organic compounds
(3β,5α,25R)-12-(Hydroxyimino)spirostan-3-yl acetate
aLaboratorio de Investigación del Jardín Botánico, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Edif. 113 Complejo de Ciencias CU, San Manuel, 72570 Puebla, Pue., Mexico, and bInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The title steroid, C29H45NO5, obtained by condensation of hecogenin acetate [systematic name: (3β,5α,25R)-12-oxospirostan-3-yl acetate] with NH2OH, has the oxime group substituting the C-12 site on the C ring of the steroid nucleus. The introduction of this allows the formation of chain motifs, using the oxime OH group as a donor and the O atom of the E ring as an acceptor. The C(8) chains formed by this intermolecular hydrogen bond are oriented parallel to the short cell axis a. The structural features of this compound are very close to those of C29H43NO5, the derivative with a C14=C15 double bond in the D ring, which crystallizes in the same and with similar unit-cell parameters.
Keywords: crystal structure; oxime steroid; spirostan; hecogenin; hydrogen bonding.
CCDC reference: 1540985
Structure description
The synthesis of steroidal ; Cui et al., 2009). Research regarding the selective synthesis of and polyoximes of naturally occurring is thus active. For example, we reported the functionalization of 23-acetyl-sarsasapogenin acetate on the position C-23 in ring F, by condensation with hydroxyl amine, affording an oxime, which seems to be rearranged to its zwitterionic form while recrystallized in slightly acidic media (Hernández Linares et al., 2009). More recently, we reported the synthesis and analysis of the antiproliferative activity of derived from diosgenin (Sánchez-Sánchez et al., 2016). We are now focused on the synthesis of of other sapogenins, including hecogenin [IUPAC name: (25R)-3β-hydroxy-5α-spirostan-12-one], a natural steroid found in many agaves. The present report is of the of the product obtained through the condensation reaction between hecogenin acetate and NH2OH.
has been of significant relevance in recent years, reflected in some reports in the literature about the possible anticancer properties of this class of compounds (Bansal & Acharya, 2014As expected, the condensation functionalizes the C-12 position of the C ring (Fig. 1). The spirostan A–F nucleus presents a conformation identical to that reported for the parent compounds, hecogenin hydrate (Soriano-García et al., 1984) and hecogenin acetate (Slavyanov et al., 1982; Rajnikant et al., 2005), and close to that observed for the Δ14,15 compound, which has been deposited in the CSD with refcode LUBDIX (Wartchow & Brunck, 2015; see Fig. 1, inset). For example, a fit between the title compound and LUBDIX gives an r.m.s. deviation of 0.21 Å. In the the C-12 centre retains the sp2 of hecogenin, and the C ring has a conformation close to the chair form: for the title compound, the puckering parameters for this ring are θ = 7.8 (2)° and φ = 315.1 (19)° (ideal value for a chair form: θ = 0°). The oxime group is configured trans, which is known to be favoured compared to the cis configuration.
The oxime functionality is a good donor group for hydrogen bonding, and as a result, C(8) chain motifs are formed in the crystal, based on intermolecular O—H⋯O hydrogen bonds of medium strength (Table 1). The chains are oriented in the [100] direction, and no interchain contacts are observed, consistent with a true one-dimensional supramolecular structure (Fig. 2).
Synthesis and crystallization
In a round-bottom flask, NH2OH·HCl (0.209 g, 3.00 mmol) was added to a solution of hecogenin acetate (1.0 g, 2.12 mmol) and KOAc (0.294 g, 3.00 mmol) in EtOH (30 ml), and the mixture was allowed to stir at reflux. After a period of 1 h, organic extraction was performed (CH2Cl2, 3 × 10 ml), the organic phase was washed with distilled water (2 × 15 ml), dried over Na2SO4 and concentrated under reduced pressure. The title oxime was obtained as a colourless solid (0.982 g, 95%), and was recrystallized from CH2Cl2; m.p. = 318–320°C, [α]D = −2.6° (c = 0.01, CHCl3), IR/νmax = 3498, 1732, 1350, 1060 cm−1. 1H NMR (500 MHz, CDCl3), δ/p.p.m.: 4.65 (1H, m, H-3), 4.32 (1H, m, H-16), 3.49 (1H, dd, J26,25 = 4 Hz, Jgem = 11 Hz, H-26a), 3.37 (1H, d, Jgem = 11 Hz, H-26e), 2.64 (1H, dd, J23a,24 e = 4.2 Hz, J23a,24a = 12.0 Hz, H-23a), 2.54 (1H, dc, J17,20 = 10 Hz, H-17), 2.37 (1H, ddd, J24 e,23a = 4 Hz, Jgem = J24 e,25a = 13 Hz, H-24e), 2.20 (1H, dd, J24a,23a = Jgem = 10 Hz, H-24a), 1.04 (3H, d, J21,20 = 6.0 Hz, CH3-21), 0.91 (3H, s, CH3-19), 0.87 (3H, s, CH3-18), 0.84 (3H, d, J27,25 = 6.0 Hz, CH3-27). 13C-NMR (125 MHz, CDCl3), δ/p.p.m.: 12.0 (C-18), 12.9 (C-21), 16.0 (C-19), 17.0 (C-27), 28.3 (C-6), 29.7 (C-5), 30.9 (C– 7), 31.2 (C-1), 31.6 (C-2), 32.0 (C-4), 34.1 (C-8), 36.1 (C-15), 36.4 (C-10), 37.7 (C-24), 37.8 (C-11), 38.8 (C-9), 44.6 (C-25), 52.3 (C-20), 55.3 (C-13), 55.4 (C-14), 55.5 (C-17), 66.1 (C-26), 70.8 (C-3), 79.4 (C-16), 109.3 (C-22), 170.7 (CH3COO-3), 164.9 (C-12).
