research communications
S,2R)-2-[(3R,4S)-3-methyl-4-phenyl-1,2,3,4-tetrahydroisoquinolin-2-yl]-1,2-diphenylethanol
of (1aLaboratoire de Recherche en Energie et Matière pour le Développement des Sciences Nucléaires, Centre National des Sciences et Technologies Nucléaires, Pôle Technologique, 2020 Sidi-Thabet, Tunisia, and bInstitut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Paris-Saclay University, 1, av. de la Terrasse, 91198 Gif-sur-Yvette, France
*Correspondence e-mail: pascal.retailleau@cnrs.fr
The synthesis and 30H29NO, are described. This compound is a member of the chiral dihydroisoquinoline-derived family, used as building blocks for functional materials and as source of in and was isolated as one of two diastereomeric β-amino the title molecule being found to be the (S,R) diastereoisomer. In the crystal, molecules are packed in a herringbone manner parallel to (103) and (10) via weak C—H⋯O and C—H⋯π(ring) interactions. Hirshfeld surface analysis showed that the surface contacts are predominantly H⋯H interactions (ca 75%). The crystal studied was refined as a two-component inversion twin.
of the title compound, CKeywords: crystal structure; chiral β-amino alcohol; tetrahydroisoquinoline; hydrogen bond; Hirshfeld surface analysis.
CCDC reference: 1950166
1. Chemical context
β-amino exhibit a broad spectrum of biological activities and are used as antibacterial and tuberculostatic agents (Yendapally & Lee, 2008). In particular, chiral β-amino are very important chiral molecules that are used as building blocks and structural motifs in pharmaceutically active molecules and natural products and which serve as the main sources of in (Lee et al., 2003; Malkov et al., 2007; Guo et al., 2017).
Among this family of chiral amino-alcohols is the title compound, (I), which we prepared through the alkylation of tetrahydroisoquinoline by the opening racemic trans-stilbene oxide reaction. Two were obtained in a 1:1 ratio as determined by 1H NMR analysis on the crude mixture. These were separated by The title molecule was found to be the (S,R) diastereoisomer.
2. Structural commentary
The structure of (I) was confirmed using single crystal X-ray diffraction. The of the orthorhombic comprises a single molecule, shown in Fig. 1. The tetrahydroisoquinoline unit is substituted by a methyl group in position 3, a phenyl substituent in position 4 and a β-alcohol substituent at the N atom. The heterocyclic ring exhibits a half-chair conformation, with atom C3 deviating by 0.706 (3) Å from the plane formed by atoms C1/N2/C4/C9/C10. The substituents in positions 3 and 4 of the heterocyclic ring are in axial positions. The molecular structure of (I) is stabilized by an intramolecular hydrogen bond between the hydroxy O19—H19 group and atom N2, and to a lesser extent, between the aromatic C21—H21 and the phenyl group in position 4 (Table 1). By reference to two unchanging chiral C18 and C19 atoms, the molecule was found to be the (18R,19S) diastereoisomer resulting from the reaction of tetrahydroisoquinoline and the (S,S) trans-stilbene oxide enantiomer.
This structure was confirmed through the means of usual 1D and 2D NMR experiments. NMR data show that the trans diequatorial arrangement of H3 and H4 is suggested by the coupling constant between H3 and H4 in 1H NMR (J3,4 ∼0 Hz), so the substituents C3-methyl and C4-phenyl are in an axial disposition. The absolute configurations of carbon atoms C18 and C19 were deduced from the NOESY maps to be R and S, respectively (Fig. 2).
3. Supramolecular features
In the crystal, molecules of (I) pack with no classical hydrogen bonds: the potential donor hydroxyl group is involved in an intramolecular interaction with the N atom. However, the oxygen atom acts as an acceptor in the short contact C6—H6⋯O19 (−x, + y, − z) with an O19⋯H distance of 2.57 Å, which is of the same order of magnitude of the H⋯O van der Waals distance (2.60 Å), whereas C—H⋯O contacts are frequently reported with H⋯O separations shorter than 2.4 Å (Taylor & Kennard, 1982). The N atom does not play a role in the packing as it is buried inside the structure. Nevertheless, these directed C—H⋯O interactions make an important contribution to the packing: zigzagging along the [010] direction, they pair molecules in ribbons, placing the isoquinoline moieties parallel to the (103) plane on both sides but without overlapping. The ribbon cohesion is reinforced by C—H⋯π interactions involving the phenyl group in position 4 and those attached to the β-alcohol part and which flank the ribbon, as shown in Fig. 3. They stack in the [100] direction as columns arranged in a herringbone manner but avoiding π-π- stacking (Fig. 4).
