Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006487/na6152sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006487/na61522sup2.hkl |
CCDC reference: 185787
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.005 Å
- R factor = 0.046
- wR factor = 0.095
- Data-to-parameter ratio = 8.4
checkCIF results
No syntax errors found
Alert Level B:
PLAT_112 Alert B ADDSYM Detects Additional (Pseudo) Symm. Elem. c
Author response: The additional symmetry is pseudo symmetry. The molecules concerned are diastereomers and can therefore not be related by a symmetry element. This pseudo symmetrie is discussed in the Comment, and illustrated in Figure 2. |
PLAT_113 Alert B ADDSYM suggests Pseudo/New Spacegroup ........ Pc
Author response: See previous VRF. |
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 4617 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4870 Completeness (_total/calc) 94.80% Alert C: < 95% complete General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 4617 Count of symmetry unique reflns 4870 Completeness (_total/calc) 94.80% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared from 284 mg (0.808 mmol) of 4-[2-(difluoromethoxy)phenyl]-5-(methoxycarbonyl)-2,6-dimethyl-1,4-dihydro- 3-pyridinecarboxylic acid, (1), by reaction of its acid chloride with 0.262 ml (2.41 mmol) of (S)-2-methyl-1-butanol, using the method of Sobolev et al. (2002). The crude product was flash chromatographed on silica gel with ethyl acetate/petroleum ether (b.p. 313–333 K, 1:3), purified again on silica gel with petroleum ether (b.p. 313–333 K)/chloroform/isopropyl alcohol (20:5:2) and crystallized from ethanol to give 276 mg (81%) as pale-yellow crystals: m.p. 406–407 K; 1H NMR (CDCl3, 200 MHz): δ 0.83 (t, 3H, J = 7.3 Hz, CH3), 0.85 (d, 3H, J = 7.4 Hz, CH3), 0.95–1.16 (m, 1H, CH2), 1.19–1.40 (m, 1H, CH2), 1.60–1.76 (m, 1H, CH), 2.28 (s, 3H, CH3), 2.30 (s, 3H, CH3), 3.59 (s, 3H, CH3), 3.77 (dd, 1H, J = 10.8, 6.9 Hz, CH2), 3.89 (dd, 1H, J = 10.8, 6.4 Hz, CH2), 5.25 (s, 1H, CH), 5.60 (br s, 1H, NH), 6.46 (dd, 1H, JH—F = 75.6, 75.8 Hz, OCHF2), 6.95- 7.13 (m, 3H, Ar—H), 7.35 (dd, 1H, J = 2.2, 7.3 Hz, Ar—H). MS m/z: 423 (M+, 9), 352 (10), 336 (5), 308 (9), 284 (6), 281 (15), 280 (100), 211 (4), 210 (36); HRMS calculated for C22H27F2O5: 423.1857, found 423.1853. Crystals suitable for X-ray analysis were obtained by recrystallization from hexane containing a small amount of methanol.
Due to the absence of significant anomalous dispersion, the absolute structure could not be determined reliably. The configuration of C9 and thereby also that of C31 was set equal to S, consistent with the starting materials used. The measured reflections reduced to 9040 unique reflections with an Rint of 0.0742. After merging of the Friedel pairs, the 4617 reflections reported above remained. H atoms of the N—H moieties were located on a difference Fourier map and their coordinates and isotropic displacement parameters were refined. All other H atoms were included at calculated positions, riding on their carrier atoms. Isotropic displacement parameters of H atoms bonded to C atoms were coupled to the equivalent isotropic displacement parameter of their carrier atoms by a fixed factor of 1.5 (methyl H atoms) or 1.2 (other H atoms).
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: PLATON.
