Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110053357/sf3143sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110053357/sf3143Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110053357/sf3143IIsup3.hkl |
CCDC references: 819302; 819303
To (1R,3S)-2-benzyl-3-(1,1-diphenylethyl)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline (0.4 g, 0.72 mmol) derived from L-DOPA (Naicker, Petzold et al., 2010) in MeOH–THF (1:1 v/v, 20 ml) was added half an equivalent by mass of 10% palladium on carbon Pd/C under hydrogen (approximately 1 atm). The reaction was stirred for 2 h. The crude product was obtained by filtering the Pd/C through a plug of Celite and the filtrate was then concentrated to dryness. The resulting residue was purified by column chromatography (50:50 EtOAc–hexane, Rf = 0.6) to yield (I) as a white solid [yield 0.2 g, 60%; m.p. 463–465 K; [α]20D -10.0 (c 0.11 in CHCl3)]. Recrystallization from ethyl acetate afforded colourless crystals suitable for X-ray analysis. Spectroscopic analysis: IR (neat, νmax, cm-1): 2934, 1514, 1448, 1244, 1224, 1063, 698; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.47–7.12 (m, 12H), 7.08 (t, J = 7.6 Hz, 2H), 6.92 (d, J = 7.6 Hz, 2H), 6.65 (s, 1H), 6.40 (s, 1H), 5.23 (s, 1H), 3.95 (dd, J = 11.5 and 3.6 Hz, 1H), 3.86 (s, 3H), 3.70 (s, 3H), 2.92–2.75 (m, 4H), 2.52 (dd, J = 16.2 and 11.5 Hz, 3H).
To a stirred solution of [(1R,3S)-3-(hydroxydiphenylmethyl)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinolin-2-yl](phenyl)methanone (0.6 g, 1.1 mmol) derived from L-DOPA (Naicker, Petzold et al., 2010) in dry dichloromethane (20 ml) and triethylamine (0.18 ml, 1.3 mmol), trimethylsilyl trifluoromethanesulfonate (0.24 ml, 1.33 mmol) was added dropwise at 273 K under an inert atmosphere. The mixture was allowed to warm to room temperature and stirred overnight. The mixture was washed with water, the organic extracts were combined and dried over anhydrous Na2SO4, and the solvent was removed in vacuo. The resulting residue was purified by column chromatography (20:80 EtOAc–hexane, Rf 0.55) to afford (II) as a white solid [yield 0.5 g, 75%; m.p. 458–460 K; [α]20D 57.58 (c 0.33 in CHCl3)]. Recrystallization from acetone afforded colourless crystals suitable for X-ray analysis. Spectroscopic analysis: IR (neat, νmax, cm-1): 2956, 1513, 1245, 839, 696; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.17 (m, 14H), 6.84 (m, 5H), 6.63 (m, 2H), 6.36 (s, 1H), 4.57 (s, 1H), 4.38 (d, J = 13.63 Hz, 1H), 4.24 (dd, J = 3.38 and 12.13 Hz, 1H), 4.00 (s, 3H), 3.73 (s, 3H), 3.39 (dd, J = 4.32 and 12.58 Hz, 1H), 3.31 (d, J = 13.85 Hz, 1H), 2.29 (dd, J = 3.38 and 16.88 Hz, 1H), 0.0 (s, 9H).
Atom H1N on N1 of (I) was located in a difference electron-density map and refined isotropically with a simple bond-length restraint of N1—H1N = 0.??(?) Å. All remaining H atoms were positioned geometrically, with C—H = 0.95 (aromatic), 0.98 (methyl), 0.99 (methylene) or 1.00 Å (methine), and refined as riding on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. For (I), the Flack x parameter (Flack, 1983) based on refinement with xxxx Friedel pairs was -0.5 (10), which indicated that no conclusions can be drawn regarding the absolute structure. Consequently, the Friedel pairs were merged before the final refinement. For (II), the Flack parameter refined to 0.00 (10) using xxxx Friedel pairs, which indicated that the refined model represents the true absolute configuration and is in accordance with expectation from the known chirality of the starting material in the synthesis.
For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C31H31NO3 | F(000) = 496 |
Mr = 465.57 | Dx = 1.260 Mg m−3 |
Monoclinic, P21 | Melting point: 464 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 11.4071 (14) Å | Cell parameters from 11498 reflections |
b = 6.4750 (8) Å | θ = 1.8–29.7° |
c = 16.961 (2) Å | µ = 0.08 mm−1 |
β = 101.707 (2)° | T = 173 K |
V = 1226.7 (3) Å3 | Block, colourless |
Z = 2 | 0.22 × 0.14 × 0.09 mm |
Bruker APEXII DUO diffractometer | 3737 independent reflections |
Radiation source: fine-focus sealed tube | 3191 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
0.5° ϕ scans and ω | θmax = 29.7°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −15→13 |
Tmin = 0.645, Tmax = 0.746 | k = −8→8 |
11498 measured reflections | l = −23→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0591P)2] where P = (Fo2 + 2Fc2)/3 |
3737 reflections | (Δ/σ)max < 0.001 |
320 parameters | Δρmax = 0.23 e Å−3 |
2 restraints | Δρmin = −0.23 e Å−3 |
C31H31NO3 | V = 1226.7 (3) Å3 |
Mr = 465.57 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.4071 (14) Å | µ = 0.08 mm−1 |
b = 6.4750 (8) Å | T = 173 K |
c = 16.961 (2) Å | 0.22 × 0.14 × 0.09 mm |
β = 101.707 (2)° |
Bruker APEXII DUO diffractometer | 3737 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | 3191 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.746 | Rint = 0.051 |
11498 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 2 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.23 e Å−3 |
3737 reflections | Δρmin = −0.23 e Å−3 |
320 parameters |
Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of ϕ and ω scans of 0.5°, 20 s per °, 2 iterations. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. For both crystals, X-ray diffraction data were collected on a Bruker APEXII Duo diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Data collection was carried out at 173 (2) K and 100 (2) K for structures (I) and (II), respectively, to minimize thermal motion effects. Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). Cell refinement and data reduction were performed using the program SAINT (Bruker, 2006). The data were scaled and empirical absorption corrections were performed using SADABS (Bruker, 2006). The structure was solved by direct methods using SHELXS97 (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F2 using SHELXL97 (Sheldrick, 2008). All non-H atoms were refined anisotropically. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.09437 (12) | 0.2273 (2) | 0.57983 (9) | 0.0308 (4) | |
O2 | 0.07975 (12) | 0.5778 (3) | 0.65284 (9) | 0.0290 (3) | |
O3 | 0.73707 (12) | 0.7122 (2) | 0.82876 (8) | 0.0240 (3) | |
N1 | 0.59801 (14) | 0.2003 (3) | 0.79457 (9) | 0.0213 (3) | |
H1N | 0.6724 (14) | 0.127 (4) | 0.8040 (15) | 0.039 (7)* | |
C1 | 0.51525 (16) | 0.1256 (3) | 0.72126 (11) | 0.0197 (4) | |
H1 | 0.4934 | −0.0198 | 0.7320 | 0.024* | |
C2 | 0.40066 (16) | 0.2505 (3) | 0.70663 (11) | 0.0197 (4) | |
C3 | 0.30026 (16) | 0.1747 (3) | 0.65138 (11) | 0.0223 (4) | |
H3 | 0.3051 | 0.0450 | 0.6260 | 0.027* | |
C4 | 0.19499 (17) | 0.2868 (3) | 0.63373 (11) | 0.0235 (4) | |
C5 | 0.18738 (17) | 0.4768 (3) | 0.67285 (12) | 0.0220 (4) | |
C6 | 0.28581 (17) | 0.5516 (3) | 0.72644 (12) | 0.0223 (4) | |
H6 | 0.2804 | 0.6804 | 0.7523 | 0.027* | |
C7 | 0.39424 (16) | 0.4399 (3) | 0.74336 (11) | 0.0202 (4) | |
C8 | 0.50033 (16) | 0.5275 (3) | 0.80131 (12) | 0.0213 (4) | |
H8A | 0.4893 | 0.5068 | 0.8572 | 0.026* | |
H8B | 0.5056 | 0.6779 | 0.7920 | 0.026* | |
C9 | 0.61606 (16) | 0.4240 (3) | 0.79094 (11) | 0.0192 (4) | |
H9 | 0.6286 | 0.4579 | 0.7357 | 0.023* | |
C10 | 0.72847 (16) | 0.4988 (3) | 0.85243 (11) | 0.0184 (4) | |
C11 | 0.84475 (19) | 0.8166 (3) | 0.86491 (13) | 0.0286 (4) | |
H11A | 0.8420 | 0.9591 | 0.8451 | 0.043* | |
H11B | 0.9135 | 0.7451 | 0.8509 | 0.043* | |
H11C | 0.8528 | 0.8174 | 0.9235 | 0.043* | |
C12 | 0.70428 (16) | 0.4858 (3) | 0.93825 (11) | 0.0203 (4) | |
C13 | 0.65850 (17) | 0.6563 (3) | 0.97170 (12) | 0.0262 (4) | |
H13 | 0.6485 | 0.7835 | 0.9431 | 0.031* | |
C14 | 0.62723 (19) | 0.6421 (4) | 1.04692 (13) | 0.0342 (5) | |
H14 | 0.5958 | 0.7592 | 1.0692 | 0.041* | |
C15 | 0.6419 (2) | 0.4581 (5) | 1.08902 (14) | 0.0386 (6) | |
H15 | 0.6210 | 0.4491 | 1.1404 | 0.046* | |
C16 | 0.6866 (2) | 0.2885 (4) | 1.05673 (13) | 0.0343 (5) | |
H16 | 0.6968 | 0.1622 | 1.0858 | 0.041* | |
C17 | 0.71712 (18) | 0.3007 (4) | 0.98122 (12) | 0.0263 (4) | |
H17 | 0.7469 | 0.1819 | 0.9589 | 0.032* | |
C18 | 0.84221 (16) | 0.3857 (3) | 0.84109 (12) | 0.0196 (4) | |
C19 | 0.93859 (18) | 0.3513 (3) | 0.90463 (12) | 0.0253 (4) | |
H19 | 0.9320 | 0.3876 | 0.9578 | 0.030* | |