4. Database survey
A search of the Cambridge Structural Database, CSD (Version 5.40; ConQuest 1.21; Groom et al., 2016) found 495 structures of tetrahydroisoquinoline derivatives. Limiting the search to compounds with tri-substitutions on positions C3, C4 and the secondary amine N reduces the number of structures to seven: ADAGOC (Gzella et al., 2006), JIPKEZ (White et al., 2007), TIBPIE (Ben Ali et al., 2007), VAHJOG (Davies et al., 2016), XOSDUE (Gzella et al., 2002), YEKKIK (Shi et al., 2012) and ZIFSUE (Guo et al., 2013). Except for the racemic VAHJOG, they all crystallize in the same P212121 The structures of ZIFSUE, TIBPIE, VAHJOG, JIPKEZ and (I) superimpose well over the heterobicycle with the same conformation, unlike ADAGOC and XOSDUE which have a different half-chair configuration. The amino alcohol TIBPIE is obviously the closest related structure, differing in the N substitution of a cyclohexane carrying the hydroxyl group which is involved in the intramolecular hydrogen bond.
5. Hirshfeld surface analysis
The intermolecular interactions were quantified using Hirshfeld surface analysis and the associated two-dimensional fingerprint plots using CrystalExplorer17.5 (Turner et al., 2017). The electrostatic potentials were calculated using TONTO, integrated within CrystalExplorer. The analysis of intermolecular interactions through the mapping of dnorm presented in Fig. 5 compares the contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, with their respective van der Waals radii. The blue, white and red colour conventions recognize the interatomic contacts as longer, at van der Waals separations and short interatomic contacts. The C—H⋯O contacts are identified in the dnorm-mapped surface as two red spots showing the interaction between the neighbouring molecules (Fig. 5a). The overall two-dimensional fingerprint plot derived form the Hirshfeld surface is a useful method to summarize the frequency of each combination of de and di across the surface of the studied molecule, encompassing all intermolecular contacts (Fig. 5b). The delineated fingerprint plots (Fig. 5b and 6a,c) focus on specific interactions, providing information about the major and minor percentage contribution of interatomic contacts in the compound. The H⋯H interactions account for the three quarters of the total (73.7%) with an evident sting at about di = de = 1.1 Å (Fig. 5b). The C⋯H/H⋯C plot, which refers to the C—H⋯π interactions previously described (22.7%,) shows two broad symmetrical wings at about di + de = 2.8 Å (Fig. 6a). These interactions are observed as red regions on the shape-index surface (Fig. 6b). The absence of C⋯C contacts, highlighted by the Hirshfeld surface with high curvedness delineated by dark-blue edges, confirms that no π–π stacking interactions take place in the crystal packing (Fig. 6c,d). The third marginal contribution is O⋯H/H⋯O (3.6%) with a pair of sharp spikes at about di + de = 2.4 Å, symmetrically disposed with respect to the diagonal, indicating the presence of intermolecular C—H⋯O interactions, which play a role in ordering the molecules inside the crystal.
6. Synthesis and crystallization
The title β-amino alcohol was obtained by mixing racemic trans-stilbene oxide (5.1g, 26mmol) with (3R,4S)-3-methyl-4-phenyl-1,2,3,4-tetrahydroisoquinoleine (3g, 13mmol), which was prepared according to the method of Bohé et al. (1999).
The mixture was heated at 353.15 K for 48 h in CF3CH2OH (65 ml), the reaction being monitored by TLC. Two were obtained in a 1:1 ratio. These were separated by Only the title compound (white solid) was successfully recrystallized. Crystals were grown by placing this dastereoisomer in a minimum amount of hot heptane. [α] D25 = −23.6 (c 1, CHCl3), m.p. 425 K.