C22H27F2NO5 | Z = 2 |
Mr = 423.45 | F(000) = 448 |
Triclinic, P1 | Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set. |
Hall symbol: P 1 | Dx = 1.330 Mg m−3 |
a = 8.2340 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7827 (18) Å | Cell parameters from 367 reflections |
c = 14.9145 (18) Å | θ = 1.6–25.0° |
α = 89.299 (11)° | µ = 0.11 mm−1 |
β = 78.697 (11)° | T = 150 K |
γ = 89.906 (7)° | Needle, colourless |
V = 1057.6 (3) Å3 | 0.3 × 0.1 × 0.1 mm |
Nonius KappaCCD area-detector diffractometer | 3257 reflections with I > 2σ(I) |
Radiation source: Rotating Anode | Rint = 0.084 |
Graphite monochromator | θmax = 27.5°, θmin = 1.4° |
Detector resolution: 18.4 pixels mm-1 | h = −10→10 |
ϕ scans, and ω scans with κ offset | k = −11→11 |
21160 measured reflections | l = −19→19 |
4617 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0468P)2] where P = (Fo2 + 2Fc2)/3 |
4617 reflections | (Δ/σ)max = 0.002 |
549 parameters | Δρmax = 0.17 e Å−3 |
3 restraints | Δρmin = −0.23 e Å−3 |
C22H27F2NO5 | γ = 89.906 (7)° |
Mr = 423.45 | V = 1057.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2340 (16) Å | Mo Kα radiation |
b = 8.7827 (18) Å | µ = 0.11 mm−1 |
c = 14.9145 (18) Å | T = 150 K |
α = 89.299 (11)° | 0.3 × 0.1 × 0.1 mm |
β = 78.697 (11)° |
Nonius KappaCCD area-detector diffractometer | 3257 reflections with I > 2σ(I) |
21160 measured reflections | Rint = 0.084 |
4617 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 3 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.17 e Å−3 |
4617 reflections | Δρmin = −0.23 e Å−3 |
549 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | ||
F1 | 0.7760 (3) | −0.0537 (2) | 0.88624 (13) | 0.0496 (8) | |
F2 | 0.7747 (3) | −0.2814 (3) | 0.84126 (17) | 0.0693 (10) | |
O1 | 0.9384 (3) | 0.2567 (3) | 0.54029 (14) | 0.0321 (8) | |
O2 | 0.7558 (3) | 0.3528 (3) | 0.65755 (14) | 0.0316 (7) | |
O3 | 0.9633 (3) | −0.1194 (2) | 0.76922 (14) | 0.0306 (7) | |
O4 | 1.5299 (3) | 0.0194 (4) | 0.71809 (18) | 0.0554 (10) | |
O5 | 1.4461 (3) | 0.0231 (3) | 0.58531 (14) | 0.0341 (8) | |
N1 | 1.0523 (4) | 0.1878 (3) | 0.83573 (19) | 0.0315 (10) | |
C1 | 0.9455 (4) | 0.2382 (4) | 0.7810 (2) | 0.0298 (11) | |
C2 | 0.9850 (4) | 0.2140 (4) | 0.6898 (2) | 0.0259 (10) | |
C3 | 1.1333 (4) | 0.1149 (4) | 0.6482 (2) | 0.0259 (10) | |
C4 | 1.2536 (4) | 0.0949 (4) | 0.7129 (2) | 0.0284 (10) | |
C5 | 1.2060 (4) | 0.1266 (4) | 0.8033 (2) | 0.0306 (11) | |
C6 | 0.7972 (5) | 0.3174 (4) | 0.8334 (2) | 0.0398 (11) | |
C7 | 0.8940 (4) | 0.2748 (3) | 0.6225 (2) | 0.0257 (11) | |
C8 | 0.6499 (4) | 0.4010 (4) | 0.5948 (2) | 0.0326 (11) | |
C9 | 0.5407 (4) | 0.5300 (4) | 0.6363 (2) | 0.0297 (11) | |
C10 | 0.4362 (6) | 0.4884 (5) | 0.7275 (3) | 0.0655 (17) | |
C11 | 0.3398 (7) | 0.6188 (7) | 0.7769 (3) | 0.093 (3) | |
C12 | 0.4350 (5) | 0.5820 (5) | 0.5690 (3) | 0.0476 (14) | |