C20 | 1.04428 (18) | 0.2646 (4) | 0.89128 (13) | 0.0321 (5) | |
H20 | 1.1088 | 0.2408 | 0.9354 | 0.039* | |
C21 | 1.05638 (18) | 0.2124 (4) | 0.81417 (14) | 0.0313 (5) | |
H21 | 1.1288 | 0.1535 | 0.8052 | 0.038* | |
C22 | 0.96216 (18) | 0.2470 (4) | 0.75069 (13) | 0.0279 (4) | |
H22 | 0.9696 | 0.2110 | 0.6976 | 0.033* | |
C23 | 0.85646 (18) | 0.3341 (3) | 0.76349 (12) | 0.0231 (4) | |
H23 | 0.7928 | 0.3591 | 0.7189 | 0.028* | |
C24 | 0.57492 (16) | 0.1204 (3) | 0.64812 (11) | 0.0224 (4) | |
C25 | 0.6553 (2) | −0.0382 (4) | 0.64257 (14) | 0.0342 (5) | |
H25 | 0.6682 | −0.1443 | 0.6820 | 0.041* | |
C26 | 0.7170 (2) | −0.0424 (5) | 0.57963 (16) | 0.0453 (7) | |
H26 | 0.7723 | −0.1504 | 0.5767 | 0.054* | |
C27 | 0.6978 (2) | 0.1107 (5) | 0.52141 (15) | 0.0468 (7) | |
H27 | 0.7395 | 0.1073 | 0.4783 | 0.056* | |
C28 | 0.6183 (2) | 0.2676 (5) | 0.52613 (14) | 0.0412 (6) | |
H28 | 0.6054 | 0.3729 | 0.4863 | 0.049* | |
C29 | 0.55619 (19) | 0.2729 (4) | 0.58943 (12) | 0.0299 (5) | |
H29 | 0.5010 | 0.3813 | 0.5922 | 0.036* | |
C30 | 0.1034 (2) | 0.0483 (4) | 0.53183 (14) | 0.0338 (5) | |
H30A | 0.0259 | 0.0222 | 0.4960 | 0.051* | |
H30B | 0.1259 | −0.0713 | 0.5670 | 0.051* | |
H30C | 0.1644 | 0.0716 | 0.4996 | 0.051* | |
C31 | 0.05904 (19) | 0.7391 (4) | 0.70544 (14) | 0.0344 (5) | |
H31A | −0.0203 | 0.7992 | 0.6854 | 0.052* | |
H31B | 0.1203 | 0.8461 | 0.7075 | 0.052* | |
H31C | 0.0628 | 0.6829 | 0.7596 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0239 (7) | 0.0337 (9) | 0.0308 (8) | 0.0000 (6) | −0.0038 (6) | −0.0068 (7) |
O2 | 0.0221 (7) | 0.0330 (9) | 0.0301 (8) | 0.0057 (6) | 0.0010 (6) | −0.0018 (6) |
O3 | 0.0260 (7) | 0.0179 (7) | 0.0270 (7) | −0.0005 (6) | 0.0028 (5) | 0.0042 (6) |
N1 | 0.0246 (8) | 0.0179 (8) | 0.0196 (8) | 0.0013 (6) | 0.0002 (6) | 0.0007 (6) |
C1 | 0.0209 (8) | 0.0166 (9) | 0.0207 (9) | 0.0018 (7) | 0.0020 (7) | −0.0023 (7) |
C2 | 0.0193 (8) | 0.0217 (9) | 0.0184 (8) | 0.0000 (7) | 0.0043 (6) | 0.0005 (7) |
C3 | 0.0243 (9) | 0.0224 (10) | 0.0203 (9) | −0.0016 (8) | 0.0045 (7) | −0.0025 (7) |
C4 | 0.0230 (9) | 0.0276 (11) | 0.0195 (9) | −0.0011 (8) | 0.0036 (7) | 0.0002 (8) |
C5 | 0.0190 (9) | 0.0257 (10) | 0.0213 (9) | 0.0015 (7) | 0.0039 (7) | 0.0019 (8) |
C6 | 0.0242 (9) | 0.0218 (10) | 0.0210 (9) | 0.0015 (8) | 0.0051 (7) | −0.0003 (7) |
C7 | 0.0186 (9) | 0.0231 (10) | 0.0190 (9) | −0.0008 (7) | 0.0042 (7) | 0.0002 (7) |
C8 | 0.0205 (9) | 0.0197 (9) | 0.0231 (9) | 0.0018 (7) | 0.0030 (7) | −0.0009 (7) |
C9 | 0.0209 (9) | 0.0193 (9) | 0.0172 (8) | 0.0012 (7) | 0.0034 (7) | 0.0000 (7) |
C10 | 0.0204 (9) | 0.0170 (9) | 0.0174 (8) | −0.0001 (7) | 0.0033 (7) | 0.0011 (7) |
C11 | 0.0282 (10) | 0.0207 (10) | 0.0373 (11) | −0.0049 (8) | 0.0073 (9) | 0.0010 (9) |
C12 | 0.0168 (8) | 0.0266 (10) | 0.0173 (8) | −0.0017 (7) | 0.0029 (7) | −0.0015 (7) |
C13 | 0.0214 (9) | 0.0289 (11) | 0.0282 (10) | −0.0026 (8) | 0.0046 (7) | −0.0052 (8) |
C14 | 0.0296 (11) | 0.0452 (15) | 0.0298 (11) | −0.0010 (10) | 0.0108 (9) | −0.0128 (10) |
C15 | 0.0386 (13) | 0.0563 (17) | 0.0239 (11) | −0.0113 (12) | 0.0134 (9) | −0.0041 (11) |
C16 | 0.0381 (12) | 0.0398 (14) | 0.0253 (10) | −0.0075 (10) | 0.0073 (9) | 0.0053 (10) |
C17 | 0.0274 (10) | 0.0296 (11) | 0.0216 (9) | −0.0019 (9) | 0.0045 (8) | 0.0002 (8) |
C18 | 0.0187 (9) | 0.0185 (9) | 0.0224 (9) | −0.0009 (7) | 0.0057 (7) | 0.0024 (7) |
C19 | 0.0225 (9) | 0.0280 (11) | 0.0248 (10) | 0.0002 (8) | 0.0035 (7) | −0.0008 (8) |
C20 | 0.0215 (10) | 0.0402 (13) | 0.0323 (11) | 0.0047 (9) | 0.0000 (8) | 0.0010 (10) |
C21 | 0.0225 (10) | 0.0322 (12) | 0.0419 (12) | 0.0044 (9) | 0.0125 (8) | −0.0011 (10) |
C22 | 0.0301 (10) | 0.0300 (11) | 0.0262 (10) | 0.0014 (9) | 0.0121 (8) | −0.0002 (8) |
C23 | 0.0241 (9) | 0.0230 (10) | 0.0224 (9) | 0.0005 (8) | 0.0052 (7) | 0.0017 (8) |
C24 | 0.0231 (9) | 0.0240 (10) | 0.0197 (9) | 0.0006 (8) | 0.0032 (7) | −0.0043 (8) |
C25 | 0.0397 (12) | 0.0317 (12) | 0.0309 (11) | 0.0110 (10) | 0.0068 (9) | −0.0024 (9) |
C26 | 0.0432 (14) | 0.0538 (17) | 0.0413 (14) | 0.0142 (13) | 0.0144 (11) | −0.0168 (13) |
C27 | 0.0463 (14) | 0.067 (2) | 0.0316 (12) | −0.0049 (14) | 0.0191 (11) | −0.0143 (13) |
C28 | 0.0446 (13) | 0.0528 (16) | 0.0288 (11) | −0.0037 (12) | 0.0132 (10) | 0.0056 (11) |
C29 | 0.0305 (10) | 0.0334 (12) | 0.0265 (10) | 0.0025 (9) | 0.0073 (8) | 0.0022 (9) |
C30 | 0.0375 (12) | 0.0324 (12) | 0.0269 (11) | −0.0027 (10) | −0.0044 (9) | −0.0058 (9) |
C31 | 0.0260 (10) | 0.0361 (13) | 0.0411 (12) | 0.0092 (9) | 0.0069 (9) | −0.0045 (10) |
O1—C4 | 1.370 (2) | C14—C15 | 1.381 (4) |
O1—C30 | 1.432 (3) | C14—H14 | 0.9500 |
O2—C5 | 1.372 (2) | C15—C16 | 1.371 (4) |
O2—C31 | 1.424 (3) | C15—H15 | 0.9500 |
O3—C11 | 1.427 (2) | C16—C17 | 1.396 (3) |
O3—C10 | 1.448 (2) | C16—H16 | 0.9500 |
N1—C9 | 1.466 (3) | C17—H17 | 0.9500 |
N1—C1 | 1.482 (2) | C18—C19 | 1.392 (3) |
N1—H1N | 0.959 (10) | C18—C23 | 1.399 (3) |
C1—C2 | 1.514 (3) | C19—C20 | 1.390 (3) |
C1—C24 | 1.532 (3) | C19—H19 | 0.9500 |
C1—H1 | 1.0000 | C20—C21 | 1.385 (3) |
C2—C7 | 1.384 (3) | C20—H20 | 0.9500 |
C2—C3 | 1.413 (3) | C21—C22 | 1.377 (3) |
C3—C4 | 1.383 (3) | C21—H21 | 0.9500 |
C3—H3 | 0.9500 | C22—C23 | 1.387 (3) |
C4—C5 | 1.408 (3) | C22—H22 | 0.9500 |
C5—C6 | 1.381 (3) | C23—H23 | 0.9500 |
C6—C7 | 1.411 (3) | C24—C29 | 1.388 (3) |
C6—H6 | 0.9500 | C24—C25 | 1.392 (3) |
C7—C8 | 1.507 (3) | C25—C26 | 1.393 (3) |
C8—C9 | 1.522 (3) | C25—H25 | 0.9500 |
C8—H8A | 0.9900 | C26—C27 | 1.385 (4) |
C8—H8B | 0.9900 | C26—H26 | 0.9500 |
C9—C10 | 1.557 (3) | C27—C28 | 1.375 (4) |
C9—H9 | 1.0000 | C27—H27 | 0.9500 |
C10—C18 | 1.536 (3) | C28—C29 | 1.402 (3) |
C10—C12 | 1.538 (2) | C28—H28 | 0.9500 |
C11—H11A | 0.9800 | C29—H29 | 0.9500 |
C11—H11B | 0.9800 | C30—H30A | 0.9800 |
C11—H11C | 0.9800 | C30—H30B | 0.9800 |
C12—C13 | 1.391 (3) | C30—H30C | 0.9800 |
C12—C17 | 1.395 (3) | C31—H31A | 0.9800 |
C13—C14 | 1.396 (3) | C31—H31B | 0.9800 |
C13—H13 | 0.9500 | C31—H31C | 0.9800 |
C4—O1—C30 | 117.41 (16) | C15—C14—C13 | 120.2 (2) |
C5—O2—C31 | 116.66 (16) | C15—C14—H14 | 119.9 |
C11—O3—C10 | 115.71 (15) | C13—C14—H14 | 119.9 |
C9—N1—C1 | 111.01 (15) | C16—C15—C14 | 120.00 (19) |
C9—N1—H1N | 111.8 (17) | C16—C15—H15 | 120.0 |
C1—N1—H1N | 111.7 (16) | C14—C15—H15 | 120.0 |
N1—C1—C2 | 110.18 (15) | C15—C16—C17 | 120.2 (2) |
N1—C1—C24 | 112.01 (15) | C15—C16—H16 | 119.9 |
C2—C1—C24 | 112.94 (15) | C17—C16—H16 | 119.9 |
N1—C1—H1 | 107.1 | C12—C17—C16 | 120.6 (2) |
C2—C1—H1 | 107.1 | C12—C17—H17 | 119.7 |
C24—C1—H1 | 107.1 | C16—C17—H17 | 119.7 |
C7—C2—C3 | 119.78 (17) | C19—C18—C23 | 117.77 (17) |
C7—C2—C1 | 121.49 (16) | C19—C18—C10 | 122.26 (17) |
C3—C2—C1 | 118.68 (17) | C23—C18—C10 | 119.61 (17) |
C4—C3—C2 | 120.84 (18) | C20—C19—C18 | 120.89 (19) |
C4—C3—H3 | 119.6 | C20—C19—H19 | 119.6 |
C2—C3—H3 | 119.6 | C18—C19—H19 | 119.6 |
O1—C4—C3 | 124.74 (19) | C21—C20—C19 | 120.6 (2) |
O1—C4—C5 | 115.90 (17) | C21—C20—H20 | 119.7 |
C3—C4—C5 | 119.36 (18) | C19—C20—H20 | 119.7 |
O2—C5—C6 | 124.25 (19) | C22—C21—C20 | 119.18 (19) |
O2—C5—C4 | 115.94 (17) | C22—C21—H21 | 120.4 |
C6—C5—C4 | 119.80 (17) | C20—C21—H21 | 120.4 |
C5—C6—C7 | 121.05 (19) | C21—C22—C23 | 120.61 (19) |
C5—C6—H6 | 119.5 | C21—C22—H22 | 119.7 |
C7—C6—H6 | 119.5 | C23—C22—H22 | 119.7 |
C2—C7—C6 | 119.14 (17) | C22—C23—C18 | 120.98 (19) |
C2—C7—C8 | 121.22 (16) | C22—C23—H23 | 119.5 |
C6—C7—C8 | 119.64 (17) | C18—C23—H23 | 119.5 |
C7—C8—C9 | 111.07 (16) | C29—C24—C25 | 118.95 (18) |
C7—C8—H8A | 109.4 | C29—C24—C1 | 122.43 (18) |
C9—C8—H8A | 109.4 | C25—C24—C1 | 118.55 (18) |
C7—C8—H8B | 109.4 | C24—C25—C26 | 120.6 (2) |
C9—C8—H8B | 109.4 | C24—C25—H25 | 119.7 |
H8A—C8—H8B | 108.0 | C26—C25—H25 | 119.7 |
N1—C9—C8 | 107.30 (16) | C27—C26—C25 | 120.1 (2) |
N1—C9—C10 | 112.49 (15) | C27—C26—H26 | 120.0 |
C8—C9—C10 | 113.68 (15) | C25—C26—H26 | 120.0 |
N1—C9—H9 | 107.7 | C28—C27—C26 | 119.9 (2) |
C8—C9—H9 | 107.7 | C28—C27—H27 | 120.1 |
C10—C9—H9 | 107.7 | C26—C27—H27 | 120.1 |
O3—C10—C18 | 108.30 (15) | C27—C28—C29 | 120.3 (3) |
O3—C10—C12 | 110.48 (15) | C27—C28—H28 | 119.9 |
C18—C10—C12 | 114.26 (15) | C29—C28—H28 | 119.9 |
O3—C10—C9 | 101.76 (14) | C24—C29—C28 | 120.3 (2) |
C18—C10—C9 | 111.71 (15) | C24—C29—H29 | 119.9 |
C12—C10—C9 | 109.61 (14) | C28—C29—H29 | 119.9 |
