research communications
S,5S,7aS,7bS,9aR,10R,12aR,12bS)-7b-hydroxy-4,4,7a,9a,12a-pentamethyl-10-[(2′R)-6-methylheptan-2-yl]-2,8,9-trioxooctadecahydrobenzo[d]indeno[4,5-b]azepin-5-yl acetate from 62-year-old crystals
of (3aaCryssmat-Lab/DETEMA, Facultad de Química, Universidad de la República, Av., Gral., Flores 2124, Montevideo 11800, Uruguay, and bDepartamento de Química Orgánica, Facultad de Química, Universidad de la República, Av. Gral. Flores 2124, Montevideo 11800, Uruguay
*Correspondence e-mail: leopoldo@fq.edu.uy
The structure of the title compound, C32H51NO6, was determined from 62-year-old crystals at room temperature and refined with 100 K data in a monoclinic (C2) This compound with a triterpenoid structure, now confirmed by this study, played an important role in the determination of the structure of lanosterol. The molecules pack in linear O—H⋯O hydrogen-bonded chains along the short axis (b), while parallel chains display weak van der Waals interactions that explain the needle-shaped crystal morphology. The structure exhibits disorder of the flexible methylheptane chain at one end of the main molecule with a small void around it. Crystals of the compounds were resistant to data collection for decades with the available cameras and Mo Kα radiation single-crystal diffractometer in our laboratory until a new instrument with Cu Kα radiation operating at 100 K allowed the structure to be solved and refined.
Keywords: crystal structure; terpenoid; lanosterol; old crystals; disorder.
CCDC reference: 1946967
1. Chemical context
Crystals of the title compound were obtained by Professor M. R. Falco (1922–2015) in 1952 after a spectroscopic et al., 1952) that was relevant for the correct determination of the structure of lanosterol (Eschenmoser et al., 1955) and were handed in the glass vial shown in Fig. 1 to Professor R. Mariezcurrena (1940–2016) in the late 80′s for by X-ray diffraction. was elusive for many years (see the Supramolecular features section for reasons) since the very thin needles available produced no measurable diffraction intensities with the available Weissenberg or Bürger cameras or a sealed-tube Mo Kα source diffractometer with a scintillator detector available at the laboratory over that period. The availability of a diffractometer with a Cu Kα source (acquired and installed at our institution in 2014 during the IYCr) allowed for the determination of the structure at room temperature where significant positional disorder of the terminal aliphatic chain was observed. Data collection at 100 K allowed for the structure reported herein, which confirms the structure determined spectroscopically in the 50′s. Professor Mariezcurrena had the chance to see the final structural model of the RT before passing away. We dedicate this manuscript to his memory, teachings and patience in keeping the glass vial in a safe place allowing for this report of the successful structure determination.
(Falco2. Structural commentary
The title compound, shown in Fig. 2 with the numbering scheme, is a tetracyclic triterpenoid with six-, seven-, six and five-membered fused rings, with no insaturations except for three exocyclic carbonyl moieties at C2, C8 and C9. The first two rings define a hydrogenated benzazepine unit while the last two define a hydrogenated indene group. The presence of fused rings of different sizes, one heteroatom and different C-atom states, together with a large number of exocyclic substituents, leads to a very strained bonding arrangement within the ring system. A full geometrical analysis performed with Mogul 1.8.2 (Build 248885) running on the May 2019 update of the CSD (Groom et al., 2016) shows that all bridgehead atoms in the molecule show atypical bond distances or angles. Table 1 shows all the bond distances and bond angles that were unexpected according to the z-score criterion in Mogul. In this table we find that C3A and C7A (bridgehead atoms in the benzazepine bicycle) C7B and C12B (bridgehead atoms of the fused azepine and indene groups) and C9A (bridgehead atom in the indene bicycle) display unusual bond distances [long C3A—C7A = 1.584 (4), C7B—C8 = 1.580 (4), C7B—C12B = 1.578 (4) Å and short C9—C9A = 1.500 (4) Å] and C7B, C9A and C12A show unusual bond angles [low O7—C7B—C8 = 97.7 (2), C12A—C9A—C9 = 102.5 (2), C12—C12A—C9A = 101.1 (2)°] in addition to other unusual features.
Another significant contribution to the strain in this region of the molecule is the diketone group C7B—C8(=O8)—C9(=O9)—C9A that also shows an elongated Csp2—Csp2 bond [C8—C9 of 1.549 (5) Å] and a large O8—C8—C9—O9 torsion angle of −43.7 (5)°. Repulsion between O8 and O9 leads to the increase of the torsion angle in the cis diketone group and lengthening of the C8—C9 bond distance, contributing to the unusual conformation of the C7B/C8/C9/C9A/C12A/C12B ring. Puckering parameters for this ring are θ = 149°(or 31° considering the inverted order of atoms) and Φ = 13.5°, which fall far from all usual parameters for frequently observed geometries of six-membered rings, between a chair and a half-chair conformation, confirming the effects of the observed bond distances and angles. Considering a distorted chair conformation, atom C7B is only 0.394 (5) Å away from the C8/C9/C12A/C12B plane [maximum deviation of 0.0382 (17) Å], while C9A is on the other side of the plane, displaced by 0.821 (4) Å. The seven-membered ring shows a chair conformation with atoms N1 and C1 lying 1.163 (5) and 1.137 (4) Å, respectively, above and C7A 0.721 (4) Å below the almost planar C3/C3A/C12B/C7B group of atoms [maximum deviation of 0.038 (1) Å for C3A]. The five-membered ring exhibits a half-chair conformation with puckering parameter Φ = 344.2 (5)°, atom C12A lying 0.655 (5) Å away from the C9A/C10–C12 plane [maximum deviation of 0.094 (2) Å for C11]. The remaining six-membered ring (C3A/C4–C7/C7A) has puckering parameters θ = 170° and Φ = 326° with atoms C5 and C7A located 0.703 (4) and −0.617 (5) Å, respectively, away from the C3A/C4/C6/C7 plane [maximum deviation of 0.0271 (16) Å for C6]. The conformation of the four rings, with most of the substituents in an equatorial configuration, makes the ring system almost planar with maximum deviations for N1 and C3 [0.794 (3) and −0.616 (3) Å, respectively] on either side. The six-methyl heptane chain C1′ to C8′ shows positional disorder, modelled over two sites with occupancies of 0.819 (6) and 0.181 (6), around a structural void of 36 Å3 surrounded by equivalent aliphatic chains. At room temperature, this chain could not be modelled properly over two sites.
3. Supramolecular features
In the crystal, molecules of the title compound pack in an elongated conformation laying parallel to the [102] direction. The packing is directed by O7—H7⋯O2i hydrogen bonds (see Table 2, Fig. 3), forming zigzag chains running along the [010] direction (determined using PLATON software; Spek, 2009). These chains are connected in the [001] direction through weak C—H⋯O interactions: C71—H71A⋯O8ii and C121—H12E⋯O52iii with H71A⋯O8ii and H12E⋯O52iii distances of 2.55 and 2.53 Å, respectively [symmetry codes: (ii) −x + , y − , −z + 1; (iii) −x + , y − , −z]. These interactions define double planes of molecules with the polar regions of the molecules in contact, leaving the terminal aliphatic chains pointing outwards. Parallel planes are only weakly bound by dispersion forces: indeed, voids of ca 39 Å3 are found between non-polar residues from parallel planes (Fig. 4). These strong interactions along [010], weak along [001] and very weak along [100] nicely explain the flat needle crystal shape observed where face indexing suggests the needle length and longer dimension of the largest planes is [010], the shorter dimension of the planes is [001] and the very narrow width of the crystals is [100]. The large the presence of positional disorder (aggravated at room temperature) and voids in the combined with the C, H, N and O composition of the crystals explain the poor scattering power that prevented with older instruments.