C13 | 1.0798 (4) | −0.0387 (3) | 0.6159 (2) | 0.0254 (10) | |
C14 | 0.9981 (4) | −0.1507 (4) | 0.6749 (2) | 0.0266 (10) | |
C15 | 0.9598 (4) | −0.2905 (4) | 0.6442 (2) | 0.0355 (12) | |
C16 | 0.9941 (4) | −0.3197 (4) | 0.5517 (2) | 0.0374 (12) | |
C17 | 1.0698 (4) | −0.2104 (4) | 0.4910 (2) | 0.0368 (11) | |
C18 | 1.1124 (4) | −0.0729 (4) | 0.5233 (2) | 0.0308 (11) | |
C19 | 0.8023 (5) | −0.1366 (4) | 0.8103 (2) | 0.0369 (11) | |
C20 | 1.4205 (4) | 0.0418 (4) | 0.6763 (2) | 0.0327 (11) | |
C21 | 1.6072 (5) | −0.0337 (4) | 0.5429 (3) | 0.0415 (12) | |
C22 | 1.3056 (5) | 0.1025 (5) | 0.8765 (2) | 0.0414 (13) | |
F3 | 0.7921 (3) | 0.7777 (2) | 0.34946 (14) | 0.0483 (8) | |
F4 | 0.7794 (3) | 0.5392 (2) | 0.38152 (13) | 0.0500 (8) | |
O6 | 0.9447 (3) | 0.2447 (3) | 0.04224 (14) | 0.0326 (8) | |
O7 | 0.7614 (3) | 0.1551 (3) | 0.16247 (14) | 0.0311 (7) | |
O8 | 0.9706 (3) | 0.6164 (2) | 0.26849 (13) | 0.0281 (7) | |
O9 | 1.5375 (3) | 0.4940 (3) | 0.21486 (18) | 0.0501 (10) | |
O10 | 1.4531 (3) | 0.4807 (3) | 0.08184 (15) | 0.0376 (8) | |
N2 | 1.0653 (3) | 0.3085 (3) | 0.33527 (18) | 0.0273 (9) | |
C23 | 0.9573 (4) | 0.2605 (4) | 0.2821 (2) | 0.0278 (11) | |
C24 | 0.9945 (4) | 0.2889 (4) | 0.1904 (2) | 0.0262 (10) | |
C25 | 1.1413 (4) | 0.3884 (3) | 0.1479 (2) | 0.0249 (10) | |
C26 | 1.2628 (4) | 0.4056 (3) | 0.2118 (2) | 0.0270 (10) | |
C27 | 1.2181 (4) | 0.3708 (3) | 0.3021 (2) | 0.0268 (10) | |
C28 | 0.8102 (5) | 0.1784 (4) | 0.3358 (2) | 0.0379 (11) | |
C29 | 0.9010 (4) | 0.2294 (3) | 0.1250 (2) | 0.0249 (10) | |
C30 | 0.6540 (4) | 0.1078 (4) | 0.1015 (2) | 0.0328 (11) | |
C31 | 0.4940 (4) | 0.0512 (4) | 0.1600 (2) | 0.0340 (11) | |
C32 | 0.5194 (4) | −0.0847 (4) | 0.2202 (2) | 0.0367 (12) | |
C33 | 0.3659 (5) | −0.1369 (5) | 0.2858 (3) | 0.0580 (17) | |
C34 | 0.3743 (5) | 0.0154 (5) | 0.0976 (3) | 0.0543 (17) | |
C35 | 1.0862 (4) | 0.5422 (3) | 0.1151 (2) | 0.0245 (10) | |
C36 | 1.0053 (4) | 0.6523 (4) | 0.1743 (2) | 0.0256 (10) | |
C37 | 0.9637 (4) | 0.7929 (4) | 0.1432 (2) | 0.0324 (11) | |
C38 | 0.9987 (4) | 0.8259 (4) | 0.0514 (2) | 0.0340 (11) | |
C39 | 1.0740 (4) | 0.7194 (4) | −0.0093 (2) | 0.0369 (11) | |
C40 | 1.1180 (4) | 0.5799 (4) | 0.0229 (2) | 0.0339 (11) | |
C41 | 0.8112 (4) | 0.6375 (4) | 0.3100 (2) | 0.0330 (11) | |
C42 | 1.4283 (4) | 0.4641 (4) | 0.1737 (2) | 0.0314 (11) | |
C43 | 1.6091 (5) | 0.5467 (4) | 0.0375 (3) | 0.0454 (12) | |
C44 | 1.3208 (5) | 0.3918 (4) | 0.3740 (2) | 0.0391 (11) | |
H1 | 1.027 (6) | 0.197 (5) | 0.901 (3) | 0.072 (14)* | |
H3 | 1.19410 | 0.17040 | 0.59280 | 0.0310* | |
H6A | 0.80260 | 0.42590 | 0.81690 | 0.0600* | |
H6B | 0.79470 | 0.30550 | 0.89910 | 0.0600* | |
H6C | 0.69670 | 0.27290 | 0.81860 | 0.0600* | |
H8A | 0.58060 | 0.31450 | 0.58270 | 0.0390* | |
H8B | 0.71900 | 0.43470 | 0.53600 | 0.0390* | |
H9 | 0.61400 | 0.61670 | 0.64550 | 0.0360* | |