Refinement
Crystal data, data collection and structure . The was assigned following that of hecogenin, since diffraction data were collected at room temperature and using a silver target (λ = 0.56083 Å).
details are summarized in Table 2Structural data
CCDC reference: 1540985
https://doi.org/10.1107/S2414314617004916/ff4016sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004916/ff4016Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617004916/ff4016Isup3.cdx
Data collection: X-AREA (Stoe & Cie, 2015); cell
X-AREA (Stoe & Cie, 2015); data reduction: X-AREA (Stoe & Cie, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).C29H45NO5 | Dx = 1.187 Mg m−3 |
Mr = 487.66 | Melting point: 591 K |
Orthorhombic, P212121 | Ag Kα radiation, λ = 0.56083 Å |
a = 8.3161 (2) Å | Cell parameters from 20674 reflections |
b = 9.9302 (5) Å | θ = 2.4–22.4° |
c = 33.0414 (11) Å | µ = 0.05 mm−1 |
V = 2728.58 (18) Å3 | T = 295 K |
Z = 4 | Prism, colourless |
F(000) = 1064 | 0.30 × 0.25 × 0.12 mm |
Stoe Stadivari diffractometer | 4035 reflections with I > 2σ(I) |
Radiation source: Sealed X-ray tube, Axo Microfocus source | Rint = 0.057 |
Mirror monochromator | θmax = 21.6°, θmin = 2.4° |
Detector resolution: 5.81 pixels mm-1 | h = −10→10 |
ω scans | k = −12→12 |
46178 measured reflections | l = −43→42 |
6173 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: mixed |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0584P)2] where P = (Fo2 + 2Fc2)/3 |
6173 reflections | (Δ/σ)max < 0.001 |
324 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
0 constraints |
x | y | z | Uiso*/Ueq | ||
N1 | 0.4565 (2) | 0.3652 (2) | 0.17143 (7) | 0.0458 (5) | |
O1 | 0.29552 (19) | 0.3875 (2) | 0.18376 (7) | 0.0615 (6) | |
H1 | 0.229 (4) | 0.347 (4) | 0.1656 (12) | 0.092* | |
C1 | 0.3684 (3) | 0.3767 (3) | 0.32591 (9) | 0.0512 (7) | |
H1A | 0.322387 | 0.450401 | 0.310503 | 0.061* | |
H1B | 0.323926 | 0.293524 | 0.315371 | 0.061* | |
C2 | 0.3182 (3) | 0.3917 (3) | 0.37039 (10) | 0.0604 (8) | |
H2A | 0.349856 | 0.479883 | 0.380159 | 0.072* | |
H2B | 0.202113 | 0.384921 | 0.372465 | 0.072* | |
C3 | 0.3952 (3) | 0.2842 (3) | 0.39652 (9) | 0.0586 (7) | |
H3A | 0.349549 | 0.196019 | 0.389748 | 0.070* | |
C4 | 0.5759 (3) | 0.2801 (3) | 0.39124 (9) | 0.0587 (7) | |
H4A | 0.619638 | 0.205676 | 0.406731 | 0.070* | |
H4B | 0.622273 | 0.362793 | 0.401670 | 0.070* | |
C5 | 0.6224 (3) | 0.2638 (3) | 0.34682 (9) | 0.0495 (6) | |
H5A | 0.574969 | 0.178673 | 0.337702 | 0.059* | |
C6 | 0.8034 (3) | 0.2500 (3) | 0.34148 (9) | 0.0614 (8) | |
H6A | 0.855311 | 0.333362 | 0.349474 | 0.074* | |
H6B | 0.842995 | 0.178824 | 0.358939 | 0.074* | |
C7 | 0.8464 (3) | 0.2182 (3) | 0.29809 (9) | 0.0552 (7) | |