4. Database survey
The May 2019 update of the CSD (Groom et al., 2016) contains no compounds displaying the same arrangement of six-, seven-, six- and five-membered rings (disregarding bond type) with an N atom in the seven-membered ring. Three pentacyclic compounds with a tetrazole ring at N1—C2 have been reported [LEXVOB (Alam et al., 2013), TZANDT (Husain et al., 1981) and VEVLAK (Rajnikant et al., 2006)], the former and latter showing very similar molecular conformation and interactions that lead to very similar unit-cell dimensions (∼35×6×12 Å). There is only one entry with the same six-, seven-, six- and five-membered ring combination containing O instead of N (HIXSAI; Morales et al., 1999) but the configuration of C5 is inverted and therefore the dihedral angle between mean planes of the six- and seven-membered rings differ significantly and thus also the molecular conformation. There are also three tetracyclic compounds with no heteroatom in the ring arrangement [OQIVIU (Kranz et al., 2011), UBEDIO (Wang et al., 2000) and WECQAY (Kranz et al., 2012)] all showing very different stereochemistry; therefore, the molecular conformations are not comparable. This is, therefore, the first report of this 6-7-6-5 ring system containing the azepine ring.
5. Synthesis and crystallization
Synthesis and crystallization were reported by Falco et al. (1952). Crystals were not recrystallized after the initial preparation.
6. Refinement
Crystal data, data collection and structure . C- and N-bound H atoms were placed in calculated positions (C—H = 0.93–0.99, N—H = 0.87 Å) and included as riding contributions. The OH H atom was found in a difference-Fourier map and refined as riding with a rotating torsion angle and O—H distance restraint. All H atoms were refined with isotropic displacement parameters set at 1.2–1.5 times the Ueq value of the parent atom.
details are summarized in Table 3
|
Supporting information
CCDC reference: 1946967
https://doi.org/10.1107/S205698901901140X/ex2022sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901901140X/ex2022Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).C32H51NO6 | F(000) = 1192 |
Mr = 545.73 | Dx = 1.190 Mg m−3 |
Monoclinic, C2 | Cu Kα radiation, λ = 1.54178 Å |
a = 34.882 (4) Å | Cell parameters from 95 reflections |
b = 6.5332 (11) Å | θ = 12.3–47.3° |
c = 13.6021 (16) Å | µ = 0.64 mm−1 |
β = 100.599 (14)° | T = 100 K |
V = 3046.9 (7) Å3 | Flat needles, yellow |
Z = 4 | 0.44 × 0.33 × 0.09 mm |
Bruker D8 Venture diffractometer | 5509 independent reflections |
Radiation source: Incoatec I microsource | 5056 reflections with I > 2σ(I) |
Detector resolution: 10.4167 pixels mm-1 | Rint = 0.034 |
ω and φ scans | θmax = 68.4°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −38→42 |
Tmin = 0.804, Tmax = 0.946 | k = −7→7 |
14487 measured reflections | l = −14→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0771P)2 + 1.6616P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
5509 reflections | Δρmax = 0.41 e Å−3 |
410 parameters | Δρmin = −0.19 e Å−3 |
179 restraints | Absolute structure: Flack x determined using 2070 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: dual | Absolute structure parameter: 0.09 (10) |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 14.9003(0.0756)x + 4.8675(0.0079)y - 7.9183(0.0216)z = 11.1840(0.0683) * -0.0587 (0.0014) C9A * 0.0916 (0.0021) C10 * -0.0937 (0.0022) C11 * 0.0609 (0.0015) C12 0.6554 (0.0051) C12A Rms deviation of fitted atoms = 0.0780 10.0303(0.0705)x + 4.8288(0.0060)y - 8.8634(0.0137)z = 7.4252(0.0575) Angle to previous plane (with approximate esd) = 9.752 ( 0.251 ) * 0.0382 (0.0017) C12A * -0.0354 (0.0015) C12B * 0.0351 (0.0015) C8 * -0.0379 (0.0017) C9 -0.8207 (0.0043) C9A 0.3944 (0.0051) C7B Rms deviation of fitted atoms = 0.0367 14.5476(0.0446)x + 3.1069(0.0108)y - 11.3991(0.0111)z = 9.7791(0.0311) Angle to previous plane (with approximate esd) = 19.404 ( 0.209 ) * -0.0351 (0.0015) C3 * 0.0382 (0.0016) C3A * -0.0374 (0.0016) C7B * 0.0343 (0.0015) C12B -0.7211 (0.0042) C7A 1.1626 (0.0045) C2 1.1371 (0.0040) N1 Rms deviation of fitted atoms = 0.0363 6.8164(0.0691)x + 4.5554(0.0061)y - 9.7096(0.0126)z = 5.1714(0.0475) Angle to previous plane (with approximate esd) = 18.692 ( 0.202 ) * -0.0271 (0.0016) C6 * 0.0261 (0.0015) C4 * 0.0270 (0.0016) C7 * -0.0261 (0.0015) C3A 0.7034 (0.0044) C5 -0.6172 (0.0045) C7A Rms deviation of fitted atoms = 0.0266 10.0303(0.0705)x + 4.8288(0.0060)y - 8.8634(0.0137)z = 7.4252(0.0575) Angle to previous plane (with approximate esd) = 7.415 ( 0.200 ) * 0.0382 (0.0017) C12A * -0.0354 (0.0015) C12B * 0.0351 (0.0015) C8 * -0.0379 (0.0017) C9 -0.8207 (0.0043) C9A 0.3944 (0.0051) C7B 0.1064 (0.0121) C4 0.4530 (0.0094) C7 0.0351 (0.0015) C8 0.0382 (0.0017) C12A Rms deviation of fitted atoms = 0.0367 14.4178(0.0111)x + 4.8025(0.0030)y - 8.2192(0.0070)z = 10.9550(0.0080) Angle to previous plane (with approximate esd) = 8.306 ( 0.172 ) * -0.3830 (0.0029) C9A * -0.2601 (0.0031) C10 * -0.4143 (0.0034) C11 * -0.2168 (0.0034) C12 * 0.3709 (0.0030) C12A * 0.0762 (0.0030) C12B * 0.4094 (0.0031) C7B * 0.1967 (0.0033) C8 * 0.3447 (0.0029) C9 * -0.1036 (0.0028) C3A * -0.6156 (0.0029) C3 * 0.5099 (0.0029) C2 * 0.7943 (0.0028) N1 * -0.3837 (0.0029) C7A * 0.1748 (0.0031) C7 * -0.2604 (0.0029) C6 * 0.2105 (0.0029) C5 * -0.4499 (0.0028) C4 Rms deviation of fitted atoms = 0.3855 All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.79213 (8) | 0.2991 (4) | 0.13482 (19) | 0.0333 (6) | |
H1 | 0.8127 (12) | 0.336 (7) | 0.112 (3) | 0.040* | |
C2 | 0.76039 (9) | 0.2296 (5) | 0.0731 (2) | 0.0328 (7) | |
O2 | 0.75912 (7) | 0.2260 (4) | −0.01801 (15) | 0.0388 (5) | |
C3 | 0.72638 (10) | 0.1796 (5) | 0.1211 (2) | 0.0352 (7) | |
H3A | 0.734863 | 0.096037 | 0.181978 | 0.042* | |
H3B | 0.706632 | 0.101249 | 0.074346 | 0.042* | |
C3A | 0.70900 (9) | 0.3854 (5) | 0.1486 (2) | 0.0306 (7) | |
H3C | 0.718787 | 0.487501 | 0.104353 | 0.037* | |
C4 | 0.66354 (10) | 0.3882 (5) | 0.1126 (2) | 0.0336 (7) | |
C41 | 0.64140 (10) | 0.2211 (6) | 0.1579 (3) | 0.0443 (8) | |
H41A | 0.654842 | 0.089874 | 0.155829 | 0.066* | |
H41B | 0.614821 | 0.210457 | 0.119331 | 0.066* | |
H41C | 0.640359 | 0.255936 | 0.227404 | 0.066* | |
C42 | 0.65520 (10) | 0.3588 (6) | −0.0024 (2) | 0.0394 (8) | |
H42A | 0.659808 | 0.215645 | −0.018299 | 0.059* | |
H42B | 0.672523 | 0.447548 | −0.032513 | 0.059* | |
H42C | 0.627994 | 0.394661 | −0.029059 | 0.059* | |
C5 | 0.65000 (9) | 0.6039 (5) | 0.1346 (2) | 0.0330 (7) | |
H5 | 0.662480 | 0.704375 | 0.094807 | 0.040* | |
O51 | 0.60807 (7) | 0.6204 (4) | 0.10484 (17) | 0.0401 (5) | |
C51 | 0.59429 (11) | 0.7431 (6) | 0.0266 (3) | 0.0442 (8) | |
O52 | 0.61444 (8) | 0.8312 (5) | −0.0233 (2) | 0.0529 (7) | |
C52 | 0.55092 (12) | 0.7562 (8) | 0.0117 (4) | 0.0652 (12) | |
H52A | 0.541075 | 0.833687 | −0.049392 | 0.098* | |
H52B | 0.543343 | 0.825485 | 0.069126 | 0.098* | |
H52C | 0.539831 | 0.617917 | 0.005627 | 0.098* | |
C6 | 0.66096 (9) | 0.6595 (5) | 0.2436 (2) | 0.0353 (7) | |
H6A | 0.650464 | 0.555997 | 0.284763 | 0.042* | |
H6B | 0.649609 | 0.794079 | 0.255533 | 0.042* | |
C7 | 0.70501 (9) | 0.6684 (5) | 0.2732 (2) | 0.0343 (7) | |
H7A | 0.711885 | 0.708535 | 0.344415 | 0.041* | |
H7B | 0.714916 | 0.776287 | 0.233210 | 0.041* | |
C7A | 0.72588 (10) | 0.4639 (5) | 0.2582 (2) | 0.0306 (7) | |
C71 | 0.71918 (11) | 0.3108 (6) | 0.3390 (2) | 0.0408 (8) | |
H71A | 0.730916 | 0.363841 | 0.405125 | 0.061* | |
H71B | 0.731235 | 0.179355 | 0.327880 | 0.061* | |
H71C | 0.691110 | 0.291401 | 0.335717 | 0.061* | |
C7B | 0.77147 (10) | 0.5111 (5) | 0.2693 (2) | 0.0317 (7) | |
O7 | 0.77907 (6) | 0.6857 (3) | 0.21275 (17) | 0.0335 (5) | |
H7 | 0.7707 (12) | 0.658 (7) | 0.156 (4) | 0.050* | |
C8 | 0.78966 (10) | 0.5958 (6) | 0.3765 (2) | 0.0391 (8) | |
O8 | 0.77191 (8) | 0.6927 (7) | 0.4278 (2) | 0.0829 (13) | |
C9 | 0.83368 (10) | 0.5661 (5) | 0.4184 (2) | 0.0335 (7) | |
C9A | 0.84696 (9) | 0.3514 (5) | 0.4047 (2) | 0.0317 (7) | |
C91 | 0.82138 (9) | 0.2065 (6) | 0.4547 (2) | 0.0360 (7) | |
H91A | 0.826979 | 0.227632 | 0.527272 | 0.054* | |
H91B | 0.827107 | 0.064266 | 0.439666 | 0.054* | |
H91C | 0.793800 | 0.235550 | 0.428959 | 0.054* | |
C10 | 0.89081 (10) | 0.2995 (6) | 0.4364 (2) | 0.0379 (7) | |