7. Refinement
Crystal data, data collection and structure . H atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The crystal studied was refined as a two-component inversion twin.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1950166
https://doi.org/10.1107/S2056989019011964/ff2162sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019011964/ff2162Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019011964/ff2162Isup3.cml
Data collection: DENZO (Otwinowski & Minor, 1997); COLLECT (Hooft, 1998); cell
CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b).C30H29NO | Dx = 1.151 Mg m−3 |
Mr = 419.54 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 6302 reflections |
a = 7.3009 (8) Å | θ = 2.0–24.2° |
b = 11.0552 (11) Å | µ = 0.07 mm−1 |
c = 30.006 (3) Å | T = 293 K |
V = 2421.8 (4) Å3 | Prism, colorless |
Z = 4 | 0.59 × 0.45 × 0.35 mm |
F(000) = 896 |
Nonius KappaCCD area detector diffractometer | 4427 independent reflections |
Radiation source: 1.5kW sealed tube | 3948 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω and φ scans | θmax = 25.4°, θmin = 2.7° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019) | h = −8→8 |
Tmin = 0.844, Tmax = 1.000 | k = −13→13 |
21751 measured reflections | l = −36→36 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0304P)2 + 0.3321P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.083 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.11 e Å−3 |
4425 reflections | Δρmin = −0.11 e Å−3 |
295 parameters | Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0139 (11) |
Primary atom site location: dual | Absolute structure: Refined as an inversion twin. |
Secondary atom site location: difference Fourier map |
Geometry. 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. |
Refinement. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3286 (4) | −0.0015 (2) | 0.21766 (7) | 0.0459 (6) | |
H1A | 0.428447 | −0.038350 | 0.234113 | 0.053* | |
H1B | 0.243483 | −0.065133 | 0.209524 | 0.053* | |
N2 | 0.4019 (2) | 0.05352 (14) | 0.17689 (6) | 0.0355 (4) | |
C3 | 0.5027 (3) | 0.16552 (19) | 0.18741 (7) | 0.0400 (5) | |
H3 | 0.556815 | 0.195001 | 0.159563 | 0.046* | |
C4 | 0.3616 (3) | 0.26023 (18) | 0.20271 (7) | 0.0379 (5) | |
H4 | 0.430488 | 0.329448 | 0.214349 | 0.044* | |
C5 | 0.1547 (3) | 0.2891 (2) | 0.26931 (7) | 0.0471 (6) | |
H5 | 0.162708 | 0.372208 | 0.264993 | 0.054* | |
C6 | 0.0507 (3) | 0.2447 (3) | 0.30407 (8) | 0.0553 (7) | |
H6 | −0.009196 | 0.297836 | 0.323159 | 0.064* | |