H10A | 0.50910 | 0.44530 | 0.76690 | 0.0790* | |
H10B | 0.35740 | 0.40780 | 0.71850 | 0.0790* | |
H11A | 0.41400 | 0.70550 | 0.77810 | 0.1400* | |
H11B | 0.29160 | 0.58700 | 0.83970 | 0.1400* | |
H11C | 0.25110 | 0.64860 | 0.74510 | 0.1400* | |
H12A | 0.50580 | 0.60030 | 0.50890 | 0.0720* | |
H12B | 0.37740 | 0.67630 | 0.59060 | 0.0720* | |
H12C | 0.35350 | 0.50290 | 0.56400 | 0.0720* | |
H15 | 0.90990 | −0.36670 | 0.68640 | 0.0430* | |
H16 | 0.96550 | −0.41520 | 0.53000 | 0.0450* | |
H17 | 1.09240 | −0.22960 | 0.42720 | 0.0440* | |
H18 | 1.16610 | 0.00120 | 0.48070 | 0.0370* | |
H19 | 0.72610 | −0.10640 | 0.76860 | 0.0440* | |
H21A | 1.69250 | 0.03980 | 0.55100 | 0.0620* | |
H21B | 1.61100 | −0.04840 | 0.47750 | 0.0620* | |
H21C | 1.62760 | −0.13120 | 0.57140 | 0.0620* | |
H22A | 1.34990 | −0.00130 | 0.87300 | 0.0620* | |
H22B | 1.23450 | 0.11760 | 0.93660 | 0.0620* | |
H22C | 1.39730 | 0.17570 | 0.86770 | 0.0620* | |
H2 | 1.038 (5) | 0.301 (4) | 0.395 (3) | 0.045 (11)* | |
H25 | 1.20130 | 0.33440 | 0.09260 | 0.0300* | |
H28A | 0.70880 | 0.22020 | 0.32000 | 0.0570* | |
H28B | 0.80700 | 0.19130 | 0.40130 | 0.0570* | |
H28C | 0.81840 | 0.06980 | 0.32120 | 0.0570* | |
H30A | 0.70730 | 0.02570 | 0.06120 | 0.0390* | |
H30B | 0.63190 | 0.19470 | 0.06270 | 0.0390* | |
H31 | 0.44560 | 0.13600 | 0.20090 | 0.0400* | |
H32A | 0.56270 | −0.17080 | 0.18030 | 0.0440* | |
H32B | 0.60480 | −0.05780 | 0.25570 | 0.0440* | |
H33A | 0.31680 | −0.05070 | 0.32260 | 0.0870* | |
H33B | 0.39530 | −0.21690 | 0.32620 | 0.0870* | |
H33C | 0.28590 | −0.17710 | 0.25140 | 0.0870* | |
H34A | 0.36590 | 0.10360 | 0.05780 | 0.0810* | |
H34B | 0.26490 | −0.00780 | 0.13460 | 0.0810* | |
H34C | 0.41480 | −0.07270 | 0.06000 | 0.0810* | |
H37 | 0.91110 | 0.86660 | 0.18530 | 0.0390* | |
H38 | 0.97070 | 0.92280 | 0.02970 | 0.0410* | |
H39 | 1.09580 | 0.74110 | −0.07310 | 0.0440* | |
H40 | 1.17180 | 0.50760 | −0.01980 | 0.0410* | |
H41 | 0.73370 | 0.62250 | 0.26690 | 0.0400* | |
H43A | 1.62010 | 0.64850 | 0.06190 | 0.0680* | |
H43B | 1.61290 | 0.55430 | −0.02850 | 0.0680* | |
H43C | 1.70010 | 0.48210 | 0.04910 | 0.0680* | |
H44A | 1.42010 | 0.32810 | 0.35990 | 0.0590* | |
H44B | 1.25570 | 0.36210 | 0.43390 | 0.0590* | |
H44C | 1.35330 | 0.49890 | 0.37510 | 0.0590* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0529 (15) | 0.0587 (14) | 0.0312 (11) | −0.0045 (11) | 0.0067 (10) | −0.0047 (10) |
F2 | 0.0818 (19) | 0.0487 (15) | 0.0623 (16) | −0.0225 (13) | 0.0230 (13) | 0.0038 (12) |
O1 | 0.0407 (15) | 0.0380 (14) | 0.0176 (12) | 0.0058 (11) | −0.0055 (10) | −0.0010 (9) |
O2 | 0.0343 (14) | 0.0384 (13) | 0.0218 (11) | 0.0111 (11) | −0.0051 (10) | −0.0019 (9) |
O3 | 0.0287 (14) | 0.0397 (13) | 0.0222 (11) | −0.0063 (10) | −0.0025 (10) | 0.0048 (10) |
O4 | 0.0384 (17) | 0.086 (2) | 0.0445 (16) | 0.0146 (15) | −0.0150 (13) | 0.0012 (14) |
