.27 (10)
C11—C12—H12B109.4O33—S32—O31109.71 (9)
H12A—C12—H12B108.0O34—S32—C35108.69 (10)
C12—C13—C18109.76 (16)O33—S32—C35108.83 (11)
C12—C13—C14107.14 (15)O31—S32—C35104.03 (9)
C18—C13—C14112.31 (14)C40—C35—C36119.8 (2)
C12—C13—C17115.15 (15)C40—C35—S32119.47 (16)
C18—C13—C17111.15 (16)C36—C35—S32120.73 (17)
C14—C13—C17101.04 (13)C37—C36—C35119.4 (2)
C8—C14—C15121.10 (15)C37—C36—H36A120.3
C8—C14—C13112.90 (14)C35—C36—H36A120.3
C15—C14—C13103.99 (14)C38—C37—C36122.1 (2)
C8—C14—H14A105.9C38—C37—H37A119.0
C15—C14—H14A105.9C36—C37—H37A119.0
C13—C14—H14A105.9C37—C38—C39117.4 (2)
C14—C15—C16100.44 (15)C37—C38—C41120.9 (3)
C14—C15—H15A111.7C39—C38—C41121.7 (3)
C16—C15—H15A111.7C40—C39—C38122.0 (2)
C14—C15—H15B111.7C40—C39—H39A119.0
C16—C15—H15B111.7C38—C39—H39A119.0
H15A—C15—H15B109.5C39—C40—C35119.4 (2)
O29—C16—C15113.67 (16)C39—C40—H40A120.3
O29—C16—C17107.18 (14)C35—C40—H40A120.3
C15—C16—C17106.85 (14)C38—C41—H41A109.5
O29—C16—H16A109.7C38—C41—H41B109.5
C15—C16—H16A109.7H41A—C41—H41B109.5
C17—C16—H16A109.7C38—C41—H41C109.5
C20—C17—C16102.53 (15)H41A—C41—H41C109.5
C20—C17—C13120.61 (15)H41B—C41—H41C109.5
C10—C1—C2—C3−56.5 (2)O29—C16—C17—C13−127.69 (15)
C1—C2—C3—O31174.77 (17)C15—C16—C17—C13−5.49 (19)
C1—C2—C3—C454.5 (2)C12—C13—C17—C20107.2 (2)
O31—C3—C4—C5−171.61 (16)C18—C13—C17—C20−18.4 (2)
C2—C3—C4—C5−54.9 (2)C14—C13—C17—C20−137.79 (17)
C3—C4—C5—C6−175.57 (17)C12—C13—C17—C16−137.32 (16)
C3—C4—C5—C1057.1 (2)C18—C13—C17—C1697.08 (17)
C4—C5—C6—O3056.6 (2)C14—C13—C17—C16−22.27 (17)
C10—C5—C6—O30−175.81 (15)C16—C17—C20—C2224.43 (18)
C4—C5—C6—C7175.44 (17)C13—C17—C20—C22141.67 (16)
C10—C5—C6—C7−57.0 (2)C16—C17—C20—C21150.96 (18)
O30—C6—C7—C8176.66 (17)C13—C17—C20—C21−91.8 (2)
C5—C6—C7—C855.2 (2)C21—C20—C22—O27−50.2 (2)
C6—C7—C8—C14−176.75 (17)C17—C20—C22—O2776.01 (17)
C6—C7—C8—C9−54.8 (2)C21—C20—C22—O29−166.88 (18)
C14—C8—C9—C11−50.40 (19)C17—C20—C22—O29−40.70 (18)
C7—C8—C9—C11−174.53 (15)C21—C20—C22—C2375.0 (2)
C14—C8—C9—C10−179.51 (15)C17—C20—C22—C23−158.82 (16)
C7—C8—C9—C1056.36 (19)O27—C22—C23—C24−52.4 (2)
C2—C1—C10—C19−64.9 (2)O29—C22—C23—C2468.4 (2)
C2—C1—C10—C9173.36 (16)C20—C22—C23—C24−176.07 (17)
C2—C1—C10—C556.5 (2)C22—C23—C24—C2552.5 (2)
