organic compounds
Diosgenin-3,6-dione: second polymorph in P212121
aFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, bLicenciatura en Biotecnología, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, cInstituto de Física, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, dCentro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, and eLaboratorio de Investigación, Herbario y Jardín Botánico Universitario, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The title steroid, [(25R)-spirost-4-en-3,6-dione, C27H38O4], is obtained by oxidation of diosgenin, using the Jones reagent (CrO3/H2SO4). The was previously reported in P212121, but nonetheless with the wrong and omitting positions for H atoms [Rajnikant et al. (2000). Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. C, 12, 101–110]. The diffraction data set reported herein is for a second polymorph in the same as evidenced by simulated powder patterns. Both forms are characterized by a similar orthorhombic and a similar arrangement of the molecules in the However, the conformation of the A/B rings in the steroid nucleus is slightly modified, leading to the observed polymorphism.
Keywords: crystal structure; steroids; diosgenin; polymorphism.
CCDC reference: 2026501
Structure description
Diosgenin [(3β,25R)-spirost-5-en-3-ol, C27H42O3] is a natural product that has played a pivotal role in the early stages of the industry of steroidal compounds, including the large-scale synthesis of cortisone, and the manufacturing of the first combined oral contraceptive pills, at Syntex S.A., in Mexico (Djerassi, 1992). Diosgenin treated with the Jones reagent gives the expected oxidation product, with carbonyl groups at C3 and C6. This compound was characterized by X-ray crystallography, and its structure reported twenty years ago (Rajnikant et al., 2000). The reported is rather technically unsound, since all H atoms were omitted in the model and the wrong was assigned to the molecule (see refcode QUPKUH in the CSD; Groom et al., 2016). Since the Jones oxidation does not affect the E/F rings of diosgenin, chiral centre C25 is expected to retains its original R configuration, while the structure currently deposited in the CSD has a 25S configuration. A suitable model can be restored after inversion of the structure and addition of H atoms in calculated positions.
While working with this molecule, we obtained high-quality, well-shaped prismatic crystals (Fig. 1), and collected diffraction data with the purpose of improving the previously reported structure. However, it soon became clear that a new form had been crystallized instead; although the crystal symmetry was unchanged, differences in cell parameters as large as 2 Å were observed. After structure (Table 1), a simulated powder diffraction pattern was compared with that obtained with the model of Rajnikant et al. (2000). Patterns are clearly different, as expected for two polymorphic forms (Fig. 2). The seems to be a consequence of a slight modification of the conformation for rings A and B (Fig. 2, inset). In the structure reported herein, ring A displays a distorted with a puckering amplitude q = 0.458 (3) Å, and ring B is a distorted half-chair, with q = 0.476 (3) Å. For the previously characterized polymorph, ring A is nearest to an half-chair, and B to a chair conformation. The conformational flexibility of the A ring of bearing a conjugated 4-ene-3,6-dione fragment had already been pointed out (Anthony et al., 1998), and related to the modulation of the steroid-receptor interactions, which control hormonal responses for these molecules (Duax et al., 1994).
Since the , the centroid of the molecule constituting the for the form reported herein is found at (0.313, 0.661, 0.380), while for the previously reported form, the centroid lies at (0.951, 1/5, 0.628). The action of the screw axis of P212121 then generates different crystal structures. This kind of resulting from the rearrangement of the within a common is certainly favoured by the lack of supramolecular interactions. The title molecule does not include donor groups for hydrogen bonds, and only very weak C—H⋯O contacts are present in the crystals. A closely related type of in P21 was reported for diosgenone [(25R)-spirost-4-en-3-one, C27H40O3; Hernández Linares et al., 2012], which crystallizes with Z′ = 2. In that case, one of the independent molecules in the changes its orientation, and unit-cell parameters vary considerably between polymorphs, even though crystal symmetry is retained.