O3—C11—H11A | 109.5 | O1—C30—H30A | 109.5 |
O3—C11—H11B | 109.5 | O1—C30—H30B | 109.5 |
H11A—C11—H11B | 109.5 | H30A—C30—H30B | 109.5 |
O3—C11—H11C | 109.5 | O1—C30—H30C | 109.5 |
H11A—C11—H11C | 109.5 | H30A—C30—H30C | 109.5 |
H11B—C11—H11C | 109.5 | H30B—C30—H30C | 109.5 |
C13—C12—C17 | 118.51 (17) | O2—C31—H31A | 109.5 |
C13—C12—C10 | 119.80 (18) | O2—C31—H31B | 109.5 |
C17—C12—C10 | 121.45 (17) | H31A—C31—H31B | 109.5 |
C12—C13—C14 | 120.5 (2) | O2—C31—H31C | 109.5 |
C12—C13—H13 | 119.8 | H31A—C31—H31C | 109.5 |
C14—C13—H13 | 119.8 | H31B—C31—H31C | 109.5 |
C9—N1—C1—C2 | −52.4 (2) | O3—C10—C12—C13 | 19.5 (2) |
C9—N1—C1—C24 | 74.18 (19) | C18—C10—C12—C13 | 141.86 (18) |
N1—C1—C2—C7 | 17.3 (2) | C9—C10—C12—C13 | −91.9 (2) |
C24—C1—C2—C7 | −108.82 (19) | O3—C10—C12—C17 | −166.31 (17) |
N1—C1—C2—C3 | −165.58 (16) | C18—C10—C12—C17 | −43.9 (2) |
C24—C1—C2—C3 | 68.3 (2) | C9—C10—C12—C17 | 82.3 (2) |
C7—C2—C3—C4 | −0.4 (3) | C17—C12—C13—C14 | 0.5 (3) |
C1—C2—C3—C4 | −177.58 (17) | C10—C12—C13—C14 | 174.93 (17) |
C30—O1—C4—C3 | −7.4 (3) | C12—C13—C14—C15 | 0.2 (3) |
C30—O1—C4—C5 | 172.58 (17) | C13—C14—C15—C16 | −0.4 (3) |
C2—C3—C4—O1 | 178.58 (18) | C14—C15—C16—C17 | −0.2 (4) |
C2—C3—C4—C5 | −1.4 (3) | C13—C12—C17—C16 | −1.1 (3) |
C31—O2—C5—C6 | −17.1 (3) | C10—C12—C17—C16 | −175.41 (18) |
C31—O2—C5—C4 | 164.18 (19) | C15—C16—C17—C12 | 0.9 (3) |
O1—C4—C5—O2 | 0.7 (2) | O3—C10—C18—C19 | 98.0 (2) |
C3—C4—C5—O2 | −179.31 (17) | C12—C10—C18—C19 | −25.5 (3) |
O1—C4—C5—C6 | −178.13 (17) | C9—C10—C18—C19 | −150.69 (18) |
C3—C4—C5—C6 | 1.9 (3) | O3—C10—C18—C23 | −74.9 (2) |
O2—C5—C6—C7 | −179.24 (17) | C12—C10—C18—C23 | 161.55 (17) |
C4—C5—C6—C7 | −0.5 (3) | C9—C10—C18—C23 | 36.4 (2) |
C3—C2—C7—C6 | 1.7 (3) | C23—C18—C19—C20 | −1.3 (3) |
C1—C2—C7—C6 | 178.84 (17) | C10—C18—C19—C20 | −174.4 (2) |
C3—C2—C7—C8 | −178.75 (17) | C18—C19—C20—C21 | 0.7 (4) |
C1—C2—C7—C8 | −1.6 (3) | C19—C20—C21—C22 | −0.2 (4) |
C5—C6—C7—C2 | −1.3 (3) | C20—C21—C22—C23 | 0.4 (4) |
C5—C6—C7—C8 | 179.19 (17) | C21—C22—C23—C18 | −1.1 (3) |
C2—C7—C8—C9 | 19.0 (2) | C19—C18—C23—C22 | 1.5 (3) |
C6—C7—C8—C9 | −161.53 (17) | C10—C18—C23—C22 | 174.74 (19) |
C1—N1—C9—C8 | 71.30 (19) | N1—C1—C24—C29 | −100.9 (2) |
C1—N1—C9—C10 | −162.95 (14) | C2—C1—C24—C29 | 24.2 (3) |
C7—C8—C9—N1 | −51.7 (2) | N1—C1—C24—C25 | 75.9 (2) |
C7—C8—C9—C10 | −176.70 (15) | C2—C1—C24—C25 | −158.95 (19) |
C11—O3—C10—C18 | −51.5 (2) | C29—C24—C25—C26 | 0.7 (3) |
C11—O3—C10—C12 | 74.29 (19) | C1—C24—C25—C26 | −176.2 (2) |
C11—O3—C10—C9 | −169.37 (15) | C24—C25—C26—C27 | −0.7 (4) |
N1—C9—C10—O3 | 171.51 (15) | C25—C26—C27—C28 | 0.4 (4) |
C8—C9—C10—O3 | −66.28 (18) | C26—C27—C28—C29 | −0.3 (4) |
N1—C9—C10—C18 | 56.2 (2) | C25—C24—C29—C28 | −0.6 (3) |
C8—C9—C10—C18 | 178.38 (16) | C1—C24—C29—C28 | 176.2 (2) |
N1—C9—C10—C12 | −71.52 (19) | C27—C28—C29—C24 | 0.4 (4) |
C8—C9—C10—C12 | 50.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···Cgi | 0.98 | 2.57 | 3.45 (2) | 150 |
C30—H30A···O1ii | 0.98 | 2.54 | 3.356 (2) | 140 |
C30—H30A···O2ii | 0.98 | 2.59 | 3.400 (2) | 140 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y−1/2, −z+1. |
C40H43NO3Si | F(000) = 1312 |
Mr = 613.84 | Dx = 1.217 Mg m−3 |
Monoclinic, P21 | Melting point: 459 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 11.045 (10) Å | Cell parameters from 37993 reflections |
b = 17.008 (15) Å | θ = 1.9–29.0° |
c = 18.489 (15) Å | µ = 0.11 mm−1 |
β = 105.287 (15)° | T = 100 K |
V = 3350 (5) Å3 | Flat, colourless |
Z = 4 | 0.22 × 0.12 × 0.10 mm |
Bruker APEXII DUO diffractometer | 17263 independent reflections |
Radiation source: fine-focus sealed tube | 11255 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
0.5° ϕ scans and ω | θmax = 29.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −14→14 |
Tmin = 0.976, Tmax = 0.989 | k = −22→23 |
37993 measured reflections | l = −24→25 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.057 | w = 1/[σ2(Fo2) + (0.0476P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.124 | (Δ/σ)max = 0.001 |
S = 0.99 | Δρmax = 0.38 e Å−3 |
17263 reflections | Δρmin = −0.41 e Å−3 |
812 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0031 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.00 (10) |
C40H43NO3Si | V = 3350 (5) Å3 |
Mr = 613.84 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.045 (10) Å | µ = 0.11 mm−1 |
b = 17.008 (15) Å | T = 100 K |
c = 18.489 (15) Å | 0.22 × 0.12 × 0.10 mm |
β = 105.287 (15)° |
Bruker APEXII DUO diffractometer | 17263 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | 11255 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.989 | Rint = 0.064 |
37993 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.124 | Δρmax = 0.38 e Å−3 |
S = 0.99 | Δρmin = −0.41 e Å−3 |
17263 reflections | Absolute structure: Flack (1983) |
812 parameters | Absolute structure parameter: 0.00 (10) |
1 restraint |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. For both crystals, X-ray diffraction data were collected on a Bruker APEXII Duo diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Data collection was carried out at 173 (2) K and 100 (2) K for structures (I) and (II), respectively, to minimize thermal motion effects. Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). Cell refinement and data reduction were performed using the program SAINT (Bruker, 2006). The data were scaled and empirical absorption corrections were performed using SADABS (Bruker, 2006). The structure was solved by direct methods using SHELXS97 (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F2 using SHELXL97 (Sheldrick, 2008). All non-H atoms were refined anisotropically. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Si1A | 1.33135 (7) | 0.65151 (5) | 0.94622 (4) | 0.02577 (17) | |
O1A | 0.53787 (16) | 0.84257 (11) | 0.86009 (10) | 0.0312 (4) | |
O2A | 0.59340 (16) | 0.70165 (11) | 0.82795 (10) | 0.0296 (4) | |
O3A | 1.30017 (16) | 0.73494 (10) | 0.98233 (10) | 0.0248 (4) | |
N1A | 1.11113 (19) | 0.87142 (13) | 0.99536 (11) | 0.0226 (5) | |
C1A | 0.9826 (2) | 0.89809 (16) | 0.99376 (15) | 0.0233 (6) | |
H1A | 0.9701 | 0.9502 | 0.9678 | 0.028* | |
C2A | 0.8812 (2) | 0.84407 (16) | 0.94961 (13) | 0.0225 (5) | |
C3A | 0.7568 (2) | 0.87099 (17) | 0.92318 (14) | 0.0253 (6) | |
H3A | 0.7379 | 0.9240 | 0.9320 | 0.030* | |
C4A | 0.6618 (2) | 0.82236 (16) | 0.88484 (14) | 0.0239 (6) | |
C5A | 0.6912 (2) | 0.74529 (16) | 0.86895 (14) | 0.0249 (6) | |
C6A | 0.8132 (2) | 0.71878 (16) | 0.89415 (14) | 0.0247 (6) | |
H6A | 0.8328 | 0.6665 | 0.8831 | 0.030* | |
C7A | 0.9088 (2) | 0.76756 (16) | 0.93568 (14) | 0.0243 (6) | |
C8A | 1.0403 (2) | 0.73529 (16) | 0.96360 (15) | 0.0249 (6) | |
H8A1 | 1.0771 | 0.7285 | 0.9206 | 0.030* | |
H8A2 | 1.0367 | 0.6830 | 0.9864 | 0.030* | |
C9A | 1.1248 (2) | 0.78935 (16) | 1.02147 (15) | 0.0241 (6) | |
H9A | 1.0921 | 0.7874 | 1.0670 | 0.029* | |
C10A | 1.2633 (2) | 0.76114 (16) | 1.04698 (14) | 0.0226 (5) | |
C11A | 1.1400 (2) | 0.88310 (16) | 0.92310 (14) | 0.0263 (6) | |
H11A | 1.0752 | 0.8563 | 0.8835 | 0.032* | |
H11B | 1.2217 | 0.8580 | 0.9251 | 0.032* | |
C12A | 1.1459 (2) | 0.96783 (17) | 0.90178 (14) | 0.0256 (6) | |
C13A | 1.1142 (3) | 0.98735 (19) | 0.82648 (16) | 0.0365 (7) | |
H13A | 1.0881 | 0.9475 | 0.7896 | 0.044* | |
C14A | 1.1205 (3) | 1.0649 (2) | 0.80471 (18) | 0.0468 (8) | |
H14A | 1.1005 | 1.0775 | 0.7528 | 0.056* | |
C15A | 1.1551 (3) | 1.1236 (2) | 0.85646 (19) | 0.0443 (8) | |
H15A | 1.1565 | 1.1768 | 0.8409 | 0.053* | |
C16A | 1.1876 (3) | 1.10468 (18) | 0.93105 (18) | 0.0365 (7) | |
H16A | 1.2122 | 1.1449 | 0.9676 | 0.044* | |
C17A | 1.1848 (3) | 1.02749 (18) | 0.95335 (16) | 0.0336 (7) | |
H17A | 1.2102 | 1.0151 | 1.0053 | 0.040* | |
C18A | 0.9739 (2) | 0.91196 (16) | 1.07361 (14) | 0.0249 (6) | |
C19A | 1.0499 (3) | 0.96910 (19) | 1.11667 (16) | 0.0362 (7) | |
H19A | 1.1068 | 0.9978 | 1.0962 | 0.043* | |
C20A | 1.0438 (3) | 0.9848 (2) | 1.18886 (17) | 0.0411 (8) | |
H20A | 1.0970 | 1.0238 | 1.2175 | 0.049* | |
C21A | 0.9622 (3) | 0.9449 (2) | 1.21979 (16) | 0.0404 (8) | |
H21A | 0.9573 | 0.9567 | 1.2692 | 0.048* | |
C22A | 0.8871 (3) | 0.88726 (19) | 1.17808 (16) | 0.0353 (7) | |
H22A | 0.8308 | 0.8586 | 1.1991 | 0.042* | |
C23A | 0.8935 (2) | 0.87094 (17) | 1.10526 (15) | 0.0280 (6) | |