H10 | 0.906192 | 0.420551 | 0.420816 | 0.045* | |
C11 | 0.89624 (11) | 0.1245 (6) | 0.3625 (3) | 0.0434 (8) | |
H11A | 0.920446 | 0.146736 | 0.335681 | 0.052* | |
H11B | 0.898237 | −0.009059 | 0.397388 | 0.052* | |
C12 | 0.86066 (11) | 0.1257 (6) | 0.2767 (2) | 0.0406 (8) | |
H12F | 0.868963 | 0.118140 | 0.211007 | 0.049* | |
H12G | 0.843224 | 0.008637 | 0.282793 | 0.049* | |
C12A | 0.84002 (9) | 0.3296 (5) | 0.2881 (2) | 0.0322 (7) | |
C12B | 0.79618 (9) | 0.3230 (5) | 0.2432 (2) | 0.0302 (6) | |
H12B | 0.785194 | 0.197165 | 0.269439 | 0.036* | |
O9 | 0.85249 (7) | 0.7097 (4) | 0.4556 (2) | 0.0465 (6) | |
C121 | 0.86154 (10) | 0.5033 (6) | 0.2422 (2) | 0.0384 (8) | |
H12C | 0.888954 | 0.506642 | 0.275413 | 0.058* | |
H12D | 0.849249 | 0.634979 | 0.251622 | 0.058* | |
H12E | 0.859974 | 0.477879 | 0.170555 | 0.058* | |
C1' | 0.90211 (11) | 0.4248 (7) | 0.6163 (3) | 0.0466 (9) | |
H1A' | 0.912000 | 0.385993 | 0.685909 | 0.070* | |
H1B' | 0.874761 | 0.466870 | 0.608998 | 0.070* | |
H1C' | 0.917589 | 0.538806 | 0.597679 | 0.070* | |
C2' | 0.90518 (10) | 0.2420 (7) | 0.5480 (3) | 0.0452 (8) | |
H2' | 0.887713 | 0.131652 | 0.565422 | 0.054* | |
C3' | 0.94661 (13) | 0.1581 (9) | 0.5657 (3) | 0.0667 (12) | 0.819 (6) |
H3A' | 0.964966 | 0.270218 | 0.558402 | 0.080* | 0.819 (6) |
H3B' | 0.948759 | 0.053055 | 0.514555 | 0.080* | 0.819 (6) |
C4' | 0.95816 (14) | 0.0619 (10) | 0.6714 (4) | 0.0536 (13) | 0.819 (6) |
H4A' | 0.963303 | 0.172770 | 0.721721 | 0.064* | 0.819 (6) |
H4B' | 0.936054 | −0.020350 | 0.686075 | 0.064* | 0.819 (6) |
C5' | 0.99339 (15) | −0.0711 (10) | 0.6805 (5) | 0.0642 (15) | 0.819 (6) |
H5A' | 1.013473 | 0.003536 | 0.651906 | 0.077* | 0.819 (6) |
H5B' | 0.986294 | −0.194616 | 0.638929 | 0.077* | 0.819 (6) |
C6' | 1.01156 (19) | −0.1401 (11) | 0.7854 (5) | 0.0712 (19) | 0.819 (6) |
H6' | 1.018694 | −0.014328 | 0.826567 | 0.085* | 0.819 (6) |
C7' | 0.98079 (16) | −0.2634 (12) | 0.8343 (5) | 0.0672 (17) | 0.819 (6) |
H7A' | 0.992903 | −0.306986 | 0.901833 | 0.101* | 0.819 (6) |
H7B' | 0.972100 | −0.384019 | 0.793412 | 0.101* | 0.819 (6) |
H7C' | 0.958335 | −0.175495 | 0.837979 | 0.101* | 0.819 (6) |
C8' | 1.04726 (19) | −0.2635 (16) | 0.7908 (7) | 0.106 (3) | 0.819 (6) |
H8A' | 1.057945 | −0.295880 | 0.860823 | 0.159* | 0.819 (6) |
H8B' | 1.066568 | −0.185930 | 0.762027 | 0.159* | 0.819 (6) |
H8C' | 1.041015 | −0.390809 | 0.753127 | 0.159* | 0.819 (6) |
C3M' | 0.94661 (13) | 0.1581 (9) | 0.5657 (3) | 0.0667 (12) | 0.181 (6) |
H3C' | 0.959002 | 0.233500 | 0.516717 | 0.080* | 0.181 (6) |
H3D' | 0.943250 | 0.016366 | 0.539797 | 0.080* | 0.181 (6) |
C4M' | 0.9799 (5) | 0.138 (3) | 0.6583 (12) | 0.059 (3) | 0.181 (6) |
H4C' | 1.005556 | 0.123911 | 0.637681 | 0.070* | 0.181 (6) |
H4D' | 0.980638 | 0.259273 | 0.702512 | 0.070* | 0.181 (6) |
C5M' | 0.9698 (6) | −0.051 (4) | 0.7099 (17) | 0.068 (4) | 0.181 (6) |
H5C' | 0.963486 | −0.159040 | 0.658307 | 0.081* | 0.181 (6) |
H6D' | 0.945500 | −0.022405 | 0.735326 | 0.081* | 0.181 (6) |
C6M' | 0.9986 (6) | −0.141 (3) | 0.7951 (14) | 0.071 (4) | 0.181 (6) |
H6M' | 0.992468 | −0.084589 | 0.858787 | 0.085* | 0.181 (6) |
C7M' | 0.9925 (9) | −0.382 (3) | 0.797 (3) | 0.102 (8) | 0.181 (6) |
H7D' | 1.006914 | −0.437939 | 0.859637 | 0.153* | 0.181 (6) |
H7E' | 1.002258 | −0.444041 | 0.740411 | 0.153* | 0.181 (6) |
H7F' | 0.964712 | −0.412719 | 0.790954 | 0.153* | 0.181 (6) |
C8M' | 1.0400 (6) | −0.100 (6) | 0.794 (3) | 0.104 (8) | 0.181 (6) |
H8D' | 1.056040 | −0.154976 | 0.855335 | 0.156* | 0.181 (6) |
H8E' | 1.044173 | 0.048171 | 0.791197 | 0.156* | 0.181 (6) |
H8F' | 1.047478 | −0.165404 | 0.735748 | 0.156* | 0.181 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0447 (15) | 0.0362 (14) | 0.0207 (13) | 0.0050 (12) | 0.0102 (11) | −0.0015 (11) |
C2 | 0.0479 (17) | 0.0257 (14) | 0.0255 (15) | 0.0077 (14) | 0.0082 (13) | −0.0045 (12) |
O2 | 0.0531 (13) | 0.0422 (13) | 0.0216 (11) | 0.0068 (11) | 0.0078 (9) | −0.0066 (10) |
C3 | 0.0479 (18) | 0.0279 (15) | 0.0296 (16) | 0.0002 (14) | 0.0064 (13) | −0.0020 (12) |
C3A | 0.0426 (17) | 0.0285 (15) | 0.0215 (14) | 0.0009 (13) | 0.0081 (12) | 0.0014 (12) |