O5 | 0.0280 (14) | 0.0421 (14) | 0.0296 (13) | 0.0021 (11) | 0.0005 (10) | −0.0015 (10) |
N1 | 0.0382 (19) | 0.0370 (17) | 0.0193 (15) | 0.0012 (13) | −0.0057 (12) | −0.0003 (12) |
C1 | 0.036 (2) | 0.0267 (18) | 0.0264 (18) | 0.0002 (15) | −0.0052 (15) | 0.0001 (13) |
C2 | 0.0285 (19) | 0.0274 (17) | 0.0205 (16) | 0.0006 (14) | −0.0015 (13) | 0.0002 (13) |
C3 | 0.0269 (19) | 0.0280 (17) | 0.0214 (16) | −0.0013 (13) | −0.0017 (13) | 0.0012 (12) |
C4 | 0.032 (2) | 0.0274 (17) | 0.0266 (17) | −0.0014 (14) | −0.0077 (14) | −0.0005 (13) |
C5 | 0.033 (2) | 0.0296 (18) | 0.0304 (18) | −0.0037 (15) | −0.0094 (15) | 0.0030 (14) |
C6 | 0.051 (2) | 0.048 (2) | 0.0199 (17) | 0.0117 (18) | −0.0056 (16) | −0.0027 (15) |
C7 | 0.031 (2) | 0.0215 (17) | 0.0247 (18) | −0.0021 (14) | −0.0056 (14) | 0.0011 (13) |
C8 | 0.034 (2) | 0.039 (2) | 0.0263 (17) | 0.0042 (15) | −0.0097 (15) | −0.0015 (14) |
C9 | 0.028 (2) | 0.0364 (19) | 0.0261 (17) | 0.0013 (15) | −0.0088 (14) | −0.0006 (14) |
C10 | 0.064 (3) | 0.069 (3) | 0.051 (3) | 0.030 (2) | 0.018 (2) | 0.023 (2) |
C11 | 0.107 (5) | 0.121 (5) | 0.039 (3) | 0.072 (4) | 0.017 (3) | 0.006 (3) |
C12 | 0.043 (2) | 0.057 (3) | 0.046 (2) | 0.0127 (19) | −0.0159 (18) | −0.0084 (18) |
C13 | 0.0234 (18) | 0.0272 (17) | 0.0259 (16) | 0.0021 (13) | −0.0057 (13) | −0.0005 (13) |
C14 | 0.0216 (18) | 0.0345 (18) | 0.0246 (17) | 0.0038 (14) | −0.0066 (14) | −0.0008 (14) |
C15 | 0.032 (2) | 0.035 (2) | 0.039 (2) | −0.0026 (16) | −0.0057 (16) | −0.0016 (15) |
C16 | 0.033 (2) | 0.038 (2) | 0.041 (2) | −0.0061 (16) | −0.0065 (17) | −0.0091 (16) |
C17 | 0.040 (2) | 0.042 (2) | 0.0291 (18) | 0.0002 (17) | −0.0084 (16) | −0.0077 (15) |
C18 | 0.028 (2) | 0.039 (2) | 0.0245 (17) | −0.0004 (15) | −0.0026 (14) | −0.0015 (14) |
C19 | 0.036 (2) | 0.045 (2) | 0.0291 (19) | 0.0013 (17) | −0.0049 (16) | 0.0012 (16) |
C20 | 0.031 (2) | 0.0345 (19) | 0.0331 (19) | −0.0041 (15) | −0.0081 (16) | 0.0052 (14) |
C21 | 0.030 (2) | 0.044 (2) | 0.046 (2) | 0.0014 (16) | 0.0041 (16) | −0.0043 (17) |
C22 | 0.042 (2) | 0.060 (3) | 0.0250 (18) | −0.0017 (18) | −0.0136 (16) | −0.0001 (16) |
F3 | 0.0560 (15) | 0.0463 (13) | 0.0390 (12) | 0.0176 (11) | −0.0003 (10) | −0.0099 (9) |
F4 | 0.0547 (15) | 0.0554 (14) | 0.0319 (11) | 0.0069 (11) | 0.0102 (10) | 0.0128 (9) |
O6 | 0.0411 (15) | 0.0366 (13) | 0.0194 (12) | −0.0046 (10) | −0.0045 (10) | 0.0003 (10) |
O7 | 0.0344 (14) | 0.0393 (13) | 0.0204 (11) | −0.0080 (11) | −0.0075 (10) | 0.0015 (9) |
O8 | 0.0299 (14) | 0.0328 (12) | 0.0208 (11) | 0.0049 (10) | −0.0030 (10) | −0.0002 (9) |
O9 | 0.0366 (16) | 0.0669 (19) | 0.0473 (16) | −0.0160 (13) | −0.0094 (13) | 0.0016 (13) |
O10 | 0.0333 (15) | 0.0433 (14) | 0.0320 (13) | −0.0031 (11) | 0.0034 (11) | 0.0026 (10) |
N2 | 0.0332 (18) | 0.0301 (15) | 0.0186 (15) | −0.0024 (12) | −0.0048 (12) | 0.0001 (11) |