H7A | 0.810830 | 0.127506 | 0.291867 | 0.066* | |
H7B | 0.962476 | 0.220425 | 0.295228 | 0.066* | |
C8 | 0.7722 (3) | 0.3154 (2) | 0.26752 (8) | 0.0416 (6) | |
H8A | 0.825583 | 0.402949 | 0.270190 | 0.050* | |
C9 | 0.5905 (2) | 0.3350 (2) | 0.27503 (8) | 0.0397 (6) | |
H9A | 0.541506 | 0.246186 | 0.271105 | 0.048* | |
C10 | 0.5517 (3) | 0.3757 (2) | 0.31936 (8) | 0.0414 (6) | |
C11 | 0.5147 (3) | 0.4270 (3) | 0.24284 (9) | 0.0482 (6) | |
H11A | 0.398821 | 0.425772 | 0.246059 | 0.058* | |
H11B | 0.551137 | 0.518566 | 0.247296 | 0.058* | |
C12 | 0.5557 (2) | 0.3861 (2) | 0.20016 (8) | 0.0393 (5) | |
C13 | 0.7324 (2) | 0.3645 (2) | 0.19139 (8) | 0.0390 (6) | |
C14 | 0.7937 (2) | 0.2660 (2) | 0.22433 (8) | 0.0417 (6) | |
H14A | 0.727003 | 0.185012 | 0.221931 | 0.050* | |
C15 | 0.9604 (3) | 0.2262 (3) | 0.20888 (9) | 0.0529 (7) | |
H15A | 1.038538 | 0.296761 | 0.213862 | 0.063* | |
H15B | 0.997228 | 0.143281 | 0.221326 | 0.063* | |
C16 | 0.9301 (2) | 0.2076 (3) | 0.16373 (8) | 0.0462 (6) | |
H16A | 0.916898 | 0.111718 | 0.157528 | 0.055* | |
C17 | 0.7749 (2) | 0.2855 (3) | 0.15244 (8) | 0.0425 (6) | |
H17A | 0.688788 | 0.221047 | 0.146506 | 0.051* | |
C18 | 0.8192 (3) | 0.4999 (3) | 0.19340 (9) | 0.0527 (7) | |
H18A | 0.931705 | 0.486828 | 0.188266 | 0.079* | |
H18B | 0.805128 | 0.538533 | 0.219805 | 0.079* | |
H18C | 0.775201 | 0.559593 | 0.173391 | 0.079* | |
C19 | 0.6199 (4) | 0.5157 (3) | 0.32935 (10) | 0.0559 (7) | |
H19A | 0.733597 | 0.516461 | 0.324314 | 0.084* | |
H19B | 0.600208 | 0.535985 | 0.357323 | 0.084* | |
H19C | 0.568539 | 0.582112 | 0.312653 | 0.084* | |
C20 | 0.8193 (3) | 0.3617 (3) | 0.11361 (9) | 0.0518 (7) | |
H20A | 0.839680 | 0.455722 | 0.120975 | 0.062* | |
C21 | 0.6906 (3) | 0.3608 (5) | 0.08069 (11) | 0.0822 (11) | |
H21A | 0.728206 | 0.410653 | 0.057666 | 0.123* | |
H21B | 0.594082 | 0.401579 | 0.090894 | 0.123* | |
H21C | 0.668478 | 0.269625 | 0.072789 | 0.123* | |
C22 | 0.9805 (3) | 0.2987 (3) | 0.10090 (8) | 0.0473 (6) | |
O22 | 1.05437 (17) | 0.26438 (19) | 0.13869 (6) | 0.0489 (5) | |
C23 | 1.0943 (3) | 0.3887 (3) | 0.07784 (10) | 0.0576 (7) | |
H23A | 1.124973 | 0.464031 | 0.094844 | 0.069* | |
H23B | 1.039656 | 0.424359 | 0.054218 | 0.069* | |
C24 | 1.2442 (3) | 0.3141 (3) | 0.06447 (10) | 0.0648 (9) | |
H24A | 1.306859 | 0.371419 | 0.046686 | 0.078* | |
H24B | 1.309526 | 0.293263 | 0.087968 | 0.078* | |
C25 | 1.2019 (3) | 0.1848 (3) | 0.04254 (10) | 0.0665 (8) | |
H25A | 1.147316 | 0.208560 | 0.017243 | 0.080* | |
C26 | 1.0866 (3) | 0.1051 (3) | 0.06821 (11) | 0.0661 (8) | |
H26A | 1.054221 | 0.024975 | 0.053508 | 0.079* | |
H26B | 1.141189 | 0.076299 | 0.092668 | 0.079* | |
