research communications
Synthesis, crystal structures, and Hirshfeld analysis of three hexahydroquinoline derivatives
aDepartment of Biomedical and Pharmaceutical Sciences, University of Montana, Missoula, MT 59812, USA, bDepartment of Chemistry, Ithaca College, 953 Danby Road, Ithaca, NY 14850, USA, and cDepartment of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA
*Correspondence e-mail: Nicholas.Natale@mso.umt.edu
Three hexahydroquinoline derivatives were synthesized and crystallized in an effort to study the structure–activity relationships of these calcium-channel antagonists. The derivatives are ethyl 4-(2-methoxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, C22H27NO4, (I), ethyl 4-(4-methoxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, C22H27NO4, (II), and ethyl 4-(3,4-dihydroxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, C21H24NO5, (III). In these hexahydroquinoline derivatives, common structural features such as a flat-boat conformation of the 1,4-dihydropyridine (1,4-DHP) ring, an of the fused cyclohexanone ring, and a substituted phenyl group at the pseudo-axial position are retained. Hydrogen bonds are the main contributors to the packing of the molecules in these crystals.
1. Chemical context
4-Aryl-1,4-dihydropyridines (DHPs) that bind the L-type voltage-gated calcium channels (VGCC) have been applied in general medical practice for over three decades (Zamponi, 2016). Many modifications on 1,4-DHP have been performed to obtain active compounds such as calcium-channel agonists or antagonists (Martín et al., 1995; Rose, 1990; Rose & Dräger, 1992; Trippier et al., 2013). One such modification is fusing a cyclohexanone ring to form hexahydroquinoline (HHQ), in which the orientation of the carbonyl group of the ester substituent at the 5-position in the 1,4-DHP ring has been fixed. This class of compounds has been shown to have calcium-channel antagonistic activity (Aygün Cevher et al., 2019), inhibit the multidrug-resistance transporter (MDR) (Shahraki et al., 2017, 2020), as well as possessing anti-inflammatory and stem-cell differentiation properties, and have been implicated in slowing neurodegenerative disorders (Trippier et al., 2013). Recently, specific substitutions of the cyclohexenone ring were found to have distinct selectivity profiles to different calcium channel subtypes (Schaller et al., 2018). Another report also showed that the 4-aryl-hexahydroquinolines, especially the ones containing a methoxy moiety, exhibit good antioxidant property as radical scavengers (Yang et al., 2011). In a continuation of our study on the structure–activity relationship of this class of 4-aryl-hexahydroquinolines (Steiger et al., 2014, 2018, 2020), and to understand stereoelectronic effects, which define selectivity, as well as to explore the scope and limitations of our synthetic methodologies (Steiger et al., 2016), we report herein the crystal structures of three 4-aryl-hexahydroquinoline derivatives.
2. Structural commentary
The P (Fig. 1). Compounds II and III both crystallize in the monoclinic P21/n. The of compound II contains two independent molecules, A and B (Fig. 2), while compound III has only one independent molecule in the (Fig. 3). Similar to the other 4-aryl-hexahydroquinoline derivatives that we have reported (Steiger, et al., 2014; 2018; 2020), compounds I, II, and III all share the common structural features such as a flattened boat conformation on the 1,4-DHP ring, of the cyclohexanone ring, and the pseudo-axial position of the 4-aryl group.
of the title compound I contains one independent molecule, which crystallizes in the triclinicThe shallow-boat confirmation of the 1,4-DHP ring is one of the factors that leads to higher calcium-channel activity (Linden et al., 2004) The shallowness of the boat conformation in these three compounds are indicated by the marginal displacements of atom N1 and C4 from the mean plane (the base of the boat) defined by the two double bonds (C2=C3 and C9=C10). The distances between N1 and the mean plane formed by C2/C3/C9/C10 are 0.159 (3), 0.110 (2), 0.110 (3), and 0.181 (2) Å for compounds I, IIA, IIB, and III, respectively. The corresponding distances between C4 and the same mean plane are 0.341 (3), 0.295 (3), 0.253 (3), and 0.399 (2) Å for compounds I, IIA, IIB, and III, respectively.
The pseudo-axial position of the C4-aryl group to the 1,4-DHP ring is another key factor that is essential for pharmacological activity (Langs et al., 1987). In the title compounds, the substituted phenyl rings are almost orthogonal to the base of the 1,4-DHP ring, with the mean plane normal to normal angles being 89.09 (7), 92.52 (6), 93.52 (6), and 90.59 (5)° for compounds I, IIA, IIB, and III, respectively (see Table 1 for calculated parameters). It is noteworthy that the para-methoxy group on the phenyl ring is flexible and can be either anti- or syn- periplanar to the H atom on C4, i.e. pointing either to (IIA) or away from (IIB) the 1,4-DHP ring.
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In all three compounds, the cyclohexanone rings adopt the θ = 54.7° (or θ =125.3° in the case of an change) and φ = n × 60°. The θ and φ values of the title compounds are very close to the ideal angles with deviations less than 10° and are listed in Table 2.
which can be quantified using Cremer & Pople's ring-puckering parameters. Ideally, the would have
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Although the carbonyl on the ester group is conjugated to the adjacent endocyclic double bond and is co-planar to the 1,4-DHP mean plane, the whole ester group is flexible. The C=O bond can be either cis (I, IIA and IIB) or trans (III) to the adjacent double bond, and the extended or curled orientations of the ethyl group are observed in these crystal structures. The disordered ethyl groups in compound I and compound II also indicate the flexibility of the ester group.
3. Supramolecular features
In compound I, hydrogen bonds between N1—H1 and O1 form a chain perpendicular to the (100) plane. Short contact C23—H23A⋯O2 links alternate enantiomers to form a pair perpendicular to the (001) plane (Table 3, Fig. 4).
In compound II, hydrogen bonds N1A—H1A⋯O1B and N1B—H1B⋯O1A link the two independent molecules A and B to form a chain perpendicular to the (010) plane. Close contacts C23B—H23B⋯O2A and C23A—H23D⋯O2B link the two independent molecules zigzaggedly along the c-axis direction (Table 4, Fig. 5).
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In compound III, a chain is formed by hydrogen bonds N1—H1⋯O1i and O4—H4⋯O2i between alternating enantiomers and runs perpendicular to the (101) plane. Hydrogen bond O5—H5⋯O1ii links the molecules in a chain perpendicular to the (100) plane and cross-links the other chain to form a sheet of molecules parallel to the (010) plane (Table 5, Fig. 6).
4. Hirshfeld surface analysis
Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) was performed, and the associated two-dimensional fingerprint plots (McKinnon et al., 2007) were generated to quantify the intermolecular interactions using Crystal Explorer 21.5 (Spackman et al., 2021). The Hirshfeld surface of the title compound I is mapped over dnorm in a fixed color scale of −0.5596 (red) to 1.4022 (blue) arbitrary units (Fig. 7). The N—H⋯O hydrogen bond is apparent as red spots on the surface. A σ–π interaction between the ester ethyl group and the phenyl ring is noticeable. The delineated two-dimensional fingerprint plots (Fig. 8) show that the contributions to the overall Hirshfeld surface area arise from H⋯H contacts (65.3%), O⋯H/H⋯O contacts (17.7%), and C⋯H/H⋯C interactions (16.4%).
For compound II, the Hirshfeld surface analysis was performed with two independent molecules, in a fixed color scale of −0.6119 (red) to 1.7055 (blue) arbitrary units. In addition to hydrogen bonds, σ–π interactions are also identifiable between C6A—H6AB and double bond C2A—C3A (Fig. 9). The delineated two-dimensional fingerprint plots shown in Fig. 10 indicate that H⋯H contacts (65.6%) make the main contribution to the overall Hirshfeld surface area. The O⋯H/H⋯O contacts and C⋯H/H⋯C interactions contribute 19.4% and 14.0% of the Hirshfeld surface, respectively.
The Hirshfeld surface of the title compound III is mapped over dnorm in a fixed color scale of −0.7001 (red) to 3.4800 (blue) arbitrary units (Fig. 11). Besides the obvious short contacts from hydrogen bonds, a short contact of 2.6137 (14) Å between H8A and C20 is also observed, indicating a σ-π- interaction between C8—H8A and ring C17–C22. The delineated two-dimensional fingerprint plots shown in Fig. 12 indicate that two main contributions to the overall Hirshfeld surface area arise from H⋯H contacts (61.2%) and O⋯H/H⋯O contacts (24.3%). C⋯H/H⋯C interactions contribute 13.1% of the Hirshfeld surface.
5. Database survey
A search for 4-phenyl-5-oxo-hexahydroquinoline-3-carboxylate in the Cambridge Structural Database (CSD version 5.43, November 2021 update; Groom et al., 2016) resulted in 53 hits, of which a meta-methoxyl-substituted 4-phenyl-5-oxo-hexahydroquinoline-3-carboxylate (refcode TANVUC; Li, 2017) should be mentioned. Similar to the title compounds I and IIA, the meta-methoxyl group in TANVUC is exo to the 1,4-DHP ring and carbonyl group on the ester is in a cis orientation to the endocyclic double bond. All of the resulting hits display common structural features, such as the flat-boat conformation of the 1,4-DHP ring, the of the fused cyclohexanone ring, and the substituted aryl ring at the pseudo-axial position to the 1,4-DHP ring.
6. Synthesis and crystallization
An oven-dried 100 ml round-bottom flask equipped with a magnetic stir bar was charged with 10 mmol of dimedone, 10 mmol of ethyl acetoacetate and 5 mol % of ytterbium(III) trifluoromethanesulfonate. The mixture was then taken up in 30 ml of absolute ethanol, capped and put under an inert atmosphere of argon, after which the solution was allowed to stir at room temperature for 20 min. the appropriate corresponding benzaldehyde (10 mmol) and 10 mmol of ammonium acetate were added to the stirring solution, the solution was allowed to stir at room temperature for 48 h. Reaction progress was monitored via TLC. Once the reaction was complete, excess solvent was removed via rotary evaporation. The solution was then purified via silica The products were crystallized from hexane and ethyl acetate (1:4 v/v) as white-to-yellow crystalline solids. Compounds I and III were recrystallized from a minimum of warm methanol, to which hexane was added dropwise to a faint opalescence, and slow evaporation produced diffraction-quality crystals.
Compound I: m.p. 520.5 K. 1H NMR: (CDCl3) δ ppm 7.28 (dd, 1H, J = 7.33 and 1.83 Hz); 7.07 (ddd, 1H, J = 8.24, 7.33 and 1.83 Hz); 6.80 (d, 1H, J = 7.33 Hz); 6.78 (d, 1H, J = 8.24 Hz); 5.69 (s, br, 1H); 5.24 (s, 1H); 4.00 (m, 2H); 3.78 (s, 3H); 2.31 (d, 1H, J = 23.81 Hz); 2.30 (s, 3H); 2.13 (q, 2H, J = 16.49 Hz); 2.11 (d, 1H, J = 32.84 Hz); 1.17 (t, 3H, J = 7.2 Hz); 1.06 (s, 3H); 0.92 (s, 3H). 13C NMR: (CDCl3) δ ppm 195.32; 167.98; 157.61; 148.12; 142.99; 134.51; 131.39; 127.34; 120.06; 111.26; 110.90; 105.26; 59.70; 55.46; 50.80; 41.47; 33.58; 32.69; 29.59; 26.99; 19.53; 14.23. HPLC–MS: calculated for [C22H27NO4+H]+ 370.46, observed m/z 370.1865 ([M + 1]+, 100% rel. intensity). Compound II: m.p. 517–527 K. 1H NMR: (CDCl3) δ ppm 7.20 (d, 2H, J = 9.16 Hz); 6.72 (d, 2H, J = 9.16 Hz); 5.76 (s, br, 1H); 4.05 (q, 2H, J = 7.33 Hz); 3.73 (s, 3H); 2.36 (s, 3H); 2.32 (d, 1H, J = 16.03 Hz); 2.22 (d, 1H, J = 16.03); 2.16 (t, 2H, J = 17.40 Hz); 1.19 (t, 3H, J = 7.33 Hz); 1.06 (s, 3H); 0.93 (s, 3H). 13C NMR: (CDCl3) δppm 195.58; 167.57; 157.83; 147.56; 143.05; 139.62; 129.06; 113.31; 112.61; 106.47; 59.91; 55.21; 50.79; 41.29; 35.75; 32.84; 29.52; 27.30; 19.61; 14.32. HPLC–MS: calculated for [C22H27NO4+H]+ 370.46, observed m/z 370.1873 ([M + 1]+, 100% rel. intensity). Compound III: 1H NMR: (acetone-d6) δ ppm 7.97 (s, 1H); 7.54 (s, 1H); 7.45 (s, 1H); 6.77 (t, 1H, J = 1.14 Hz); 6.59 (d, 2H, J = 1.14 Hz); 4.88 (s, 1H); 4.00 (q, 2H, J = 7.2 Hz); 2.42 (d, 1H, J = 16.94 Hz); 2.31 (s, 3H); 2.30 (dd, 1H, J = 16.94 and 1.37 Hz); 2.15 (d, 1H, J = 16.03 Hz); 2.00 (dd, 1H, J = 16.03 and 1.37 Hz); 1.16 (t, 3H, J = 7.2 Hz); 1.02 (s, 3H); 0.90 (s, 3H). 13C NMR: (acetone-d6) δ ppm 193.99; 167.22; 148.25; 144.26; 144.13; 143.04; 140.03; 119.24; 115.27; 114.44; 111.46; 104.96; 58.99; 50.60; 40.03; 35.49; 32.22; 26.35; 22.47; 17.99; 13.84. HPLC–MS: calculated for [C21H25NO5+H]+ 372.43, observed m/z 372.1657 ([M + 1]+, 100% rel. intensity).