is unchanged, there is a degree of similarity between the crystal structures for the polymorphic forms: the molecules, placed in general positions, lie approximately parallel to [010]. However, if a common orientation is chosen for the asymmetric units in both forms, the position of the molecule in the is shifted. With the selection made in Fig. 3Synthesis and crystallization
To a solution of diosgenin (2.0 g, 4.8 mmol) in 20 mL of CH2Cl2 and 40 mL of acetone was slowly added a solution of Jones reagent (10 mL: 1.8 g, 18.4 mmol of CrO3 in H2O/H2SO4 8:2) over 10 min in an ice bath. The reaction was kept under stirring at room temperature and monitored by TLC until a change in colour (orange to green) was observed. Subsequently, 2-propanol was added to quench unreacted Jones reagent, and the reaction mixture was poured into a separating funnel and extracted with ethyl acetate. The solution was washed with distilled H2O, neutralized with NaHCO3, separated, dried over Na2SO4 and evaporated to dryness under reduced pressure. The purification was carried out on a chromatographic column with silica gel (hexane:EtOAc, 9:1), affording 1.63 g (80% yield) of the title compound, while remaining solid was identified as starting material (20%). Single crystals for the compound of interest were obtained by slow evaporation of the corresponding chromatographic fraction.
Structural data
CCDC reference: 2026501
https://doi.org/10.1107/S2414314620012006/zq4041sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620012006/zq4041Isup2.hkl
Data collection: X-AREA (Stoe & Cie, 2018); cell
X-AREA (Stoe & Cie, 2018); data reduction: X-AREA (Stoe & Cie, 2018); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).C27H38O4 | Dx = 1.204 Mg m−3 |
Mr = 426.57 | Melting point: 453 K |
Orthorhombic, P212121 | Ag Kα radiation, λ = 0.56083 Å |
a = 7.4768 (3) Å | Cell parameters from 25730 reflections |
b = 16.2190 (9) Å | θ = 2.3–25.0° |
c = 19.4101 (10) Å | µ = 0.05 mm−1 |
V = 2353.8 (2) Å3 | T = 295 K |
Z = 4 | Prism, yellow |
F(000) = 928 | 0.50 × 0.40 × 0.15 mm |
Stoe Stadivari diffractometer | 5150 independent reflections |
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source | 3345 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.073 |
Detector resolution: 5.81 pixels mm-1 | θmax = 21.0°, θmin = 2.3° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2018) | k = −20→20 |
Tmin = 0.471, Tmax = 1.000 | l = −24→24 |
47703 measured reflections |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0488P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max < 0.001 |