O26 | 0.9463 (2) | 0.1799 (2) | 0.07908 (6) | 0.0590 (5) | |
C27 | 1.3511 (4) | 0.1021 (4) | 0.03202 (13) | 0.0933 (12) | |
H27A | 1.420097 | 0.153832 | 0.014691 | 0.140* | |
H27B | 1.319152 | 0.021065 | 0.018363 | 0.140* | |
H27C | 1.407643 | 0.079391 | 0.056413 | 0.140* | |
O27 | 0.3659 (3) | 0.3137 (2) | 0.43916 (7) | 0.0703 (6) | |
C28 | 0.2274 (5) | 0.2758 (4) | 0.45557 (12) | 0.0844 (11) | |
O28 | 0.1243 (4) | 0.2166 (4) | 0.43712 (11) | 0.1265 (12) | |
C29 | 0.2163 (6) | 0.3213 (5) | 0.49833 (12) | 0.1153 (16) | |
H29A | 0.304051 | 0.284095 | 0.513545 | 0.173* | |
H29B | 0.116352 | 0.291509 | 0.509754 | 0.173* | |
H29C | 0.221460 | 0.417872 | 0.499312 | 0.173* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0350 (8) | 0.0568 (13) | 0.0456 (15) | 0.0015 (9) | −0.0037 (9) | −0.0028 (10) |
O1 | 0.0355 (7) | 0.0914 (15) | 0.0576 (15) | 0.0036 (9) | −0.0045 (8) | −0.0161 (11) |
C1 | 0.0498 (12) | 0.0575 (16) | 0.046 (2) | 0.0045 (12) | 0.0016 (12) | 0.0016 (13) |
C2 | 0.0613 (14) | 0.0718 (19) | 0.048 (2) | 0.0082 (15) | 0.0084 (14) | 0.0013 (15) |
C3 | 0.0713 (16) | 0.0646 (18) | 0.040 (2) | 0.0006 (14) | 0.0069 (14) | 0.0002 (14) |
C4 | 0.0680 (15) | 0.0657 (18) | 0.042 (2) | 0.0115 (14) | 0.0011 (14) | 0.0083 (14) |
C5 | 0.0581 (13) | 0.0486 (15) | 0.0418 (18) | 0.0087 (12) | 0.0010 (12) | 0.0034 (12) |
C6 | 0.0619 (14) | 0.076 (2) | 0.046 (2) | 0.0208 (15) | −0.0041 (14) | 0.0093 (15) |
C7 | 0.0536 (13) | 0.0654 (18) | 0.0468 (19) | 0.0197 (13) | 0.0000 (12) | 0.0070 (14) |
C8 | 0.0413 (10) | 0.0438 (13) | 0.0396 (17) | 0.0041 (10) | −0.0042 (10) | 0.0028 (11) |
C9 | 0.0423 (10) | 0.0379 (12) | 0.0388 (16) | 0.0002 (9) | −0.0019 (10) | −0.0004 (10) |
C10 | 0.0466 (11) | 0.0412 (12) | 0.0365 (17) | 0.0012 (11) | −0.0025 (11) | −0.0005 (11) |
C11 | 0.0464 (11) | 0.0585 (15) | 0.0397 (19) | 0.0111 (11) | −0.0071 (11) | −0.0047 (12) |
C12 | 0.0383 (10) | 0.0407 (12) | 0.0388 (16) | 0.0012 (10) | −0.0051 (10) | −0.0004 (11) |
C13 | 0.0366 (9) | 0.0415 (13) | 0.0389 (16) | −0.0024 (10) | −0.0050 (10) | −0.0008 (11) |
C14 | 0.0387 (10) | 0.0419 (13) | 0.0445 (17) | 0.0024 (10) | 0.0002 (11) | 0.0009 (11) |
C15 | 0.0429 (11) | 0.0685 (17) | 0.047 (2) | 0.0135 (12) | 0.0003 (12) | 0.0064 (13) |
C16 | 0.0372 (10) | 0.0562 (15) | 0.0451 (18) | 0.0000 (11) | 0.0039 (11) | −0.0007 (12) |
C17 | 0.0355 (10) | 0.0530 (14) | 0.0391 (17) | −0.0037 (10) | −0.0009 (10) | −0.0036 (12) |
C18 | 0.0583 (14) | 0.0509 (15) | 0.049 (2) | −0.0131 (12) | −0.0062 (13) | 0.0027 (13) |
C19 | 0.0732 (16) | 0.0485 (15) | 0.046 (2) | −0.0019 (13) | −0.0038 (15) | −0.0047 (13) |
C20 | 0.0425 (11) | 0.0718 (18) | 0.0413 (19) | 0.0020 (12) | −0.0011 (11) | 0.0046 (14) |