7. Refinement
Crystal data, data collection and structure . Carbon-bound hydrogen atoms on all three compounds were fixed geometrically and treated as riding with C—H = 0.95–0.98 Å and refined with Uiso(H) = 1.2Ueq (CH, CH2) or 1.5Ueq (CH3). Hydrogen atoms attached to nitrogen and oxygen were found in difference-Fourier map and refined freely. Eight reflections (010, 00, 0, 011, 00, 001, 002, and 00) in compound I and eight reflections (040, 020, 123, 23, 076, 031, 112, and 516) in compound III were omitted because of poor agreement between the observed and calculated intensities.
details are summarized in Table 6
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Data of compound I were acquired at room temperature due to the disintegration of the crystals at low temperatures. The sample measured was identified as two crystals, mis-oriented by 0.24° approximately about the [001] reciprocal-space axis. For the purposes of data collection and subsequent structure SHELXL (Sheldrick, 2015), yielding a ratio of 0.866 (2):0.134 (2) for the two crystals. In compound I, the ethyl group on the carboxylic ester is disordered and was modeled at 50% occupancy at each site. Atomic displacement equivalency restraints and bond-length restraints (Sheldrick, 2015) were applied to the carbon atoms and the single-bond oxygen atom of the disordered ester group.
the structure was treated using facilities for handling by non-merohedry, namely HKLF5 data inThe crystals of compound II were found to be pseudo-merohedric twins by a 180° rotation about the c axis. Application of the (−1, 0, 0, 0, −1, 0, 0, 0, 1) yielded a twin component ratio of 0.6938 (8):0.3062 (8). The ester group on molecule B is also disordered. Atomic displacement equivalency restraints were applied to the two carbons and the single bond oxygen on the ethyl group. Restraints were applied to bond lengths on the atoms of the ester as well.
Compound III was co-crystallized with hexanes. However, being a mixture of disordered hexane isomers, the OLEX2 SMTBX (Rees et al., 2005) solvent-masking procedure was used to calculate and mask the solvent-accessible void. There are 192 electrons found in a volume of 464 Å3 in one void per This is consistent with the presence of one C6H14 molecule per which accounts for 200 electrons per unit cell.
around the hexanes did not give satisfactory results. TheSupporting information
https://doi.org/10.1107/S2056989022009495/jy2021sup1.cif
contains datablocks I, II, III. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009495/jy2021Isup5.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989022009495/jy2021Isup5.cml
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022009495/jy2021IIsup6.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989022009495/jy2021IIsup6.cml
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989022009495/jy2021IIIsup7.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989022009495/jy2021IIIsup7.cml
For all structures, data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C22H27NO4 | Z = 2 |
Mr = 369.44 | F(000) = 396 |
Triclinic, P1 | Dx = 1.253 Mg m−3 |
a = 7.2941 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.6773 (3) Å | Cell parameters from 7681 reflections |
c = 14.4302 (4) Å | θ = 2.5–22.8° |
α = 82.1992 (17)° | µ = 0.09 mm−1 |
β = 88.3216 (16)° | T = 300 K |
γ = 75.9397 (16)° | Prism, colourless |
V = 978.92 (5) Å3 | 0.35 × 0.19 × 0.14 mm |
Bruker SMART BREEZE CCD diffractometer | 22410 reflections with I > 2σ(I) |
Radiation source: 2 kW sealed X-ray tube | θmax = 28.4°, θmin = 2.9° |
φ and ω scans | h = −9→9 |
34490 measured reflections | k = −12→12 |
34490 independent reflections | l = −19→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.1957P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
34490 reflections | Δρmax = 0.25 e Å−3 |
285 parameters | Δρmin = −0.17 e Å−3 |
39 restraints |
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 twin. Twin law (-1 0 0 0 -1 0 0.0123 -0.407 1) was applied and the structure was refined using HKLF5 data, yielding a ratio of 0.866 (2):0.134 (2) for the two twin components. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.25132 (18) | 0.32563 (17) | 0.92561 (11) | 0.0527 (4) | |
O2 | 0.6827 (3) | 0.6344 (2) | 0.60678 (12) | 0.0767 (6) | |
O4 | 0.2571 (2) | 0.3067 (2) | 0.67486 (12) | 0.0678 (5) | |
N1 | 0.8600 (2) | 0.39276 (19) | 0.87300 (13) | 0.0423 (5) | |
H1 | 0.973 (3) | 0.384 (2) | 0.8957 (16) | 0.059 (7)* | |
C2 | 0.8111 (3) | 0.4770 (2) | 0.78765 (15) | 0.0392 (5) | |
C3 | 0.6490 (3) | 0.4763 (2) | 0.74504 (14) | 0.0367 (5) | |
C4 | 0.5269 (3) | 0.3751 (2) | 0.78681 (13) | 0.0353 (5) | |
H4 | 0.393905 | 0.425869 | 0.777076 | 0.042* | |
C5 | 0.4146 (3) | 0.3084 (2) | 0.95350 (14) | 0.0356 (5) | |
C6 | 0.4605 (3) | 0.2630 (2) | 1.05554 (14) | 0.0428 (5) | |
H6A | 0.385700 | 0.195992 | 1.080077 | 0.051* | |
H6B | 0.421654 | 0.346858 | 1.087912 | 0.051* | |
C7 | 0.6677 (3) | 0.1929 (2) | 1.07869 (14) | 0.0415 (5) | |
C8 | 0.7858 (3) | 0.2895 (2) | 1.02836 (14) | 0.0415 (5) | |
H8A | 0.772188 | 0.373330 | 1.060330 | 0.050* | |
H8B | 0.917788 | 0.238044 | 1.031904 | 0.050* | |
C9 | 0.7317 (3) | 0.3380 (2) | 0.92783 (14) | 0.0343 (5) | |
C10 | 0.5631 (2) | 0.3384 (2) | 0.89123 (13) | 0.0332 (5) | |
C11 | 0.7238 (3) | 0.0433 (2) | 1.04788 (19) | 0.0628 (7) | |
H11A | 0.646747 | −0.015615 | 1.079713 | 0.094* | |
H11B | 0.854309 | 0.000489 | 1.063006 | 0.094* | |
H11C | 0.705584 | 0.051153 | 0.981582 | 0.094* | |
C12 | 0.7000 (4) | 0.1791 (3) | 1.18439 (16) | 0.0682 (8) | |
H12A | 0.667684 | 0.272852 | 1.204085 | 0.102* | |
H12B | 0.830489 | 0.134601 | 1.198617 | 0.102* | |
H12C | 0.622130 | 0.121222 | 1.216662 | 0.102* | |
C13 | 0.9461 (3) | 0.5694 (3) | 0.75745 (17) | 0.0561 (6) | |
H13A | 0.928499 | 0.645503 | 0.795594 | 0.084* | |
H13B | 0.922670 | 0.609745 | 0.693126 | 0.084* | |
H13C | 1.073547 | 0.512033 | 0.764320 | 0.084* | |
C14 | 0.5891 (3) | 0.5687 (2) | 0.65630 (15) | 0.0449 (5) | |
C17 | 0.5638 (3) | 0.2400 (2) | 0.73826 (14) | 0.0390 (5) | |
C18 | 0.4292 (3) | 0.2107 (2) | 0.68159 (15) | 0.0457 (5) | |
C19 | 0.4721 (4) | 0.0891 (3) | 0.63638 (17) | 0.0579 (7) | |
H19 | 0.382214 | 0.071800 | 0.597968 | 0.069* | |
C20 | 0.6446 (4) | −0.0051 (3) | 0.64774 (18) | 0.0659 (7) | |
H20 | 0.671714 | −0.086456 | 0.617278 | 0.079* | |
C21 | 0.7777 (4) | 0.0195 (3) | 0.70378 (19) | 0.0685 (8) | |
H21 | 0.895172 | −0.045139 | 0.712177 | 0.082* | |
C22 | 0.7362 (3) | 0.1416 (2) | 0.74789 (16) | 0.0532 (6) | |
H22 | 0.828068 | 0.157980 | 0.785496 | 0.064* | |
C23 | 0.1214 (4) | 0.2879 (4) | 0.61208 (19) | 0.0818 (9) | |
H23A | 0.174511 | 0.285596 | 0.550485 | 0.123* | |
H23B | 0.011391 | 0.366392 | 0.610837 | 0.123* | |
H23C | 0.086578 | 0.199208 | 0.632473 | 0.123* | |
O3 | 0.4114 (15) | 0.559 (2) | 0.6315 (8) | 0.048 (2) | 0.67 (7) |
C15 | 0.3262 (10) | 0.6449 (8) | 0.5454 (4) | 0.0569 (15) | 0.777 (19) |
H15A | 0.251974 | 0.591524 | 0.516476 | 0.068* | 0.777 (19) |
H15B | 0.425664 | 0.660874 | 0.502199 | 0.068* | 0.777 (19) |
C16 | 0.2017 (8) | 0.7873 (7) | 0.5621 (3) | 0.0705 (16) | 0.87 (2) |
H16A | 0.145669 | 0.838148 | 0.504055 | 0.106* | 0.87 (2) |
H16B | 0.275985 | 0.842813 | 0.587485 | 0.106* | 0.87 (2) |
H16C | 0.104003 | 0.772189 | 0.605509 | 0.106* | 0.87 (2) |
O3A | 0.415 (3) | 0.601 (5) | 0.6407 (19) | 0.059 (4) | 0.33 (7) |
C15A | 0.370 (3) | 0.698 (3) | 0.5526 (14) | 0.061 (5) | 0.223 (19) |
H15C | 0.405562 | 0.787441 | 0.555021 | 0.073* | 0.223 (19) |
H15D | 0.432489 | 0.653296 | 0.500041 | 0.073* | 0.223 (19) |
C16A | 0.169 (5) | 0.720 (8) | 0.546 (3) | 0.095 (11) | 0.13 (2) |
H16D | 0.124851 | 0.778836 | 0.488685 | 0.142* | 0.13 (2) |
H16E | 0.110947 | 0.767237 | 0.597962 | 0.142* | 0.13 (2) |
H16F | 0.137650 | 0.629016 | 0.548632 | 0.142* | 0.13 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0281 (8) | 0.0690 (11) | 0.0605 (10) | −0.0152 (7) | −0.0053 (7) | 0.0009 (8) |