C23 | 0.033 (2) | 0.0262 (17) | 0.0244 (18) | −0.0017 (14) | −0.0059 (15) | −0.0013 (13) |
C24 | 0.0267 (19) | 0.0289 (17) | 0.0224 (16) | 0.0014 (14) | −0.0033 (13) | −0.0008 (13) |
C25 | 0.0252 (18) | 0.0253 (17) | 0.0226 (16) | 0.0033 (13) | −0.0011 (13) | −0.0011 (12) |
C26 | 0.029 (2) | 0.0246 (17) | 0.0269 (17) | 0.0041 (14) | −0.0042 (14) | 0.0002 (13) |
C27 | 0.027 (2) | 0.0248 (17) | 0.0295 (17) | 0.0039 (14) | −0.0074 (14) | −0.0007 (13) |
C28 | 0.049 (2) | 0.044 (2) | 0.0191 (17) | −0.0162 (18) | −0.0029 (15) | −0.0001 (15) |
C29 | 0.031 (2) | 0.0203 (16) | 0.0237 (17) | 0.0018 (14) | −0.0059 (14) | 0.0003 (12) |
C30 | 0.037 (2) | 0.037 (2) | 0.0271 (17) | −0.0012 (16) | −0.0124 (15) | −0.0033 (14) |
C31 | 0.031 (2) | 0.040 (2) | 0.0337 (19) | 0.0026 (15) | −0.0129 (16) | −0.0035 (15) |
C32 | 0.034 (2) | 0.039 (2) | 0.037 (2) | −0.0042 (16) | −0.0072 (16) | 0.0024 (16) |
C33 | 0.048 (3) | 0.062 (3) | 0.058 (3) | −0.010 (2) | 0.004 (2) | 0.008 (2) |
C34 | 0.042 (3) | 0.071 (3) | 0.055 (3) | −0.005 (2) | −0.022 (2) | −0.001 (2) |
C35 | 0.0185 (18) | 0.0264 (16) | 0.0279 (17) | −0.0030 (13) | −0.0026 (13) | 0.0007 (13) |
C36 | 0.0190 (18) | 0.0313 (18) | 0.0259 (16) | −0.0016 (13) | −0.0033 (13) | 0.0028 (13) |
C37 | 0.031 (2) | 0.033 (2) | 0.0322 (19) | 0.0042 (15) | −0.0038 (15) | −0.0007 (14) |
C38 | 0.031 (2) | 0.0326 (19) | 0.0358 (19) | 0.0027 (15) | −0.0011 (15) | 0.0110 (15) |
C39 | 0.040 (2) | 0.041 (2) | 0.0262 (18) | 0.0065 (17) | 0.0017 (15) | 0.0084 (15) |
C40 | 0.038 (2) | 0.037 (2) | 0.0235 (17) | 0.0040 (16) | 0.0017 (14) | 0.0041 (14) |
C41 | 0.035 (2) | 0.040 (2) | 0.0225 (17) | 0.0010 (16) | −0.0017 (15) | −0.0012 (14) |
C42 | 0.031 (2) | 0.0283 (18) | 0.0336 (19) | 0.0021 (15) | −0.0032 (16) | −0.0038 (14) |
C43 | 0.040 (2) | 0.043 (2) | 0.045 (2) | −0.0052 (18) | 0.0118 (18) | 0.0026 (18) |
C44 | 0.044 (2) | 0.047 (2) | 0.0296 (18) | 0.0001 (17) | −0.0152 (16) | 0.0007 (16) |
F1—C19 | 1.335 (4) | C15—H15 | 0.9498 |
F2—C19 | 1.352 (4) | C16—H16 | 0.9491 |
F3—C41 | 1.367 (4) | C17—H17 | 0.9502 |
F4—C41 | 1.349 (4) | C18—H18 | 0.9505 |
O1—C7 | 1.221 (4) | C19—H19 | 0.9996 |
O2—C8 | 1.458 (4) | C21—H21C | 0.9802 |
O2—C7 | 1.346 (4) | C21—H21B | 0.9799 |
O3—C19 | 1.355 (5) | C21—H21A | 0.9804 |
O3—C14 | 1.410 (4) | C22—H22B | 0.9802 |
O4—C20 | 1.206 (4) | C22—H22C | 0.9805 |
O5—C20 | 1.344 (4) | C22—H22A | 0.9795 |
O5—C21 | 1.444 (5) | N2—C23 | 1.372 (4) |
O6—C29 | 1.222 (4) | N2—C27 | 1.371 (4) |
O7—C30 | 1.452 (4) | C23—C24 | 1.362 (4) |
O7—C29 | 1.342 (4) | C23—C28 | 1.496 (5) |
O8—C41 | 1.350 (4) | C24—C25 | 1.522 (5) |
O8—C36 | 1.409 (4) | C24—C29 | 1.458 (4) |
O9—C42 | 1.215 (4) | C25—C35 | 1.529 (4) |
O10—C42 | 1.351 (4) | C25—C26 | 1.520 (5) |
O10—C43 | 1.443 (5) | C26—C42 | 1.461 (5) |
N1—C1 | 1.381 (4) | C26—C27 | 1.356 (4) |
N1—C5 | 1.374 (5) | C27—C44 | 1.503 (5) |
N1—H1 | 0.96 (4) | C30—C31 | 1.512 (5) |