5150 reflections | Δρmax = 0.23 e Å−3 |
285 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0162 (19) |
Primary atom site location: dual |
Refinement. All H atoms were placed in calculated positions and refined as riding to their carrier C-atoms (Sheldrick, 2015b). |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0439 (3) | 0.97069 (16) | 0.37910 (14) | 0.0522 (7) | |
H1A | −0.071025 | 0.943263 | 0.382619 | 0.063* | |
H1B | 0.090567 | 0.977185 | 0.425417 | 0.063* | |
C2 | 0.0159 (4) | 1.05554 (17) | 0.34782 (16) | 0.0606 (7) | |
H2A | −0.060529 | 1.050286 | 0.307687 | 0.073* | |
H2B | −0.045802 | 1.090035 | 0.381014 | 0.073* | |
C3 | 0.1843 (4) | 1.09697 (19) | 0.32713 (19) | 0.0755 (9) | |
O3 | 0.1874 (4) | 1.16980 (15) | 0.3114 (2) | 0.1337 (13) | |
C4 | 0.3462 (4) | 1.04615 (18) | 0.32287 (16) | 0.0643 (8) | |
H4 | 0.455697 | 1.072524 | 0.317233 | 0.077* | |
C5 | 0.3444 (3) | 0.96390 (17) | 0.32668 (13) | 0.0479 (6) | |
C6 | 0.5191 (3) | 0.91992 (17) | 0.31852 (13) | 0.0504 (7) | |
O6 | 0.6482 (2) | 0.95624 (13) | 0.29488 (12) | 0.0731 (6) | |
C7 | 0.5344 (3) | 0.83377 (17) | 0.34334 (15) | 0.0548 (7) | |
H7A | 0.585728 | 0.834932 | 0.389224 | 0.066* | |
H7B | 0.618289 | 0.805013 | 0.313743 | 0.066* | |
C8 | 0.3615 (3) | 0.78329 (14) | 0.34624 (13) | 0.0423 (6) | |
H8 | 0.326505 | 0.768461 | 0.299195 | 0.051* | |
C9 | 0.2114 (3) | 0.83575 (14) | 0.37883 (12) | 0.0406 (6) | |
H9 | 0.256600 | 0.853585 | 0.423812 | 0.049* | |
C10 | 0.1720 (3) | 0.91550 (15) | 0.33790 (12) | 0.0415 (6) | |
C11 | 0.0418 (3) | 0.78446 (15) | 0.39364 (15) | 0.0518 (7) | |
H11A | −0.041358 | 0.817845 | 0.419956 | 0.062* | |
H11B | −0.015180 | 0.770631 | 0.350262 | 0.062* | |
C12 | 0.0794 (3) | 0.70518 (16) | 0.43324 (14) | 0.0513 (7) | |
H12A | 0.122140 | 0.718791 | 0.479036 | 0.062* | |
H12B | −0.030678 | 0.674098 | 0.438101 | 0.062* | |
C13 | 0.2181 (3) | 0.65227 (14) | 0.39675 (12) | 0.0394 (6) | |
C14 | 0.3879 (3) | 0.70496 (15) | 0.38761 (13) | 0.0420 (6) | |
H14 | 0.421477 | 0.722961 | 0.434037 | 0.050* | |
C15 | 0.5293 (3) | 0.64196 (16) | 0.36631 (15) | 0.0549 (7) | |
H15A | 0.517289 | 0.627142 | 0.318116 | 0.066* | |
H15B | 0.649095 | 0.662747 | 0.374435 | 0.066* | |
C16 | 0.4875 (3) | 0.56896 (16) | 0.41304 (14) | 0.0499 (6) | |
H16 | 0.572569 | 0.566620 | 0.451408 | 0.060* | |
O16 | 0.4847 (2) | 0.49248 (10) | 0.37698 (9) | 0.0516 (5) | |
C17 | 0.2937 (3) | 0.58071 (16) | 0.44046 (13) | 0.0450 (6) | |