O2 | 0.0943 (14) | 0.0879 (14) | 0.0531 (11) | −0.0447 (12) | 0.0001 (10) | 0.0141 (10) |
O4 | 0.0469 (10) | 0.0883 (13) | 0.0737 (12) | −0.0127 (9) | −0.0184 (8) | −0.0322 (10) |
N1 | 0.0260 (9) | 0.0524 (12) | 0.0487 (11) | −0.0131 (8) | −0.0046 (8) | 0.0003 (9) |
C2 | 0.0344 (11) | 0.0393 (12) | 0.0436 (13) | −0.0091 (9) | 0.0055 (9) | −0.0055 (10) |
C3 | 0.0365 (11) | 0.0347 (11) | 0.0378 (12) | −0.0062 (9) | 0.0022 (9) | −0.0060 (9) |
C4 | 0.0275 (10) | 0.0407 (12) | 0.0367 (12) | −0.0062 (8) | −0.0040 (8) | −0.0039 (9) |
C5 | 0.0297 (10) | 0.0340 (11) | 0.0438 (12) | −0.0080 (8) | −0.0012 (9) | −0.0066 (9) |
C6 | 0.0383 (12) | 0.0474 (13) | 0.0429 (13) | −0.0111 (10) | 0.0027 (10) | −0.0057 (10) |
C7 | 0.0412 (12) | 0.0423 (12) | 0.0394 (12) | −0.0084 (10) | −0.0043 (9) | −0.0016 (10) |
C8 | 0.0352 (11) | 0.0449 (13) | 0.0447 (13) | −0.0093 (10) | −0.0094 (9) | −0.0054 (10) |
C9 | 0.0292 (10) | 0.0357 (11) | 0.0386 (12) | −0.0083 (8) | −0.0011 (9) | −0.0061 (9) |
C10 | 0.0275 (10) | 0.0351 (11) | 0.0367 (11) | −0.0064 (8) | −0.0034 (8) | −0.0053 (9) |
C11 | 0.0600 (15) | 0.0419 (14) | 0.0818 (19) | −0.0060 (12) | −0.0071 (14) | −0.0017 (13) |
C12 | 0.0687 (17) | 0.090 (2) | 0.0428 (15) | −0.0203 (15) | −0.0092 (12) | 0.0054 (14) |
C13 | 0.0487 (14) | 0.0604 (15) | 0.0646 (16) | −0.0262 (12) | 0.0055 (12) | −0.0040 (13) |
C14 | 0.0553 (15) | 0.0398 (13) | 0.0385 (13) | −0.0086 (11) | 0.0041 (11) | −0.0074 (10) |
C17 | 0.0411 (12) | 0.0416 (12) | 0.0352 (12) | −0.0130 (10) | −0.0012 (9) | −0.0027 (10) |
C18 | 0.0457 (13) | 0.0524 (14) | 0.0432 (13) | −0.0196 (11) | −0.0011 (10) | −0.0066 (11) |
C19 | 0.0748 (18) | 0.0606 (16) | 0.0493 (15) | −0.0332 (15) | −0.0029 (13) | −0.0142 (13) |
C20 | 0.095 (2) | 0.0472 (15) | 0.0603 (17) | −0.0204 (15) | 0.0043 (15) | −0.0175 (13) |
C21 | 0.0742 (18) | 0.0518 (16) | 0.0733 (19) | 0.0020 (13) | −0.0064 (15) | −0.0167 (14) |
C22 | 0.0511 (14) | 0.0502 (14) | 0.0563 (15) | −0.0044 (11) | −0.0088 (11) | −0.0130 (12) |
C23 | 0.0526 (15) | 0.135 (3) | 0.0679 (19) | −0.0298 (17) | −0.0130 (14) | −0.0334 (18) |
O3 | 0.052 (2) | 0.048 (5) | 0.042 (2) | −0.010 (2) | −0.0128 (16) | 0.003 (3) |
C15 | 0.067 (3) | 0.060 (3) | 0.041 (2) | −0.015 (2) | −0.0144 (19) | 0.003 (2) |
C16 | 0.083 (3) | 0.058 (3) | 0.063 (3) | −0.009 (2) | −0.0144 (19) | 0.006 (2) |
O3A | 0.062 (5) | 0.057 (9) | 0.044 (5) | 0.004 (6) | −0.010 (4) | 0.008 (6) |
C15A | 0.077 (9) | 0.057 (10) | 0.038 (7) | −0.005 (8) | −0.009 (6) | 0.012 (7) |
C16A | 0.104 (19) | 0.10 (2) | 0.074 (16) | −0.016 (18) | −0.034 (14) | 0.016 (18) |
O1—C5 | 1.233 (2) | C13—H13A | 0.9600 |
O2—C14 | 1.200 (2) | C13—H13B | 0.9600 |
O4—C18 | 1.366 (3) | C13—H13C | 0.9600 |
O4—C23 | 1.420 (3) | C14—O3 | 1.382 (10) |
N1—H1 | 0.88 (2) | C14—O3A | 1.25 (3) |
N1—C2 | 1.386 (3) | C17—C18 | 1.399 (3) |
N1—C9 | 1.366 (2) | C17—C22 | 1.378 (3) |
C2—C3 | 1.350 (3) | C18—C19 | 1.388 (3) |
C2—C13 | 1.502 (3) | C19—H19 | 0.9300 |
C3—C4 | 1.532 (3) | C19—C20 | 1.362 (3) |
C3—C14 | 1.471 (3) | C20—H20 | 0.9300 |
C4—H4 | 0.9800 | C20—C21 | 1.366 (3) |
C4—C10 | 1.516 (3) | C21—H21 | 0.9300 |
C4—C17 | 1.529 (3) | C21—C22 | 1.383 (3) |
C5—C6 | 1.502 (3) | C22—H22 | 0.9300 |
C5—C10 | 1.446 (3) | C23—H23A | 0.9600 |
C6—H6A | 0.9700 | C23—H23B | 0.9600 |
C6—H6B | 0.9700 | C23—H23C | 0.9600 |
C6—C7 | 1.525 (3) | O3—C15 | 1.460 (10) |
C7—C8 | 1.521 (3) | C15—H15A | 0.9700 |
C7—C11 | 1.528 (3) | C15—H15B | 0.9700 |
C7—C12 | 1.533 (3) | C15—C16 | 1.501 (8) |
C8—H8A | 0.9700 | C16—H16A | 0.9600 |
C8—H8B | 0.9700 | C16—H16B | 0.9600 |
C8—C9 | 1.496 (3) | C16—H16C | 0.9600 |
C9—C10 | 1.351 (2) | O3A—C15A | 1.47 (2) |
C11—H11A | 0.9600 | C15A—H15C | 0.9700 |
C11—H11B | 0.9600 | C15A—H15D | 0.9700 |
C11—H11C | 0.9600 | C15A—C16A | 1.43 (4) |
C12—H12A | 0.9600 | C16A—H16D | 0.9600 |
C12—H12B | 0.9600 | C16A—H16E | 0.9600 |
C12—H12C | 0.9600 | C16A—H16F | 0.9600 |
C18—O4—C23 | 118.3 (2) | H13A—C13—H13B | 109.5 |
C2—N1—H1 | 118.3 (15) | H13A—C13—H13C | 109.5 |
C9—N1—H1 | 118.9 (15) | H13B—C13—H13C | 109.5 |
C9—N1—C2 | 122.25 (17) | O2—C14—C3 | 126.6 (2) |
N1—C2—C13 | 112.68 (18) | O2—C14—O3 | 123.1 (5) |
C3—C2—N1 | 119.51 (18) | O2—C14—O3A | 116.9 (14) |
C3—C2—C13 | 127.6 (2) | O3—C14—C3 | 110.0 (5) |
C2—C3—C4 | 120.45 (17) | O3A—C14—C3 | 115.2 (11) |
C2—C3—C14 | 120.91 (19) | C18—C17—C4 | 122.77 (19) |
C14—C3—C4 | 118.61 (18) | C22—C17—C4 | 120.36 (18) |
C3—C4—H4 | 108.2 | C22—C17—C18 | 116.9 (2) |
C10—C4—C3 | 109.37 (15) | O4—C18—C17 | 116.32 (19) |
C10—C4—H4 | 108.2 | O4—C18—C19 | 123.2 (2) |
C10—C4—C17 | 111.63 (16) | C19—C18—C17 | 120.5 (2) |
C17—C4—C3 | 111.17 (16) | C18—C19—H19 | 119.7 |
C17—C4—H4 | 108.2 | C20—C19—C18 | 120.6 (2) |
O1—C5—C6 | 119.83 (18) | C20—C19—H19 | 119.7 |
O1—C5—C10 | 121.75 (18) | C19—C20—H20 | 119.9 |
C10—C5—C6 | 118.34 (16) | C19—C20—C21 | 120.2 (2) |
C5—C6—H6A | 108.4 | C21—C20—H20 | 119.9 |
C5—C6—H6B | 108.4 | C20—C21—H21 | 120.3 |
C5—C6—C7 | 115.67 (17) | C20—C21—C22 | 119.3 (2) |
H6A—C6—H6B | 107.4 | C22—C21—H21 | 120.3 |
C7—C6—H6A | 108.4 | C17—C22—C21 | 122.5 (2) |
C7—C6—H6B | 108.4 | C17—C22—H22 | 118.7 |
C6—C7—C11 | 110.41 (18) | C21—C22—H22 | 118.7 |
C6—C7—C12 | 109.80 (18) | O4—C23—H23A | 109.5 |
C8—C7—C6 | 107.87 (16) | O4—C23—H23B | 109.5 |
C8—C7—C11 | 110.68 (19) | O4—C23—H23C | 109.5 |
C8—C7—C12 | 109.10 (18) | H23A—C23—H23B | 109.5 |
C11—C7—C12 | 108.95 (19) | H23A—C23—H23C | 109.5 |
C7—C8—H8A | 108.9 | H23B—C23—H23C | 109.5 |
C7—C8—H8B | 108.9 | C14—O3—C15 | 118.3 (9) |
H8A—C8—H8B | 107.7 | O3—C15—H15A | 109.1 |
C9—C8—C7 | 113.37 (16) | O3—C15—H15B | 109.1 |
C9—C8—H8A | 108.9 | O3—C15—C16 | 112.5 (9) |
C9—C8—H8B | 108.9 | H15A—C15—H15B | 107.8 |
N1—C9—C8 | 116.06 (17) | C16—C15—H15A | 109.1 |
C10—C9—N1 | 119.62 (18) | C16—C15—H15B | 109.1 |
C10—C9—C8 | 124.19 (18) | C15—C16—H16A | 109.5 |
C5—C10—C4 | 120.18 (16) | C15—C16—H16B | 109.5 |
C9—C10—C4 | 120.76 (17) | C15—C16—H16C | 109.5 |
C9—C10—C5 | 119.03 (18) | H16A—C16—H16B | 109.5 |
C7—C11—H11A | 109.5 | H16A—C16—H16C | 109.5 |
C7—C11—H11B | 109.5 | H16B—C16—H16C | 109.5 |
C7—C11—H11C | 109.5 | C14—O3A—C15A | 111 (2) |
H11A—C11—H11B | 109.5 | O3A—C15A—H15C | 111.3 |
H11A—C11—H11C | 109.5 | O3A—C15A—H15D | 111.3 |
H11B—C11—H11C | 109.5 | H15C—C15A—H15D | 109.2 |
C7—C12—H12A | 109.5 | C16A—C15A—O3A | 102 (2) |
C7—C12—H12B | 109.5 | C16A—C15A—H15C | 111.3 |
C7—C12—H12C | 109.5 | C16A—C15A—H15D | 111.3 |
H12A—C12—H12B | 109.5 | C15A—C16A—H16D | 109.5 |
H12A—C12—H12C | 109.5 | C15A—C16A—H16E | 109.5 |
H12B—C12—H12C | 109.5 | C15A—C16A—H16F | 109.5 |
C2—C13—H13A | 109.5 | H16D—C16A—H16E | 109.5 |
C2—C13—H13B | 109.5 | H16D—C16A—H16F | 109.5 |
C2—C13—H13C | 109.5 | H16E—C16A—H16F | 109.5 |
O1—C5—C6—C7 | 158.59 (18) | C6—C5—C10—C4 | 175.97 (18) |
O1—C5—C10—C4 | −7.4 (3) | C6—C5—C10—C9 | −6.2 (3) |
O1—C5—C10—C9 | 170.39 (19) | C6—C7—C8—C9 | −47.3 (2) |
O2—C14—O3—C15 | −6 (2) | C7—C8—C9—N1 | −163.74 (17) |
O2—C14—O3A—C15A | 10 (4) | C7—C8—C9—C10 | 20.4 (3) |
O4—C18—C19—C20 | −178.1 (2) | C8—C9—C10—C4 | −173.83 (18) |
N1—C2—C3—C4 | −4.4 (3) | C8—C9—C10—C5 | 8.4 (3) |
N1—C2—C3—C14 | 177.57 (19) | C9—N1—C2—C3 | −17.4 (3) |
N1—C9—C10—C4 | 10.5 (3) | C9—N1—C2—C13 | 158.14 (19) |
N1—C9—C10—C5 | −167.32 (18) | C10—C4—C17—C18 | 125.8 (2) |
C2—N1—C9—C8 | −161.64 (19) | C10—C4—C17—C22 | −55.3 (2) |
C2—N1—C9—C10 | 14.4 (3) | C10—C5—C6—C7 | −24.7 (3) |
C2—C3—C4—C10 | 25.1 (3) | C11—C7—C8—C9 | 73.6 (2) |
C2—C3—C4—C17 | −98.6 (2) | C12—C7—C8—C9 | −166.52 (19) |
C2—C3—C14—O2 | 11.7 (3) | C13—C2—C3—C4 | −179.3 (2) |
C2—C3—C14—O3 | −174.2 (9) | C13—C2—C3—C14 | 2.7 (3) |
C2—C3—C14—O3A | −155 (3) | C14—C3—C4—C10 | −156.85 (17) |
C3—C4—C10—C5 | 149.48 (17) | C14—C3—C4—C17 | 79.4 (2) |
C3—C4—C10—C9 | −28.3 (2) | C14—O3—C15—C16 | −93.5 (15) |
C3—C4—C17—C18 | −111.8 (2) | C14—O3A—C15A—C16A | 179 (5) |
C3—C4—C17—C22 | 67.1 (2) | C17—C4—C10—C5 | −87.1 (2) |
C3—C14—O3—C15 | 179.4 (11) | C17—C4—C10—C9 | 95.2 (2) |
C3—C14—O3A—C15A | 178 (2) | C17—C18—C19—C20 | 1.2 (3) |
C4—C3—C14—O2 | −166.3 (2) | C18—C17—C22—C21 | 0.4 (3) |