C7 | 0.0357 (4) | 0.1222 (3) | 0.31050 (8) | 0.0576 (7) | |
H7 | −0.035474 | 0.092057 | 0.333677 | 0.066* | |
C8 | 0.1265 (3) | 0.0443 (2) | 0.28246 (8) | 0.0518 (6) | |
H8 | 0.116921 | −0.038604 | 0.287084 | 0.060* | |
C9 | 0.2328 (3) | 0.0871 (2) | 0.24723 (7) | 0.0405 (5) | |
C10 | 0.2479 (3) | 0.2114 (2) | 0.24055 (7) | 0.0383 (5) | |
C11 | 0.6589 (3) | 0.1502 (2) | 0.22101 (9) | 0.0567 (7) | |
H11A | 0.726198 | 0.224575 | 0.223262 | 0.068* | |
H11B | 0.739191 | 0.086877 | 0.211187 | 0.068* | |
H11C | 0.609065 | 0.129700 | 0.249634 | 0.068* | |
C12 | 0.2492 (3) | 0.30571 (18) | 0.16372 (7) | 0.0400 (5) | |
C13 | 0.3195 (4) | 0.3956 (2) | 0.13673 (8) | 0.0570 (7) | |
H13 | 0.431991 | 0.430129 | 0.143737 | 0.066* | |
C14 | 0.2254 (5) | 0.4350 (3) | 0.09946 (9) | 0.0707 (9) | |
H14 | 0.275393 | 0.495164 | 0.081543 | 0.081* | |
C15 | 0.0593 (5) | 0.3858 (3) | 0.08888 (9) | 0.0699 (9) | |
H15 | −0.003927 | 0.412441 | 0.063832 | 0.080* | |
C16 | −0.0138 (4) | 0.2967 (3) | 0.11542 (9) | 0.0623 (7) | |
H16 | −0.126869 | 0.262995 | 0.108399 | 0.072* | |
C17 | 0.0809 (3) | 0.2573 (2) | 0.15257 (8) | 0.0488 (6) | |
H17 | 0.030362 | 0.197119 | 0.170385 | 0.056* | |
C18 | 0.5032 (3) | −0.03477 (18) | 0.14947 (7) | 0.0367 (5) | |
H18 | 0.600714 | −0.070012 | 0.167776 | 0.042* | |
C19 | 0.3684 (3) | −0.13740 (19) | 0.13610 (8) | 0.0416 (5) | |
H19 | 0.338016 | −0.182861 | 0.163143 | 0.048* | |
O19 | 0.2046 (2) | −0.08765 (16) | 0.11933 (6) | 0.0560 (5) | |
HOH | 0.198 (4) | −0.016 (3) | 0.1307 (9) | 0.067* | |
C20 | 0.5896 (3) | 0.02111 (19) | 0.10855 (7) | 0.0394 (5) | |
C21 | 0.4942 (4) | 0.0997 (2) | 0.08094 (8) | 0.0553 (7) | |
H21 | 0.377223 | 0.125320 | 0.088719 | 0.064* | |
C22 | 0.5742 (5) | 0.1398 (3) | 0.04165 (9) | 0.0730 (8) | |
H22 | 0.510686 | 0.192712 | 0.023154 | 0.084* | |
C23 | 0.7467 (5) | 0.1018 (3) | 0.02999 (10) | 0.0778 (10) | |
H23 | 0.798359 | 0.127746 | 0.003312 | 0.089* | |
C24 | 0.8428 (4) | 0.0263 (3) | 0.05729 (10) | 0.0685 (8) | |
H24 | 0.960600 | 0.001927 | 0.049589 | 0.079* | |
C25 | 0.7644 (3) | −0.0137 (2) | 0.09627 (8) | 0.0502 (6) | |
H25 | 0.830335 | −0.065258 | 0.114775 | 0.058* | |
C26 | 0.4523 (3) | −0.22470 (19) | 0.10333 (7) | 0.0434 (5) | |
C27 | 0.4150 (4) | −0.2197 (2) | 0.05843 (9) | 0.0648 (8) | |
H27 | 0.330932 | −0.163529 | 0.047712 | 0.075* | |
C28 | 0.5013 (5) | −0.2974 (3) | 0.02915 (9) | 0.0816 (10) | |
H28 | 0.474735 | −0.293390 | −0.001130 | 0.094* | |