H17 | 0.298534 | 0.597779 | 0.488857 | 0.054* | |
C18 | 0.1451 (3) | 0.62202 (17) | 0.32730 (13) | 0.0537 (7) | |
H18A | 0.033182 | 0.594318 | 0.334407 | 0.081* | |
H18B | 0.229110 | 0.584524 | 0.306835 | 0.081* | |
H18C | 0.127487 | 0.668280 | 0.297204 | 0.081* | |
C19 | 0.0918 (3) | 0.89664 (18) | 0.26624 (13) | 0.0535 (7) | |
H19A | −0.024407 | 0.872328 | 0.271690 | 0.080* | |
H19B | 0.168538 | 0.858988 | 0.242108 | 0.080* | |
H19C | 0.081458 | 0.946891 | 0.240411 | 0.080* | |
C20 | 0.2104 (3) | 0.49410 (16) | 0.43591 (14) | 0.0498 (7) | |
H20 | 0.123711 | 0.494455 | 0.398032 | 0.060* | |
C21 | 0.1124 (4) | 0.46656 (19) | 0.50102 (16) | 0.0696 (9) | |
H21A | 0.192388 | 0.469427 | 0.539642 | 0.104* | |
H21B | 0.071525 | 0.410860 | 0.495363 | 0.104* | |
H21C | 0.011807 | 0.502070 | 0.508975 | 0.104* | |
C22 | 0.3684 (3) | 0.43940 (16) | 0.41412 (14) | 0.0477 (6) | |
C23 | 0.3208 (3) | 0.36802 (17) | 0.36779 (15) | 0.0570 (7) | |
H23A | 0.270637 | 0.388837 | 0.325116 | 0.068* | |
H23B | 0.230978 | 0.334086 | 0.390046 | 0.068* | |
C24 | 0.4848 (4) | 0.31596 (18) | 0.35199 (15) | 0.0627 (8) | |
H24A | 0.449256 | 0.267618 | 0.325940 | 0.075* | |
H24B | 0.567501 | 0.347584 | 0.324002 | 0.075* | |
C25 | 0.5769 (4) | 0.28929 (18) | 0.41780 (16) | 0.0649 (8) | |
H25 | 0.496066 | 0.252466 | 0.442952 | 0.078* | |
C26 | 0.6121 (4) | 0.36431 (18) | 0.46214 (15) | 0.0629 (8) | |
H26A | 0.663372 | 0.346687 | 0.505617 | 0.076* | |
H26B | 0.698909 | 0.399318 | 0.439267 | 0.076* | |
O26 | 0.4536 (2) | 0.41104 (11) | 0.47543 (9) | 0.0548 (5) | |
C27 | 0.7500 (5) | 0.2427 (2) | 0.4031 (2) | 0.0991 (13) | |
H27A | 0.725690 | 0.197330 | 0.372742 | 0.149* | |
H27B | 0.798657 | 0.222111 | 0.445573 | 0.149* | |
H27C | 0.834658 | 0.279181 | 0.381880 | 0.149* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0547 (13) | 0.0515 (16) | 0.0503 (16) | 0.0115 (12) | 0.0024 (13) | −0.0007 (13) |
C2 | 0.0636 (16) | 0.0550 (17) | 0.0631 (18) | 0.0144 (14) | 0.0016 (14) | 0.0002 (15) |
C3 | 0.074 (2) | 0.0483 (19) | 0.104 (3) | −0.0016 (15) | −0.0102 (19) | −0.0028 (18) |
O3 | 0.0990 (19) | 0.0509 (15) | 0.251 (4) | −0.0007 (14) | 0.004 (2) | 0.020 (2) |
C4 | 0.0515 (14) | 0.0590 (19) | 0.082 (2) | −0.0071 (13) | −0.0075 (14) | 0.0043 (17) |
C5 | 0.0440 (12) | 0.0564 (16) | 0.0432 (16) | −0.0002 (11) | −0.0065 (11) | 0.0027 (13) |
C6 | 0.0366 (12) | 0.0634 (18) | 0.0514 (16) | −0.0059 (12) | −0.0057 (11) | 0.0028 (13) |
O6 | 0.0471 (10) | 0.0768 (14) | 0.0954 (16) | −0.0070 (10) | 0.0063 (10) | 0.0133 (13) |