N2—H2 | 0.88 (4) | C31—C32 | 1.524 (5) |
C1—C2 | 1.354 (4) | C31—C34 | 1.518 (5) |
C1—C6 | 1.491 (5) | C32—C33 | 1.507 (5) |
C2—C7 | 1.461 (4) | C35—C40 | 1.385 (4) |
C2—C3 | 1.532 (5) | C35—C36 | 1.395 (4) |
C3—C4 | 1.521 (5) | C36—C37 | 1.380 (5) |
C3—C13 | 1.532 (4) | C37—C38 | 1.370 (4) |
C4—C20 | 1.454 (5) | C38—C39 | 1.370 (5) |
C4—C5 | 1.360 (4) | C39—C40 | 1.384 (5) |
C5—C22 | 1.501 (5) | C25—H25 | 0.9992 |
C8—C9 | 1.507 (5) | C28—H28A | 0.9805 |
C9—C12 | 1.518 (5) | C28—H28B | 0.9800 |
C9—C10 | 1.501 (5) | C28—H28C | 0.9802 |
C10—C11 | 1.508 (7) | C30—H30A | 0.9899 |
C13—C14 | 1.394 (4) | C30—H30B | 0.9902 |
C13—C18 | 1.391 (4) | C31—H31 | 1.0002 |
C14—C15 | 1.374 (5) | C32—H32A | 0.9900 |
C15—C16 | 1.380 (4) | C32—H32B | 0.9900 |
C16—C17 | 1.374 (5) | C33—H33A | 0.9798 |
C17—C18 | 1.377 (5) | C33—H33B | 0.9806 |
C3—H3 | 0.9999 | C33—H33C | 0.9795 |
C6—H6A | 0.9802 | C34—H34A | 0.9807 |
C6—H6B | 0.9804 | C34—H34B | 0.9800 |
C6—H6C | 0.9803 | C34—H34C | 0.9802 |
C8—H8B | 0.9895 | C37—H37 | 0.9504 |
C8—H8A | 0.9902 | C38—H38 | 0.9508 |
C9—H9 | 0.9997 | C39—H39 | 0.9501 |
C10—H10A | 0.9904 | C40—H40 | 0.9505 |
C10—H10B | 0.9890 | C41—H41 | 1.0005 |
C11—H11B | 0.9803 | C43—H43A | 0.9804 |
C11—H11A | 0.9796 | C43—H43B | 0.9802 |
C11—H11C | 0.9793 | C43—H43C | 0.9799 |
C12—H12B | 0.9798 | C44—H44A | 0.9797 |
C12—H12C | 0.9803 | C44—H44B | 0.9801 |
C12—H12A | 0.9804 | C44—H44C | 0.9796 |
F1···N1 | 3.090 (4) | C42···H44C | 2.9652 |
F1···C1 | 3.168 (4) | C42···H44A | 2.9982 |
F1···C6 | 3.341 (4) | C42···H31vi | 2.9123 |
F2···C15 | 3.036 (4) | C44···H12Cvi | 3.0696 |
F2···C43i | 3.323 (5) | H1···H6B | 2.1406 |
F3···C37 | 3.125 (4) | H1···O6ii | 2.13 (4) |
F4···N2 | 3.083 (3) | H1···H22B | 2.0075 |
F4···C8 | 3.363 (4) | H2···O1 | 2.19 (4) |
F4···C23 | 3.092 (4) | H2···H28B | 2.1186 |
F4···C28 | 3.249 (4) | H2···H44B | 2.0631 |
F1···H30Aii | 2.6608 | H3···H18 | 2.2956 |
F2···H43Bi | 2.5600 | H3···O1 | 2.4995 |
F2···H6Aiii | 2.6041 | H3···O5 | 2.4281 |
F2···H15 | 2.4833 | H6A···O2 | 2.5702 |
F3···H21Biv | 2.6741 | H6A···F2v | 2.6041 |
F3···H28Cv | 2.5972 | H6B···O6ii | 2.7151 |
F3···H32Bv | 2.6851 | H6B···H1 | 2.1406 |
F3···H37 | 2.5651 | H6C···C7 | 3.0545 |
F4···H12A | 2.7048 | H6C···H10A | 2.3883 |
F4···H8B | 2.4287 | H6C···H22Cviii | 2.5742 |
O1···C18 | 3.218 (4) | H6C···O2 | 2.4496 |
O1···C13 | 3.129 (4) | H8A···O5viii | 2.7871 |
O1···N2 | 3.060 (3) | H8A···H10B | 2.5938 |
O2···C6 | 2.724 (4) | H8A···H12C | 2.5486 |
O3···C5 | 3.059 (4) | H8A···H21Aviii | 2.5967 |
O3···N1 | 3.026 (3) | H8A···C20viii | 2.9377 |
O3···C1 | 3.149 (4) | H8B···O1 | 2.3969 |
O3···C4 | 3.025 (4) | H8B···H12A | 2.3698 |
O3···C2 | 3.137 (4) | H8B···F4 | 2.4287 |
O4···C22 | 2.802 (4) | H8B···H16v | 2.4084 |
O4···C19vi | 3.155 (5) | H9···H21Civ | 2.4553 |
O5···C18 | 3.184 (4) | H9···H11A | 2.4471 |
O5···C13 | 3.010 (4) | H9···C15v | 2.9593 |