H23A | 0.8416 | 0.8310 | 1.0772 | 0.034* | |
C24A | 0.5037 (3) | 0.91827 (17) | 0.88058 (17) | 0.0340 (7) | |
H24A | 0.4133 | 0.9261 | 0.8598 | 0.051* | |
H24B | 0.5497 | 0.9586 | 0.8608 | 0.051* | |
H24C | 0.5245 | 0.9224 | 0.9353 | 0.051* | |
C25A | 0.6170 (3) | 0.62008 (16) | 0.81876 (15) | 0.0293 (6) | |
H25A | 0.5404 | 0.5949 | 0.7887 | 0.044* | |
H25B | 0.6431 | 0.5948 | 0.8681 | 0.044* | |
H25C | 0.6839 | 0.6146 | 0.7932 | 0.044* | |
C26A | 1.3508 (2) | 0.82724 (15) | 1.08281 (14) | 0.0242 (6) | |
C27A | 1.3299 (3) | 0.86698 (17) | 1.14408 (15) | 0.0299 (6) | |
H27A | 1.2573 | 0.8555 | 1.1605 | 0.036* | |
C28A | 1.4142 (3) | 0.92320 (17) | 1.18143 (17) | 0.0363 (7) | |
H28A | 1.3989 | 0.9503 | 1.2230 | 0.044* | |
C29A | 1.5203 (3) | 0.93986 (18) | 1.15842 (19) | 0.0402 (8) | |
H29A | 1.5789 | 0.9776 | 1.1847 | 0.048* | |
C30A | 1.5407 (3) | 0.90201 (18) | 1.0979 (2) | 0.0411 (8) | |
H30A | 1.6134 | 0.9141 | 1.0817 | 0.049* | |
C31A | 1.4568 (2) | 0.84619 (17) | 1.05963 (17) | 0.0324 (6) | |
H31A | 1.4720 | 0.8206 | 1.0172 | 0.039* | |
C32A | 1.2823 (2) | 0.69397 (15) | 1.10513 (14) | 0.0238 (6) | |
C33A | 1.1858 (3) | 0.65404 (18) | 1.12427 (14) | 0.0300 (6) | |
H33A | 1.1013 | 0.6698 | 1.1031 | 0.036* | |
C34A | 1.2113 (3) | 0.59145 (17) | 1.17387 (17) | 0.0354 (7) | |
H34A | 1.1440 | 0.5637 | 1.1854 | 0.042* | |
C35A | 1.3331 (3) | 0.56905 (18) | 1.20664 (16) | 0.0381 (7) | |
H35A | 1.3499 | 0.5262 | 1.2408 | 0.046* | |
C36A | 1.4316 (3) | 0.60949 (16) | 1.18957 (15) | 0.0321 (7) | |
H36A | 1.5161 | 0.5948 | 1.2123 | 0.039* | |
C37A | 1.4053 (2) | 0.67123 (17) | 1.13930 (14) | 0.0283 (6) | |
H37A | 1.4727 | 0.6988 | 1.1278 | 0.034* | |
C38A | 1.2849 (3) | 0.6699 (2) | 0.84373 (14) | 0.0399 (8) | |
H38A | 1.3319 | 0.7150 | 0.8323 | 0.060* | |
H38B | 1.1948 | 0.6812 | 0.8274 | 0.060* | |
H38C | 1.3035 | 0.6233 | 0.8174 | 0.060* | |
C39A | 1.5018 (3) | 0.6298 (2) | 0.97843 (17) | 0.0385 (7) | |
H39A | 1.5495 | 0.6748 | 0.9673 | 0.058* | |
H39B | 1.5207 | 0.5831 | 0.9524 | 0.058* | |
H39C | 1.5252 | 0.6202 | 1.0326 | 0.058* | |
C40A | 1.2444 (3) | 0.56648 (18) | 0.96826 (18) | 0.0385 (7) | |
H40A | 1.2695 | 0.5569 | 1.0224 | 0.058* | |
H40B | 1.2633 | 0.5199 | 0.9419 | 0.058* | |
H40C | 1.1541 | 0.5773 | 0.9521 | 0.058* | |
Si1B | 0.38084 (8) | 0.66516 (6) | 0.54431 (4) | 0.0387 (2) | |
O1B | −0.32660 (18) | 0.48951 (12) | 0.64426 (11) | 0.0372 (5) | |
O2B | −0.2299 (2) | 0.62700 (12) | 0.67946 (11) | 0.0388 (5) | |
O3B | 0.31506 (17) | 0.58420 (12) | 0.50317 (10) | 0.0328 (5) | |
N1B | 0.1118 (2) | 0.45253 (14) | 0.49797 (12) | 0.0270 (5) | |
C1B | −0.0135 (2) | 0.42695 (17) | 0.50334 (14) | 0.0262 (6) | |
H1B | −0.0002 | 0.3765 | 0.5321 | 0.031* | |
C2B | −0.0730 (2) | 0.48319 (17) | 0.54735 (14) | 0.0271 (6) | |
C3B | −0.1721 (2) | 0.45851 (17) | 0.57508 (15) | 0.0281 (6) | |
H3B | −0.2029 | 0.4064 | 0.5651 | 0.034* | |
C4B | −0.2268 (3) | 0.50776 (17) | 0.61670 (15) | 0.0288 (6) | |
C5B | −0.1769 (3) | 0.58327 (17) | 0.63382 (15) | 0.0321 (7) | |
C6B | −0.0803 (3) | 0.60837 (18) | 0.60552 (15) | 0.0306 (6) | |
H6B | −0.0477 | 0.6599 | 0.6168 | 0.037* | |
C7B | −0.0289 (2) | 0.55947 (17) | 0.56035 (14) | 0.0268 (6) | |
C8B | 0.0742 (3) | 0.59037 (17) | 0.52872 (16) | 0.0303 (6) | |
H8B1 | 0.1514 | 0.5977 | 0.5699 | 0.036* | |
H8B2 | 0.0493 | 0.6423 | 0.5052 | 0.036* | |
C9B | 0.1011 (2) | 0.53415 (17) | 0.47056 (15) | 0.0268 (6) | |
H9B | 0.0256 | 0.5358 | 0.4266 | 0.032* | |
C10B | 0.2137 (2) | 0.56176 (17) | 0.44107 (14) | 0.0271 (6) | |
C11B | 0.2086 (3) | 0.44284 (18) | 0.56911 (15) | 0.0334 (7) | |
H11C | 0.1820 | 0.4717 | 0.6088 | 0.040* | |
H11D | 0.2874 | 0.4672 | 0.5641 | 0.040* | |
C12B | 0.2349 (2) | 0.35864 (18) | 0.59348 (16) | 0.0319 (7) | |
C13B | 0.2207 (3) | 0.2966 (2) | 0.54393 (18) | 0.0439 (8) | |
H13B | 0.1935 | 0.3060 | 0.4915 | 0.053* | |
C14B | 0.2460 (3) | 0.2202 (2) | 0.5705 (2) | 0.0520 (9) | |
H14B | 0.2324 | 0.1775 | 0.5362 | 0.062* | |
C15B | 0.2902 (3) | 0.2060 (2) | 0.6456 (2) | 0.0588 (10) | |
H15B | 0.3084 | 0.1538 | 0.6634 | 0.071* | |
C16B | 0.3079 (3) | 0.2670 (2) | 0.6944 (2) | 0.0572 (10) | |
H16B | 0.3405 | 0.2575 | 0.7466 | 0.069* | |
C17B | 0.2793 (3) | 0.3423 (2) | 0.66951 (17) | 0.0433 (8) | |
H17B | 0.2899 | 0.3840 | 0.7048 | 0.052* | |
C18B | −0.0976 (2) | 0.40728 (16) | 0.42588 (15) | 0.0268 (6) | |
C19B | −0.0678 (3) | 0.3434 (2) | 0.38787 (17) | 0.0411 (8) | |
H19B | 0.0082 | 0.3157 | 0.4083 | 0.049* | |
C20B | −0.1469 (3) | 0.3190 (2) | 0.32044 (18) | 0.0504 (9) | |
H20B | −0.1257 | 0.2740 | 0.2959 | 0.061* | |
C21B | −0.2553 (3) | 0.3592 (2) | 0.28871 (18) | 0.0458 (8) | |
H21B | −0.3104 | 0.3414 | 0.2431 | 0.055* | |
C22B | −0.2835 (3) | 0.4254 (2) | 0.32355 (17) | 0.0429 (8) | |
H22B | −0.3563 | 0.4553 | 0.3009 | 0.051* | |
C23B | −0.2048 (3) | 0.44862 (19) | 0.39232 (16) | 0.0345 (7) | |
H23B | −0.2256 | 0.4940 | 0.4165 | 0.041* | |
C24B | −0.3904 (3) | 0.4183 (2) | 0.61850 (19) | 0.0423 (8) | |
H24D | −0.4600 | 0.4114 | 0.6416 | 0.063* | |
H24E | −0.3320 | 0.3741 | 0.6322 | 0.063* | |
H24F | −0.4233 | 0.4203 | 0.5639 | 0.063* | |
C25B | −0.1827 (4) | 0.70334 (19) | 0.6976 (2) | 0.0527 (10) | |
H25D | −0.2281 | 0.7286 | 0.7302 | 0.079* | |
H25E | −0.1938 | 0.7342 | 0.6515 | 0.079* | |
H25F | −0.0932 | 0.7004 | 0.7236 | 0.079* | |
C26B | 0.2586 (2) | 0.49462 (17) | 0.39940 (14) | 0.0270 (6) | |
C27B | 0.3819 (3) | 0.4690 (2) | 0.42015 (18) | 0.0404 (8) | |
H27B | 0.4389 | 0.4908 | 0.4632 | 0.048* | |
C28B | 0.4227 (3) | 0.4120 (2) | 0.3787 (2) | 0.0492 (9) | |
H28B | 0.5072 | 0.3942 | 0.3939 | 0.059* | |
C29B | 0.3414 (3) | 0.38082 (19) | 0.3155 (2) | 0.0478 (9) | |
H29B | 0.3699 | 0.3425 | 0.2865 | 0.057* | |
C30B | 0.2189 (3) | 0.40568 (17) | 0.29503 (18) | 0.0385 (7) | |
H30B | 0.1622 | 0.3837 | 0.2520 | 0.046* | |
C31B | 0.1773 (3) | 0.46200 (17) | 0.33600 (15) | 0.0306 (6) | |
H31B | 0.0923 | 0.4788 | 0.3209 | 0.037* | |
C32B | 0.1799 (3) | 0.63189 (16) | 0.38652 (14) | 0.0275 (6) | |
C33B | 0.2748 (3) | 0.65991 (18) | 0.35603 (15) | 0.0317 (6) | |
H33B | 0.3541 | 0.6344 | 0.3681 | 0.038* | |
C34B | 0.2547 (3) | 0.72437 (18) | 0.30844 (16) | 0.0370 (7) | |
H34B | 0.3199 | 0.7426 | 0.2879 | 0.044* | |
C35B | 0.1408 (3) | 0.76182 (18) | 0.29110 (17) | 0.0392 (7) | |
H35B | 0.1274 | 0.8067 | 0.2593 | 0.047* | |
C36B | 0.0459 (3) | 0.73433 (18) | 0.31978 (17) | 0.0373 (7) | |
H36B | −0.0333 | 0.7601 | 0.3073 | 0.045* | |
C37B | 0.0649 (3) | 0.66940 (18) | 0.36666 (15) | 0.0322 (6) | |
H37B | −0.0019 | 0.6504 | 0.3854 | 0.039* | |
C38B | 0.4147 (4) | 0.6441 (3) | 0.64494 (17) | 0.0623 (11) | |
H38D | 0.4661 | 0.5965 | 0.6565 | 0.093* | |
H38E | 0.3358 | 0.6362 | 0.6587 | 0.093* | |
H38F | 0.4604 | 0.6885 | 0.6734 | 0.093* | |
C39B | 0.5308 (3) | 0.6801 (3) | 0.5205 (2) | 0.0605 (10) | |
H39D | 0.5145 | 0.6916 | 0.4668 | 0.091* | |
H39E | 0.5819 | 0.6324 | 0.5323 | 0.091* | |
H39F | 0.5759 | 0.7243 | 0.5495 | 0.091* | |
C40B | 0.2853 (3) | 0.7554 (2) | 0.52123 (19) | 0.0472 (8) | |
H40D | 0.2670 | 0.7655 | 0.4672 | 0.071* | |
H40E | 0.3318 | 0.8000 | 0.5488 | 0.071* | |
H40F | 0.2065 | 0.7486 | 0.5354 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1A | 0.0261 (4) | 0.0277 (4) | 0.0248 (4) | 0.0030 (3) | 0.0089 (3) | 0.0001 (3) |
O1A | 0.0248 (10) | 0.0287 (11) | 0.0363 (11) | 0.0017 (8) | 0.0015 (8) | −0.0033 (9) |
O2A | 0.0277 (10) | 0.0255 (11) | 0.0319 (10) | −0.0064 (8) | 0.0014 (8) | −0.0046 (9) |
O3A | 0.0300 (10) | 0.0221 (10) | 0.0256 (9) | 0.0008 (8) | 0.0132 (8) | 0.0011 (8) |
N1A | 0.0235 (11) | 0.0215 (12) | 0.0224 (10) | 0.0010 (9) | 0.0056 (8) | 0.0012 (9) |
C1A | 0.0227 (13) | 0.0202 (15) | 0.0266 (13) | −0.0020 (11) | 0.0054 (10) | 0.0004 (11) |
C2A | 0.0261 (13) | 0.0224 (15) | 0.0197 (12) | −0.0041 (11) | 0.0073 (10) | −0.0018 (11) |
C3A | 0.0293 (14) | 0.0226 (15) | 0.0247 (13) | 0.0013 (11) | 0.0083 (11) | 0.0007 (11) |
C4A | 0.0228 (13) | 0.0272 (16) | 0.0215 (12) | −0.0010 (11) | 0.0056 (10) | 0.0002 (11) |
C5A | 0.0251 (13) | 0.0278 (16) | 0.0219 (13) | −0.0049 (11) | 0.0066 (10) | 0.0013 (11) |
C6A | 0.0290 (14) | 0.0228 (15) | 0.0225 (13) | 0.0003 (11) | 0.0073 (11) | −0.0032 (11) |
C7A | 0.0267 (13) | 0.0262 (15) | 0.0210 (13) | −0.0010 (11) | 0.0083 (10) | 0.0012 (11) |