C4 | 0.0414 (18) | 0.0324 (16) | 0.0284 (16) | −0.0033 (14) | 0.0102 (13) | −0.0009 (13) |
C41 | 0.0492 (19) | 0.0392 (18) | 0.046 (2) | −0.0052 (17) | 0.0134 (15) | 0.0025 (16) |
C42 | 0.0433 (18) | 0.0434 (19) | 0.0303 (17) | −0.0023 (15) | 0.0034 (13) | −0.0047 (14) |
C5 | 0.0349 (16) | 0.0364 (16) | 0.0279 (16) | −0.0022 (14) | 0.0061 (12) | 0.0011 (13) |
O51 | 0.0365 (12) | 0.0477 (13) | 0.0359 (12) | 0.0013 (10) | 0.0060 (9) | 0.0032 (10) |
C51 | 0.0500 (19) | 0.0427 (19) | 0.0364 (18) | 0.0023 (16) | −0.0012 (15) | −0.0024 (15) |
O52 | 0.0624 (16) | 0.0534 (16) | 0.0389 (14) | 0.0012 (14) | −0.0009 (12) | 0.0102 (12) |
C52 | 0.046 (2) | 0.078 (3) | 0.066 (3) | 0.014 (2) | −0.0057 (19) | −0.007 (2) |
C6 | 0.0419 (17) | 0.0376 (17) | 0.0276 (16) | 0.0061 (14) | 0.0101 (12) | 0.0000 (13) |
C7 | 0.0425 (17) | 0.0375 (17) | 0.0230 (14) | 0.0052 (14) | 0.0066 (12) | −0.0034 (13) |
C7A | 0.0422 (17) | 0.0322 (15) | 0.0185 (14) | 0.0041 (13) | 0.0080 (12) | 0.0012 (12) |
C71 | 0.0511 (19) | 0.0480 (19) | 0.0263 (16) | 0.0096 (17) | 0.0146 (14) | 0.0078 (15) |
C7B | 0.0453 (18) | 0.0321 (16) | 0.0172 (14) | 0.0064 (14) | 0.0048 (12) | −0.0016 (12) |
O7 | 0.0410 (12) | 0.0309 (11) | 0.0268 (11) | 0.0015 (9) | 0.0013 (9) | −0.0003 (9) |
C8 | 0.0478 (19) | 0.0443 (18) | 0.0240 (16) | 0.0122 (16) | 0.0033 (13) | −0.0064 (14) |
O8 | 0.0574 (16) | 0.139 (3) | 0.0445 (16) | 0.042 (2) | −0.0106 (13) | −0.051 (2) |
C9 | 0.0451 (19) | 0.0354 (17) | 0.0208 (14) | 0.0023 (14) | 0.0080 (13) | 0.0001 (12) |
C9A | 0.0411 (17) | 0.0335 (16) | 0.0209 (14) | 0.0053 (13) | 0.0068 (12) | 0.0037 (12) |
C91 | 0.0460 (17) | 0.0408 (17) | 0.0214 (14) | 0.0025 (16) | 0.0064 (12) | 0.0056 (13) |
C10 | 0.0421 (18) | 0.0443 (18) | 0.0280 (17) | 0.0088 (15) | 0.0083 (13) | 0.0058 (14) |
C11 | 0.049 (2) | 0.0478 (19) | 0.0349 (18) | 0.0173 (17) | 0.0106 (14) | 0.0058 (16) |
C12 | 0.055 (2) | 0.0412 (18) | 0.0270 (16) | 0.0173 (16) | 0.0111 (14) | 0.0002 (14) |
C12A | 0.0438 (17) | 0.0326 (16) | 0.0221 (15) | 0.0077 (14) | 0.0109 (12) | 0.0027 (12) |
C12B | 0.0427 (17) | 0.0307 (15) | 0.0181 (14) | 0.0040 (14) | 0.0077 (12) | 0.0010 (12) |
O9 | 0.0492 (14) | 0.0379 (13) | 0.0503 (14) | 0.0015 (12) | 0.0036 (11) | −0.0011 (12) |
C121 | 0.0401 (18) | 0.0472 (19) | 0.0297 (16) | 0.0076 (15) | 0.0111 (13) | 0.0100 (15) |
C1' | 0.046 (2) | 0.061 (2) | 0.0303 (18) | −0.0031 (18) | 0.0013 (14) | 0.0018 (16) |
C2' | 0.0460 (18) | 0.057 (2) | 0.0310 (17) | 0.0100 (17) | 0.0036 (14) | 0.0074 (16) |
C3' | 0.058 (2) | 0.092 (3) | 0.047 (2) | 0.025 (2) | −0.0009 (17) | 0.008 (2) |
C4' | 0.040 (2) | 0.081 (3) | 0.039 (2) | 0.002 (2) | 0.0031 (19) | 0.007 (2) |
C5' | 0.041 (3) | 0.085 (4) | 0.069 (3) | 0.005 (3) | 0.014 (2) | 0.026 (3) |
C6' | 0.056 (4) | 0.076 (4) | 0.075 (4) | −0.013 (3) | −0.005 (3) | 0.026 (3) |
C7' | 0.053 (3) | 0.087 (4) | 0.058 (3) | 0.015 (3) | 0.000 (2) | 0.023 (3) |
C8' | 0.064 (4) | 0.127 (7) | 0.127 (6) | 0.017 (4) | 0.019 (4) | 0.072 (6) |
C3M' | 0.058 (2) | 0.092 (3) | 0.047 (2) | 0.025 (2) | −0.0009 (17) | 0.008 (2) |
C4M' | 0.039 (6) | 0.085 (6) | 0.051 (6) | 0.014 (6) | 0.006 (5) | 0.013 (6) |
C5M' | 0.052 (6) | 0.080 (6) | 0.069 (6) | 0.003 (6) | 0.007 (6) | 0.016 (6) |
C6M' | 0.059 (8) | 0.082 (7) | 0.073 (7) | −0.007 (7) | 0.014 (7) | 0.026 (7) |
C7M' | 0.088 (14) | 0.110 (15) | 0.100 (14) | −0.004 (14) | −0.003 (13) | −0.003 (14) |
C8M' | 0.075 (13) | 0.103 (15) | 0.136 (15) | −0.004 (14) | 0.027 (13) | 0.017 (14) |
N1—C2 | 1.340 (4) | C10—H10 | 1.0000 |
N1—C12B | 1.464 (4) | C11—C12 | 1.539 (5) |
N1—H1 | 0.87 (4) | C11—H11A | 0.9900 |
C2—O2 | 1.232 (4) | C11—H11B | 0.9900 |
C2—C3 | 1.492 (5) | C12—C12A | 1.536 (5) |
C3—C3A | 1.549 (4) | C12—H12F | 0.9900 |
C3—H3A | 0.9900 | C12—H12G | 0.9900 |
C3—H3B | 0.9900 | C12A—C12B | 1.540 (4) |
C3A—C4 | 1.571 (5) | C12A—C121 | 1.554 (5) |
C3A—C7A | 1.584 (4) | C12B—H12B | 1.0000 |
C3A—H3C | 1.0000 | C121—H12C | 0.9800 |
C4—C41 | 1.530 (5) | C121—H12D | 0.9800 |
C4—C5 | 1.533 (5) | C121—H12E | 0.9800 |
C4—C42 | 1.550 (4) | C1'—C2' | 1.529 (6) |
C41—H41A | 0.9800 | C1'—H1A' | 0.9800 |