C29 | 0.6252 (5) | −0.3798 (3) | 0.04431 (11) | 0.0786 (9) | |
H29 | 0.684240 | −0.431168 | 0.024431 | 0.090* | |
C30 | 0.6622 (4) | −0.3865 (2) | 0.08887 (11) | 0.0693 (8) | |
H30 | 0.746120 | −0.442975 | 0.099374 | 0.080* | |
C31 | 0.5752 (4) | −0.3097 (2) | 0.11835 (9) | 0.0533 (6) | |
H31 | 0.599963 | −0.315488 | 0.148673 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0562 (15) | 0.0388 (12) | 0.0426 (13) | −0.0048 (11) | 0.0068 (11) | 0.0038 (10) |
N2 | 0.0361 (10) | 0.0336 (8) | 0.0369 (9) | −0.0008 (8) | 0.0058 (8) | 0.0001 (7) |
C3 | 0.0384 (12) | 0.0391 (11) | 0.0426 (12) | −0.0037 (10) | 0.0039 (10) | −0.0003 (9) |
C4 | 0.0419 (13) | 0.0322 (10) | 0.0395 (12) | −0.0059 (10) | 0.0006 (10) | −0.0037 (9) |
C5 | 0.0441 (13) | 0.0536 (14) | 0.0437 (13) | 0.0038 (11) | −0.0043 (11) | −0.0078 (11) |
C6 | 0.0421 (14) | 0.0826 (19) | 0.0413 (13) | 0.0074 (14) | 0.0005 (11) | −0.0127 (13) |
C7 | 0.0482 (15) | 0.0850 (19) | 0.0395 (13) | −0.0076 (14) | 0.0064 (12) | 0.0015 (13) |
C8 | 0.0552 (15) | 0.0596 (14) | 0.0406 (13) | −0.0126 (13) | 0.0031 (12) | 0.0036 (11) |
C9 | 0.0423 (13) | 0.0472 (12) | 0.0320 (11) | −0.0030 (11) | 0.0010 (10) | 0.0002 (9) |
C10 | 0.0364 (12) | 0.0442 (12) | 0.0342 (11) | 0.0002 (10) | −0.0019 (10) | −0.0030 (9) |
C11 | 0.0433 (14) | 0.0589 (15) | 0.0680 (17) | −0.0014 (12) | −0.0081 (13) | −0.0064 (13) |
C12 | 0.0494 (14) | 0.0319 (10) | 0.0387 (12) | 0.0043 (11) | 0.0068 (10) | −0.0036 (9) |
C13 | 0.0653 (17) | 0.0470 (13) | 0.0586 (16) | −0.0024 (13) | 0.0074 (14) | 0.0085 (12) |
C14 | 0.093 (2) | 0.0637 (17) | 0.0558 (17) | 0.0100 (18) | 0.0123 (17) | 0.0203 (14) |
C15 | 0.091 (2) | 0.0766 (19) | 0.0426 (15) | 0.0331 (19) | −0.0020 (15) | 0.0037 (14) |
C16 | 0.0589 (16) | 0.0737 (17) | 0.0544 (16) | 0.0111 (15) | −0.0078 (14) | −0.0108 (14) |
C17 | 0.0526 (15) | 0.0485 (13) | 0.0452 (13) | 0.0024 (12) | −0.0009 (11) | 0.0013 (11) |
C18 | 0.0336 (11) | 0.0391 (11) | 0.0375 (11) | 0.0034 (10) | −0.0016 (10) | 0.0010 (9) |
C19 | 0.0396 (12) | 0.0390 (11) | 0.0463 (13) | 0.0003 (10) | −0.0006 (10) | −0.0009 (10) |
O19 | 0.0414 (9) | 0.0551 (10) | 0.0715 (12) | 0.0037 (8) | −0.0092 (9) | −0.0069 (9) |
C20 | 0.0415 (13) | 0.0403 (11) | 0.0364 (12) | −0.0010 (10) | 0.0015 (10) | −0.0042 (9) |
C21 | 0.0617 (17) | 0.0595 (14) | 0.0448 (14) | 0.0047 (14) | 0.0015 (12) | 0.0049 (12) |
C22 | 0.097 (2) | 0.0752 (19) | 0.0467 (15) | −0.0039 (19) | −0.0026 (17) | 0.0129 (14) |
C23 | 0.095 (3) | 0.091 (2) | 0.0469 (16) | −0.024 (2) | 0.0244 (17) | −0.0042 (16) |