C8A | 0.0243 (13) | 0.0243 (15) | 0.0282 (13) | −0.0018 (11) | 0.0104 (11) | −0.0038 (12) |
C9A | 0.0251 (13) | 0.0210 (15) | 0.0276 (14) | −0.0027 (11) | 0.0093 (11) | 0.0007 (12) |
C10A | 0.0232 (13) | 0.0223 (14) | 0.0244 (13) | −0.0011 (11) | 0.0101 (10) | −0.0024 (11) |
C11A | 0.0297 (14) | 0.0250 (15) | 0.0248 (13) | −0.0013 (12) | 0.0080 (11) | 0.0006 (12) |
C12A | 0.0209 (13) | 0.0284 (16) | 0.0279 (14) | −0.0007 (11) | 0.0072 (11) | 0.0004 (12) |
C13A | 0.0453 (18) | 0.0342 (18) | 0.0277 (15) | −0.0014 (14) | 0.0055 (13) | 0.0040 (13) |
C14A | 0.066 (2) | 0.040 (2) | 0.0291 (16) | 0.0030 (17) | 0.0042 (15) | 0.0107 (15) |
C15A | 0.0494 (19) | 0.0308 (18) | 0.0496 (19) | −0.0036 (15) | 0.0079 (15) | 0.0107 (16) |
C16A | 0.0380 (17) | 0.0300 (18) | 0.0415 (17) | −0.0095 (13) | 0.0106 (14) | −0.0034 (14) |
C17A | 0.0351 (16) | 0.0354 (18) | 0.0294 (15) | −0.0069 (13) | 0.0069 (12) | 0.0019 (13) |
C18A | 0.0255 (13) | 0.0220 (15) | 0.0261 (13) | 0.0031 (11) | 0.0050 (11) | −0.0017 (11) |
C19A | 0.0361 (16) | 0.0366 (18) | 0.0358 (16) | −0.0037 (14) | 0.0093 (13) | −0.0057 (14) |
C20A | 0.0429 (18) | 0.044 (2) | 0.0342 (16) | −0.0063 (15) | 0.0059 (14) | −0.0171 (15) |
C21A | 0.0430 (17) | 0.051 (2) | 0.0270 (15) | 0.0102 (16) | 0.0080 (13) | −0.0075 (15) |
C22A | 0.0344 (16) | 0.042 (2) | 0.0316 (15) | 0.0051 (14) | 0.0119 (12) | 0.0060 (14) |
C23A | 0.0304 (14) | 0.0251 (16) | 0.0273 (14) | 0.0013 (12) | 0.0054 (11) | −0.0005 (12) |
C24A | 0.0271 (14) | 0.0266 (16) | 0.0455 (17) | −0.0011 (12) | 0.0048 (13) | −0.0026 (14) |
C25A | 0.0325 (15) | 0.0279 (16) | 0.0273 (14) | −0.0068 (12) | 0.0075 (12) | −0.0034 (12) |
C26A | 0.0244 (13) | 0.0211 (15) | 0.0255 (13) | 0.0013 (11) | 0.0037 (10) | 0.0048 (11) |
C27A | 0.0294 (14) | 0.0267 (16) | 0.0307 (14) | −0.0016 (12) | 0.0029 (11) | 0.0014 (12) |
C28A | 0.0450 (17) | 0.0231 (16) | 0.0359 (16) | 0.0001 (13) | 0.0019 (13) | −0.0007 (13) |
C29A | 0.0320 (16) | 0.0238 (17) | 0.055 (2) | −0.0078 (13) | −0.0058 (14) | 0.0012 (15) |
C30A | 0.0288 (15) | 0.0265 (18) | 0.067 (2) | −0.0047 (13) | 0.0104 (15) | 0.0064 (16) |
C31A | 0.0263 (14) | 0.0263 (16) | 0.0450 (17) | −0.0035 (12) | 0.0099 (12) | 0.0037 (14) |
C32A | 0.0317 (14) | 0.0169 (14) | 0.0226 (13) | −0.0023 (11) | 0.0070 (11) | −0.0032 (10) |
C33A | 0.0362 (15) | 0.0270 (16) | 0.0299 (14) | −0.0058 (13) | 0.0142 (11) | −0.0006 (13) |
C34A | 0.0496 (18) | 0.0234 (16) | 0.0405 (16) | −0.0034 (14) | 0.0247 (14) | 0.0034 (13) |
C35A | 0.061 (2) | 0.0254 (17) | 0.0297 (15) | 0.0039 (15) | 0.0152 (14) | 0.0044 (13) |
C36A | 0.0431 (17) | 0.0200 (16) | 0.0307 (15) | 0.0023 (13) | 0.0053 (13) | 0.0004 (12) |
C37A | 0.0317 (14) | 0.0250 (16) | 0.0277 (13) | −0.0042 (12) | 0.0072 (11) | −0.0005 (12) |
C38A | 0.0474 (18) | 0.046 (2) | 0.0241 (14) | 0.0100 (16) | 0.0065 (12) | 0.0006 (14) |
C39A | 0.0319 (15) | 0.047 (2) | 0.0391 (16) | 0.0116 (14) | 0.0135 (13) | 0.0041 (15) |
C40A | 0.0439 (17) | 0.0254 (17) | 0.0500 (19) | 0.0005 (14) | 0.0191 (15) | −0.0037 (15) |
Si1B | 0.0361 (4) | 0.0450 (6) | 0.0311 (4) | −0.0035 (4) | 0.0022 (3) | −0.0033 (4) |
O1B | 0.0424 (12) | 0.0347 (13) | 0.0427 (12) | 0.0006 (10) | 0.0256 (10) | 0.0028 (10) |
O2B | 0.0571 (13) | 0.0303 (12) | 0.0369 (11) | 0.0082 (10) | 0.0264 (10) | 0.0011 (9) |
O3B | 0.0280 (10) | 0.0446 (13) | 0.0226 (9) | −0.0032 (9) | 0.0009 (8) | 0.0003 (9) |
N1B | 0.0275 (11) | 0.0311 (14) | 0.0223 (11) | 0.0023 (10) | 0.0067 (9) | 0.0001 (10) |
C1B | 0.0303 (13) | 0.0250 (15) | 0.0239 (13) | 0.0020 (12) | 0.0083 (10) | 0.0006 (12) |
C2B | 0.0294 (14) | 0.0284 (16) | 0.0227 (13) | 0.0032 (12) | 0.0057 (11) | 0.0001 (12) |
C3B | 0.0311 (14) | 0.0263 (16) | 0.0278 (14) | 0.0009 (12) | 0.0093 (11) | 0.0008 (12) |
C4B | 0.0305 (14) | 0.0338 (18) | 0.0255 (13) | 0.0057 (12) | 0.0136 (11) | 0.0061 (12) |
C5B | 0.0429 (17) | 0.0302 (17) | 0.0263 (14) | 0.0110 (13) | 0.0146 (12) | 0.0029 (12) |
C6B | 0.0391 (16) | 0.0282 (17) | 0.0264 (14) | 0.0003 (13) | 0.0123 (12) | −0.0001 (12) |
C7B | 0.0313 (14) | 0.0289 (16) | 0.0221 (13) | 0.0001 (12) | 0.0102 (11) | −0.0005 (12) |
C8B | 0.0336 (15) | 0.0277 (16) | 0.0319 (14) | −0.0046 (12) | 0.0129 (12) | −0.0055 (13) |
C9B | 0.0252 (14) | 0.0301 (16) | 0.0254 (13) | −0.0006 (12) | 0.0073 (11) | −0.0040 (12) |
C10B | 0.0235 (13) | 0.0348 (17) | 0.0221 (13) | −0.0031 (12) | 0.0045 (10) | −0.0023 (12) |
C11B | 0.0339 (15) | 0.0420 (19) | 0.0223 (13) | 0.0013 (13) | 0.0040 (11) | −0.0029 (13) |
C12B | 0.0251 (14) | 0.0366 (18) | 0.0328 (15) | 0.0023 (13) | 0.0055 (12) | 0.0011 (13) |
C13B | 0.0461 (19) | 0.044 (2) | 0.0371 (17) | 0.0172 (16) | 0.0031 (14) | −0.0041 (16) |
C14B | 0.047 (2) | 0.047 (2) | 0.058 (2) | 0.0106 (17) | 0.0059 (17) | −0.0102 (19) |
C15B | 0.058 (2) | 0.054 (3) | 0.061 (2) | 0.0184 (19) | 0.0101 (19) | 0.015 (2) |
C16B | 0.066 (2) | 0.067 (3) | 0.0361 (19) | 0.010 (2) | 0.0094 (17) | 0.015 (2) |
C17B | 0.0442 (18) | 0.054 (2) | 0.0298 (15) | 0.0042 (16) | 0.0071 (13) | 0.0048 (16) |
C18B | 0.0276 (14) | 0.0266 (16) | 0.0275 (14) | −0.0030 (12) | 0.0097 (11) | −0.0028 (12) |
C19B | 0.0357 (16) | 0.045 (2) | 0.0382 (16) | 0.0070 (15) | 0.0014 (13) | −0.0083 (15) |
C20B | 0.057 (2) | 0.049 (2) | 0.0388 (18) | 0.0030 (17) | 0.0020 (16) | −0.0164 (16) |
C21B | 0.0474 (19) | 0.051 (2) | 0.0333 (16) | −0.0082 (17) | 0.0016 (14) | −0.0050 (16) |
C22B | 0.0383 (17) | 0.053 (2) | 0.0334 (16) | 0.0078 (16) | 0.0020 (13) | 0.0083 (16) |
C23B | 0.0373 (16) | 0.0371 (19) | 0.0294 (14) | 0.0043 (14) | 0.0095 (12) | 0.0000 (13) |
C24B | 0.0363 (16) | 0.045 (2) | 0.0494 (19) | −0.0015 (15) | 0.0189 (14) | 0.0072 (16) |
C25B | 0.093 (3) | 0.030 (2) | 0.052 (2) | 0.0032 (18) | 0.048 (2) | −0.0019 (16) |
C26B | 0.0286 (14) | 0.0295 (16) | 0.0254 (13) | 0.0016 (12) | 0.0113 (11) | 0.0050 (12) |
C27B | 0.0375 (17) | 0.046 (2) | 0.0383 (17) | 0.0103 (15) | 0.0111 (14) | 0.0064 (15) |
C28B | 0.0470 (19) | 0.044 (2) | 0.063 (2) | 0.0194 (17) | 0.0255 (18) | 0.0134 (19) |
C29B | 0.068 (2) | 0.0264 (19) | 0.064 (2) | 0.0080 (17) | 0.044 (2) | 0.0017 (17) |
C30B | 0.056 (2) | 0.0257 (17) | 0.0398 (17) | −0.0032 (15) | 0.0226 (15) | −0.0018 (14) |
C31B | 0.0315 (15) | 0.0291 (16) | 0.0329 (15) | 0.0039 (12) | 0.0119 (12) | 0.0041 (13) |
C32B | 0.0386 (15) | 0.0235 (16) | 0.0199 (12) | −0.0044 (12) | 0.0069 (11) | −0.0063 (11) |
C33B | 0.0352 (15) | 0.0296 (16) | 0.0311 (14) | 0.0047 (13) | 0.0101 (11) | −0.0016 (13) |
C34B | 0.0508 (19) | 0.0323 (18) | 0.0308 (15) | −0.0063 (15) | 0.0160 (14) | −0.0001 (14) |
C35B | 0.054 (2) | 0.0253 (17) | 0.0379 (17) | −0.0001 (15) | 0.0119 (15) | 0.0013 (14) |
C36B | 0.0400 (17) | 0.0317 (18) | 0.0372 (16) | 0.0014 (14) | 0.0050 (13) | −0.0034 (14) |
C37B | 0.0344 (15) | 0.0322 (17) | 0.0308 (14) | −0.0008 (13) | 0.0100 (11) | −0.0017 (13) |
C38B | 0.070 (2) | 0.076 (3) | 0.0331 (17) | −0.003 (2) | 0.0000 (16) | −0.0083 (19) |
C39B | 0.0418 (19) | 0.066 (3) | 0.066 (2) | −0.0136 (18) | 0.0020 (17) | −0.001 (2) |
C40B | 0.056 (2) | 0.041 (2) | 0.0415 (18) | 0.0014 (16) | 0.0073 (15) | −0.0086 (16) |
Si1A—O3A | 1.643 (2) | Si1B—O3B | 1.647 (2) |
Si1A—C40A | 1.840 (3) | Si1B—C38B | 1.834 (4) |
Si1A—C38A | 1.855 (3) | Si1B—C39B | 1.841 (4) |
Si1A—C39A | 1.856 (3) | Si1B—C40B | 1.848 (4) |
O1A—C4A | 1.368 (3) | O1B—C4B | 1.366 (3) |
O1A—C24A | 1.421 (4) | O1B—C24B | 1.419 (4) |
O2A—C5A | 1.364 (3) | O2B—C5B | 1.367 (3) |
O2A—C25A | 1.430 (3) | O2B—C25B | 1.406 (4) |
O3A—C10A | 1.432 (3) | O3B—C10B | 1.428 (3) |
N1A—C11A | 1.467 (3) | N1B—C11B | 1.469 (3) |
N1A—C9A | 1.472 (4) | N1B—C9B | 1.472 (4) |
N1A—C1A | 1.483 (3) | N1B—C1B | 1.479 (4) |
C1A—C2A | 1.511 (4) | C1B—C2B | 1.513 (4) |
C1A—C18A | 1.523 (4) | C1B—C18B | 1.524 (4) |
C1A—H1A | 1.0000 | C1B—H1B | 1.0000 |
C2A—C7A | 1.376 (4) | C2B—C7B | 1.384 (4) |
C2A—C3A | 1.409 (4) | C2B—C3B | 1.390 (4) |
C3A—C4A | 1.376 (4) | C3B—C4B | 1.380 (4) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.400 (4) | C4B—C5B | 1.401 (4) |
C5A—C6A | 1.380 (4) | C5B—C6B | 1.374 (4) |
C6A—C7A | 1.402 (4) | C6B—C7B | 1.400 (4) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—C8A | 1.511 (4) | C7B—C8B | 1.505 (4) |
C8A—C9A | 1.528 (4) | C8B—C9B | 1.526 (4) |
C8A—H8A1 | 0.9900 | C8B—H8B1 | 0.9900 |
C8A—H8A2 | 0.9900 | C8B—H8B2 | 0.9900 |