C7 | 0.0341 (11) | 0.0633 (18) | 0.0669 (18) | 0.0033 (11) | 0.0019 (12) | 0.0072 (15) |
C8 | 0.0340 (11) | 0.0520 (15) | 0.0409 (14) | 0.0035 (10) | −0.0014 (10) | −0.0007 (12) |
C9 | 0.0375 (11) | 0.0466 (15) | 0.0378 (14) | 0.0042 (10) | −0.0018 (10) | −0.0049 (12) |
C10 | 0.0379 (11) | 0.0494 (15) | 0.0373 (14) | 0.0045 (10) | −0.0013 (10) | −0.0007 (12) |
C11 | 0.0379 (11) | 0.0494 (15) | 0.0682 (18) | 0.0069 (11) | 0.0106 (12) | 0.0001 (14) |
C12 | 0.0440 (13) | 0.0485 (16) | 0.0615 (18) | 0.0040 (11) | 0.0125 (12) | −0.0017 (14) |
C13 | 0.0333 (10) | 0.0446 (14) | 0.0402 (14) | 0.0035 (10) | 0.0002 (10) | −0.0049 (12) |
C14 | 0.0353 (11) | 0.0483 (15) | 0.0424 (15) | 0.0027 (10) | −0.0042 (10) | −0.0033 (12) |
C15 | 0.0358 (11) | 0.0571 (17) | 0.0718 (19) | 0.0073 (11) | 0.0039 (12) | 0.0051 (15) |
C16 | 0.0401 (12) | 0.0511 (16) | 0.0584 (16) | 0.0047 (12) | −0.0068 (12) | −0.0021 (14) |
O16 | 0.0461 (9) | 0.0493 (11) | 0.0593 (11) | 0.0051 (8) | 0.0042 (8) | −0.0001 (9) |
C17 | 0.0418 (11) | 0.0505 (15) | 0.0426 (14) | 0.0018 (11) | −0.0016 (11) | −0.0027 (12) |
C18 | 0.0539 (14) | 0.0549 (16) | 0.0524 (17) | −0.0021 (13) | −0.0117 (12) | −0.0033 (13) |
C19 | 0.0458 (13) | 0.0684 (18) | 0.0462 (16) | 0.0077 (12) | −0.0069 (12) | −0.0036 (14) |
C20 | 0.0444 (13) | 0.0497 (16) | 0.0553 (17) | 0.0040 (12) | −0.0008 (12) | −0.0018 (14) |
C21 | 0.0601 (16) | 0.0624 (19) | 0.086 (2) | 0.0003 (14) | 0.0207 (16) | 0.0036 (17) |
C22 | 0.0464 (12) | 0.0491 (16) | 0.0478 (15) | 0.0022 (12) | −0.0022 (12) | 0.0003 (13) |
C23 | 0.0549 (14) | 0.0574 (17) | 0.0586 (18) | −0.0007 (13) | −0.0019 (13) | −0.0072 (15) |
C24 | 0.0678 (18) | 0.0545 (17) | 0.0657 (19) | 0.0029 (14) | 0.0051 (15) | −0.0107 (15) |
C25 | 0.0748 (19) | 0.0535 (18) | 0.066 (2) | 0.0132 (14) | 0.0097 (16) | 0.0111 (16) |
C26 | 0.0606 (16) | 0.067 (2) | 0.061 (2) | 0.0149 (15) | −0.0047 (14) | 0.0072 (16) |
O26 | 0.0579 (10) | 0.0583 (11) | 0.0483 (11) | 0.0113 (9) | −0.0048 (9) | 0.0006 (9) |
C27 | 0.111 (3) | 0.092 (3) | 0.095 (3) | 0.052 (2) | 0.007 (2) | 0.011 (2) |
C1—C2 | 1.519 (4) | C15—H15A | 0.9700 |
C1—C10 | 1.536 (3) | C15—H15B | 0.9700 |
C1—H1A | 0.9700 | C16—O16 | 1.424 (3) |
C1—H1B | 0.9700 | C16—C17 | 1.556 (3) |
C2—C3 | 1.483 (4) | C16—H16 | 0.9800 |
C2—H2A | 0.9700 | O16—C22 | 1.420 (3) |
C2—H2B | 0.9700 | C17—C20 | 1.539 (4) |
C3—O3 | 1.220 (4) | C17—H17 | 0.9800 |
C3—C4 | 1.467 (4) | C18—H18A | 0.9600 |
C4—C5 | 1.336 (4) | C18—H18B | 0.9600 |
C4—H4 | 0.9300 | C18—H18C | 0.9600 |