C4—C3—C14—O3 | 7.7 (9) | C18—C19—C20—C21 | −0.2 (4) |
C4—C3—C14—O3A | 27 (3) | C19—C20—C21—C22 | −0.7 (4) |
C4—C17—C18—O4 | −3.0 (3) | C20—C21—C22—C17 | 0.5 (4) |
C4—C17—C18—C19 | 177.7 (2) | C22—C17—C18—O4 | 178.08 (19) |
C4—C17—C22—C21 | −178.6 (2) | C22—C17—C18—C19 | −1.3 (3) |
C5—C6—C7—C8 | 50.3 (2) | C23—O4—C18—C17 | 174.8 (2) |
C5—C6—C7—C11 | −70.8 (2) | C23—O4—C18—C19 | −5.8 (3) |
C5—C6—C7—C12 | 169.07 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 (2) | 2.01 (2) | 2.870 (2) | 165 (2) |
C13—H13B···O2 | 0.96 | 2.13 | 2.846 (3) | 131 |
C13—H13C···O4i | 0.96 | 2.59 | 3.300 (3) | 131 |
C23—H23A···O2ii | 0.96 | 2.57 | 3.492 (3) | 161 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1. |
C22H27NO4 | F(000) = 1584 |
Mr = 369.44 | Dx = 1.239 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 15.3492 (15) Å | Cell parameters from 9980 reflections |
b = 14.0314 (14) Å | θ = 2.3–26.4° |
c = 18.3862 (18) Å | µ = 0.09 mm−1 |
β = 90.0834 (17)° | T = 120 K |
V = 3959.8 (7) Å3 | Rod, colourless |
Z = 8 | 0.35 × 0.15 × 0.14 mm |
Bruker APEXII CCD diffractometer | Rint = 0.055 |
φ and ω scans | θmax = 26.4°, θmin = 1.3° |
66519 measured reflections | h = −19→19 |
8085 independent reflections | k = −17→17 |
7121 reflections with I > 2σ(I) | l = −22→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0433P)2 + 1.0284P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
8085 reflections | Δρmax = 0.33 e Å−3 |
536 parameters | Δρmin = −0.30 e Å−3 |
39 restraints |
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 twin. Application of the twin law (-1, 0, 0, 0, -1, 0, 0, 0, 1) yielded a twin domain ratio of 0.6938 (8):0.3062 (8). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1A | 0.45938 (8) | 1.14027 (8) | 0.37758 (7) | 0.0261 (3) | |
O2A | 0.83266 (9) | 0.94867 (10) | 0.38491 (8) | 0.0353 (3) | |
O3A | 0.76656 (8) | 1.07646 (9) | 0.33709 (7) | 0.0239 (3) | |
O4A | 0.58302 (9) | 1.01706 (9) | 0.04318 (7) | 0.0279 (3) | |
N1A | 0.57551 (10) | 0.83505 (11) | 0.40985 (8) | 0.0195 (3) | |
H1A | 0.5659 (13) | 0.7789 (15) | 0.4186 (11) | 0.023 (5)* | |
C2A | 0.66070 (11) | 0.86446 (12) | 0.39877 (9) | 0.0196 (4) | |
C3A | 0.67643 (11) | 0.95409 (12) | 0.37482 (9) | 0.0186 (4) | |
C4A | 0.60238 (10) | 1.01965 (12) | 0.35175 (9) | 0.0175 (3) | |
H4A | 0.616041 | 1.085397 | 0.369398 | 0.021* | |
C5A | 0.44879 (11) | 1.05602 (12) | 0.39480 (9) | 0.0182 (4) | |
C6A | 0.36366 (11) | 1.02348 (12) | 0.42708 (10) | 0.0200 (4) | |
H6AA | 0.315982 | 1.062202 | 0.406008 | 0.024* | |
H6AB | 0.364850 | 1.035734 | 0.480100 | 0.024* | |
C7A | 0.34314 (11) | 0.91751 (12) | 0.41443 (9) | 0.0193 (4) | |
C8A | 0.42224 (11) | 0.85979 (12) | 0.43937 (9) | 0.0186 (3) | |
H8AA | 0.424860 | 0.860609 | 0.493173 | 0.022* | |
H8AB | 0.414748 | 0.792748 | 0.423785 | 0.022* | |
C9A | 0.50663 (11) | 0.89679 (12) | 0.40982 (9) | 0.0170 (3) | |
C10A | 0.51830 (11) | 0.98787 (12) | 0.38714 (9) | 0.0167 (3) | |
C11A | 0.32322 (12) | 0.90078 (13) | 0.33413 (10) | 0.0248 (4) | |
H11D | 0.275190 | 0.942331 | 0.318973 | 0.037* | |
H11E | 0.306604 | 0.834047 | 0.326715 | 0.037* | |
H11F | 0.375071 | 0.915231 | 0.305108 | 0.037* | |
C12A | 0.26398 (12) | 0.88893 (13) | 0.45999 (11) | 0.0266 (4) | |
H12D | 0.276470 | 0.900163 | 0.511574 | 0.040* | |
H12E | 0.251289 | 0.821217 | 0.452347 | 0.040* | |
H12F | 0.213502 | 0.927113 | 0.445243 | 0.040* | |
C13A | 0.72712 (12) | 0.79058 (13) | 0.41851 (11) | 0.0263 (4) | |
H13D | 0.752914 | 0.806281 | 0.465804 | 0.039* | |
H13E | 0.772869 | 0.789171 | 0.381402 | 0.039* | |
H13F | 0.699027 | 0.727966 | 0.421239 | 0.039* | |
C14A | 0.76640 (11) | 0.98918 (13) | 0.36709 (9) | 0.0214 (4) | |
C15A | 0.85044 (12) | 1.11883 (14) | 0.32108 (11) | 0.0289 (4) | |
H15E | 0.893385 | 1.068708 | 0.308859 | 0.035* | |
H15F | 0.872177 | 1.154790 | 0.363730 | 0.035* | |
C16A | 0.83761 (13) | 1.18449 (14) | 0.25765 (12) | 0.0352 (5) | |
H16G | 0.811091 | 1.149255 | 0.217271 | 0.053* | |
H16H | 0.894095 | 1.210040 | 0.242322 | 0.053* | |
H16I | 0.799255 | 1.237092 | 0.271891 | 0.053* | |
C17A | 0.59364 (10) | 1.02320 (12) | 0.26930 (9) | 0.0177 (4) | |
C18A | 0.57574 (11) | 0.93988 (12) | 0.23039 (9) | 0.0214 (4) | |
H18A | 0.565952 | 0.882052 | 0.255969 | 0.026* | |
C19A | 0.57207 (11) | 0.94030 (13) | 0.15539 (10) | 0.0218 (4) | |
H19A | 0.560018 | 0.882987 | 0.129776 | 0.026* | |
C20A | 0.58598 (11) | 1.02449 (13) | 0.11729 (9) | 0.0217 (4) | |
C21A | 0.60189 (11) | 1.10830 (13) | 0.15485 (10) | 0.0232 (4) | |
H21A | 0.610207 | 1.166456 | 0.129332 | 0.028* | |
C22A | 0.60553 (11) | 1.10619 (12) | 0.23063 (10) | 0.0216 (4) | |
H22A | 0.616536 | 1.163699 | 0.256321 | 0.026* | |
C23A | 0.58707 (15) | 1.10334 (15) | 0.00256 (11) | 0.0359 (5) | |
H23D | 0.581901 | 1.088987 | −0.049428 | 0.054* | |
H23E | 0.642866 | 1.135061 | 0.011879 | 0.054* | |
H23F | 0.539242 | 1.145358 | 0.017281 | 0.054* | |
O1B | 0.53248 (9) | 0.63931 (8) | 0.41653 (7) | 0.0275 (3) | |
O2B | 0.16407 (8) | 0.44710 (11) | 0.34002 (8) | 0.0367 (3) | |
O4B | 0.45174 (10) | 0.69033 (9) | 0.07234 (7) | 0.0325 (3) | |
N1B | 0.41867 (10) | 0.33580 (11) | 0.37064 (9) | 0.0232 (3) | |
H1B | 0.4275 (14) | 0.2749 (16) | 0.3763 (12) | 0.037 (6)* | |
C2B | 0.33400 (11) | 0.36815 (12) | 0.36142 (10) | 0.0224 (4) | |
C3B | 0.31849 (11) | 0.46259 (13) | 0.35623 (10) | 0.0226 (4) | |
C4B | 0.39216 (11) | 0.53471 (12) | 0.35400 (10) | 0.0201 (4) | |
H4B | 0.375782 | 0.589307 | 0.386149 | 0.024* | |
C5B | 0.54390 (12) | 0.55231 (12) | 0.41031 (9) | 0.0207 (4) | |
C6B | 0.62933 (12) | 0.50822 (13) | 0.43392 (10) | 0.0236 (4) | |
H6BA | 0.629257 | 0.502553 | 0.487587 | 0.028* | |
H6BB | 0.677155 | 0.552131 | 0.420484 | 0.028* | |
C7B | 0.64891 (12) | 0.41011 (13) | 0.40149 (10) | 0.0223 (4) | |
C8B | 0.56843 (11) | 0.34797 (12) | 0.41231 (10) | 0.0221 (4) | |
H8BA | 0.576211 | 0.287574 | 0.385247 | 0.026* | |
H8BB | 0.562928 | 0.332075 | 0.464561 | 0.026* | |
C9B | 0.48608 (11) | 0.39520 (12) | 0.38717 (10) | 0.0195 (4) | |
C10B | 0.47532 (11) | 0.49112 (12) | 0.38389 (10) | 0.0190 (4) | |
C11B | 0.67057 (13) | 0.41894 (14) | 0.32069 (10) | 0.0290 (4) | |
H11A | 0.681145 | 0.355422 | 0.300374 | 0.044* | |
H11B | 0.722849 | 0.458254 | 0.314753 | 0.044* | |
H11C | 0.621608 | 0.448806 | 0.295120 | 0.044* | |
C12B | 0.72593 (12) | 0.36470 (15) | 0.44191 (12) | 0.0314 (5) | |
H12A | 0.711607 | 0.358440 | 0.493620 | 0.047* | |
H12B | 0.777587 | 0.405106 | 0.436484 | 0.047* | |
H12C | 0.737796 | 0.301528 | 0.421460 | 0.047* | |
C13B | 0.26813 (12) | 0.28863 (14) | 0.35968 (12) | 0.0323 (5) | |
H13A | 0.297954 | 0.227423 | 0.365980 | 0.048* | |
H13B | 0.237582 | 0.289167 | 0.312845 | 0.048* | |
H13C | 0.226000 | 0.297564 | 0.399095 | 0.048* | |
C14B | 0.22780 (13) | 0.49593 (14) | 0.34891 (12) | 0.0317 (4) | |
C17B | 0.40645 (11) | 0.57381 (12) | 0.27734 (10) | 0.0204 (4) | |
C18B | 0.41311 (12) | 0.51382 (13) | 0.21751 (10) | 0.0235 (4) | |
H18B | 0.407494 | 0.446967 | 0.224204 | 0.028* | |
C19B | 0.42785 (12) | 0.54948 (13) | 0.14796 (10) | 0.0247 (4) | |
H19B | 0.432202 | 0.507346 | 0.107685 | 0.030* | |
C20B | 0.43611 (11) | 0.64698 (13) | 0.13795 (10) | 0.0231 (4) | |
C21B | 0.42916 (11) | 0.70792 (12) | 0.19706 (10) | 0.0231 (4) | |
H21B | 0.434268 | 0.774830 | 0.190398 | 0.028* | |
C22B | 0.41482 (12) | 0.67106 (12) | 0.26552 (10) | 0.0220 (4) | |
H22B | 0.410556 | 0.713382 | 0.305688 | 0.026* | |
C23B | 0.46826 (19) | 0.62980 (17) | 0.01175 (12) | 0.0469 (6) | |
H23A | 0.481787 | 0.668742 | −0.031018 | 0.070* | |
H23B | 0.416580 | 0.590883 | 0.001799 | 0.070* | |
H23C | 0.517779 | 0.588112 | 0.022755 | 0.070* | |
O3B | 0.2269 (3) | 0.5956 (3) | 0.3723 (4) | 0.0335 (6) | 0.432 (8) |
C15B | 0.1402 (3) | 0.6417 (4) | 0.3742 (3) | 0.0372 (7) | 0.465 (5) |
H15A | 0.138304 | 0.689695 | 0.413646 | 0.045* | 0.465 (5) |
H15B | 0.094562 | 0.593444 | 0.383626 | 0.045* | 0.465 (5) |
C16B | 0.1245 (4) | 0.6886 (5) | 0.3024 (3) | 0.0467 (11) | 0.465 (5) |