C9A—C10A | 1.553 (4) | C9B—C10B | 1.556 (4) |
C9A—H9A | 1.0000 | C9B—H9B | 1.0000 |
C10A—C26A | 1.516 (4) | C10B—C26B | 1.532 (4) |
C10A—C32A | 1.545 (4) | C10B—C32B | 1.543 (4) |
C11A—C12A | 1.500 (4) | C11B—C12B | 1.507 (4) |
C11A—H11A | 0.9900 | C11B—H11C | 0.9900 |
C11A—H11B | 0.9900 | C11B—H11D | 0.9900 |
C12A—C17A | 1.381 (4) | C12B—C13B | 1.379 (4) |
C12A—C13A | 1.384 (4) | C12B—C17B | 1.389 (4) |
C13A—C14A | 1.387 (5) | C13B—C14B | 1.391 (5) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.365 (5) | C14B—C15B | 1.366 (5) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—C16A | 1.369 (4) | C15B—C16B | 1.356 (5) |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
C16A—C17A | 1.379 (4) | C16B—C17B | 1.369 (5) |
C16A—H16A | 0.9500 | C16B—H16B | 0.9500 |
C17A—H17A | 0.9500 | C17B—H17B | 0.9500 |
C18A—C23A | 1.376 (4) | C18B—C23B | 1.376 (4) |
C18A—C19A | 1.389 (4) | C18B—C19B | 1.380 (4) |
C19A—C20A | 1.380 (4) | C19B—C20B | 1.384 (4) |
C19A—H19A | 0.9500 | C19B—H19B | 0.9500 |
C20A—C21A | 1.368 (4) | C20B—C21B | 1.369 (5) |
C20A—H20A | 0.9500 | C20B—H20B | 0.9500 |
C21A—C22A | 1.380 (4) | C21B—C22B | 1.374 (5) |
C21A—H21A | 0.9500 | C21B—H21B | 0.9500 |
C22A—C23A | 1.394 (4) | C22B—C23B | 1.395 (4) |
C22A—H22A | 0.9500 | C22B—H22B | 0.9500 |
C23A—H23A | 0.9500 | C23B—H23B | 0.9500 |
C24A—H24A | 0.9800 | C24B—H24D | 0.9800 |
C24A—H24B | 0.9800 | C24B—H24E | 0.9800 |
C24A—H24C | 0.9800 | C24B—H24F | 0.9800 |
C25A—H25A | 0.9800 | C25B—H25D | 0.9800 |
C25A—H25B | 0.9800 | C25B—H25E | 0.9800 |
C25A—H25C | 0.9800 | C25B—H25F | 0.9800 |
C26A—C31A | 1.387 (4) | C26B—C27B | 1.383 (4) |
C26A—C27A | 1.390 (4) | C26B—C31B | 1.391 (4) |
C27A—C28A | 1.385 (4) | C27B—C28B | 1.383 (5) |
C27A—H27A | 0.9500 | C27B—H27B | 0.9500 |
C28A—C29A | 1.377 (5) | C28B—C29B | 1.378 (5) |
C28A—H28A | 0.9500 | C28B—H28B | 0.9500 |
C29A—C30A | 1.361 (5) | C29B—C30B | 1.372 (5) |
C29A—H29A | 0.9500 | C29B—H29B | 0.9500 |
C30A—C31A | 1.383 (4) | C30B—C31B | 1.374 (4) |
C30A—H30A | 0.9500 | C30B—H30B | 0.9500 |
C31A—H31A | 0.9500 | C31B—H31B | 0.9500 |
C32A—C33A | 1.386 (4) | C32B—C37B | 1.382 (4) |
C32A—C37A | 1.393 (4) | C32B—C33B | 1.398 (4) |
C33A—C34A | 1.385 (4) | C33B—C34B | 1.386 (4) |
C33A—H33A | 0.9500 | C33B—H33B | 0.9500 |
C34A—C35A | 1.375 (4) | C34B—C35B | 1.371 (4) |
C34A—H34A | 0.9500 | C34B—H34B | 0.9500 |
C35A—C36A | 1.392 (4) | C35B—C36B | 1.375 (4) |
C35A—H35A | 0.9500 | C35B—H35B | 0.9500 |
C36A—C37A | 1.381 (4) | C36B—C37B | 1.385 (4) |
C36A—H36A | 0.9500 | C36B—H36B | 0.9500 |
C37A—H37A | 0.9500 | C37B—H37B | 0.9500 |
C38A—H38A | 0.9800 | C38B—H38D | 0.9800 |
C38A—H38B | 0.9800 | C38B—H38E | 0.9800 |
C38A—H38C | 0.9800 | C38B—H38F | 0.9800 |
C39A—H39A | 0.9800 | C39B—H39D | 0.9800 |
C39A—H39B | 0.9800 | C39B—H39E | 0.9800 |
C39A—H39C | 0.9800 | C39B—H39F | 0.9800 |
C40A—H40A | 0.9800 | C40B—H40D | 0.9800 |
C40A—H40B | 0.9800 | C40B—H40E | 0.9800 |
C40A—H40C | 0.9800 | C40B—H40F | 0.9800 |
O3A—Si1A—C40A | 114.29 (13) | O3B—Si1B—C38B | 104.64 (16) |
O3A—Si1A—C38A | 103.77 (13) | O3B—Si1B—C39B | 108.67 (16) |
C40A—Si1A—C38A | 109.83 (15) | C38B—Si1B—C39B | 108.31 (18) |
O3A—Si1A—C39A | 110.17 (13) | O3B—Si1B—C40B | 115.63 (14) |
C40A—Si1A—C39A | 108.50 (15) | C38B—Si1B—C40B | 110.35 (18) |
C38A—Si1A—C39A | 110.21 (14) | C39B—Si1B—C40B | 108.98 (19) |
C4A—O1A—C24A | 116.8 (2) | C4B—O1B—C24B | 116.5 (2) |
C5A—O2A—C25A | 116.8 (2) | C5B—O2B—C25B | 117.2 (2) |
C10A—O3A—Si1A | 138.11 (16) | C10B—O3B—Si1B | 138.74 (19) |
C11A—N1A—C9A | 113.5 (2) | C11B—N1B—C9B | 112.8 (2) |
C11A—N1A—C1A | 112.2 (2) | C11B—N1B—C1B | 112.3 (2) |
C9A—N1A—C1A | 108.1 (2) | C9B—N1B—C1B | 108.0 (2) |
N1A—C1A—C2A | 113.2 (2) | N1B—C1B—C2B | 113.4 (2) |
N1A—C1A—C18A | 109.4 (2) | N1B—C1B—C18B | 110.5 (2) |
C2A—C1A—C18A | 113.0 (2) | C2B—C1B—C18B | 113.6 (2) |
N1A—C1A—H1A | 106.9 | N1B—C1B—H1B | 106.2 |
C2A—C1A—H1A | 106.9 | C2B—C1B—H1B | 106.2 |
C18A—C1A—H1A | 106.9 | C18B—C1B—H1B | 106.2 |
C7A—C2A—C3A | 119.1 (2) | C7B—C2B—C3B | 119.6 (3) |
C7A—C2A—C1A | 120.5 (2) | C7B—C2B—C1B | 120.2 (2) |
C3A—C2A—C1A | 120.4 (2) | C3B—C2B—C1B | 120.2 (3) |
C4A—C3A—C2A | 121.6 (3) | C4B—C3B—C2B | 121.7 (3) |
C4A—C3A—H3A | 119.2 | C4B—C3B—H3B | 119.2 |
C2A—C3A—H3A | 119.2 | C2B—C3B—H3B | 119.2 |
O1A—C4A—C3A | 125.5 (2) | O1B—C4B—C3B | 125.8 (3) |
O1A—C4A—C5A | 115.6 (2) | O1B—C4B—C5B | 115.6 (2) |
C3A—C4A—C5A | 118.9 (2) | C3B—C4B—C5B | 118.6 (3) |
O2A—C5A—C6A | 124.7 (3) | O2B—C5B—C6B | 124.6 (3) |
O2A—C5A—C4A | 115.7 (2) | O2B—C5B—C4B | 115.5 (3) |
C6A—C5A—C4A | 119.6 (2) | C6B—C5B—C4B | 119.9 (3) |
C5A—C6A—C7A | 121.3 (3) | C5B—C6B—C7B | 121.3 (3) |
C5A—C6A—H6A | 119.4 | C5B—C6B—H6B | 119.3 |
C7A—C6A—H6A | 119.4 | C7B—C6B—H6B | 119.3 |
C2A—C7A—C6A | 119.3 (2) | C2B—C7B—C6B | 118.8 (2) |
C2A—C7A—C8A | 121.3 (2) | C2B—C7B—C8B | 121.8 (2) |
C6A—C7A—C8A | 119.3 (2) | C6B—C7B—C8B | 119.4 (3) |
C7A—C8A—C9A | 112.0 (2) | C7B—C8B—C9B | 111.3 (2) |
C7A—C8A—H8A1 | 109.2 | C7B—C8B—H8B1 | 109.4 |
C9A—C8A—H8A1 | 109.2 | C9B—C8B—H8B1 | 109.4 |
C7A—C8A—H8A2 | 109.2 | C7B—C8B—H8B2 | 109.4 |
C9A—C8A—H8A2 | 109.2 | C9B—C8B—H8B2 | 109.4 |
H8A1—C8A—H8A2 | 107.9 | H8B1—C8B—H8B2 | 108.0 |
N1A—C9A—C8A | 110.5 (2) | N1B—C9B—C8B | 111.2 (2) |
N1A—C9A—C10A | 113.6 (2) | N1B—C9B—C10B | 114.0 (2) |
C8A—C9A—C10A | 113.4 (2) | C8B—C9B—C10B | 112.3 (2) |
N1A—C9A—H9A | 106.2 | N1B—C9B—H9B | 106.2 |
C8A—C9A—H9A | 106.2 | C8B—C9B—H9B | 106.2 |
C10A—C9A—H9A | 106.2 | C10B—C9B—H9B | 106.2 |
O3A—C10A—C26A | 107.9 (2) | O3B—C10B—C26B | 108.3 (2) |
O3A—C10A—C32A | 109.5 (2) | O3B—C10B—C32B | 108.8 (2) |
C26A—C10A—C32A | 106.9 (2) | C26B—C10B—C32B | 107.6 (2) |
O3A—C10A—C9A | 108.5 (2) | O3B—C10B—C9B | 109.2 (2) |
C26A—C10A—C9A | 111.5 (2) | C26B—C10B—C9B | 110.3 (2) |
C32A—C10A—C9A | 112.5 (2) | C32B—C10B—C9B | 112.6 (2) |
N1A—C11A—C12A | 113.9 (2) | N1B—C11B—C12B | 114.3 (2) |
N1A—C11A—H11A | 108.8 | N1B—C11B—H11C | 108.7 |
C12A—C11A—H11A | 108.8 | C12B—C11B—H11C | 108.7 |
N1A—C11A—H11B | 108.8 | N1B—C11B—H11D | 108.7 |
C12A—C11A—H11B | 108.8 | C12B—C11B—H11D | 108.7 |
H11A—C11A—H11B | 107.7 | H11C—C11B—H11D | 107.6 |
C17A—C12A—C13A | 117.9 (3) | C13B—C12B—C17B | 117.8 (3) |
C17A—C12A—C11A | 123.5 (2) | C13B—C12B—C11B | 123.4 (3) |
C13A—C12A—C11A | 118.6 (3) | C17B—C12B—C11B | 118.8 (3) |
C12A—C13A—C14A | 120.1 (3) | C12B—C13B—C14B | 120.2 (3) |
C12A—C13A—H13A | 119.9 | C12B—C13B—H13B | 119.9 |
C14A—C13A—H13A | 119.9 | C14B—C13B—H13B | 119.9 |
C15A—C14A—C13A | 121.2 (3) | C15B—C14B—C13B | 120.6 (4) |
C15A—C14A—H14A | 119.4 | C15B—C14B—H14B | 119.7 |
C13A—C14A—H14A | 119.4 | C13B—C14B—H14B | 119.7 |
C14A—C15A—C16A | 119.0 (3) | C16B—C15B—C14B | 119.5 (4) |
C14A—C15A—H15A | 120.5 | C16B—C15B—H15B | 120.3 |
C16A—C15A—H15A | 120.5 | C14B—C15B—H15B | 120.3 |
C15A—C16A—C17A | 120.3 (3) | C15B—C16B—C17B | 120.8 (3) |
C15A—C16A—H16A | 119.9 | C15B—C16B—H16B | 119.6 |
C17A—C16A—H16A | 119.9 | C17B—C16B—H16B | 119.6 |
C16A—C17A—C12A | 121.4 (3) | C16B—C17B—C12B | 121.1 (3) |
C16A—C17A—H17A | 119.3 | C16B—C17B—H17B | 119.5 |
C12A—C17A—H17A | 119.3 | C12B—C17B—H17B | 119.5 |
C23A—C18A—C19A | 118.1 (3) | C23B—C18B—C19B | 117.7 (3) |
C23A—C18A—C1A | 123.1 (2) | C23B—C18B—C1B | 123.4 (3) |
C19A—C18A—C1A | 118.8 (2) | C19B—C18B—C1B | 118.9 (2) |
C20A—C19A—C18A | 120.9 (3) | C18B—C19B—C20B | 121.1 (3) |
C20A—C19A—H19A | 119.6 | C18B—C19B—H19B | 119.5 |
C18A—C19A—H19A | 119.6 | C20B—C19B—H19B | 119.5 |
C21A—C20A—C19A | 121.0 (3) | C21B—C20B—C19B | 120.6 (3) |
C21A—C20A—H20A | 119.5 | C21B—C20B—H20B | 119.7 |
C19A—C20A—H20A | 119.5 | C19B—C20B—H20B | 119.7 |
C20A—C21A—C22A | 118.9 (3) | C20B—C21B—C22B | 119.3 (3) |
C20A—C21A—H21A | 120.6 | C20B—C21B—H21B | 120.4 |
C22A—C21A—H21A | 120.6 | C22B—C21B—H21B | 120.4 |
C21A—C22A—C23A | 120.3 (3) | C21B—C22B—C23B | 119.7 (3) |
C21A—C22A—H22A | 119.8 | C21B—C22B—H22B | 120.1 |
C23A—C22A—H22A | 119.8 | C23B—C22B—H22B | 120.1 |
C18A—C23A—C22A | 120.8 (3) | C18B—C23B—C22B | 121.4 (3) |
C18A—C23A—H23A | 119.6 | C18B—C23B—H23B | 119.3 |
C22A—C23A—H23A | 119.6 | C22B—C23B—H23B | 119.3 |
O1A—C24A—H24A | 109.5 | O1B—C24B—H24D | 109.5 |
O1A—C24A—H24B | 109.5 | O1B—C24B—H24E | 109.5 |
H24A—C24A—H24B | 109.5 | H24D—C24B—H24E | 109.5 |
O1A—C24A—H24C | 109.5 | O1B—C24B—H24F | 109.5 |
H24A—C24A—H24C | 109.5 | H24D—C24B—H24F | 109.5 |