C21 | 0.0481 (13) | 0.152 (3) | 0.046 (2) | 0.0102 (18) | −0.0069 (14) | 0.015 (2) |
C22 | 0.0408 (11) | 0.0627 (16) | 0.0383 (17) | −0.0033 (11) | −0.0045 (11) | −0.0036 (13) |
O22 | 0.0362 (7) | 0.0722 (12) | 0.0383 (12) | −0.0022 (8) | −0.0024 (7) | −0.0006 (8) |
C23 | 0.0510 (13) | 0.0698 (18) | 0.052 (2) | −0.0077 (13) | 0.0011 (13) | 0.0043 (15) |
C24 | 0.0506 (13) | 0.092 (2) | 0.052 (2) | −0.0025 (14) | 0.0115 (13) | 0.0122 (17) |
C25 | 0.0643 (15) | 0.094 (2) | 0.041 (2) | 0.0110 (16) | 0.0077 (15) | 0.0012 (17) |
C26 | 0.0676 (16) | 0.074 (2) | 0.057 (2) | −0.0006 (15) | 0.0025 (15) | −0.0153 (16) |
O26 | 0.0514 (9) | 0.0753 (13) | 0.0503 (14) | −0.0099 (9) | −0.0010 (9) | −0.0140 (10) |
C27 | 0.088 (2) | 0.121 (3) | 0.072 (3) | 0.030 (2) | 0.024 (2) | 0.006 (2) |
O27 | 0.0795 (13) | 0.0911 (16) | 0.0404 (14) | −0.0015 (12) | 0.0103 (11) | −0.0018 (11) |
C28 | 0.091 (2) | 0.103 (3) | 0.059 (3) | −0.006 (2) | 0.025 (2) | 0.003 (2) |
O28 | 0.115 (2) | 0.171 (3) | 0.094 (3) | −0.055 (2) | 0.0312 (19) | −0.017 (2) |
C29 | 0.127 (3) | 0.167 (5) | 0.052 (3) | 0.004 (3) | 0.033 (3) | −0.010 (3) |
N1—C12 | 1.275 (3) | C15—H15B | 0.9700 |
N1—O1 | 1.416 (2) | C16—O22 | 1.439 (3) |
O1—H1 | 0.91 (4) | C16—C17 | 1.551 (3) |
C1—C2 | 1.535 (4) | C16—H16A | 0.9800 |
C1—C10 | 1.539 (3) | C17—C20 | 1.534 (4) |
C1—H1A | 0.9700 | C17—H17A | 0.9800 |
C1—H1B | 0.9700 | C18—H18A | 0.9600 |
C2—C3 | 1.515 (4) | C18—H18B | 0.9600 |
C2—H2A | 0.9700 | C18—H18C | 0.9600 |
C2—H2B | 0.9700 | C19—H19A | 0.9600 |
C3—O27 | 1.459 (4) | C19—H19B | 0.9600 |
C3—C4 | 1.513 (4) | C19—H19C | 0.9600 |
C3—H3A | 0.9800 | C20—C21 | 1.526 (4) |
C4—C5 | 1.526 (4) | C20—C22 | 1.538 (3) |
C4—H4A | 0.9700 | C20—H20A | 0.9800 |
C4—H4B | 0.9700 | C21—H21A | 0.9600 |
C5—C6 | 1.522 (3) | C21—H21B | 0.9600 |
C5—C10 | 1.551 (4) | C21—H21C | 0.9600 |
C5—H5A | 0.9800 | C22—O26 | 1.412 (3) |
C6—C7 | 1.511 (4) | C22—O22 | 1.433 (3) |
C6—H6A | 0.9700 | C22—C23 | 1.508 (4) |
C6—H6B | 0.9700 | C23—C24 | 1.516 (4) |
C7—C8 | 1.528 (4) | C23—H23A | 0.9700 |
C7—H7A | 0.9700 | C23—H23B | 0.9700 |
C7—H7B | 0.9700 | C24—C25 | 1.515 (4) |
C8—C14 | 1.520 (4) | C24—H24A | 0.9700 |
C8—C9 | 1.543 (3) | C24—H24B | 0.9700 |
C8—H8A | 0.9800 | C25—C26 | 1.506 (4) |
C9—C11 | 1.537 (4) | C25—C27 | 1.528 (4) |
C9—C10 | 1.554 (4) | C25—H25A | 0.9800 |
C9—H9A | 0.9800 | C26—O26 | 1.429 (3) |
C10—C19 | 1.537 (4) | C26—H26A | 0.9700 |
C11—C12 | 1.507 (4) | C26—H26B | 0.9700 |
C11—H11A | 0.9700 | C27—H27A | 0.9600 |
C11—H11B | 0.9700 | C27—H27B | 0.9600 |
C12—C13 | 1.512 (3) | C27—H27C | 0.9600 |
C13—C18 | 1.528 (3) | O27—C28 | 1.328 (4) |
C13—C17 | 1.548 (4) | C28—O28 | 1.205 (5) |
C13—C14 | 1.550 (4) | C28—C29 | 1.486 (5) |