H16A | 0.123933 | 0.640269 | 0.263942 | 0.070* | 0.465 (5) |
H16B | 0.171021 | 0.734776 | 0.292792 | 0.070* | 0.465 (5) |
H16C | 0.068246 | 0.721642 | 0.303351 | 0.070* | 0.465 (5) |
O3C | 0.21906 (19) | 0.5876 (2) | 0.3397 (3) | 0.0334 (5) | 0.568 (8) |
C15C | 0.1290 (2) | 0.6186 (3) | 0.3293 (3) | 0.0363 (7) | 0.535 (5) |
H15C | 0.107508 | 0.596737 | 0.281287 | 0.044* | 0.535 (5) |
H15D | 0.091485 | 0.590425 | 0.367375 | 0.044* | 0.535 (5) |
C16C | 0.1252 (3) | 0.7220 (3) | 0.3332 (3) | 0.0423 (10) | 0.535 (5) |
H16D | 0.164743 | 0.749457 | 0.297027 | 0.063* | 0.535 (5) |
H16E | 0.142609 | 0.742950 | 0.381911 | 0.063* | 0.535 (5) |
H16F | 0.065517 | 0.743317 | 0.323217 | 0.063* | 0.535 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0244 (6) | 0.0130 (6) | 0.0411 (8) | 0.0011 (5) | 0.0035 (6) | 0.0025 (5) |
O2A | 0.0192 (7) | 0.0410 (8) | 0.0458 (9) | 0.0025 (6) | −0.0023 (6) | 0.0152 (7) |
O3A | 0.0159 (6) | 0.0237 (7) | 0.0323 (7) | −0.0027 (5) | 0.0006 (5) | 0.0033 (5) |
O4A | 0.0322 (7) | 0.0335 (7) | 0.0180 (7) | −0.0002 (6) | −0.0006 (5) | 0.0040 (5) |
N1A | 0.0205 (7) | 0.0116 (7) | 0.0264 (8) | 0.0011 (6) | −0.0005 (6) | 0.0012 (6) |
C2A | 0.0206 (9) | 0.0202 (9) | 0.0180 (9) | 0.0027 (7) | −0.0015 (7) | −0.0033 (7) |
C3A | 0.0174 (8) | 0.0211 (9) | 0.0172 (8) | 0.0029 (7) | −0.0001 (7) | −0.0001 (7) |
C4A | 0.0176 (8) | 0.0147 (8) | 0.0201 (9) | −0.0010 (6) | −0.0002 (7) | −0.0001 (7) |
C5A | 0.0211 (9) | 0.0153 (8) | 0.0182 (8) | −0.0009 (7) | −0.0017 (7) | −0.0008 (7) |
C6A | 0.0211 (9) | 0.0169 (9) | 0.0221 (9) | 0.0026 (7) | 0.0024 (7) | −0.0022 (7) |
C7A | 0.0186 (8) | 0.0176 (8) | 0.0216 (9) | −0.0006 (7) | 0.0004 (7) | 0.0010 (7) |
C8A | 0.0219 (9) | 0.0146 (8) | 0.0194 (9) | −0.0019 (7) | 0.0000 (7) | −0.0005 (6) |
C9A | 0.0210 (8) | 0.0145 (8) | 0.0156 (8) | 0.0015 (7) | −0.0021 (7) | −0.0002 (7) |
C10A | 0.0181 (8) | 0.0160 (8) | 0.0161 (8) | 0.0009 (7) | −0.0015 (7) | −0.0010 (7) |
C11A | 0.0224 (9) | 0.0259 (10) | 0.0260 (10) | 0.0016 (7) | −0.0045 (7) | −0.0046 (8) |
C12A | 0.0227 (9) | 0.0234 (10) | 0.0337 (11) | −0.0014 (8) | 0.0040 (8) | 0.0002 (8) |
C13A | 0.0242 (9) | 0.0220 (9) | 0.0325 (11) | 0.0054 (7) | −0.0024 (8) | 0.0009 (8) |
C14A | 0.0212 (9) | 0.0249 (9) | 0.0180 (9) | 0.0015 (7) | −0.0019 (7) | −0.0001 (7) |
C15A | 0.0172 (9) | 0.0315 (10) | 0.0380 (11) | −0.0060 (8) | 0.0015 (8) | −0.0021 (9) |
C16A | 0.0258 (10) | 0.0281 (11) | 0.0518 (13) | −0.0037 (8) | 0.0069 (9) | 0.0071 (10) |
C17A | 0.0137 (8) | 0.0190 (9) | 0.0204 (9) | 0.0022 (7) | 0.0005 (7) | 0.0008 (7) |
C18A | 0.0221 (9) | 0.0171 (9) | 0.0249 (9) | 0.0007 (7) | 0.0005 (7) | 0.0027 (7) |
C19A | 0.0215 (9) | 0.0202 (9) | 0.0236 (9) | 0.0013 (7) | −0.0013 (7) | −0.0018 (7) |
C20A | 0.0162 (8) | 0.0305 (10) | 0.0183 (9) | −0.0004 (7) | 0.0003 (7) | 0.0035 (7) |
C21A | 0.0209 (9) | 0.0232 (9) | 0.0253 (10) | −0.0046 (7) | −0.0007 (7) | 0.0066 (8) |
C22A | 0.0210 (9) | 0.0199 (9) | 0.0240 (9) | −0.0032 (7) | −0.0016 (7) | 0.0012 (7) |
C23A | 0.0439 (12) | 0.0408 (12) | 0.0230 (10) | −0.0123 (10) | 0.0000 (9) | 0.0099 (9) |
O1B | 0.0316 (7) | 0.0147 (6) | 0.0361 (8) | −0.0032 (5) | 0.0028 (6) | −0.0020 (6) |
O2B | 0.0181 (7) | 0.0555 (10) | 0.0366 (8) | −0.0001 (7) | −0.0001 (6) | 0.0014 (7) |
O4B | 0.0461 (9) | 0.0282 (7) | 0.0234 (7) | −0.0002 (6) | 0.0002 (6) | 0.0053 (6) |
N1B | 0.0199 (7) | 0.0121 (7) | 0.0378 (9) | 0.0002 (6) | −0.0020 (7) | 0.0013 (7) |
C2B | 0.0194 (9) | 0.0217 (9) | 0.0261 (9) | −0.0015 (7) | −0.0002 (7) | 0.0032 (7) |
C3B | 0.0192 (9) | 0.0240 (9) | 0.0246 (9) | 0.0010 (7) | 0.0029 (7) | 0.0044 (8) |
C4B | 0.0193 (9) | 0.0153 (8) | 0.0258 (9) | 0.0034 (7) | 0.0029 (7) | 0.0006 (7) |
C5B | 0.0224 (9) | 0.0187 (9) | 0.0209 (9) | −0.0017 (7) | 0.0041 (7) | 0.0009 (7) |
C6B | 0.0225 (9) | 0.0221 (9) | 0.0262 (10) | −0.0057 (7) | −0.0002 (7) | 0.0008 (7) |
C7B | 0.0193 (9) | 0.0212 (9) | 0.0265 (10) | 0.0011 (7) | 0.0018 (7) | 0.0042 (7) |
C8B | 0.0206 (9) | 0.0167 (8) | 0.0288 (10) | 0.0017 (7) | 0.0009 (7) | 0.0028 (7) |
C9B | 0.0188 (8) | 0.0180 (9) | 0.0218 (9) | 0.0015 (7) | 0.0015 (7) | 0.0012 (7) |
C10B | 0.0200 (9) | 0.0150 (8) | 0.0220 (9) | 0.0002 (7) | 0.0030 (7) | 0.0004 (7) |
C11B | 0.0278 (10) | 0.0287 (10) | 0.0306 (11) | 0.0054 (8) | 0.0068 (8) | 0.0029 (8) |
C12B | 0.0215 (10) | 0.0331 (11) | 0.0396 (12) | 0.0022 (8) | 0.0004 (8) | 0.0102 (9) |
C13B | 0.0238 (10) | 0.0266 (10) | 0.0464 (12) | −0.0043 (8) | −0.0029 (9) | 0.0054 (9) |
C14B | 0.0222 (7) | 0.0316 (8) | 0.0411 (10) | 0.0077 (6) | 0.0042 (7) | 0.0096 (8) |
C17B | 0.0158 (8) | 0.0191 (9) | 0.0263 (9) | 0.0024 (7) | 0.0013 (7) | 0.0025 (7) |
C18B | 0.0227 (9) | 0.0160 (9) | 0.0319 (10) | −0.0016 (7) | −0.0005 (8) | 0.0006 (7) |
C19B | 0.0239 (9) | 0.0238 (9) | 0.0263 (10) | 0.0000 (7) | −0.0022 (8) | −0.0026 (8) |
C20B | 0.0197 (9) | 0.0244 (9) | 0.0252 (9) | 0.0003 (7) | −0.0018 (7) | 0.0046 (7) |
C21B | 0.0227 (9) | 0.0154 (8) | 0.0313 (10) | 0.0008 (7) | −0.0008 (8) | 0.0031 (7) |
C22B | 0.0217 (9) | 0.0159 (8) | 0.0285 (10) | 0.0047 (7) | −0.0002 (7) | −0.0003 (7) |
C23B | 0.0762 (18) | 0.0404 (13) | 0.0241 (11) | −0.0068 (12) | 0.0019 (11) | 0.0017 (10) |
O3B | 0.0235 (9) | 0.0329 (10) | 0.0440 (13) | 0.0081 (9) | 0.0033 (10) | 0.0089 (11) |
C15B | 0.0271 (12) | 0.0375 (13) | 0.0470 (15) | 0.0070 (11) | 0.0016 (12) | 0.0084 (13) |
C16B | 0.0342 (18) | 0.051 (2) | 0.055 (2) | 0.0052 (18) | 0.0014 (18) | 0.0084 (19) |
O3C | 0.0231 (8) | 0.0314 (9) | 0.0456 (12) | 0.0106 (7) | 0.0001 (9) | 0.0067 (10) |
C15C | 0.0255 (11) | 0.0327 (12) | 0.0507 (15) | 0.0126 (10) | −0.0021 (11) | 0.0033 (11) |
C16C | 0.0303 (16) | 0.0355 (18) | 0.061 (2) | 0.0114 (15) | −0.0032 (16) | −0.0035 (17) |
O1A—C5A | 1.235 (2) | N1B—H1B | 0.87 (2) |
O2A—C14A | 1.210 (2) | N1B—C2B | 1.387 (2) |
O3A—C14A | 1.343 (2) | N1B—C9B | 1.363 (2) |
O3A—C15A | 1.449 (2) | C2B—C3B | 1.350 (2) |
O4A—C20A | 1.367 (2) | C2B—C13B | 1.506 (2) |
O4A—C23A | 1.424 (2) | C3B—C4B | 1.518 (2) |
N1A—H1A | 0.82 (2) | C3B—C14B | 1.474 (3) |
N1A—C2A | 1.386 (2) | C4B—H4B | 1.0000 |
N1A—C9A | 1.367 (2) | C4B—C10B | 1.518 (2) |
C2A—C3A | 1.354 (2) | C4B—C17B | 1.529 (2) |
C2A—C13A | 1.498 (2) | C5B—C6B | 1.513 (3) |
C3A—C4A | 1.522 (2) | C5B—C10B | 1.442 (2) |
C3A—C14A | 1.473 (2) | C6B—H6BA | 0.9900 |
C4A—H4A | 1.0000 | C6B—H6BB | 0.9900 |
C4A—C10A | 1.513 (2) | C6B—C7B | 1.530 (3) |
C4A—C17A | 1.523 (2) | C7B—C8B | 1.525 (2) |
C5A—C6A | 1.507 (2) | C7B—C11B | 1.528 (3) |
C5A—C10A | 1.440 (2) | C7B—C12B | 1.534 (3) |
C6A—H6AA | 0.9900 | C8B—H8BA | 0.9900 |
C6A—H6AB | 0.9900 | C8B—H8BB | 0.9900 |
C6A—C7A | 1.538 (2) | C8B—C9B | 1.500 (2) |
C7A—C8A | 1.529 (2) | C9B—C10B | 1.357 (2) |
C7A—C11A | 1.526 (2) | C11B—H11A | 0.9800 |
C7A—C12A | 1.530 (2) | C11B—H11B | 0.9800 |
C8A—H8AA | 0.9900 | C11B—H11C | 0.9800 |
C8A—H8AB | 0.9900 | C12B—H12A | 0.9800 |
C8A—C9A | 1.498 (2) | C12B—H12B | 0.9800 |
C9A—C10A | 1.356 (2) | C12B—H12C | 0.9800 |
C11A—H11D | 0.9800 | C13B—H13A | 0.9800 |
C11A—H11E | 0.9800 | C13B—H13B | 0.9800 |
C11A—H11F | 0.9800 | C13B—H13C | 0.9800 |
C12A—H12D | 0.9800 | C14B—O3B | 1.464 (5) |
C12A—H12E | 0.9800 | C14B—O3C | 1.305 (4) |
C12A—H12F | 0.9800 | C17B—C18B | 1.389 (3) |
C13A—H13D | 0.9800 | C17B—C22B | 1.388 (2) |
C13A—H13E | 0.9800 | C18B—H18B | 0.9500 |
C13A—H13F | 0.9800 | C18B—C19B | 1.392 (3) |
C15A—H15E | 0.9900 | C19B—H19B | 0.9500 |
C15A—H15F | 0.9900 | C19B—C20B | 1.386 (2) |
C15A—C16A | 1.499 (3) | C20B—C21B | 1.387 (3) |
C16A—H16G | 0.9800 | C21B—H21B | 0.9500 |
C16A—H16H | 0.9800 | C21B—C22B | 1.379 (3) |
C16A—H16I | 0.9800 | C22B—H22B | 0.9500 |
C17A—C18A | 1.398 (2) | C23B—H23A | 0.9800 |
C17A—C22A | 1.377 (2) | C23B—H23B | 0.9800 |
C18A—H18A | 0.9500 | C23B—H23C | 0.9800 |
C18A—C19A | 1.380 (2) | O3B—C15B | 1.480 (5) |
C19A—H19A | 0.9500 | C15B—H15A | 0.9900 |
C19A—C20A | 1.390 (3) | C15B—H15B | 0.9900 |
C20A—C21A | 1.385 (3) | C15B—C16B | 1.495 (7) |
C21A—H21A | 0.9500 | C16B—H16A | 0.9800 |