H24B—C24A—H24C | 109.5 | H24E—C24B—H24F | 109.5 |
O2A—C25A—H25A | 109.5 | O2B—C25B—H25D | 109.5 |
O2A—C25A—H25B | 109.5 | O2B—C25B—H25E | 109.5 |
H25A—C25A—H25B | 109.5 | H25D—C25B—H25E | 109.5 |
O2A—C25A—H25C | 109.5 | O2B—C25B—H25F | 109.5 |
H25A—C25A—H25C | 109.5 | H25D—C25B—H25F | 109.5 |
H25B—C25A—H25C | 109.5 | H25E—C25B—H25F | 109.5 |
C31A—C26A—C27A | 118.3 (3) | C27B—C26B—C31B | 118.6 (3) |
C31A—C26A—C10A | 122.0 (2) | C27B—C26B—C10B | 121.4 (3) |
C27A—C26A—C10A | 119.6 (2) | C31B—C26B—C10B | 119.9 (2) |
C28A—C27A—C26A | 120.5 (3) | C28B—C27B—C26B | 120.5 (3) |
C28A—C27A—H27A | 119.7 | C28B—C27B—H27B | 119.7 |
C26A—C27A—H27A | 119.7 | C26B—C27B—H27B | 119.7 |
C29A—C28A—C27A | 120.2 (3) | C29B—C28B—C27B | 120.3 (3) |
C29A—C28A—H28A | 119.9 | C29B—C28B—H28B | 119.8 |
C27A—C28A—H28A | 119.9 | C27B—C28B—H28B | 119.8 |
C30A—C29A—C28A | 119.7 (3) | C30B—C29B—C28B | 119.3 (3) |
C30A—C29A—H29A | 120.1 | C30B—C29B—H29B | 120.3 |
C28A—C29A—H29A | 120.1 | C28B—C29B—H29B | 120.3 |
C29A—C30A—C31A | 120.7 (3) | C29B—C30B—C31B | 120.8 (3) |
C29A—C30A—H30A | 119.6 | C29B—C30B—H30B | 119.6 |
C31A—C30A—H30A | 119.6 | C31B—C30B—H30B | 119.6 |
C30A—C31A—C26A | 120.5 (3) | C30B—C31B—C26B | 120.5 (3) |
C30A—C31A—H31A | 119.7 | C30B—C31B—H31B | 119.8 |
C26A—C31A—H31A | 119.7 | C26B—C31B—H31B | 119.8 |
C33A—C32A—C37A | 118.1 (3) | C37B—C32B—C33B | 118.0 (3) |
C33A—C32A—C10A | 124.5 (2) | C37B—C32B—C10B | 125.2 (2) |
C37A—C32A—C10A | 117.3 (2) | C33B—C32B—C10B | 116.7 (2) |
C34A—C33A—C32A | 120.7 (3) | C34B—C33B—C32B | 121.0 (3) |
C34A—C33A—H33A | 119.7 | C34B—C33B—H33B | 119.5 |
C32A—C33A—H33A | 119.7 | C32B—C33B—H33B | 119.5 |
C35A—C34A—C33A | 120.6 (3) | C35B—C34B—C33B | 119.9 (3) |
C35A—C34A—H34A | 119.7 | C35B—C34B—H34B | 120.0 |
C33A—C34A—H34A | 119.7 | C33B—C34B—H34B | 120.0 |
C34A—C35A—C36A | 119.7 (3) | C34B—C35B—C36B | 119.9 (3) |
C34A—C35A—H35A | 120.2 | C34B—C35B—H35B | 120.1 |
C36A—C35A—H35A | 120.2 | C36B—C35B—H35B | 120.1 |
C37A—C36A—C35A | 119.3 (3) | C35B—C36B—C37B | 120.5 (3) |
C37A—C36A—H36A | 120.3 | C35B—C36B—H36B | 119.8 |
C35A—C36A—H36A | 120.3 | C37B—C36B—H36B | 119.8 |
C36A—C37A—C32A | 121.5 (3) | C32B—C37B—C36B | 120.7 (3) |
C36A—C37A—H37A | 119.2 | C32B—C37B—H37B | 119.6 |
C32A—C37A—H37A | 119.2 | C36B—C37B—H37B | 119.6 |
Si1A—C38A—H38A | 109.5 | Si1B—C38B—H38D | 109.5 |
Si1A—C38A—H38B | 109.5 | Si1B—C38B—H38E | 109.5 |
H38A—C38A—H38B | 109.5 | H38D—C38B—H38E | 109.5 |
Si1A—C38A—H38C | 109.5 | Si1B—C38B—H38F | 109.5 |
H38A—C38A—H38C | 109.5 | H38D—C38B—H38F | 109.5 |
H38B—C38A—H38C | 109.5 | H38E—C38B—H38F | 109.5 |
Si1A—C39A—H39A | 109.5 | Si1B—C39B—H39D | 109.5 |
Si1A—C39A—H39B | 109.5 | Si1B—C39B—H39E | 109.5 |
H39A—C39A—H39B | 109.5 | H39D—C39B—H39E | 109.5 |
Si1A—C39A—H39C | 109.5 | Si1B—C39B—H39F | 109.5 |
H39A—C39A—H39C | 109.5 | H39D—C39B—H39F | 109.5 |
H39B—C39A—H39C | 109.5 | H39E—C39B—H39F | 109.5 |
Si1A—C40A—H40A | 109.5 | Si1B—C40B—H40D | 109.5 |
Si1A—C40A—H40B | 109.5 | Si1B—C40B—H40E | 109.5 |
H40A—C40A—H40B | 109.5 | H40D—C40B—H40E | 109.5 |
Si1A—C40A—H40C | 109.5 | Si1B—C40B—H40F | 109.5 |
H40A—C40A—H40C | 109.5 | H40D—C40B—H40F | 109.5 |
H40B—C40A—H40C | 109.5 | H40E—C40B—H40F | 109.5 |
C40A—Si1A—O3A—C10A | 30.2 (3) | C38B—Si1B—O3B—C10B | 138.9 (3) |
C38A—Si1A—O3A—C10A | 149.7 (2) | C39B—Si1B—O3B—C10B | −105.6 (3) |
C39A—Si1A—O3A—C10A | −92.3 (3) | C40B—Si1B—O3B—C10B | 17.3 (3) |
C11A—N1A—C1A—C2A | 72.9 (3) | C11B—N1B—C1B—C2B | 73.3 (3) |
C9A—N1A—C1A—C2A | −53.1 (3) | C9B—N1B—C1B—C2B | −51.7 (3) |
C11A—N1A—C1A—C18A | −160.1 (2) | C11B—N1B—C1B—C18B | −157.9 (2) |
C9A—N1A—C1A—C18A | 74.0 (3) | C9B—N1B—C1B—C18B | 77.1 (3) |
N1A—C1A—C2A—C7A | 20.3 (3) | N1B—C1B—C2B—C7B | 17.6 (3) |
C18A—C1A—C2A—C7A | −104.8 (3) | C18B—C1B—C2B—C7B | −109.7 (3) |
N1A—C1A—C2A—C3A | −160.8 (2) | N1B—C1B—C2B—C3B | −162.3 (2) |
C18A—C1A—C2A—C3A | 74.1 (3) | C18B—C1B—C2B—C3B | 70.5 (3) |
C7A—C2A—C3A—C4A | 1.0 (4) | C7B—C2B—C3B—C4B | −1.2 (4) |
C1A—C2A—C3A—C4A | −177.9 (2) | C1B—C2B—C3B—C4B | 178.7 (2) |
C24A—O1A—C4A—C3A | −4.8 (4) | C24B—O1B—C4B—C3B | −9.8 (4) |
C24A—O1A—C4A—C5A | 175.1 (2) | C24B—O1B—C4B—C5B | 170.9 (2) |
C2A—C3A—C4A—O1A | 177.0 (2) | C2B—C3B—C4B—O1B | 177.9 (2) |
C2A—C3A—C4A—C5A | −2.9 (4) | C2B—C3B—C4B—C5B | −2.8 (4) |
C25A—O2A—C5A—C6A | 8.1 (4) | C25B—O2B—C5B—C6B | 0.9 (4) |
C25A—O2A—C5A—C4A | −172.5 (2) | C25B—O2B—C5B—C4B | −179.7 (3) |
O1A—C4A—C5A—O2A | 2.9 (3) | O1B—C4B—C5B—O2B | 3.7 (4) |
C3A—C4A—C5A—O2A | −177.2 (2) | C3B—C4B—C5B—O2B | −175.7 (2) |
O1A—C4A—C5A—C6A | −177.7 (2) | O1B—C4B—C5B—C6B | −176.9 (2) |
C3A—C4A—C5A—C6A | 2.3 (4) | C3B—C4B—C5B—C6B | 3.8 (4) |
O2A—C5A—C6A—C7A | 179.6 (2) | O2B—C5B—C6B—C7B | 178.6 (2) |
C4A—C5A—C6A—C7A | 0.2 (4) | C4B—C5B—C6B—C7B | −0.9 (4) |
C3A—C2A—C7A—C6A | 1.4 (4) | C3B—C2B—C7B—C6B | 4.2 (4) |
C1A—C2A—C7A—C6A | −179.6 (2) | C1B—C2B—C7B—C6B | −175.7 (2) |
C3A—C2A—C7A—C8A | −179.2 (2) | C3B—C2B—C7B—C8B | −177.2 (2) |
C1A—C2A—C7A—C8A | −0.2 (4) | C1B—C2B—C7B—C8B | 2.9 (4) |
C5A—C6A—C7A—C2A | −2.0 (4) | C5B—C6B—C7B—C2B | −3.2 (4) |
C5A—C6A—C7A—C8A | 178.6 (2) | C5B—C6B—C7B—C8B | 178.2 (3) |
C2A—C7A—C8A—C9A | 13.2 (3) | C2B—C7B—C8B—C9B | 11.4 (4) |
C6A—C7A—C8A—C9A | −167.4 (2) | C6B—C7B—C8B—C9B | −170.0 (2) |
C11A—N1A—C9A—C8A | −57.8 (3) | C11B—N1B—C9B—C8B | −56.9 (3) |
C1A—N1A—C9A—C8A | 67.3 (3) | C1B—N1B—C9B—C8B | 67.8 (3) |
C11A—N1A—C9A—C10A | 70.9 (3) | C11B—N1B—C9B—C10B | 71.3 (3) |
C1A—N1A—C9A—C10A | −163.9 (2) | C1B—N1B—C9B—C10B | −163.9 (2) |
C7A—C8A—C9A—N1A | −46.8 (3) | C7B—C8B—C9B—N1B | −46.9 (3) |
C7A—C8A—C9A—C10A | −175.7 (2) | C7B—C8B—C9B—C10B | −176.0 (2) |
Si1A—O3A—C10A—C26A | 130.4 (2) | Si1B—O3B—C10B—C26B | 137.0 (2) |
Si1A—O3A—C10A—C32A | 14.4 (3) | Si1B—O3B—C10B—C32B | 20.3 (3) |
Si1A—O3A—C10A—C9A | −108.7 (3) | Si1B—O3B—C10B—C9B | −103.0 (3) |
N1A—C9A—C10A—O3A | −84.8 (3) | N1B—C9B—C10B—O3B | −81.1 (3) |
C8A—C9A—C10A—O3A | 42.4 (3) | C8B—C9B—C10B—O3B | 46.5 (3) |
N1A—C9A—C10A—C26A | 33.8 (3) | N1B—C9B—C10B—C26B | 37.7 (3) |
C8A—C9A—C10A—C26A | 161.1 (2) | C8B—C9B—C10B—C26B | 165.3 (2) |
N1A—C9A—C10A—C32A | 153.9 (2) | N1B—C9B—C10B—C32B | 157.9 (2) |
C8A—C9A—C10A—C32A | −78.9 (3) | C8B—C9B—C10B—C32B | −74.5 (3) |
C9A—N1A—C11A—C12A | −171.0 (2) | C9B—N1B—C11B—C12B | −171.9 (2) |
C1A—N1A—C11A—C12A | 66.1 (3) | C1B—N1B—C11B—C12B | 65.8 (3) |
N1A—C11A—C12A—C17A | 31.6 (4) | N1B—C11B—C12B—C13B | 29.3 (4) |
N1A—C11A—C12A—C13A | −150.3 (2) | N1B—C11B—C12B—C17B | −152.6 (3) |
C17A—C12A—C13A—C14A | −0.8 (4) | C17B—C12B—C13B—C14B | 2.3 (5) |
C11A—C12A—C13A—C14A | −179.0 (3) | C11B—C12B—C13B—C14B | −179.6 (3) |
C12A—C13A—C14A—C15A | −1.5 (5) | C12B—C13B—C14B—C15B | −2.8 (5) |
C13A—C14A—C15A—C16A | 2.0 (5) | C13B—C14B—C15B—C16B | 0.8 (6) |
C14A—C15A—C16A—C17A | −0.3 (5) | C14B—C15B—C16B—C17B | 1.5 (6) |
C15A—C16A—C17A—C12A | −2.0 (5) | C15B—C16B—C17B—C12B | −1.9 (5) |
C13A—C12A—C17A—C16A | 2.5 (4) | C13B—C12B—C17B—C16B | 0.0 (5) |
C11A—C12A—C17A—C16A | −179.4 (3) | C11B—C12B—C17B—C16B | −178.2 (3) |
N1A—C1A—C18A—C23A | −118.5 (3) | N1B—C1B—C18B—C23B | −115.4 (3) |
C2A—C1A—C18A—C23A | 8.6 (4) | C2B—C1B—C18B—C23B | 13.3 (4) |
N1A—C1A—C18A—C19A | 62.0 (3) | N1B—C1B—C18B—C19B | 66.7 (3) |
C2A—C1A—C18A—C19A | −170.8 (2) | C2B—C1B—C18B—C19B | −164.6 (3) |
C23A—C18A—C19A—C20A | −0.7 (4) | C23B—C18B—C19B—C20B | −3.7 (5) |
C1A—C18A—C19A—C20A | 178.8 (3) | C1B—C18B—C19B—C20B | 174.3 (3) |
C18A—C19A—C20A—C21A | −0.5 (5) | C18B—C19B—C20B—C21B | 1.8 (5) |
C19A—C20A—C21A—C22A | 1.2 (5) | C19B—C20B—C21B—C22B | 1.7 (5) |
C20A—C21A—C22A—C23A | −0.9 (4) | C20B—C21B—C22B—C23B | −3.1 (5) |
C19A—C18A—C23A—C22A | 1.0 (4) | C19B—C18B—C23B—C22B | 2.3 (4) |
C1A—C18A—C23A—C22A | −178.5 (2) | C1B—C18B—C23B—C22B | −175.6 (3) |
C21A—C22A—C23A—C18A | −0.2 (4) | C21B—C22B—C23B—C18B | 1.1 (5) |
O3A—C10A—C26A—C31A | −8.9 (3) | O3B—C10B—C26B—C27B | −4.4 (4) |
C32A—C10A—C26A—C31A | 108.8 (3) | C32B—C10B—C26B—C27B | 113.0 (3) |
C9A—C10A—C26A—C31A | −127.9 (3) | C9B—C10B—C26B—C27B | −123.8 (3) |
O3A—C10A—C26A—C27A | 175.6 (2) | O3B—C10B—C26B—C31B | −179.7 (2) |
C32A—C10A—C26A—C27A | −66.7 (3) | C32B—C10B—C26B—C31B | −62.3 (3) |
C9A—C10A—C26A—C27A | 56.6 (3) | C9B—C10B—C26B—C31B | 60.9 (3) |
C31A—C26A—C27A—C28A | −0.9 (4) | C31B—C26B—C27B—C28B | −0.3 (5) |
C10A—C26A—C27A—C28A | 174.8 (2) | C10B—C26B—C27B—C28B | −175.6 (3) |