C14—C15 | 1.529 (3) | C29—H29A | 0.9600 |
C14—H14A | 0.9800 | C29—H29B | 0.9600 |
C15—C16 | 1.524 (4) | C29—H29C | 0.9600 |
C15—H15A | 0.9700 | ||
C12—N1—O1 | 111.9 (2) | C14—C15—H15B | 111.4 |
N1—O1—H1 | 109 (2) | H15A—C15—H15B | 109.2 |
C2—C1—C10 | 113.9 (2) | O22—C16—C15 | 113.38 (19) |
C2—C1—H1A | 108.8 | O22—C16—C17 | 105.3 (2) |
C10—C1—H1A | 108.8 | C15—C16—C17 | 108.2 (2) |
C2—C1—H1B | 108.8 | O22—C16—H16A | 109.9 |
C10—C1—H1B | 108.8 | C15—C16—H16A | 109.9 |
H1A—C1—H1B | 107.7 | C17—C16—H16A | 109.9 |
C3—C2—C1 | 111.2 (2) | C20—C17—C13 | 120.0 (2) |
C3—C2—H2A | 109.4 | C20—C17—C16 | 104.29 (18) |
C1—C2—H2A | 109.4 | C13—C17—C16 | 104.05 (19) |
C3—C2—H2B | 109.4 | C20—C17—H17A | 109.3 |
C1—C2—H2B | 109.4 | C13—C17—H17A | 109.3 |
H2A—C2—H2B | 108.0 | C16—C17—H17A | 109.3 |
O27—C3—C4 | 106.4 (2) | C13—C18—H18A | 109.5 |
O27—C3—C2 | 109.7 (2) | C13—C18—H18B | 109.5 |
C4—C3—C2 | 111.9 (2) | H18A—C18—H18B | 109.5 |
O27—C3—H3A | 109.6 | C13—C18—H18C | 109.5 |
C4—C3—H3A | 109.6 | H18A—C18—H18C | 109.5 |
C2—C3—H3A | 109.6 | H18B—C18—H18C | 109.5 |
C3—C4—C5 | 111.4 (2) | C10—C19—H19A | 109.5 |
C3—C4—H4A | 109.3 | C10—C19—H19B | 109.5 |
C5—C4—H4A | 109.3 | H19A—C19—H19B | 109.5 |
C3—C4—H4B | 109.3 | C10—C19—H19C | 109.5 |
C5—C4—H4B | 109.3 | H19A—C19—H19C | 109.5 |
H4A—C4—H4B | 108.0 | H19B—C19—H19C | 109.5 |
C6—C5—C4 | 111.8 (2) | C21—C20—C17 | 115.1 (2) |
C6—C5—C10 | 111.8 (2) | C21—C20—C22 | 114.5 (2) |
C4—C5—C10 | 112.9 (2) | C17—C20—C22 | 103.8 (2) |
C6—C5—H5A | 106.6 | C21—C20—H20A | 107.7 |
C4—C5—H5A | 106.6 | C17—C20—H20A | 107.7 |
C10—C5—H5A | 106.6 | C22—C20—H20A | 107.7 |
C7—C6—C5 | 111.3 (2) | C20—C21—H21A | 109.5 |
C7—C6—H6A | 109.4 | C20—C21—H21B | 109.5 |
C5—C6—H6A | 109.4 | H21A—C21—H21B | 109.5 |
C7—C6—H6B | 109.4 | C20—C21—H21C | 109.5 |
C5—C6—H6B | 109.4 | H21A—C21—H21C | 109.5 |
H6A—C6—H6B | 108.0 | H21B—C21—H21C | 109.5 |
C6—C7—C8 | 113.6 (2) | O26—C22—O22 | 109.4 (2) |
C6—C7—H7A | 108.9 | O26—C22—C23 | 111.3 (2) |
C8—C7—H7A | 108.9 | O22—C22—C23 | 108.22 (19) |
C6—C7—H7B | 108.9 | O26—C22—C20 | 107.67 (19) |
C8—C7—H7B | 108.9 | O22—C22—C20 | 103.5 (2) |
H7A—C7—H7B | 107.7 | C23—C22—C20 | 116.4 (2) |
C14—C8—C7 | 111.6 (2) | C22—O22—C16 | 106.66 (16) |
C14—C8—C9 | 107.89 (19) | C22—C23—C24 | 112.0 (2) |
C7—C8—C9 | 111.6 (2) | C22—C23—H23A | 109.2 |
C14—C8—H8A | 108.5 | C24—C23—H23A | 109.2 |
C7—C8—H8A | 108.5 | C22—C23—H23B | 109.2 |
C9—C8—H8A | 108.5 | C24—C23—H23B | 109.2 |
C11—C9—C8 | 111.4 (2) | H23A—C23—H23B | 107.9 |
C11—C9—C10 | 114.36 (19) | C25—C24—C23 | 111.3 (2) |
C8—C9—C10 | 112.82 (19) | C25—C24—H24A | 109.4 |
C11—C9—H9A | 105.8 | C23—C24—H24A | 109.4 |
C8—C9—H9A | 105.8 | C25—C24—H24B | 109.4 |