C21A—C22A | 1.395 (3) | C16B—H16B | 0.9800 |
C22A—H22A | 0.9500 | C16B—H16C | 0.9800 |
C23A—H23D | 0.9800 | O3C—C15C | 1.461 (4) |
C23A—H23E | 0.9800 | C15C—H15C | 0.9900 |
C23A—H23F | 0.9800 | C15C—H15D | 0.9900 |
O1B—C5B | 1.239 (2) | C15C—C16C | 1.454 (6) |
O2B—C14B | 1.205 (2) | C16C—H16D | 0.9800 |
O4B—C20B | 1.372 (2) | C16C—H16E | 0.9800 |
O4B—C23B | 1.424 (3) | C16C—H16F | 0.9800 |
C14A—O3A—C15A | 117.37 (14) | C2B—C3B—C14B | 118.97 (17) |
C20A—O4A—C23A | 117.16 (15) | C14B—C3B—C4B | 119.29 (15) |
C2A—N1A—H1A | 119.1 (14) | C3B—C4B—H4B | 107.9 |
C9A—N1A—H1A | 118.1 (14) | C3B—C4B—C17B | 111.84 (15) |
C9A—N1A—C2A | 122.74 (15) | C10B—C4B—C3B | 110.35 (14) |
N1A—C2A—C13A | 113.58 (15) | C10B—C4B—H4B | 107.9 |
C3A—C2A—N1A | 119.53 (15) | C10B—C4B—C17B | 110.91 (14) |
C3A—C2A—C13A | 126.84 (16) | C17B—C4B—H4B | 107.9 |
C2A—C3A—C4A | 121.22 (15) | O1B—C5B—C6B | 119.96 (16) |
C2A—C3A—C14A | 120.62 (15) | O1B—C5B—C10B | 120.96 (16) |
C14A—C3A—C4A | 118.09 (15) | C10B—C5B—C6B | 119.02 (15) |
C3A—C4A—H4A | 108.1 | C5B—C6B—H6BA | 108.5 |
C3A—C4A—C17A | 111.21 (14) | C5B—C6B—H6BB | 108.5 |
C10A—C4A—C3A | 109.82 (13) | C5B—C6B—C7B | 115.26 (15) |
C10A—C4A—H4A | 108.1 | H6BA—C6B—H6BB | 107.5 |
C10A—C4A—C17A | 111.34 (14) | C7B—C6B—H6BA | 108.5 |
C17A—C4A—H4A | 108.1 | C7B—C6B—H6BB | 108.5 |
O1A—C5A—C6A | 120.38 (15) | C6B—C7B—C12B | 109.67 (16) |
O1A—C5A—C10A | 120.86 (16) | C8B—C7B—C6B | 107.70 (14) |
C10A—C5A—C6A | 118.72 (14) | C8B—C7B—C11B | 110.52 (15) |
C5A—C6A—H6AA | 108.7 | C8B—C7B—C12B | 108.84 (15) |
C5A—C6A—H6AB | 108.7 | C11B—C7B—C6B | 110.43 (15) |
C5A—C6A—C7A | 114.27 (14) | C11B—C7B—C12B | 109.64 (15) |
H6AA—C6A—H6AB | 107.6 | C7B—C8B—H8BA | 109.0 |
C7A—C6A—H6AA | 108.7 | C7B—C8B—H8BB | 109.0 |
C7A—C6A—H6AB | 108.7 | H8BA—C8B—H8BB | 107.8 |
C8A—C7A—C6A | 107.72 (13) | C9B—C8B—C7B | 112.93 (14) |
C8A—C7A—C12A | 109.13 (14) | C9B—C8B—H8BA | 109.0 |
C11A—C7A—C6A | 109.63 (14) | C9B—C8B—H8BB | 109.0 |
C11A—C7A—C8A | 111.51 (14) | N1B—C9B—C8B | 115.97 (15) |
C11A—C7A—C12A | 109.35 (14) | C10B—C9B—N1B | 120.28 (16) |
C12A—C7A—C6A | 109.46 (14) | C10B—C9B—C8B | 123.67 (16) |
C7A—C8A—H8AA | 108.9 | C5B—C10B—C4B | 119.68 (15) |
C7A—C8A—H8AB | 108.9 | C9B—C10B—C4B | 121.19 (15) |
H8AA—C8A—H8AB | 107.7 | C9B—C10B—C5B | 119.12 (16) |
C9A—C8A—C7A | 113.21 (14) | C7B—C11B—H11A | 109.5 |
C9A—C8A—H8AA | 108.9 | C7B—C11B—H11B | 109.5 |
C9A—C8A—H8AB | 108.9 | C7B—C11B—H11C | 109.5 |
N1A—C9A—C8A | 116.70 (14) | H11A—C11B—H11B | 109.5 |
C10A—C9A—N1A | 119.66 (15) | H11A—C11B—H11C | 109.5 |
C10A—C9A—C8A | 123.56 (15) | H11B—C11B—H11C | 109.5 |
C5A—C10A—C4A | 118.62 (14) | C7B—C12B—H12A | 109.5 |
C9A—C10A—C4A | 121.53 (15) | C7B—C12B—H12B | 109.5 |
C9A—C10A—C5A | 119.83 (15) | C7B—C12B—H12C | 109.5 |
C7A—C11A—H11D | 109.5 | H12A—C12B—H12B | 109.5 |
C7A—C11A—H11E | 109.5 | H12A—C12B—H12C | 109.5 |
C7A—C11A—H11F | 109.5 | H12B—C12B—H12C | 109.5 |
H11D—C11A—H11E | 109.5 | C2B—C13B—H13A | 109.5 |
H11D—C11A—H11F | 109.5 | C2B—C13B—H13B | 109.5 |
H11E—C11A—H11F | 109.5 | C2B—C13B—H13C | 109.5 |
C7A—C12A—H12D | 109.5 | H13A—C13B—H13B | 109.5 |
C7A—C12A—H12E | 109.5 | H13A—C13B—H13C | 109.5 |
C7A—C12A—H12F | 109.5 | H13B—C13B—H13C | 109.5 |
H12D—C12A—H12E | 109.5 | O2B—C14B—C3B | 126.73 (18) |
H12D—C12A—H12F | 109.5 | O2B—C14B—O3B | 125.1 (2) |
H12E—C12A—H12F | 109.5 | O2B—C14B—O3C | 117.4 (2) |
C2A—C13A—H13D | 109.5 | O3B—C14B—C3B | 106.6 (2) |
C2A—C13A—H13E | 109.5 | O3C—C14B—C3B | 114.9 (2) |
C2A—C13A—H13F | 109.5 | C18B—C17B—C4B | 121.57 (15) |
H13D—C13A—H13E | 109.5 | C22B—C17B—C4B | 120.71 (16) |
H13D—C13A—H13F | 109.5 | C22B—C17B—C18B | 117.71 (17) |
H13E—C13A—H13F | 109.5 | C17B—C18B—H18B | 119.3 |
O2A—C14A—O3A | 122.52 (16) | C17B—C18B—C19B | 121.46 (16) |
O2A—C14A—C3A | 127.20 (17) | C19B—C18B—H18B | 119.3 |
O3A—C14A—C3A | 110.28 (14) | C18B—C19B—H19B | 120.3 |
O3A—C15A—H15E | 110.3 | C20B—C19B—C18B | 119.46 (17) |
O3A—C15A—H15F | 110.3 | C20B—C19B—H19B | 120.3 |
O3A—C15A—C16A | 107.13 (15) | O4B—C20B—C19B | 124.77 (17) |
H15E—C15A—H15F | 108.5 | O4B—C20B—C21B | 115.41 (15) |
C16A—C15A—H15E | 110.3 | C19B—C20B—C21B | 119.81 (17) |
C16A—C15A—H15F | 110.3 | C20B—C21B—H21B | 120.1 |
C15A—C16A—H16G | 109.5 | C22B—C21B—C20B | 119.77 (16) |
C15A—C16A—H16H | 109.5 | C22B—C21B—H21B | 120.1 |
C15A—C16A—H16I | 109.5 | C17B—C22B—H22B | 119.1 |
H16G—C16A—H16H | 109.5 | C21B—C22B—C17B | 121.79 (17) |
H16G—C16A—H16I | 109.5 | C21B—C22B—H22B | 119.1 |
H16H—C16A—H16I | 109.5 | O4B—C23B—H23A | 109.5 |
C18A—C17A—C4A | 119.95 (15) | O4B—C23B—H23B | 109.5 |
C22A—C17A—C4A | 122.03 (15) | O4B—C23B—H23C | 109.5 |
C22A—C17A—C18A | 117.99 (16) | H23A—C23B—H23B | 109.5 |
C17A—C18A—H18A | 119.5 | H23A—C23B—H23C | 109.5 |
C19A—C18A—C17A | 121.04 (16) | H23B—C23B—H23C | 109.5 |
C19A—C18A—H18A | 119.5 | C14B—O3B—C15B | 115.7 (4) |
C18A—C19A—H19A | 120.0 | O3B—C15B—H15A | 110.0 |
C18A—C19A—C20A | 120.08 (17) | O3B—C15B—H15B | 110.0 |
C20A—C19A—H19A | 120.0 | O3B—C15B—C16B | 108.4 (5) |
O4A—C20A—C19A | 115.63 (16) | H15A—C15B—H15B | 108.4 |
O4A—C20A—C21A | 124.56 (16) | C16B—C15B—H15A | 110.0 |
C21A—C20A—C19A | 119.81 (16) | C16B—C15B—H15B | 110.0 |
C20A—C21A—H21A | 120.4 | C15B—C16B—H16A | 109.5 |
C20A—C21A—C22A | 119.13 (16) | C15B—C16B—H16B | 109.5 |
C22A—C21A—H21A | 120.4 | C15B—C16B—H16C | 109.5 |
C17A—C22A—C21A | 121.92 (17) | H16A—C16B—H16B | 109.5 |
C17A—C22A—H22A | 119.0 | H16A—C16B—H16C | 109.5 |
C21A—C22A—H22A | 119.0 | H16B—C16B—H16C | 109.5 |
O4A—C23A—H23D | 109.5 | C14B—O3C—C15C | 114.0 (3) |
O4A—C23A—H23E | 109.5 | O3C—C15C—H15C | 109.8 |
O4A—C23A—H23F | 109.5 | O3C—C15C—H15D | 109.8 |
H23D—C23A—H23E | 109.5 | H15C—C15C—H15D | 108.3 |
H23D—C23A—H23F | 109.5 | C16C—C15C—O3C | 109.2 (4) |
H23E—C23A—H23F | 109.5 | C16C—C15C—H15C | 109.8 |
C20B—O4B—C23B | 117.05 (15) | C16C—C15C—H15D | 109.8 |
C2B—N1B—H1B | 118.7 (15) | C15C—C16C—H16D | 109.5 |
C9B—N1B—H1B | 117.1 (15) | C15C—C16C—H16E | 109.5 |
C9B—N1B—C2B | 122.57 (15) | C15C—C16C—H16F | 109.5 |
N1B—C2B—C13B | 112.90 (15) | H16D—C16C—H16E | 109.5 |
C3B—C2B—N1B | 119.68 (16) | H16D—C16C—H16F | 109.5 |
C3B—C2B—C13B | 127.41 (17) | H16E—C16C—H16F | 109.5 |
C2B—C3B—C4B | 121.67 (15) | ||
O1A—C5A—C6A—C7A | 153.92 (16) | O2B—C14B—O3B—C15B | −9.3 (6) |
O1A—C5A—C10A—C4A | −5.0 (2) | O2B—C14B—O3C—C15C | 7.8 (5) |
O1A—C5A—C10A—C9A | 176.67 (16) | O4B—C20B—C21B—C22B | −179.01 (16) |
O4A—C20A—C21A—C22A | −178.33 (16) | N1B—C2B—C3B—C4B | 5.1 (3) |
N1A—C2A—C3A—C4A | −6.9 (2) | N1B—C2B—C3B—C14B | −177.98 (17) |
N1A—C2A—C3A—C14A | 176.06 (15) | N1B—C9B—C10B—C4B | −6.9 (3) |
N1A—C9A—C10A—C4A | 8.8 (2) | N1B—C9B—C10B—C5B | 172.28 (16) |
N1A—C9A—C10A—C5A | −172.89 (15) | C2B—N1B—C9B—C8B | 166.25 (16) |
C2A—N1A—C9A—C8A | −166.11 (15) | C2B—N1B—C9B—C10B | −10.6 (3) |
C2A—N1A—C9A—C10A | 10.6 (2) | C2B—C3B—C4B—C10B | −19.6 (2) |
C2A—C3A—C4A—C10A | 22.8 (2) | C2B—C3B—C4B—C17B | 104.42 (19) |
C2A—C3A—C4A—C17A | −100.92 (19) | C2B—C3B—C14B—O2B | −7.6 (3) |
C2A—C3A—C14A—O2A | −5.7 (3) | C2B—C3B—C14B—O3B | 158.7 (3) |
C2A—C3A—C14A—O3A | 174.96 (15) | C2B—C3B—C14B—O3C | −176.0 (3) |
C3A—C4A—C10A—C5A | 157.86 (15) | C3B—C4B—C10B—C5B | −158.71 (15) |
C3A—C4A—C10A—C9A | −23.8 (2) | C3B—C4B—C10B—C9B | 20.4 (2) |
C3A—C4A—C17A—C18A | 60.5 (2) | C3B—C4B—C17B—C18B | −48.7 (2) |
C3A—C4A—C17A—C22A | −117.40 (18) | C3B—C4B—C17B—C22B | 132.47 (17) |
C4A—C3A—C14A—O2A | 177.13 (18) | C3B—C14B—O3B—C15B | −175.9 (4) |
C4A—C3A—C14A—O3A | −2.2 (2) | C3B—C14B—O3C—C15C | 177.3 (3) |
C4A—C17A—C18A—C19A | −176.55 (16) | C4B—C3B—C14B—O2B | 169.4 (2) |
C4A—C17A—C22A—C21A | 176.66 (16) | C4B—C3B—C14B—O3B | −24.3 (3) |
C5A—C6A—C7A—C8A | 51.96 (19) | C4B—C3B—C14B—O3C | 1.0 (4) |
C5A—C6A—C7A—C11A | −69.55 (18) | C4B—C17B—C18B—C19B | −178.71 (16) |
C5A—C6A—C7A—C12A | 170.51 (15) | C4B—C17B—C22B—C21B | 178.92 (16) |
C6A—C5A—C10A—C4A | 177.41 (15) | C5B—C6B—C7B—C8B | −49.4 (2) |
C6A—C5A—C10A—C9A | −0.9 (2) | C5B—C6B—C7B—C11B | 71.33 (19) |
C6A—C7A—C8A—C9A | −48.74 (18) | C5B—C6B—C7B—C12B | −167.74 (15) |
C7A—C8A—C9A—N1A | −160.18 (15) | C6B—C5B—C10B—C4B | −174.81 (15) |