C41—H41B | 0.9800 | C1'—H1B' | 0.9800 |
C41—H41C | 0.9800 | C1'—H1C' | 0.9800 |
C42—H42A | 0.9800 | C2'—C3M' | 1.523 (5) |
C42—H42B | 0.9800 | C2'—C3' | 1.523 (5) |
C42—H42C | 0.9800 | C2'—H2' | 1.0000 |
C5—O51 | 1.448 (4) | C3'—C4' | 1.552 (6) |
C5—C6 | 1.506 (4) | C3'—H3A' | 0.9900 |
C5—H5 | 1.0000 | C3'—H3B' | 0.9900 |
O51—C51 | 1.348 (4) | C4'—C5' | 1.492 (7) |
C51—O52 | 1.209 (5) | C4'—H4A' | 0.9900 |
C51—C52 | 1.492 (5) | C4'—H4B' | 0.9900 |
C52—H52A | 0.9800 | C5'—C6' | 1.519 (8) |
C52—H52B | 0.9800 | C5'—H5A' | 0.9900 |
C52—H52C | 0.9800 | C5'—H5B' | 0.9900 |
C6—C7 | 1.516 (4) | C6'—C8' | 1.474 (10) |
C6—H6A | 0.9900 | C6'—C7' | 1.583 (9) |
C6—H6B | 0.9900 | C6'—H6' | 1.0000 |
C7—C7A | 1.553 (4) | C7'—H7A' | 0.9800 |
C7—H7A | 0.9900 | C7'—H7B' | 0.9800 |
C7—H7B | 0.9900 | C7'—H7C' | 0.9800 |
C7A—C71 | 1.536 (4) | C8'—H8A' | 0.9800 |
C7A—C7B | 1.599 (5) | C8'—H8B' | 0.9800 |
C71—H71A | 0.9800 | C8'—H8C' | 0.9800 |
C71—H71B | 0.9800 | C3M'—C4M' | 1.554 (9) |
C71—H71C | 0.9800 | C3M'—H3C' | 0.9900 |
C7B—O7 | 1.427 (4) | C3M'—H3D' | 0.9900 |
C7B—C12B | 1.578 (4) | C4M'—C5M' | 1.497 (10) |
C7B—C8 | 1.580 (4) | C4M'—H4C' | 0.9900 |
O7—H7 | 0.79 (5) | C4M'—H4D' | 0.9900 |
C8—O8 | 1.196 (4) | C5M'—C6M' | 1.506 (10) |
C8—C9 | 1.549 (5) | C5M'—H5C' | 0.9900 |
C9—O9 | 1.202 (4) | C5M'—H6D' | 0.9900 |
C9—C9A | 1.500 (4) | C6M'—C8M' | 1.474 (12) |
C9A—C91 | 1.542 (4) | C6M'—C7M' | 1.588 (11) |
C9A—C10 | 1.548 (4) | C6M'—H6M' | 1.0000 |
C9A—C12A | 1.566 (4) | C7M'—H7D' | 0.9800 |
C91—H91A | 0.9800 | C7M'—H7E' | 0.9800 |
C91—H91B | 0.9800 | C7M'—H7F' | 0.9800 |
C91—H91C | 0.9800 | C8M'—H8D' | 0.9800 |
C10—C2' | 1.554 (4) | C8M'—H8E' | 0.9800 |
C10—C11 | 1.557 (5) | C8M'—H8F' | 0.9800 |
C2—N1—C12B | 125.6 (3) | H11A—C11—H11B | 108.4 |
C2—N1—H1 | 121 (3) | C12A—C12—C11 | 104.8 (3) |
C12B—N1—H1 | 113 (3) | C12A—C12—H12F | 110.8 |
O2—C2—N1 | 120.6 (3) | C11—C12—H12F | 110.8 |
O2—C2—C3 | 123.5 (3) | C12A—C12—H12G | 110.8 |
N1—C2—C3 | 115.6 (3) | C11—C12—H12G | 110.8 |
C2—C3—C3A | 107.1 (3) | H12F—C12—H12G | 108.9 |
C2—C3—H3A | 110.3 | C12—C12A—C12B | 112.7 (3) |
C3A—C3—H3A | 110.3 | C12—C12A—C121 | 108.8 (3) |
C2—C3—H3B | 110.3 | C12B—C12A—C121 | 112.3 (3) |
C3A—C3—H3B | 110.3 | C12—C12A—C9A | 101.1 (2) |
H3A—C3—H3B | 108.6 | C12B—C12A—C9A | 111.2 (2) |
C3—C3A—C4 | 110.6 (2) | C121—C12A—C9A | 110.2 (3) |
C3—C3A—C7A | 114.4 (3) | N1—C12B—C12A | 107.9 (2) |
C4—C3A—C7A | 118.0 (3) | N1—C12B—C7B | 110.7 (2) |
C3—C3A—H3C | 104.0 | C12A—C12B—C7B | 115.7 (3) |
C4—C3A—H3C | 104.0 | N1—C12B—H12B | 107.4 |
C7A—C3A—H3C | 104.0 | C12A—C12B—H12B | 107.4 |
C41—C4—C5 | 112.4 (3) | C7B—C12B—H12B | 107.4 |
C41—C4—C42 | 107.6 (3) | C12A—C121—H12C | 109.5 |
C5—C4—C42 | 107.7 (3) | C12A—C121—H12D | 109.5 |
C41—C4—C3A | 114.9 (3) | H12C—C121—H12D | 109.5 |
C5—C4—C3A | 106.2 (2) | C12A—C121—H12E | 109.5 |
C42—C4—C3A | 107.7 (2) | H12C—C121—H12E | 109.5 |
C4—C41—H41A | 109.5 | H12D—C121—H12E | 109.5 |
C4—C41—H41B | 109.5 | C2'—C1'—H1A' | 109.5 |
H41A—C41—H41B | 109.5 | C2'—C1'—H1B' | 109.5 |
C4—C41—H41C | 109.5 | H1A'—C1'—H1B' | 109.5 |
H41A—C41—H41C | 109.5 | C2'—C1'—H1C' | 109.5 |
H41B—C41—H41C | 109.5 | H1A'—C1'—H1C' | 109.5 |
C4—C42—H42A | 109.5 | H1B'—C1'—H1C' | 109.5 |
C4—C42—H42B | 109.5 | C3M'—C2'—C1' | 110.8 (3) |
H42A—C42—H42B | 109.5 | C3'—C2'—C1' | 110.8 (3) |
C4—C42—H42C | 109.5 | C3M'—C2'—C10 | 111.6 (3) |
H42A—C42—H42C | 109.5 | C3'—C2'—C10 | 111.6 (3) |
H42B—C42—H42C | 109.5 | C1'—C2'—C10 | 111.0 (3) |
O51—C5—C6 | 108.5 (2) | C3'—C2'—H2' | 107.8 |
O51—C5—C4 | 110.2 (3) | C1'—C2'—H2' | 107.8 |
C6—C5—C4 | 112.5 (3) | C10—C2'—H2' | 107.8 |
O51—C5—H5 | 108.5 | C2'—C3'—C4' | 111.7 (4) |
C6—C5—H5 | 108.5 | C2'—C3'—H3A' | 109.3 |
C4—C5—H5 | 108.5 | C4'—C3'—H3A' | 109.3 |
C51—O51—C5 | 117.4 (3) | C2'—C3'—H3B' | 109.3 |
O52—C51—O51 | 124.5 (3) | C4'—C3'—H3B' | 109.3 |
O52—C51—C52 | 125.2 (4) | H3A'—C3'—H3B' | 107.9 |
O51—C51—C52 | 110.3 (3) | C5'—C4'—C3' | 112.5 (4) |
C51—C52—H52A | 109.5 | C5'—C4'—H4A' | 109.1 |
C51—C52—H52B | 109.5 | C3'—C4'—H4A' | 109.1 |
H52A—C52—H52B | 109.5 | C5'—C4'—H4B' | 109.1 |
C51—C52—H52C | 109.5 | C3'—C4'—H4B' | 109.1 |
H52A—C52—H52C | 109.5 | H4A'—C4'—H4B' | 107.8 |