C24 | 0.0622 (18) | 0.082 (2) | 0.0616 (18) | −0.0138 (17) | 0.0209 (15) | −0.0176 (16) |
C25 | 0.0452 (14) | 0.0532 (14) | 0.0522 (15) | −0.0035 (12) | 0.0073 (11) | −0.0090 (11) |
C26 | 0.0456 (14) | 0.0384 (11) | 0.0461 (13) | −0.0055 (11) | −0.0012 (11) | −0.0046 (10) |
C27 | 0.086 (2) | 0.0577 (15) | 0.0507 (16) | 0.0103 (16) | −0.0131 (15) | −0.0060 (12) |
C28 | 0.122 (3) | 0.076 (2) | 0.0477 (16) | 0.007 (2) | −0.0009 (18) | −0.0158 (15) |
C29 | 0.095 (2) | 0.0622 (18) | 0.078 (2) | 0.0071 (19) | 0.0216 (19) | −0.0239 (16) |
C30 | 0.069 (2) | 0.0568 (16) | 0.082 (2) | 0.0137 (15) | 0.0011 (17) | −0.0151 (15) |
C31 | 0.0581 (16) | 0.0453 (12) | 0.0563 (15) | 0.0058 (12) | −0.0049 (13) | −0.0066 (11) |
C1—N2 | 1.467 (3) | C16—C17 | 1.382 (3) |
C1—C9 | 1.496 (3) | C16—H16 | 0.9300 |
C1—H1A | 0.9700 | C17—H17 | 0.9300 |
C1—H1B | 0.9700 | C18—C20 | 1.512 (3) |
N2—C3 | 1.475 (3) | C18—C19 | 1.555 (3) |
N2—C18 | 1.475 (3) | C18—H18 | 0.9800 |
C3—C11 | 1.531 (3) | C19—O19 | 1.409 (3) |
C3—C4 | 1.539 (3) | C19—C26 | 1.508 (3) |
C3—H3 | 0.9800 | C19—H19 | 0.9800 |
C4—C10 | 1.507 (3) | O19—HOH | 0.86 (3) |
C4—C12 | 1.515 (3) | C20—C25 | 1.383 (3) |
C4—H4 | 0.9800 | C20—C21 | 1.388 (3) |
C5—C6 | 1.380 (3) | C21—C22 | 1.389 (4) |
C5—C10 | 1.395 (3) | C21—H21 | 0.9300 |
C5—H5 | 0.9300 | C22—C23 | 1.373 (4) |
C6—C7 | 1.372 (4) | C22—H22 | 0.9300 |
C6—H6 | 0.9300 | C23—C24 | 1.364 (4) |
C7—C8 | 1.374 (4) | C23—H23 | 0.9300 |
C7—H7 | 0.9300 | C24—C25 | 1.375 (4) |
C8—C9 | 1.394 (3) | C24—H24 | 0.9300 |
C8—H8 | 0.9300 | C25—H25 | 0.9300 |
C9—C10 | 1.393 (3) | C26—C31 | 1.375 (3) |
C11—H11A | 0.9600 | C26—C27 | 1.376 (3) |
C11—H11B | 0.9600 | C27—C28 | 1.381 (4) |
C11—H11C | 0.9600 | C27—H27 | 0.9300 |
C12—C13 | 1.380 (3) | C28—C29 | 1.362 (4) |
C12—C17 | 1.381 (3) | C28—H28 | 0.9300 |
C13—C14 | 1.383 (4) | C29—C30 | 1.366 (4) |
C13—H13 | 0.9300 | C29—H29 | 0.9300 |
C14—C15 | 1.367 (4) | C30—C31 | 1.381 (4) |
C14—H14 | 0.9300 | C30—H30 | 0.9300 |
C15—C16 | 1.374 (4) | C31—H31 | 0.9300 |
C15—H15 | 0.9300 | ||
N2—C1—C9 | 113.18 (17) | C16—C15—H15 | 120.2 |
N2—C1—H1A | 108.9 | C15—C16—C17 | 119.9 (3) |
C9—C1—H1A | 108.9 | C15—C16—H16 | 120.0 |
N2—C1—H1B | 108.9 | C17—C16—H16 | 120.0 |
C9—C1—H1B | 108.9 | C12—C17—C16 | 121.2 (2) |
H1A—C1—H1B | 107.8 | C12—C17—H17 | 119.4 |
C1—N2—C3 | 110.59 (16) | C16—C17—H17 | 119.4 |
C1—N2—C18 | 111.93 (16) | N2—C18—C20 | 113.06 (16) |
C3—N2—C18 | 115.13 (16) | N2—C18—C19 | 108.02 (16) |