C7A—C8A—C9A—C10A | 23.2 (2) | C6B—C5B—C10B—C9B | 6.0 (2) |
C8A—C9A—C10A—C4A | −174.68 (15) | C6B—C7B—C8B—C9B | 50.18 (19) |
C8A—C9A—C10A—C5A | 3.6 (3) | C7B—C8B—C9B—N1B | 157.48 (16) |
C9A—N1A—C2A—C3A | −11.6 (2) | C7B—C8B—C9B—C10B | −25.8 (2) |
C9A—N1A—C2A—C13A | 166.11 (16) | C8B—C9B—C10B—C4B | 176.56 (16) |
C10A—C4A—C17A—C18A | −62.3 (2) | C8B—C9B—C10B—C5B | −4.3 (3) |
C10A—C4A—C17A—C22A | 119.77 (17) | C9B—N1B—C2B—C3B | 11.5 (3) |
C10A—C5A—C6A—C7A | −28.5 (2) | C9B—N1B—C2B—C13B | −167.51 (17) |
C11A—C7A—C8A—C9A | 71.59 (18) | C10B—C4B—C17B—C18B | 74.9 (2) |
C12A—C7A—C8A—C9A | −167.50 (14) | C10B—C4B—C17B—C22B | −103.88 (18) |
C13A—C2A—C3A—C4A | 175.76 (16) | C10B—C5B—C6B—C7B | 22.6 (2) |
C13A—C2A—C3A—C14A | −1.3 (3) | C11B—C7B—C8B—C9B | −70.53 (19) |
C14A—O3A—C15A—C16A | 151.27 (16) | C12B—C7B—C8B—C9B | 169.02 (16) |
C14A—C3A—C4A—C10A | −160.11 (14) | C13B—C2B—C3B—C4B | −176.03 (18) |
C14A—C3A—C4A—C17A | 76.19 (19) | C13B—C2B—C3B—C14B | 0.9 (3) |
C15A—O3A—C14A—O2A | 4.7 (3) | C14B—C3B—C4B—C10B | 163.53 (17) |
C15A—O3A—C14A—C3A | −175.91 (15) | C14B—C3B—C4B—C17B | −72.5 (2) |
C17A—C4A—C10A—C5A | −78.52 (19) | C14B—O3B—C15B—C16B | −91.8 (6) |
C17A—C4A—C10A—C9A | 99.81 (19) | C14B—O3C—C15C—C16C | 169.5 (5) |
C17A—C18A—C19A—C20A | −0.2 (3) | C17B—C4B—C10B—C5B | 76.8 (2) |
C18A—C17A—C22A—C21A | −1.3 (3) | C17B—C4B—C10B—C9B | −104.08 (19) |
C18A—C19A—C20A—O4A | 178.51 (16) | C17B—C18B—C19B—C20B | 0.0 (3) |
C18A—C19A—C20A—C21A | −1.2 (3) | C18B—C17B—C22B—C21B | 0.1 (3) |
C19A—C20A—C21A—C22A | 1.4 (3) | C18B—C19B—C20B—O4B | 179.16 (16) |
C20A—C21A—C22A—C17A | −0.1 (3) | C18B—C19B—C20B—C21B | −0.4 (3) |
C22A—C17A—C18A—C19A | 1.5 (3) | C19B—C20B—C21B—C22B | 0.6 (3) |
C23A—O4A—C20A—C19A | 173.05 (16) | C20B—C21B—C22B—C17B | −0.4 (3) |
C23A—O4A—C20A—C21A | −7.2 (3) | C22B—C17B—C18B—C19B | 0.1 (3) |
O1B—C5B—C6B—C7B | −160.26 (16) | C23B—O4B—C20B—C19B | −5.9 (3) |
O1B—C5B—C10B—C4B | 8.1 (2) | C23B—O4B—C20B—C21B | 173.67 (18) |
O1B—C5B—C10B—C9B | −171.09 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O1B | 0.82 (2) | 2.02 (2) | 2.827 (2) | 167 (2) |
N1B—H1B···O1Ai | 0.87 (2) | 1.95 (2) | 2.8167 (19) | 172 (2) |
Symmetry code: (i) x, y−1, z. |
C21H25NO5 | F(000) = 792 |
Mr = 371.42 | Dx = 1.113 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2745 (3) Å | Cell parameters from 9215 reflections |
b = 22.1655 (7) Å | θ = 2.5–28.3° |
c = 11.3475 (4) Å | µ = 0.08 mm−1 |
β = 108.2014 (17)° | T = 100 K |
V = 2216.03 (13) Å3 | Plate, brown |
Z = 4 | 0.64 × 0.13 × 0.06 mm |
Bruker SMART BREEZE CCD diffractometer | Rint = 0.046 |
Radiation source: 2 kW sealed X-ray tube | θmax = 28.4°, θmin = 2.5° |
φ and ω scans | h = −12→12 |
40175 measured reflections | k = −29→29 |
5517 independent reflections | l = −15→15 |
4263 reflections with I > 2σ(I) |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0628P)2 + 0.7593P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
5517 reflections | Δρmax = 0.41 e Å−3 |
260 parameters | Δρmin = −0.21 e Å−3 |
0 restraints |
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. Disordered hexanes molecules were identified in the final stage of refinement. The disorder of the hexanes was dealt with by application of the Olex2/smtbx_masks (Rees, et al., 2005), which allows for the mathematical compensation of the electron contribution of disordered solvent contained in the voids to the calculated diffraction intensities. |
x | y | z | Uiso*/Ueq | ||
O1 | 1.16874 (11) | 0.16574 (4) | 0.51737 (9) | 0.0186 (2) | |
O2 | 0.97871 (12) | 0.34503 (5) | 0.68766 (9) | 0.0208 (2) | |
O4 | 0.45936 (11) | 0.14086 (5) | 0.41764 (10) | 0.0240 (2) | |
O5 | 0.49133 (12) | 0.12980 (5) | 0.65976 (10) | 0.0218 (2) | |
O3 | 0.87314 (12) | 0.41878 (4) | 0.55338 (9) | 0.0216 (2) | |
N1 | 0.78891 (13) | 0.29217 (5) | 0.26502 (10) | 0.0156 (2) | |
C5 | 1.08644 (15) | 0.18180 (6) | 0.41329 (12) | 0.0149 (3) | |
C8 | 0.89609 (15) | 0.21511 (6) | 0.16440 (12) | 0.0160 (3) | |
H8A | 0.958420 | 0.240536 | 0.127373 | 0.019* | |
H8B | 0.792707 | 0.212750 | 0.104128 | 0.019* | |
C4 | 0.93969 (14) | 0.25570 (6) | 0.50871 (11) | 0.0139 (3) | |
H4A | 1.037134 | 0.257551 | 0.578628 | 0.017* | |
C6 | 1.10852 (15) | 0.15446 (6) | 0.29827 (12) | 0.0174 (3) | |
H6A | 1.148756 | 0.113046 | 0.318085 | 0.021* | |
H6B | 1.185931 | 0.178302 | 0.275254 | 0.021* | |
C17 | 0.82560 (15) | 0.21896 (6) | 0.55115 (12) | 0.0149 (3) | |
C18 | 0.69686 (15) | 0.19536 (6) | 0.46308 (12) | 0.0160 (3) | |
H18 | 0.684531 | 0.200209 | 0.377301 | 0.019* | |
C22 | 0.84222 (16) | 0.21058 (6) | 0.67665 (12) | 0.0177 (3) | |
H22 | 0.930164 | 0.225397 | 0.737945 | 0.021* | |
C20 | 0.60235 (15) | 0.15836 (6) | 0.62458 (13) | 0.0173 (3) | |
C9 | 0.88732 (14) | 0.24475 (6) | 0.28105 (12) | 0.0145 (3) | |
C2 | 0.79999 (15) | 0.33426 (6) | 0.35723 (12) | 0.0155 (3) | |
C19 | 0.58740 (15) | 0.16513 (6) | 0.49897 (12) | 0.0169 (3) | |
C3 | 0.88223 (15) | 0.31999 (6) | 0.47602 (12) | 0.0149 (3) | |
C13 | 0.71604 (17) | 0.39170 (7) | 0.30927 (13) | 0.0215 (3) | |
H13A | 0.788056 | 0.422485 | 0.300887 | 0.032* | |
H13B | 0.664522 | 0.405840 | 0.367496 | 0.032* | |
H13C | 0.640811 | 0.384230 | 0.228143 | 0.032* | |
C10 | 0.97144 (14) | 0.22778 (6) | 0.39745 (12) | 0.0145 (3) | |
C14 | 0.91478 (15) | 0.36129 (6) | 0.58100 (12) | 0.0158 (3) | |
C12 | 1.00654 (17) | 0.13217 (7) | 0.07145 (13) | 0.0222 (3) | |
H12A | 0.914860 | 0.130802 | −0.000786 | 0.033* | |
H12B | 1.053357 | 0.092077 | 0.085603 | 0.033* | |
H12C | 1.078437 | 0.161201 | 0.056243 | 0.033* | |
C7 | 0.96430 (15) | 0.15158 (6) | 0.18598 (12) | 0.0163 (3) | |
C21 | 0.73077 (16) | 0.18065 (7) | 0.71252 (12) | 0.0185 (3) | |
H21 | 0.742940 | 0.175475 | 0.798193 | 0.022* | |
C11 | 0.85119 (17) | 0.10672 (7) | 0.20946 (14) | 0.0224 (3) | |
H11A | 0.825571 | 0.118927 | 0.283507 | 0.034* | |
H11B | 0.896573 | 0.066356 | 0.222225 | 0.034* | |
H11C | 0.758898 | 0.106099 | 0.137716 | 0.034* | |
C15 | 0.90744 (19) | 0.46064 (7) | 0.65759 (14) | 0.0261 (3) | |
H15A | 1.018040 | 0.461676 | 0.701111 | 0.031* | |
H15B | 0.854928 | 0.448188 | 0.717373 | 0.031* | |
C16 | 0.8524 (2) | 0.52160 (7) | 0.60416 (16) | 0.0379 (4) | |
H16A | 0.899073 | 0.531841 | 0.540303 | 0.057* | |
H16B | 0.880369 | 0.551964 | 0.670189 | 0.057* | |
H16C | 0.741720 | 0.520718 | 0.567149 | 0.057* | |
H1 | 0.741 (2) | 0.3036 (8) | 0.1889 (17) | 0.024 (4)* | |
H4 | 0.467 (2) | 0.1431 (10) | 0.343 (2) | 0.043 (6)* | |
H5 | 0.412 (3) | 0.1256 (10) | 0.597 (2) | 0.050 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0193 (5) | 0.0216 (5) | 0.0118 (5) | 0.0028 (4) | 0.0004 (4) | 0.0001 (4) |
O2 | 0.0256 (5) | 0.0223 (5) | 0.0116 (5) | 0.0036 (4) | 0.0016 (4) | −0.0014 (4) |
O4 | 0.0182 (5) | 0.0382 (6) | 0.0143 (5) | −0.0089 (4) | 0.0033 (4) | −0.0007 (5) |
O5 | 0.0209 (5) | 0.0285 (6) | 0.0175 (5) | −0.0020 (4) | 0.0084 (4) | 0.0032 (4) |
O3 | 0.0317 (6) | 0.0170 (5) | 0.0131 (5) | 0.0018 (4) | 0.0024 (4) | −0.0023 (4) |
N1 | 0.0169 (5) | 0.0181 (6) | 0.0089 (5) | 0.0018 (4) | 0.0000 (4) | 0.0000 (4) |
C5 | 0.0150 (6) | 0.0160 (6) | 0.0128 (6) | −0.0027 (5) | 0.0031 (5) | −0.0007 (5) |
C8 | 0.0165 (6) | 0.0198 (7) | 0.0101 (6) | 0.0003 (5) | 0.0018 (5) | −0.0002 (5) |
C4 | 0.0132 (6) | 0.0173 (6) | 0.0090 (6) | 0.0014 (5) | 0.0002 (5) | −0.0004 (5) |
C6 | 0.0154 (6) | 0.0216 (7) | 0.0135 (6) | 0.0037 (5) | 0.0020 (5) | −0.0017 (5) |
C17 | 0.0159 (6) | 0.0148 (6) | 0.0135 (6) | 0.0027 (5) | 0.0041 (5) | 0.0010 (5) |
C18 | 0.0167 (6) | 0.0199 (7) | 0.0109 (6) | 0.0018 (5) | 0.0035 (5) | 0.0014 (5) |
C22 | 0.0197 (6) | 0.0192 (7) | 0.0123 (6) | 0.0011 (5) | 0.0021 (5) | −0.0009 (5) |
C20 | 0.0187 (6) | 0.0179 (7) | 0.0163 (7) | 0.0025 (5) | 0.0068 (5) | 0.0024 (5) |
C9 | 0.0134 (6) | 0.0161 (6) | 0.0136 (6) | −0.0030 (5) | 0.0034 (5) | −0.0010 (5) |
C2 | 0.0152 (6) | 0.0170 (7) | 0.0141 (6) | −0.0008 (5) | 0.0042 (5) | 0.0003 (5) |
C19 | 0.0154 (6) | 0.0192 (7) | 0.0142 (6) | 0.0016 (5) | 0.0021 (5) | 0.0002 (5) |