C5—C6 | 1.497 (3) | C19—H19A | 0.9600 |
C5—C10 | 1.525 (3) | C19—H19B | 0.9600 |
C6—O6 | 1.220 (3) | C19—H19C | 0.9600 |
C6—C7 | 1.482 (4) | C20—C21 | 1.528 (4) |
C7—C8 | 1.531 (3) | C20—C22 | 1.537 (3) |
C7—H7A | 0.9700 | C20—H20 | 0.9800 |
C7—H7B | 0.9700 | C21—H21A | 0.9600 |
C8—C14 | 1.516 (3) | C21—H21B | 0.9600 |
C8—C9 | 1.544 (3) | C21—H21C | 0.9600 |
C8—H8 | 0.9800 | C22—O26 | 1.426 (3) |
C9—C11 | 1.543 (3) | C22—C23 | 1.508 (3) |
C9—C10 | 1.546 (3) | C23—C24 | 1.520 (4) |
C9—H9 | 0.9800 | C23—H23A | 0.9700 |
C10—C19 | 1.545 (3) | C23—H23B | 0.9700 |
C11—C12 | 1.524 (3) | C24—C25 | 1.514 (4) |
C11—H11A | 0.9700 | C24—H24A | 0.9700 |
C11—H11B | 0.9700 | C24—H24B | 0.9700 |
C12—C13 | 1.521 (3) | C25—C26 | 1.513 (4) |
C12—H12A | 0.9700 | C25—C27 | 1.526 (4) |
C12—H12B | 0.9700 | C25—H25 | 0.9800 |
C13—C18 | 1.535 (3) | C26—O26 | 1.430 (3) |
C13—C14 | 1.540 (3) | C26—H26A | 0.9700 |
C13—C17 | 1.545 (3) | C26—H26B | 0.9700 |
C14—C15 | 1.527 (3) | C27—H27A | 0.9600 |
C14—H14 | 0.9800 | C27—H27B | 0.9600 |
C15—C16 | 1.524 (4) | C27—H27C | 0.9600 |
C2—C1—C10 | 113.9 (2) | C14—C15—H15B | 111.3 |
C2—C1—H1A | 108.8 | H15A—C15—H15B | 109.2 |
C10—C1—H1A | 108.8 | O16—C16—C15 | 112.8 (2) |
C2—C1—H1B | 108.8 | O16—C16—C17 | 105.13 (19) |
C10—C1—H1B | 108.8 | C15—C16—C17 | 107.42 (19) |
H1A—C1—H1B | 107.7 | O16—C16—H16 | 110.4 |
C3—C2—C1 | 113.7 (2) | C15—C16—H16 | 110.4 |
C3—C2—H2A | 108.8 | C17—C16—H16 | 110.4 |
C1—C2—H2A | 108.8 | C22—O16—C16 | 106.70 (18) |
C3—C2—H2B | 108.8 | C20—C17—C13 | 120.4 (2) |
C1—C2—H2B | 108.8 | C20—C17—C16 | 104.2 (2) |
H2A—C2—H2B | 107.7 | C13—C17—C16 | 104.2 (2) |
O3—C3—C4 | 120.9 (3) | C20—C17—H17 | 109.1 |
O3—C3—C2 | 121.5 (3) | C13—C17—H17 | 109.1 |
C4—C3—C2 | 117.5 (3) | C16—C17—H17 | 109.1 |
C5—C4—C3 | 123.3 (3) | C13—C18—H18A | 109.5 |
C5—C4—H4 | 118.3 | C13—C18—H18B | 109.5 |
C3—C4—H4 | 118.3 | H18A—C18—H18B | 109.5 |
C4—C5—C6 | 117.4 (2) | C13—C18—H18C | 109.5 |
C4—C5—C10 | 122.0 (2) | H18A—C18—H18C | 109.5 |
C6—C5—C10 | 120.5 (2) | H18B—C18—H18C | 109.5 |
O6—C6—C7 | 121.1 (2) | C10—C19—H19A | 109.5 |
O6—C6—C5 | 120.0 (2) | C10—C19—H19B | 109.5 |
C7—C6—C5 | 118.8 (2) | H19A—C19—H19B | 109.5 |
C6—C7—C8 | 116.8 (2) | C10—C19—H19C | 109.5 |
C6—C7—H7A | 108.1 | H19A—C19—H19C | 109.5 |
C8—C7—H7A | 108.1 | H19B—C19—H19C | 109.5 |
C6—C7—H7B | 108.1 | C21—C20—C22 | 115.3 (2) |
C8—C7—H7B | 108.1 | C21—C20—C17 | 114.4 (2) |
H7A—C7—H7B | 107.3 | C22—C20—C17 | 103.40 (19) |
C14—C8—C7 | 110.98 (19) | C21—C20—H20 | 107.8 |
C14—C8—C9 | 109.83 (19) | C22—C20—H20 | 107.8 |