C10—C9—H9A | 105.8 | C23—C24—H24B | 109.4 |
C19—C10—C1 | 109.2 (2) | H24A—C24—H24B | 108.0 |
C19—C10—C5 | 112.5 (2) | C26—C25—C24 | 108.9 (3) |
C1—C10—C5 | 107.3 (2) | C26—C25—C27 | 111.2 (3) |
C19—C10—C9 | 111.2 (2) | C24—C25—C27 | 112.1 (3) |
C1—C10—C9 | 109.9 (2) | C26—C25—H25A | 108.2 |
C5—C10—C9 | 106.61 (19) | C24—C25—H25A | 108.2 |
C12—C11—C9 | 113.3 (2) | C27—C25—H25A | 108.2 |
C12—C11—H11A | 108.9 | O26—C26—C25 | 112.8 (3) |
C9—C11—H11A | 108.9 | O26—C26—H26A | 109.0 |
C12—C11—H11B | 108.9 | C25—C26—H26A | 109.0 |
C9—C11—H11B | 108.9 | O26—C26—H26B | 109.0 |
H11A—C11—H11B | 107.7 | C25—C26—H26B | 109.0 |
N1—C12—C11 | 126.5 (2) | H26A—C26—H26B | 107.8 |
N1—C12—C13 | 117.6 (2) | C22—O26—C26 | 113.50 (19) |
C11—C12—C13 | 115.9 (2) | C25—C27—H27A | 109.5 |
C12—C13—C18 | 109.0 (2) | C25—C27—H27B | 109.5 |
C12—C13—C17 | 116.93 (19) | H27A—C27—H27B | 109.5 |
C18—C13—C17 | 112.0 (2) | C25—C27—H27C | 109.5 |
C12—C13—C14 | 105.97 (19) | H27A—C27—H27C | 109.5 |
C18—C13—C14 | 111.69 (19) | H27B—C27—H27C | 109.5 |
C17—C13—C14 | 100.90 (19) | C28—O27—C3 | 118.8 (3) |
C8—C14—C15 | 120.3 (2) | O28—C28—O27 | 123.3 (4) |
C8—C14—C13 | 114.6 (2) | O28—C28—C29 | 125.8 (4) |
C15—C14—C13 | 103.1 (2) | O27—C28—C29 | 110.8 (4) |
C8—C14—H14A | 105.9 | C28—C29—H29A | 109.5 |
C15—C14—H14A | 105.9 | C28—C29—H29B | 109.5 |
C13—C14—H14A | 105.9 | H29A—C29—H29B | 109.5 |
C16—C15—C14 | 102.04 (19) | C28—C29—H29C | 109.5 |
C16—C15—H15A | 111.4 | H29A—C29—H29C | 109.5 |
C14—C15—H15A | 111.4 | H29B—C29—H29C | 109.5 |
C16—C15—H15B | 111.4 | ||
C10—C1—C2—C3 | −54.9 (3) | C17—C13—C14—C8 | 179.03 (18) |
C1—C2—C3—O27 | 171.1 (2) | C12—C13—C14—C15 | 168.8 (2) |
C1—C2—C3—C4 | 53.2 (3) | C18—C13—C14—C15 | −72.6 (3) |
O27—C3—C4—C5 | −174.3 (2) | C17—C13—C14—C15 | 46.5 (2) |
C2—C3—C4—C5 | −54.5 (3) | C8—C14—C15—C16 | −170.7 (2) |
C3—C4—C5—C6 | −176.1 (3) | C13—C14—C15—C16 | −41.6 (2) |
C3—C4—C5—C10 | 56.7 (3) | C14—C15—C16—O22 | 137.2 (2) |
C4—C5—C6—C7 | 173.6 (2) | C14—C15—C16—C17 | 20.8 (3) |
C10—C5—C6—C7 | −58.6 (3) | C12—C13—C17—C20 | 97.2 (3) |
C5—C6—C7—C8 | 52.1 (3) | C18—C13—C17—C20 | −29.5 (3) |
C6—C7—C8—C14 | −170.0 (2) | C14—C13—C17—C20 | −148.44 (19) |
C6—C7—C8—C9 | −49.1 (3) | C12—C13—C17—C16 | −146.8 (2) |
C14—C8—C9—C11 | −54.0 (3) | C18—C13—C17—C16 | 86.5 (2) |
C7—C8—C9—C11 | −177.0 (2) | C14—C13—C17—C16 | −32.4 (2) |
C14—C8—C9—C10 | 175.84 (19) | O22—C16—C17—C20 | 12.7 (3) |
C7—C8—C9—C10 | 52.8 (3) | C15—C16—C17—C20 | 134.2 (2) |
C2—C1—C10—C19 | −67.8 (3) | O22—C16—C17—C13 | −113.9 (2) |
C2—C1—C10—C5 | 54.4 (3) | C15—C16—C17—C13 | 7.6 (3) |
C2—C1—C10—C9 | 170.0 (2) | C13—C17—C20—C21 | −106.5 (3) |
C6—C5—C10—C19 | −62.1 (3) | C16—C17—C20—C21 | 137.6 (3) |