C26A—C27A—C28A—C29A | −0.5 (4) | C26B—C27B—C28B—C29B | 1.0 (5) |
C27A—C28A—C29A—C30A | 1.3 (4) | C27B—C28B—C29B—C30B | −1.4 (5) |
C28A—C29A—C30A—C31A | −0.8 (5) | C28B—C29B—C30B—C31B | 1.1 (5) |
C29A—C30A—C31A—C26A | −0.6 (4) | C29B—C30B—C31B—C26B | −0.3 (4) |
C27A—C26A—C31A—C30A | 1.4 (4) | C27B—C26B—C31B—C30B | −0.1 (4) |
C10A—C26A—C31A—C30A | −174.2 (3) | C10B—C26B—C31B—C30B | 175.3 (3) |
O3A—C10A—C32A—C33A | −111.0 (3) | O3B—C10B—C32B—C37B | −119.0 (3) |
C26A—C10A—C32A—C33A | 132.4 (3) | C26B—C10B—C32B—C37B | 123.8 (3) |
C9A—C10A—C32A—C33A | 9.7 (4) | C9B—C10B—C32B—C37B | 2.1 (4) |
O3A—C10A—C32A—C37A | 67.6 (3) | O3B—C10B—C32B—C33B | 59.9 (3) |
C26A—C10A—C32A—C37A | −49.0 (3) | C26B—C10B—C32B—C33B | −57.2 (3) |
C9A—C10A—C32A—C37A | −171.7 (2) | C9B—C10B—C32B—C33B | −178.9 (2) |
C37A—C32A—C33A—C34A | −2.4 (4) | C37B—C32B—C33B—C34B | 1.2 (4) |
C10A—C32A—C33A—C34A | 176.2 (2) | C10B—C32B—C33B—C34B | −177.8 (2) |
C32A—C33A—C34A—C35A | 1.8 (4) | C32B—C33B—C34B—C35B | 0.4 (4) |
C33A—C34A—C35A—C36A | −0.2 (4) | C33B—C34B—C35B—C36B | −1.3 (4) |
C34A—C35A—C36A—C37A | −0.6 (4) | C34B—C35B—C36B—C37B | 0.6 (5) |
C35A—C36A—C37A—C32A | −0.1 (4) | C33B—C32B—C37B—C36B | −2.0 (4) |
C33A—C32A—C37A—C36A | 1.6 (4) | C10B—C32B—C37B—C36B | 177.0 (3) |
C10A—C32A—C37A—C36A | −177.2 (2) | C35B—C36B—C37B—C32B | 1.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C35A—H35A···Cgi | 0.95 | 2.80 | 3.669 (3) | 152 |
C40A—H40B···Cg | 0.98 | 2.71 | 3.540 (3) | 143 |
C40B—H40D···Cg | 0.98 | 2.64 | 3.449 (4) | 140 |
Symmetry code: (i) −x+1, y+1/2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C31H31NO3 | C40H43NO3Si |
Mr | 465.57 | 613.84 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 173 | 100 |
a, b, c (Å) | 11.4071 (14), 6.4750 (8), 16.961 (2) | 11.045 (10), 17.008 (15), 18.489 (15) |
β (°) | 101.707 (2) | 105.287 (15) |
V (Å3) | 1226.7 (3) | 3350 (5) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.11 |
Crystal size (mm) | 0.22 × 0.14 × 0.09 | 0.22 × 0.12 × 0.10 |
Data collection | ||
Diffractometer | Bruker APEXII DUO diffractometer | Bruker APEXII DUO diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008) | Multi-scan (SADABS; Sheldrick, 2008) |
Tmin, Tmax | 0.645, 0.746 | 0.976, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11498, 3737, 3191 | 37993, 17263, 11255 |
Rint | 0.051 | 0.064 |
(sin θ/λ)max (Å−1) | 0.697 | 0.681 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.108, 1.05 | 0.057, 0.124, 0.99 |
No. of reflections | 3737 | 17263 |
No. of parameters | 320 | 812 |
No. of restraints | 2 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.23 | 0.38, −0.41 |
Absolute structure | ? | Flack (1983) |
Absolute structure parameter | ? | 0.00 (10) |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···Cgi | 0.98 | 2.57 | 3.45 (2) | 150 |
C30—H30A···O1ii | 0.98 | 2.54 | 3.356 (2) | 140 |
C30—H30A···O2ii | 0.98 | 2.59 | 3.400 (2) | 140 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y−1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C35A—H35A···Cgi | 0.95 | 2.80 | 3.669 (3) | 152 |
C40A—H40B···Cg | 0.98 | 2.71 | 3.540 (3) | 143 |
C40B—H40D···Cg | 0.98 | 2.64 | 3.449 (4) | 140 |
Symmetry code: (i) −x+1, y+1/2, −z+1. |
The tetrahydroisoquinoline (TIQ) molecule and its derivatives have been widely investigated, due to their biological and pharmaceutical properties. Given our recent success with TIQ-based ligands for catalytic asymmetric transfer hydrogenation of prochiral ketones, Henry reactions and hydrogenation of olefins, we decided to investigate the potential of TIQ derivatives as organocatalysts (Peters et al. 2010). Compound (I) has recently been synthesized and evaluated as a novel iminium activated organocatalyst in an asymmetric Diels–Alder reaction (Naicker, Petzold et al., 2010). Compound (II) is novel and is the precursor to the same class of organocatalysts based on a (1R,3S)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline backbone.
Derived from commercially available L-DOPA, the absolute stereochemistry of (I) and (II) was confirmed to be R,S at the C1 and C9 positions by 1H NMR, as shown in Figs. 1 and 2, respectively.
Both structures have monoclinic (P21) symmetry. Compound (I) has a single molecule in the asymmetric unit, while (II) has two molecules within the asymmetric unit. Molecule (I) has a methyl group at the O3 position, whilst (II) has a trimethylsilyl group in this position. In addition, (II) has a benzyl group on the N atom.
In the structure of (I), intermolecular C—H···π and C—H···O interactions involving atoms O1 and O2 link the molecules into extended chains which run parallel to the b axis (Table 1 and Fig. 3). In the chain, the molecules are arranged so that their tails, linked by the C—H···O interactions, point towards the core of the chain and their heads protrude to the outer edges of the chain, with adjacent molecules alternating from side-to-side. The C—H···π interactions link the heads of those molecules lying on the same side of the chain core.
In the structure of (I), intermolecular C—H···π and C—H···O bonds involving atoms O1 and O2 link the molecules together, as illustrated in Fig. 3 (see Table 1).
In the structure of (II), each independent molecule displays an intramolecular C—H···π interaction, while a single intermolecular C—H···π interaction involving C30A—H links just the two independent molecules (Table 2). An extended network of interactions is not present. The crystal packing of (II) reveals that the pseudosymmetry relates the two independent molecules within the asymmetric unit resulting in a layered packing along the a axis (Fig 4).
Intermolecular C—H···π bonds link the molecules in the crystal structure of (II) (see Table 2), as shown in Fig. 4.
From the crystal structures, it is evident that the N-containing six-membered rings assume half-chair conformations (Figs. 1 and 2). This result differs from two analogous compounds which assume a half-boat conformation (Naicker et al., 2009; Naicker, Govender et al., 2010a). The current study confirms our previous postulation that the change in conformation is a result of the introduction of the phenyl groups at the C1 position.
According to the Cambridge Structural Database (Version?; Allen, 2002), the only other crystal structure of a tetrahydroisoquinoline derivative with diaryl substitution at the C10 position is compound (III) (see scheme), which we reported recently (Naicker, Govender et al., 2010b). In this crystal structure, the methanol O atom is a free OH. Due to the lack of analogous structures, these diaryl tetrahydroisoquinoline alcohols were compared with proline diaryl alcohols (Seebach et al., 2008). Compound (III) displayed a similar conformation to its proline analogue, which displays a gauche or sc-endo (synclinal) conformation around the O3—C10—C9—N1 bond, with the OH group partially covering the piperidine ring with a torsion angle of -77.0 (2)°.
Compound (I) displays an ap (antiperiplanar) conformation around the exocyclic C9—C10 bond, with an O3—C10—C9—N1 torsion angle of 171.5 (1)°. This conformation has only been found in a few examples of N-amino prolinol methyl esters (Seebach et al., 2008).
Proline diphenyl OTMS (Define OTMS?) analogues exhibit an sc-exo conformation around the exocyclic ethane bond, with a torsion angle of 61.0°. Both molecules of (II) (Fig. 2) display an sc-endo conformation, with torsion angles of -81.1 (3) and -84.8 (2)°. A possible reason for this change could be that the benzyl group on the N atom forces the phenyl rings at the C10 atom to be the furthest away from it, hence adopting the sc-endo conformation.
Proline diaryl alcohols have been used as successful chiral catalysts by exploiting the same rotation along the C9—C10 bond (Diner et al., 2008). This change, which is brought about by different groups on the methanol oxygen, makes the current study particularly useful. This feature is found in (I) which, when tested for its catalytic activity in the Diels–Alder reaction, showed poor yields. The structural data demonstrated how we could improve the catalytic reactivity by reducing the steric bulk of the ligand. A successful catalyst was obtained by removing the phenyl moieties from (I) (Naicker, Petzold et al., 2010).