C7—C8—C9 | 109.53 (19) | C17—C20—H20 | 107.8 |
C14—C8—H8 | 108.8 | C20—C21—H21A | 109.5 |
C7—C8—H8 | 108.8 | C20—C21—H21B | 109.5 |
C9—C8—H8 | 108.8 | H21A—C21—H21B | 109.5 |
C11—C9—C8 | 112.12 (19) | C20—C21—H21C | 109.5 |
C11—C9—C10 | 112.97 (17) | H21A—C21—H21C | 109.5 |
C8—C9—C10 | 112.89 (19) | H21B—C21—H21C | 109.5 |
C11—C9—H9 | 106.1 | O16—C22—O26 | 110.21 (18) |
C8—C9—H9 | 106.1 | O16—C22—C23 | 107.9 (2) |
C10—C9—H9 | 106.1 | O26—C22—C23 | 110.8 (2) |
C5—C10—C1 | 107.5 (2) | O16—C22—C20 | 105.09 (19) |
C5—C10—C19 | 107.54 (19) | O26—C22—C20 | 107.5 (2) |
C1—C10—C19 | 110.02 (19) | C23—C22—C20 | 115.2 (2) |
C5—C10—C9 | 110.05 (18) | C22—C23—C24 | 110.9 (2) |
C1—C10—C9 | 109.80 (19) | C22—C23—H23A | 109.5 |
C19—C10—C9 | 111.8 (2) | C24—C23—H23A | 109.5 |
C12—C11—C9 | 113.40 (19) | C22—C23—H23B | 109.5 |
C12—C11—H11A | 108.9 | C24—C23—H23B | 109.5 |
C9—C11—H11A | 108.9 | H23A—C23—H23B | 108.0 |
C12—C11—H11B | 108.9 | C25—C24—C23 | 110.8 (2) |
C9—C11—H11B | 108.9 | C25—C24—H24A | 109.5 |
H11A—C11—H11B | 107.7 | C23—C24—H24A | 109.5 |
C13—C12—C11 | 111.5 (2) | C25—C24—H24B | 109.5 |
C13—C12—H12A | 109.3 | C23—C24—H24B | 109.5 |
C11—C12—H12A | 109.3 | H24A—C24—H24B | 108.1 |
C13—C12—H12B | 109.3 | C26—C25—C24 | 109.2 (2) |
C11—C12—H12B | 109.3 | C26—C25—C27 | 110.9 (3) |
H12A—C12—H12B | 108.0 | C24—C25—C27 | 111.7 (3) |
C12—C13—C18 | 110.30 (19) | C26—C25—H25 | 108.3 |
C12—C13—C14 | 107.60 (19) | C24—C25—H25 | 108.3 |
C18—C13—C14 | 111.7 (2) | C27—C25—H25 | 108.3 |
C12—C13—C17 | 114.7 (2) | O26—C26—C25 | 112.6 (2) |
C18—C13—C17 | 111.9 (2) | O26—C26—H26A | 109.1 |
C14—C13—C17 | 100.30 (17) | C25—C26—H26A | 109.1 |
C8—C14—C15 | 120.5 (2) | O26—C26—H26B | 109.1 |
C8—C14—C13 | 114.77 (18) | C25—C26—H26B | 109.1 |
C15—C14—C13 | 103.32 (19) | H26A—C26—H26B | 107.8 |
C8—C14—H14 | 105.7 | C22—O26—C26 | 113.00 (19) |
C15—C14—H14 | 105.7 | C25—C27—H27A | 109.5 |
C13—C14—H14 | 105.7 | C25—C27—H27B | 109.5 |
C16—C15—C14 | 102.52 (19) | H27A—C27—H27B | 109.5 |
C16—C15—H15A | 111.3 | C25—C27—H27C | 109.5 |
C14—C15—H15A | 111.3 | H27A—C27—H27C | 109.5 |
C16—C15—H15B | 111.3 | H27B—C27—H27C | 109.5 |
C10—C1—C2—C3 | −47.1 (3) | C17—C13—C14—C8 | −179.5 (2) |
C1—C2—C3—O3 | −168.3 (4) | C12—C13—C14—C15 | 167.6 (2) |
C1—C2—C3—C4 | 14.7 (4) | C18—C13—C14—C15 | −71.3 (2) |
O3—C3—C4—C5 | −166.9 (4) | C17—C13—C14—C15 | 47.4 (2) |
C2—C3—C4—C5 | 10.1 (5) | C8—C14—C15—C16 | −170.6 (2) |
C3—C4—C5—C6 | 177.4 (3) | C13—C14—C15—C16 | −40.9 (2) |
C3—C4—C5—C10 | −1.7 (5) | C14—C15—C16—O16 | 133.7 (2) |