C3 | 0.0148 (6) | 0.0168 (7) | 0.0123 (6) | 0.0000 (5) | 0.0033 (5) | −0.0003 (5) |
C13 | 0.0264 (7) | 0.0210 (7) | 0.0148 (7) | 0.0053 (6) | 0.0031 (6) | 0.0016 (5) |
C10 | 0.0148 (6) | 0.0162 (6) | 0.0115 (6) | −0.0013 (5) | 0.0030 (5) | −0.0008 (5) |
C14 | 0.0143 (6) | 0.0178 (7) | 0.0147 (6) | −0.0005 (5) | 0.0037 (5) | −0.0002 (5) |
C12 | 0.0233 (7) | 0.0277 (8) | 0.0147 (6) | 0.0043 (6) | 0.0048 (6) | −0.0035 (6) |
C7 | 0.0161 (6) | 0.0197 (7) | 0.0120 (6) | 0.0011 (5) | 0.0027 (5) | −0.0018 (5) |
C21 | 0.0231 (7) | 0.0210 (7) | 0.0113 (6) | 0.0034 (5) | 0.0050 (5) | 0.0018 (5) |
C11 | 0.0239 (7) | 0.0213 (7) | 0.0210 (7) | −0.0028 (6) | 0.0054 (6) | −0.0038 (6) |
C15 | 0.0369 (9) | 0.0198 (7) | 0.0168 (7) | 0.0017 (6) | 0.0016 (6) | −0.0048 (6) |
C16 | 0.0608 (12) | 0.0201 (8) | 0.0272 (8) | 0.0067 (8) | 0.0055 (8) | −0.0037 (7) |
O1—C5 | 1.2413 (16) | C18—C19 | 1.3798 (19) |
O2—C14 | 1.2240 (16) | C22—H22 | 0.9500 |
O4—C19 | 1.3662 (16) | C22—C21 | 1.392 (2) |
O4—H4 | 0.87 (2) | C20—C19 | 1.3964 (19) |
O5—C20 | 1.3701 (17) | C20—C21 | 1.3842 (19) |
O5—H5 | 0.85 (2) | C9—C10 | 1.3605 (18) |
O3—C14 | 1.3400 (17) | C2—C3 | 1.3625 (18) |
O3—C15 | 1.4578 (17) | C2—C13 | 1.5029 (19) |
N1—C9 | 1.3666 (17) | C3—C14 | 1.4573 (18) |
N1—C2 | 1.3814 (17) | C13—H13A | 0.9800 |
N1—H1 | 0.876 (18) | C13—H13B | 0.9800 |
C5—C6 | 1.5099 (18) | C13—H13C | 0.9800 |
C5—C10 | 1.4453 (19) | C12—H12A | 0.9800 |
C8—H8A | 0.9900 | C12—H12B | 0.9800 |
C8—H8B | 0.9900 | C12—H12C | 0.9800 |
C8—C9 | 1.5026 (18) | C12—C7 | 1.5316 (19) |
C8—C7 | 1.5317 (19) | C7—C11 | 1.528 (2) |
C4—H4A | 1.0000 | C21—H21 | 0.9500 |
C4—C17 | 1.5275 (18) | C11—H11A | 0.9800 |
C4—C3 | 1.5260 (19) | C11—H11B | 0.9800 |
C4—C10 | 1.5153 (18) | C11—H11C | 0.9800 |
C6—H6A | 0.9900 | C15—H15A | 0.9900 |
C6—H6B | 0.9900 | C15—H15B | 0.9900 |
C6—C7 | 1.5336 (18) | C15—C16 | 1.504 (2) |
C17—C18 | 1.3973 (18) | C16—H16A | 0.9800 |
C17—C22 | 1.3961 (18) | C16—H16B | 0.9800 |
C18—H18 | 0.9500 | C16—H16C | 0.9800 |
C19—O4—H4 | 108.5 (14) | C2—C3—C4 | 120.15 (12) |
C20—O5—H5 | 109.9 (15) | C2—C3—C14 | 124.88 (12) |
C14—O3—C15 | 116.21 (11) | C14—C3—C4 | 114.86 (11) |
C9—N1—C2 | 122.01 (11) | C2—C13—H13A | 109.5 |
C9—N1—H1 | 117.7 (12) | C2—C13—H13B | 109.5 |
C2—N1—H1 | 116.6 (12) | C2—C13—H13C | 109.5 |
O1—C5—C6 | 119.89 (12) | H13A—C13—H13B | 109.5 |
O1—C5—C10 | 122.08 (12) | H13A—C13—H13C | 109.5 |
C10—C5—C6 | 118.01 (11) | H13B—C13—H13C | 109.5 |
H8A—C8—H8B | 107.7 | C5—C10—C4 | 120.82 (11) |
C9—C8—H8A | 108.9 | C9—C10—C5 | 119.53 (12) |
C9—C8—H8B | 108.9 | C9—C10—C4 | 119.62 (12) |
C9—C8—C7 | 113.23 (11) | O2—C14—O3 | 121.77 (12) |
C7—C8—H8A | 108.9 | O2—C14—C3 | 122.42 (13) |
C7—C8—H8B | 108.9 | O3—C14—C3 | 115.80 (11) |
C17—C4—H4A | 108.4 | H12A—C12—H12B | 109.5 |
C3—C4—H4A | 108.4 | H12A—C12—H12C | 109.5 |
C3—C4—C17 | 110.54 (11) | H12B—C12—H12C | 109.5 |
C10—C4—H4A | 108.4 | C7—C12—H12A | 109.5 |
C10—C4—C17 | 112.27 (11) | C7—C12—H12B | 109.5 |
C10—C4—C3 | 108.83 (11) | C7—C12—H12C | 109.5 |
C5—C6—H6A | 108.6 | C8—C7—C6 | 107.70 (11) |
C5—C6—H6B | 108.6 | C12—C7—C8 | 108.96 (11) |
C5—C6—C7 | 114.61 (11) | C12—C7—C6 | 109.20 (11) |
H6A—C6—H6B | 107.6 | C11—C7—C8 | 110.75 (11) |
C7—C6—H6A | 108.6 | C11—C7—C6 | 110.50 (11) |
C7—C6—H6B | 108.6 | C11—C7—C12 | 109.67 (12) |
C18—C17—C4 | 119.69 (11) | C22—C21—H21 | 119.7 |
C22—C17—C4 | 121.73 (12) | C20—C21—C22 | 120.64 (13) |
C22—C17—C18 | 118.51 (12) | C20—C21—H21 | 119.7 |
C17—C18—H18 | 119.5 | C7—C11—H11A | 109.5 |
C19—C18—C17 | 120.91 (12) | C7—C11—H11B | 109.5 |
C19—C18—H18 | 119.5 | C7—C11—H11C | 109.5 |
C17—C22—H22 | 119.8 | H11A—C11—H11B | 109.5 |
C21—C22—C17 | 120.41 (12) | H11A—C11—H11C | 109.5 |
C21—C22—H22 | 119.8 | H11B—C11—H11C | 109.5 |
O5—C20—C19 | 120.20 (12) | O3—C15—H15A | 110.4 |
O5—C20—C21 | 120.70 (12) | O3—C15—H15B | 110.4 |
C21—C20—C19 | 119.10 (13) | O3—C15—C16 | 106.51 (12) |
N1—C9—C8 | 115.90 (11) | H15A—C15—H15B | 108.6 |
C10—C9—N1 | 119.90 (12) | C16—C15—H15A | 110.4 |
C10—C9—C8 | 124.20 (12) | C16—C15—H15B | 110.4 |
N1—C2—C13 | 112.97 (11) | C15—C16—H16A | 109.5 |
C3—C2—N1 | 118.61 (12) | C15—C16—H16B | 109.5 |
C3—C2—C13 | 128.42 (13) | C15—C16—H16C | 109.5 |
O4—C19—C18 | 123.80 (12) | H16A—C16—H16B | 109.5 |
O4—C19—C20 | 115.81 (12) | H16A—C16—H16C | 109.5 |
C18—C19—C20 | 120.38 (12) | H16B—C16—H16C | 109.5 |
O1—C5—C6—C7 | 150.87 (13) | C22—C17—C18—C19 | 0.8 (2) |
O1—C5—C10—C4 | −4.0 (2) | C9—N1—C2—C3 | −17.94 (19) |
O1—C5—C10—C9 | 178.22 (13) | C9—N1—C2—C13 | 161.87 (12) |
O5—C20—C19—O4 | −1.13 (19) | C9—C8—C7—C6 | −47.01 (15) |
O5—C20—C19—C18 | 178.15 (13) | C9—C8—C7—C12 | −165.35 (11) |
O5—C20—C21—C22 | −178.88 (13) | C9—C8—C7—C11 | 73.93 (14) |
N1—C9—C10—C5 | −173.59 (12) | C2—N1—C9—C8 | −160.56 (12) |
N1—C9—C10—C4 | 8.57 (19) | C2—N1—C9—C10 | 18.4 (2) |
N1—C2—C3—C4 | −9.26 (19) | C2—C3—C14—O2 | 173.96 (13) |
N1—C2—C3—C14 | 174.56 (12) | C2—C3—C14—O3 | −7.4 (2) |
C5—C6—C7—C8 | 53.26 (15) | C19—C20—C21—C22 | 1.4 (2) |
C5—C6—C7—C12 | 171.44 (12) | C3—C4—C17—C18 | 79.11 (15) |
C5—C6—C7—C11 | −67.84 (15) | C3—C4—C17—C22 | −97.69 (14) |
C8—C9—C10—C5 | 5.3 (2) | C3—C4—C10—C5 | 151.08 (12) |
C8—C9—C10—C4 | −172.52 (12) | C3—C4—C10—C9 | −31.10 (16) |
C4—C17—C18—C19 | −176.06 (12) | C13—C2—C3—C4 | 170.96 (13) |
C4—C17—C22—C21 | 175.27 (12) | C13—C2—C3—C14 | −5.2 (2) |
C4—C3—C14—O2 | −2.40 (19) | C10—C5—C6—C7 | −31.05 (17) |
C4—C3—C14—O3 | 176.26 (11) | C10—C4—C17—C18 | −42.63 (16) |
C6—C5—C10—C4 | 178.00 (12) | C10—C4—C17—C22 | 140.57 (13) |
C6—C5—C10—C9 | 0.18 (19) | C10—C4—C3—C2 | 31.57 (16) |
C17—C4—C3—C2 | −92.17 (14) | C10—C4—C3—C14 | −151.88 (11) |
C17—C4—C3—C14 | 84.38 (13) | C14—O3—C15—C16 | 179.42 (14) |
C17—C4—C10—C5 | −86.21 (14) | C7—C8—C9—N1 | −160.98 (11) |
C17—C4—C10—C9 | 91.60 (15) | C7—C8—C9—C10 | 20.07 (19) |
C17—C18—C19—O4 | −179.79 (13) | C21—C20—C19—O4 | 178.62 (13) |
C17—C18—C19—C20 | 1.0 (2) | C21—C20—C19—C18 | −2.1 (2) |
C17—C22—C21—C20 | 0.5 (2) | C15—O3—C14—O2 | −0.38 (19) |
C18—C17—C22—C21 | −1.6 (2) | C15—O3—C14—C3 | −179.05 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.876 (18) | 1.971 (19) | 2.8378 (15) | 169.8 (16) |
O4—H4···O2i | 0.87 (2) | 1.82 (2) | 2.6894 (14) | 175 (2) |
O5—H5···O1ii | 0.85 (2) | 2.33 (2) | 3.0293 (14) | 140 (2) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1, y, z. |
Compound | 1,4-DHP mean plane (C2/C3/C10/C9) r.m.s.d | N to ring mean plane distance | C to ring mean plane distance | Phenyl ring to 1,4-DHP mean planes normal-to-normal angle | N1—C4—C17—C18 torsion angle |
I | 0.015 | 0.159 (3) | 0.341 (3) | 89.09 (7) | 173.28 (16) |
IIA | 0.005 | 0.110 (2) | 0.295 (3) | 92.52 (6) | 1.16 (18) |
IIB | 0.005 | 0.110 (3) | 0.253 (3) | 93.52 (6) | 13.41 (14) |
III | 0.001 | 0.181 (2) | 0.399 (2) | 90.59 (5) | 18.38 (15) |
Compound | Mean plane (C5/C6/C8–C10) r.m.s.d | C7 to mean plane distance | C11—C7—C4—C17 torsion angle | Ring puckering parameters | ||
Q | θ | φ | ||||
I | 0.025 | 0.636 (3) | 2.53 (18) | 0.458 (2) | 60.7 (3) | 117.2 (3) |
IIA | 0.015 | 0.644 (2) | 7.96 (14) | 0.4616 (18) | 56.1 (2) | 115.7 (3) |
IIB | 0.019 | 0.645 (3) | 13.85 (14) | 0.4638 (19) | 121.2 (2) | 303.0 (3) |
III | 0.028 | 0.6408 (19) | 0.8 (1) | 0.4623 (15) | 56.53 (19) | 111.1 (2) |
Footnotes
‡Current address: Washington State University, Pullman WA, USA, scott.steiger@wsu.edu.
Acknowledgements
The authors thank the University of Montana for grant 325490. CL thanks all the faculty in the ACA Summer Course 2016, from whom CL has learned a lot in refining disordered and twinned structures. The authors also thank Eric Schultz for mass spectra, supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award No. P30GM140963.
Funding information
Funding for this research was provided by: University of Montana (grant No. 325490 to Nicholas R. Natale); National Institutes of Health, National Institute of General Medical Sciences (grant No. P30GM140963 to Nicholas R. Natale).
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