C8—C9—C10—C1−173.24 (15)C23—C24—C25—C26−52.1 (2)
C11—C9—C10—C158.0 (2)C23—C24—C25—C28−174.71 (18)
C8—C9—C10—C1966.14 (19)C24—C25—C26—O2754.8 (2)
C11—C9—C10—C19−62.6 (2)C28—C25—C26—O27178.89 (18)
C8—C9—C10—C5−57.08 (19)O29—C22—O27—C26−63.9 (2)
C11—C9—C10—C5174.17 (16)C23—C22—O27—C2655.4 (2)
C6—C5—C10—C1175.76 (15)C20—C22—O27—C26−175.73 (15)
C4—C5—C10—C1−56.9 (2)C25—C26—O27—C22−58.3 (2)
C6—C5—C10—C19−65.0 (2)O27—C22—O29—C16−73.14 (18)
C4—C5—C10—C1962.4 (2)C23—C22—O29—C16165.92 (16)
C6—C5—C10—C957.39 (19)C20—C22—O29—C1641.62 (18)
C4—C5—C10—C9−175.26 (16)C15—C16—O29—C22−143.50 (16)
C8—C9—C11—C1248.6 (2)C17—C16—O29—C22−25.66 (18)
C10—C9—C11—C12176.91 (17)C2—C3—O31—S32142.58 (15)
C9—C11—C12—C13−52.6 (2)C4—C3—O31—S32−95.9 (2)
C11—C12—C13—C18−64.8 (2)C3—O31—S32—O34−162.55 (15)
C11—C12—C13—C1457.4 (2)C3—O31—S32—O33−32.69 (18)
C11—C12—C13—C17168.88 (15)C3—O31—S32—C3583.60 (16)
C7—C8—C14—C15−53.7 (2)O34—S32—C35—C40−42.7 (2)
C9—C8—C14—C15−176.44 (16)O33—S32—C35—C40−175.16 (17)
C7—C8—C14—C13−177.83 (15)O31—S32—C35—C4067.93 (18)
C9—C8—C14—C1359.4 (2)O34—S32—C35—C36138.8 (2)
C12—C13—C14—C8−63.21 (19)O33—S32—C35—C366.4 (2)
C18—C13—C14—C857.4 (2)O31—S32—C35—C36−110.5 (2)
C17—C13—C14—C8175.91 (15)C40—C35—C36—C37−0.5 (4)
C12—C13—C14—C15163.71 (15)S32—C35—C36—C37177.9 (2)
C18—C13—C14—C15−75.69 (18)C35—C36—C37—C380.9 (4)
C17—C13—C14—C1542.83 (17)C36—C37—C38—C39−0.8 (4)
C8—C14—C15—C16−174.43 (16)C36—C37—C38—C41179.3 (3)
C13—C14—C15—C16−46.22 (17)C37—C38—C39—C400.4 (4)
C14—C15—C16—O29149.34 (15)C41—C38—C39—C40−179.7 (3)
C14—C15—C16—C1731.31 (18)C38—C39—C40—C35−0.1 (4)
O29—C16—C17—C20−0.41 (18)C36—C35—C40—C390.1 (3)
C15—C16—C17—C20121.79 (16)S32—C35—C40—C39−178.35 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O30—H30···O33i0.78 (3)2.35 (3)3.098 (2)159 (3)
C40—H40A···O34ii0.932.653.352 (3)133
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O30—H30···O33i0.78 (3)2.35 (3)3.098 (2)159 (3)
C40—H40A···O34ii0.932.653.352 (3)133.3
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+2.
Acknowledgements top

The authors thank CONACYT for the Repatriation grant 166040 and PROMEP for the grant PROMEP/103.5/12/4367 BUAP-PTC-301.

references
References top

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