H52B—C52—H52C | 109.5 | C4'—C5'—C6' | 116.5 (5) |
C5—C6—C7 | 109.4 (2) | C4'—C5'—H5A' | 108.2 |
C5—C6—H6A | 109.8 | C6'—C5'—H5A' | 108.2 |
C7—C6—H6A | 109.8 | C4'—C5'—H5B' | 108.2 |
C5—C6—H6B | 109.8 | C6'—C5'—H5B' | 108.2 |
C7—C6—H6B | 109.8 | H5A'—C5'—H5B' | 107.3 |
H6A—C6—H6B | 108.2 | C8'—C6'—C5' | 114.3 (6) |
C6—C7—C7A | 114.1 (3) | C8'—C6'—C7' | 109.4 (6) |
C6—C7—H7A | 108.7 | C5'—C6'—C7' | 110.4 (5) |
C7A—C7—H7A | 108.7 | C8'—C6'—H6' | 107.5 |
C6—C7—H7B | 108.7 | C5'—C6'—H6' | 107.5 |
C7A—C7—H7B | 108.7 | C7'—C6'—H6' | 107.5 |
H7A—C7—H7B | 107.6 | C6'—C7'—H7A' | 109.5 |
C71—C7A—C7 | 109.3 (3) | C6'—C7'—H7B' | 109.5 |
C71—C7A—C3A | 112.6 (3) | H7A'—C7'—H7B' | 109.5 |
C7—C7A—C3A | 107.4 (2) | C6'—C7'—H7C' | 109.5 |
C71—C7A—C7B | 109.7 (3) | H7A'—C7'—H7C' | 109.5 |
C7—C7A—C7B | 107.7 (3) | H7B'—C7'—H7C' | 109.5 |
C3A—C7A—C7B | 110.0 (2) | C6'—C8'—H8A' | 109.5 |
C7A—C71—H71A | 109.5 | C6'—C8'—H8B' | 109.5 |
C7A—C71—H71B | 109.5 | H8A'—C8'—H8B' | 109.5 |
H71A—C71—H71B | 109.5 | C6'—C8'—H8C' | 109.5 |
C7A—C71—H71C | 109.5 | H8A'—C8'—H8C' | 109.5 |
H71A—C71—H71C | 109.5 | H8B'—C8'—H8C' | 109.5 |
H71B—C71—H71C | 109.5 | C2'—C3M'—C4M' | 134.8 (10) |
O7—C7B—C12B | 109.8 (2) | C2'—C3M'—H3C' | 103.5 |
O7—C7B—C8 | 97.7 (2) | C4M'—C3M'—H3C' | 103.5 |
C12B—C7B—C8 | 109.7 (2) | C2'—C3M'—H3D' | 103.5 |
O7—C7B—C7A | 112.5 (2) | C4M'—C3M'—H3D' | 103.5 |
C12B—C7B—C7A | 113.8 (3) | H3C'—C3M'—H3D' | 105.3 |
C8—C7B—C7A | 112.2 (2) | C5M'—C4M'—C3M' | 104.0 (9) |
C7B—O7—H7 | 106 (3) | C5M'—C4M'—H4C' | 111.0 |
O8—C8—C9 | 115.9 (3) | C3M'—C4M'—H4C' | 111.0 |
O8—C8—C7B | 124.1 (3) | C5M'—C4M'—H4D' | 111.0 |
C9—C8—C7B | 119.9 (3) | C3M'—C4M'—H4D' | 111.0 |
O9—C9—C9A | 128.7 (3) | H4C'—C4M'—H4D' | 109.0 |
O9—C9—C8 | 119.0 (3) | C4M'—C5M'—C6M' | 120.1 (10) |
C9A—C9—C8 | 112.3 (3) | C4M'—C5M'—H5C' | 107.3 |
C9—C9A—C91 | 107.6 (3) | C6M'—C5M'—H5C' | 107.3 |
C9—C9A—C10 | 118.8 (3) | C4M'—C5M'—H6D' | 107.3 |
C91—C9A—C10 | 111.4 (3) | C6M'—C5M'—H6D' | 107.3 |
C9—C9A—C12A | 102.5 (2) | H5C'—C5M'—H6D' | 106.9 |
C91—C9A—C12A | 113.4 (3) | C8M'—C6M'—C5M' | 116.1 (12) |
C10—C9A—C12A | 102.9 (2) | C8M'—C6M'—C7M' | 108.3 (11) |
C9A—C91—H91A | 109.5 | C5M'—C6M'—C7M' | 109.0 (11) |
C9A—C91—H91B | 109.5 | C8M'—C6M'—H6M' | 107.7 |
H91A—C91—H91B | 109.5 | C5M'—C6M'—H6M' | 107.7 |
C9A—C91—H91C | 109.5 | C7M'—C6M'—H6M' | 107.7 |
H91A—C91—H91C | 109.5 | C6M'—C7M'—H7D' | 109.5 |
H91B—C91—H91C | 109.5 | C6M'—C7M'—H7E' | 109.5 |
C9A—C10—C2' | 116.7 (3) | H7D'—C7M'—H7E' | 109.5 |
C9A—C10—C11 | 102.2 (3) | C6M'—C7M'—H7F' | 109.5 |
C2'—C10—C11 | 113.4 (3) | H7D'—C7M'—H7F' | 109.5 |
C9A—C10—H10 | 108.0 | H7E'—C7M'—H7F' | 109.5 |
C2'—C10—H10 | 108.0 | C6M'—C8M'—H8D' | 109.5 |
C11—C10—H10 | 108.0 | C6M'—C8M'—H8E' | 109.5 |
C12—C11—C10 | 108.0 (3) | H8D'—C8M'—H8E' | 109.5 |
C12—C11—H11A | 110.1 | C6M'—C8M'—H8F' | 109.5 |
C10—C11—H11A | 110.1 | H8D'—C8M'—H8F' | 109.5 |
C12—C11—H11B | 110.1 | H8E'—C8M'—H8F' | 109.5 |
C10—C11—H11B | 110.1 | ||
C12B—N1—C2—O2 | 175.9 (3) | C8—C9—C9A—C10 | 176.1 (3) |
C12B—N1—C2—C3 | 1.9 (4) | O9—C9—C9A—C12A | −115.8 (4) |
O2—C2—C3—C3A | −101.2 (3) | C8—C9—C9A—C12A | 63.6 (3) |
N1—C2—C3—C3A | 72.6 (3) | C9—C9A—C10—C2' | 85.6 (4) |
C2—C3—C3A—C4 | 131.8 (3) | C91—C9A—C10—C2' | −40.3 (4) |
C2—C3—C3A—C7A | −92.1 (3) | C12A—C9A—C10—C2' | −162.1 (3) |
C3—C3A—C4—C41 | 60.2 (3) | C9—C9A—C10—C11 | −150.0 (3) |
C7A—C3A—C4—C41 | −74.3 (4) | C91—C9A—C10—C11 | 84.1 (3) |
C3—C3A—C4—C5 | −174.8 (2) | C12A—C9A—C10—C11 | −37.7 (3) |
C7A—C3A—C4—C5 | 50.7 (3) | C9A—C10—C11—C12 | 15.6 (4) |
C3—C3A—C4—C42 | −59.7 (3) | C2'—C10—C11—C12 | 142.1 (3) |
C7A—C3A—C4—C42 | 165.8 (3) | C10—C11—C12—C12A | 13.0 (4) |
C41—C4—C5—O51 | −52.8 (3) | C11—C12—C12A—C12B | −154.6 (3) |
C42—C4—C5—O51 | 65.6 (3) | C11—C12—C12A—C121 | 80.2 (3) |
C3A—C4—C5—O51 | −179.3 (2) | C11—C12—C12A—C9A | −35.8 (3) |
C41—C4—C5—C6 | 68.4 (4) | C9—C9A—C12A—C12 | 170.1 (3) |
C42—C4—C5—C6 | −173.2 (3) | C91—C9A—C12A—C12 | −74.3 (3) |
C3A—C4—C5—C6 | −58.1 (3) | C10—C9A—C12A—C12 | 46.2 (3) |
C6—C5—O51—C51 | 124.5 (3) | C9—C9A—C12A—C12B | −70.1 (3) |
C4—C5—O51—C51 | −112.0 (3) | C91—C9A—C12A—C12B | 45.6 (3) |