N2—C3—C11 | 114.83 (18) | C20—C18—C19 | 110.66 (17) |
N2—C3—C4 | 107.52 (17) | N2—C18—H18 | 108.3 |
C11—C3—C4 | 112.15 (18) | C20—C18—H18 | 108.3 |
N2—C3—H3 | 107.3 | C19—C18—H18 | 108.3 |
C11—C3—H3 | 107.3 | O19—C19—C26 | 111.22 (19) |
C4—C3—H3 | 107.3 | O19—C19—C18 | 110.15 (17) |
C10—C4—C12 | 113.71 (18) | C26—C19—C18 | 112.22 (18) |
C10—C4—C3 | 110.49 (17) | O19—C19—H19 | 107.7 |
C12—C4—C3 | 110.99 (17) | C26—C19—H19 | 107.7 |
C10—C4—H4 | 107.1 | C18—C19—H19 | 107.7 |
C12—C4—H4 | 107.1 | C19—O19—HOH | 105 (2) |
C3—C4—H4 | 107.1 | C25—C20—C21 | 118.6 (2) |
C6—C5—C10 | 121.1 (2) | C25—C20—C18 | 119.2 (2) |
C6—C5—H5 | 119.4 | C21—C20—C18 | 122.1 (2) |
C10—C5—H5 | 119.4 | C20—C21—C22 | 119.7 (3) |
C7—C6—C5 | 120.1 (2) | C20—C21—H21 | 120.1 |
C7—C6—H6 | 120.0 | C22—C21—H21 | 120.1 |
C5—C6—H6 | 120.0 | C23—C22—C21 | 120.3 (3) |
C6—C7—C8 | 119.6 (2) | C23—C22—H22 | 119.9 |
C6—C7—H7 | 120.2 | C21—C22—H22 | 119.9 |
C8—C7—H7 | 120.2 | C24—C23—C22 | 120.4 (3) |
C7—C8—C9 | 121.3 (2) | C24—C23—H23 | 119.8 |
C7—C8—H8 | 119.3 | C22—C23—H23 | 119.8 |
C9—C8—H8 | 119.3 | C23—C24—C25 | 119.5 (3) |
C10—C9—C8 | 119.2 (2) | C23—C24—H24 | 120.2 |
C10—C9—C1 | 121.60 (19) | C25—C24—H24 | 120.2 |
C8—C9—C1 | 119.2 (2) | C24—C25—C20 | 121.4 (3) |
C9—C10—C5 | 118.7 (2) | C24—C25—H25 | 119.3 |
C9—C10—C4 | 120.36 (19) | C20—C25—H25 | 119.3 |
C5—C10—C4 | 121.0 (2) | C31—C26—C27 | 118.6 (2) |
C3—C11—H11A | 109.5 | C31—C26—C19 | 119.3 (2) |
C3—C11—H11B | 109.5 | C27—C26—C19 | 122.2 (2) |
H11A—C11—H11B | 109.5 | C26—C27—C28 | 120.5 (3) |
C3—C11—H11C | 109.5 | C26—C27—H27 | 119.8 |
H11A—C11—H11C | 109.5 | C28—C27—H27 | 119.8 |
H11B—C11—H11C | 109.5 | C29—C28—C27 | 120.4 (3) |
C13—C12—C17 | 117.9 (2) | C29—C28—H28 | 119.8 |
C13—C12—C4 | 119.3 (2) | C27—C28—H28 | 119.8 |
C17—C12—C4 | 122.7 (2) | C28—C29—C30 | 119.7 (3) |
C12—C13—C14 | 121.1 (3) | C28—C29—H29 | 120.2 |
C12—C13—H13 | 119.5 | C30—C29—H29 | 120.2 |
C14—C13—H13 | 119.5 | C29—C30—C31 | 120.2 (3) |
C15—C14—C13 | 120.2 (3) | C29—C30—H30 | 119.9 |
C15—C14—H14 | 119.9 | C31—C30—H30 | 119.9 |
C13—C14—H14 | 119.9 | C26—C31—C30 | 120.7 (3) |
C14—C15—C16 | 119.7 (3) | C26—C31—H31 | 119.7 |
C14—C15—H15 | 120.2 | C30—C31—H31 | 119.7 |
C9—C1—N2—C3 | 47.4 (2) | C13—C12—C17—C16 | 0.5 (3) |
C9—C1—N2—C18 | 177.26 (19) | C4—C12—C17—C16 | −176.6 (2) |
C1—N2—C3—C11 | 56.3 (2) | C15—C16—C17—C12 | −0.1 (4) |
C18—N2—C3—C11 | −71.7 (2) | C1—N2—C18—C20 | −176.66 (18) |
C1—N2—C3—C4 | −69.2 (2) | C3—N2—C18—C20 | −49.2 (2) |