C4—C5—C6—O6 | −15.3 (4) | C14—C15—C16—C17 | 18.3 (3) |
C10—C5—C6—O6 | 163.9 (2) | C15—C16—O16—C22 | −153.07 (18) |
C4—C5—C6—C7 | 161.2 (3) | C17—C16—O16—C22 | −36.3 (2) |
C10—C5—C6—C7 | −19.6 (3) | C12—C13—C17—C20 | 94.0 (3) |
O6—C6—C7—C8 | −157.6 (3) | C18—C13—C17—C20 | −32.6 (3) |
C5—C6—C7—C8 | 25.9 (4) | C14—C13—C17—C20 | −151.1 (2) |
C6—C7—C8—C14 | −166.6 (2) | C12—C13—C17—C16 | −149.8 (2) |
C6—C7—C8—C9 | −45.2 (3) | C18—C13—C17—C16 | 83.7 (2) |
C14—C8—C9—C11 | −49.0 (3) | C14—C13—C17—C16 | −34.9 (2) |
C7—C8—C9—C11 | −171.1 (2) | O16—C16—C17—C20 | 17.4 (3) |
C14—C8—C9—C10 | −177.97 (19) | C15—C16—C17—C20 | 137.7 (2) |
C7—C8—C9—C10 | 59.9 (3) | O16—C16—C17—C13 | −109.7 (2) |
C4—C5—C10—C1 | −29.0 (3) | C15—C16—C17—C13 | 10.7 (3) |
C6—C5—C10—C1 | 151.8 (2) | C13—C17—C20—C21 | −111.6 (3) |
C4—C5—C10—C19 | 89.4 (3) | C16—C17—C20—C21 | 132.2 (2) |
C6—C5—C10—C19 | −89.7 (3) | C13—C17—C20—C22 | 122.2 (2) |
C4—C5—C10—C9 | −148.6 (3) | C16—C17—C20—C22 | 6.0 (3) |
C6—C5—C10—C9 | 32.2 (3) | C16—O16—C22—O26 | −74.8 (2) |
C2—C1—C10—C5 | 52.6 (3) | C16—O16—C22—C23 | 164.07 (18) |
C2—C1—C10—C19 | −64.3 (3) | C16—O16—C22—C20 | 40.7 (2) |
C2—C1—C10—C9 | 172.3 (2) | C21—C20—C22—O16 | −153.3 (2) |
C11—C9—C10—C5 | 178.7 (2) | C17—C20—C22—O16 | −27.6 (2) |
C8—C9—C10—C5 | −52.8 (2) | C21—C20—C22—O26 | −35.9 (3) |
C11—C9—C10—C1 | 60.5 (3) | C17—C20—C22—O26 | 89.8 (2) |
C8—C9—C10—C1 | −171.03 (19) | C21—C20—C22—C23 | 88.2 (3) |
C11—C9—C10—C19 | −61.9 (2) | C17—C20—C22—C23 | −146.2 (2) |
C8—C9—C10—C19 | 66.6 (2) | O16—C22—C23—C24 | 65.5 (3) |
C8—C9—C11—C12 | 50.4 (3) | O26—C22—C23—C24 | −55.2 (3) |
C10—C9—C11—C12 | 179.3 (2) | C20—C22—C23—C24 | −177.5 (2) |
C9—C11—C12—C13 | −55.1 (3) | C22—C23—C24—C25 | 53.6 (3) |
C11—C12—C13—C18 | −65.2 (3) | C23—C24—C25—C26 | −52.4 (3) |
C11—C12—C13—C14 | 56.8 (3) | C23—C24—C25—C27 | −175.5 (3) |
C11—C12—C13—C17 | 167.5 (2) | C24—C25—C26—O26 | 54.8 (3) |
C7—C8—C14—C15 | −58.7 (3) | C27—C25—C26—O26 | 178.3 (3) |
C9—C8—C14—C15 | −179.9 (2) | O16—C22—O26—C26 | −61.5 (3) |
C7—C8—C14—C13 | 176.8 (2) | C23—C22—O26—C26 | 57.9 (3) |
C9—C8—C14—C13 | 55.6 (3) | C20—C22—O26—C26 | −175.5 (2) |
C12—C13—C14—C8 | −59.3 (3) | C25—C26—O26—C22 | −58.6 (3) |
C18—C13—C14—C8 | 61.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23A···O6i | 0.97 | 2.64 | 3.474 (4) | 144 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Funding information
Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnología (grant No. 268178; grant No. 294412).
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