C4—C5—C10—C19 | 65.1 (3) | C13—C17—C20—C22 | 127.6 (2) |
C6—C5—C10—C1 | 177.7 (2) | C16—C17—C20—C22 | 11.7 (3) |
C4—C5—C10—C1 | −55.1 (3) | C21—C20—C22—O26 | −42.8 (3) |
C6—C5—C10—C9 | 60.0 (3) | C17—C20—C22—O26 | 83.5 (3) |
C4—C5—C10—C9 | −172.8 (2) | C21—C20—C22—O22 | −158.6 (2) |
C11—C9—C10—C19 | −62.9 (3) | C17—C20—C22—O22 | −32.3 (2) |
C8—C9—C10—C19 | 65.7 (3) | C21—C20—C22—C23 | 82.9 (3) |
C11—C9—C10—C1 | 58.1 (3) | C17—C20—C22—C23 | −150.8 (2) |
C8—C9—C10—C1 | −173.2 (2) | O26—C22—O22—C16 | −72.4 (2) |
C11—C9—C10—C5 | 174.1 (2) | C23—C22—O22—C16 | 166.2 (2) |
C8—C9—C10—C5 | −57.2 (2) | C20—C22—O22—C16 | 42.2 (2) |
C8—C9—C11—C12 | 50.0 (3) | C15—C16—O22—C22 | −152.7 (2) |
C10—C9—C11—C12 | 179.39 (19) | C17—C16—O22—C22 | −34.5 (2) |
O1—N1—C12—C11 | 1.1 (3) | O26—C22—C23—C24 | −52.4 (3) |
O1—N1—C12—C13 | 179.3 (2) | O22—C22—C23—C24 | 67.9 (3) |
C9—C11—C12—N1 | 127.4 (3) | C20—C22—C23—C24 | −176.2 (2) |
C9—C11—C12—C13 | −50.8 (3) | C22—C23—C24—C25 | 51.2 (3) |
N1—C12—C13—C18 | 113.2 (2) | C23—C24—C25—C26 | −51.5 (3) |
C11—C12—C13—C18 | −68.4 (3) | C23—C24—C25—C27 | −175.1 (3) |
N1—C12—C13—C17 | −15.0 (3) | C24—C25—C26—O26 | 55.2 (3) |
C11—C12—C13—C17 | 163.4 (2) | C27—C25—C26—O26 | 179.3 (3) |
N1—C12—C13—C14 | −126.4 (2) | O22—C22—O26—C26 | −63.4 (3) |
C11—C12—C13—C14 | 51.9 (3) | C23—C22—O26—C26 | 56.2 (3) |
C7—C8—C14—C15 | −52.0 (3) | C20—C22—O26—C26 | −175.2 (2) |
C9—C8—C14—C15 | −175.0 (2) | C25—C26—O26—C22 | −59.0 (3) |
C7—C8—C14—C13 | −175.77 (19) | C4—C3—O27—C28 | −155.5 (3) |
C9—C8—C14—C13 | 61.2 (2) | C2—C3—O27—C28 | 83.2 (3) |
C12—C13—C14—C8 | −58.6 (2) | C3—O27—C28—O28 | 0.8 (6) |
C18—C13—C14—C8 | 59.9 (3) | C3—O27—C28—C29 | −176.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O22i | 0.91 (4) | 1.89 (4) | 2.781 (2) | 166 (3) |
C15—H15A···O1ii | 0.97 | 2.52 | 3.320 (3) | 139 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Acknowledgements
The reported structure is the first one collected using the new X-ray facility installed at IF-UAP, Puebla. The authors thank the funding agency (CONACyT), VIEP–BUAP for support, and the companies involved in the installation: Spectramex SA de CV (Mexico), and Stoe & Cie GmbH (Darmstadt, Germany), with special thanks to Dr rer. nat. Jens Meyer and Dipl.-Phys. Steffen Sandner. MGHL thanks BUAP for financial support (PRODEP-NPTC-DSA/103.5/16/10420).
Funding information
Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnologíahttps://doi.org/10.13039/501100003141 (award No. 268178, Infraestructura); Benemérita Universidad Autónoma de Pueblahttps://doi.org/10.13039/501100006348 (award No. PRODEP-NPTC-DSA/103.5/16/10420).
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