C18—N2—C3—C4 | 162.68 (16) | C1—N2—C18—C19 | 60.5 (2) |
N2—C3—C4—C10 | 54.4 (2) | C3—N2—C18—C19 | −172.04 (17) |
C11—C3—C4—C10 | −72.8 (2) | N2—C18—C19—O19 | 48.5 (2) |
N2—C3—C4—C12 | −72.7 (2) | C20—C18—C19—O19 | −75.7 (2) |
C11—C3—C4—C12 | 160.16 (19) | N2—C18—C19—C26 | 173.03 (17) |
C10—C5—C6—C7 | −0.8 (4) | C20—C18—C19—C26 | 48.8 (2) |
C5—C6—C7—C8 | 0.8 (4) | N2—C18—C20—C25 | 138.8 (2) |
C6—C7—C8—C9 | −0.6 (4) | C19—C18—C20—C25 | −99.9 (2) |
C7—C8—C9—C10 | 0.4 (4) | N2—C18—C20—C21 | −46.1 (3) |
C7—C8—C9—C1 | −179.9 (2) | C19—C18—C20—C21 | 75.2 (2) |
N2—C1—C9—C10 | −12.7 (3) | C25—C20—C21—C22 | 1.0 (4) |
N2—C1—C9—C8 | 167.7 (2) | C18—C20—C21—C22 | −174.2 (2) |
C8—C9—C10—C5 | −0.4 (3) | C20—C21—C22—C23 | 0.2 (4) |
C1—C9—C10—C5 | 179.9 (2) | C21—C22—C23—C24 | −1.4 (5) |
C8—C9—C10—C4 | −179.9 (2) | C22—C23—C24—C25 | 1.3 (4) |
C1—C9—C10—C4 | 0.4 (3) | C23—C24—C25—C20 | −0.1 (4) |
C6—C5—C10—C9 | 0.6 (3) | C21—C20—C25—C24 | −1.1 (3) |
C6—C5—C10—C4 | −179.8 (2) | C18—C20—C25—C24 | 174.2 (2) |
C12—C4—C10—C9 | 104.1 (2) | O19—C19—C26—C31 | −159.3 (2) |
C3—C4—C10—C9 | −21.5 (3) | C18—C19—C26—C31 | 76.8 (3) |
C12—C4—C10—C5 | −75.4 (2) | O19—C19—C26—C27 | 23.1 (3) |
C3—C4—C10—C5 | 159.02 (19) | C18—C19—C26—C27 | −100.8 (3) |
C10—C4—C12—C13 | 152.5 (2) | C31—C26—C27—C28 | −0.9 (4) |
C3—C4—C12—C13 | −82.2 (2) | C19—C26—C27—C28 | 176.8 (3) |
C10—C4—C12—C17 | −30.5 (3) | C26—C27—C28—C29 | −0.2 (5) |
C3—C4—C12—C17 | 94.8 (2) | C27—C28—C29—C30 | 0.9 (5) |
C17—C12—C13—C14 | −0.7 (4) | C28—C29—C30—C31 | −0.4 (5) |
C4—C12—C13—C14 | 176.5 (2) | C27—C26—C31—C30 | 1.4 (4) |
C12—C13—C14—C15 | 0.5 (4) | C19—C26—C31—C30 | −176.4 (2) |
C13—C14—C15—C16 | −0.1 (4) | C29—C30—C31—C26 | −0.8 (4) |
C14—C15—C16—C17 | −0.1 (4) |
Cg2, Cg3, Cg4 and Cg5 are the centroids of the C5–C10, C12-C17, C20–C25, and C26–C31 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
O19—HOH···N2 | 0.86 (3) | 2.18 (3) | 2.737 (2) | 123 (2) |
C27—H27···O19 | 0.93 | 2.48 | 2.798 (3) | 100 |
C21—H21···Cg3 | 0.93 | 3.14 | 3.930 (4) | 144 |
C6—H6···O19i | 0.93 | 2.57 | 3.492 (3) | 170 |
C14—H14···Cg5ii | 0.93 | 2.95 | 3.770 (4) | 147 |
C16—H16···Cg4iii | 0.93 | 2.92 | 3.743 (3) | 148 |
C31—H31···Cg2iv | 0.93 | 2.96 | 3.803 (3) | 152 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2. |
Acknowledgements
The authors are indebted to Dr Mathias Meyer (Rigaku) for his invaluable help in converting ancient KappaCCD images into a format readable by CrysAlis PRO software.
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