C5—O51—C51—O52 | 4.1 (5) | C10—C9A—C12A—C12B | 166.1 (3) |
C5—O51—C51—C52 | −175.2 (3) | C9—C9A—C12A—C121 | 55.0 (3) |
O51—C5—C6—C7 | −173.2 (3) | C91—C9A—C12A—C121 | 170.7 (3) |
C4—C5—C6—C7 | 64.7 (3) | C10—C9A—C12A—C121 | −68.8 (3) |
C5—C6—C7—C7A | −59.9 (3) | C2—N1—C12B—C12A | 159.7 (3) |
C6—C7—C7A—C71 | −73.1 (3) | C2—N1—C12B—C7B | −72.9 (4) |
C6—C7—C7A—C3A | 49.3 (3) | C12—C12A—C12B—N1 | −66.3 (3) |
C6—C7—C7A—C7B | 167.8 (2) | C121—C12A—C12B—N1 | 57.0 (3) |
C3—C3A—C7A—C71 | −59.0 (4) | C9A—C12A—C12B—N1 | −179.1 (3) |
C4—C3A—C7A—C71 | 73.8 (3) | C12—C12A—C12B—C7B | 169.1 (3) |
C3—C3A—C7A—C7 | −179.3 (3) | C121—C12A—C12B—C7B | −67.5 (3) |
C4—C3A—C7A—C7 | −46.5 (3) | C9A—C12A—C12B—C7B | 56.4 (3) |
C3—C3A—C7A—C7B | 63.8 (3) | O7—C7B—C12B—N1 | −48.4 (3) |
C4—C3A—C7A—C7B | −163.4 (2) | C8—C7B—C12B—N1 | −154.7 (3) |
C71—C7A—C7B—O7 | −166.2 (3) | C7A—C7B—C12B—N1 | 78.7 (3) |
C7—C7A—C7B—O7 | −47.4 (3) | O7—C7B—C12B—C12A | 74.6 (3) |
C3A—C7A—C7B—O7 | 69.4 (3) | C8—C7B—C12B—C12A | −31.6 (4) |
C71—C7A—C7B—C12B | 68.1 (3) | C7A—C7B—C12B—C12A | −158.2 (2) |
C7—C7A—C7B—C12B | −173.1 (2) | C9A—C10—C2'—C3M' | 169.8 (4) |
C3A—C7A—C7B—C12B | −56.3 (3) | C11—C10—C2'—C3M' | 51.4 (5) |
C71—C7A—C7B—C8 | −57.2 (3) | C9A—C10—C2'—C3' | 169.8 (4) |
C7—C7A—C7B—C8 | 61.7 (3) | C11—C10—C2'—C3' | 51.4 (5) |
C3A—C7A—C7B—C8 | 178.5 (3) | C9A—C10—C2'—C1' | −66.1 (4) |
O7—C7B—C8—O8 | 88.8 (5) | C11—C10—C2'—C1' | 175.5 (3) |
C12B—C7B—C8—O8 | −156.9 (4) | C1'—C2'—C3'—C4' | 66.8 (6) |
C7A—C7B—C8—O8 | −29.4 (5) | C10—C2'—C3'—C4' | −169.0 (4) |
O7—C7B—C8—C9 | −87.4 (3) | C2'—C3'—C4'—C5' | 163.9 (5) |
C12B—C7B—C8—C9 | 26.9 (4) | C3'—C4'—C5'—C6' | 168.9 (5) |
C7A—C7B—C8—C9 | 154.3 (3) | C4'—C5'—C6'—C8' | −177.4 (7) |
O8—C8—C9—O9 | −43.7 (5) | C4'—C5'—C6'—C7' | 58.7 (8) |
C7B—C8—C9—O9 | 132.8 (3) | C1'—C2'—C3M'—C4M' | 33.6 (11) |
O8—C8—C9—C9A | 136.8 (4) | C10—C2'—C3M'—C4M' | 157.8 (10) |
C7B—C8—C9—C9A | −46.7 (4) | C2'—C3M'—C4M'—C5M' | 82 (2) |
O9—C9—C9A—C91 | 124.4 (4) | C3M'—C4M'—C5M'—C6M' | 170 (2) |
C8—C9—C9A—C91 | −56.2 (3) | C4M'—C5M'—C6M'—C8M' | −27 (3) |
O9—C9—C9A—C10 | −3.4 (5) | C4M'—C5M'—C6M'—C7M' | −150 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O2i | 0.79 (5) | 2.02 (5) | 2.750 (3) | 153 (5) |
C3A—H3C···O2i | 1.00 | 2.18 | 3.173 (4) | 176 |
C121—H12E···O52ii | 0.98 | 2.53 | 3.428 (4) | 153 |
C71—H71A···O8iii | 0.98 | 2.55 | 3.224 (4) | 126 |
C91—H91B···O9iv | 0.98 | 2.48 | 3.422 (5) | 162 |
Symmetry codes: (i) −x+3/2, y+1/2, −z; (ii) −x+3/2, y−1/2, −z; (iii) −x+3/2, y−1/2, −z+1; (iv) x, y−1, z. |
z-score = |d - dmean|/SD, where dmean and SD are the mean and standard deviation of N observed values in the Mogul database. The z-score for bond angles is calculated replacing d by φ. A bond distance or angle is considered unusual if the z-score > 2. |
Bond | N | bond distance (d) | dmean | SD | z-score |
C7A—C3A | 563 | 1.584 | 1.559 | 0.011 | 2.211 |
C7B—C8 | 16 | 1.579 | 1.529 | 0.008 | 6.313 |
C9A—C9 | 20 | 1.500 | 1.520 | 0.009 | 2.374 |
C7B—C12B | 18 | 1.579 | 1.547 | 0.016 | 1.957a |
Angle | N | φ | φmean | SD | z-score |
C3A—C3—C2 | 5 | 107.1 | 114.1 | 3.6 | 2.088 |
O51—C5—C4 | 158 | 110.2 | 107.8 | 1.2 | 2.067 |
O7—C7B—C8 | 16 | 97.7 | 105.7 | 3.7 | 2.131 |
O8—C8—C9 | 18 | 115.9 | 120.9 | 1.3 | 3.773 |
C9A—C9—C8 | 28 | 112.3 | 118.3 | 1.8 | 2.577 |
O9—C9—C9A | 20 | 128.7 | 122.9 | 2.2 | 2.138 |
C12A—C9A—C9 | 15 | 102.5 | 110.0 | 3.2 | 2.369 |
C12—C11—C10 | 894 | 108.0 | 104.4 | 1.7 | 2.138 |
C12—C12A—C9A | 13 | 101.14 | 103.11 | 0.87 | 2.264 |
C121—C12A—C9A | 8 | 110.1 | 113.2 | 1.4 | 2.136 |
Note: (a) This value is lower than 2 but this bond is still unusually long and relevant for the discussion. |
Acknowledgements
The authors are indebted to Professor A. W. Mombrú and Professor P. Moyna for being involved in keeping the crystals in a safe place, and to Dr G. Carrau for his assistance in naming the compound and creating a proper scheme and to the anonymous referee who suggested using the z-score for the discussion. Funding for this research was provided by PEDECIBA - Química (bursary to L. Suescun, H. Heinzen).
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