O6···N1vii | 3.080 (4) | H10A···O2 | 2.4849 |
O6···C40 | 3.259 (4) | H10A···C6 | 2.9596 |
O6···C35 | 3.153 (4) | H10A···H6C | 2.3883 |
O7···C28 | 2.703 (4) | H10B···C4viii | 2.8863 |
O8···C23 | 3.131 (4) | H10B···H8A | 2.5938 |
O8···C26 | 3.026 (4) | H10B···H12C | 2.4475 |
O8···C27 | 3.069 (4) | H10B···C5viii | 2.9272 |
O8···N2 | 3.024 (3) | H11A···H9 | 2.4471 |
O8···C24 | 3.108 (4) | H11B···C40xii | 2.8245 |
O9···C44 | 2.814 (4) | H11B···H39xii | 2.3101 |
O9···C41vi | 3.160 (4) | H11B···C39xii | 2.8478 |
O10···C40 | 3.173 (4) | H11B···H40xii | 2.2376 |
O10···C35 | 3.013 (4) | H11C···C14iv | 3.0563 |
O1···H21Aviii | 2.7627 | H11C···H12B | 2.3448 |
O1···H8B | 2.3969 | H11C···C12 | 2.8300 |
O1···H16v | 2.8905 | H12A···H8B | 2.3698 |
O1···H2 | 2.19 (4) | H12A···F4 | 2.7048 |
O1···H28B | 2.5900 | H12B···C11 | 2.7749 |
O1···H3 | 2.4995 | H12B···H11C | 2.3448 |
O2···H15v | 2.8486 | H12C···H8A | 2.5486 |
O2···H6C | 2.4496 | H12C···H10B | 2.4475 |
O2···H10A | 2.4849 | H12C···C44viii | 3.0696 |
O2···H6A | 2.5702 | H12C···H44Bviii | 2.5724 |
O4···H22A | 2.4932 | H15···C19 | 2.7798 |
O4···H21A | 2.5917 | H15···F2 | 2.4833 |
O4···H22C | 2.6778 | H15···O2iii | 2.8486 |
O4···H19vi | 2.2020 | H16···O1iii | 2.8905 |
O4···H21C | 2.5614 | H16···C7iii | 3.0426 |
O5···H8Avi | 2.7871 | H16···C8iii | 3.0470 |
O5···H3 | 2.4281 | H16···H8Biii | 2.4084 |
O6···H1vii | 2.13 (4) | H17···C33vi | 2.8782 |
O6···H25 | 2.5082 | H18···H33Avi | 2.4870 |
O6···H30A | 2.7171 | H18···H3 | 2.2956 |
O6···H22Bvii | 2.8254 | H19···C15 | 2.9023 |
O6···H38iii | 2.8406 | H19···O4viii | 2.2020 |
O6···H43Cviii | 2.8853 | H21A···O1vi | 2.7627 |
O6···H6Bvii | 2.7151 | H21A···O4 | 2.5917 |
O6···H30B | 2.5714 | H21A···H28Bvi | 2.5982 |
O7···H28A | 2.3807 | H21A···C7vi | 2.9847 |
O7···H37iii | 2.8616 | H21A···H8Avi | 2.5967 |
O7···H32B | 2.5167 | H21B···F3xiii | 2.6741 |
O7···H28C | 2.6033 | H21C···O4 | 2.5614 |
O9···H41vi | 2.2372 | H21C···C12xiii | 2.9830 |
O9···H43A | 2.6129 | H21C···H9xiii | 2.4553 |
O9···H43C | 2.5737 | H22A···O4 | 2.4932 |
O9···H44A | 2.6162 | H22A···C20 | 2.8970 |
O9···H44C | 2.5681 | H22B···H34Aix | 2.2834 |
O10···H25 | 2.4184 | H22B···O6ii | 2.8254 |
O10···H30Bvi | 2.8981 | H22B···H1 | 2.0075 |
N1···O6ii | 3.080 (4) | H22B···C34ix | 2.9873 |
N1···O3 | 3.026 (3) | H22C···C20 | 3.0718 |
N1···F1 | 3.090 (4) | H22C···H6Cvi | 2.5742 |
N2···O8 | 3.024 (3) | H22C···O4 | 2.6778 |
N2···O1 | 3.060 (3) | H25···O6 | 2.5082 |
N2···F4 | 3.083 (3) | H25···O10 | 2.4184 |
C1···C19 | 3.492 (5) | H25···H34Avi | 2.4405 |
C1···O3 | 3.149 (4) | H25···H40 | 2.2977 |
C1···F1 | 3.168 (4) | H28A···O7 | 2.3807 |
C2···O3 | 3.137 (4) | H28A···C29 | 3.0265 |
C4···O3 | 3.025 (4) | H28A···H44Aviii | 2.5209 |
C5···O3 | 3.059 (4) | H28B···O1 | 2.5900 |
C6···F1 | 3.341 (4) | H28B···H2 | 2.1186 |
C6···O2 | 2.724 (4) | H28B···H21Aviii | 2.5982 |
C8···F4 | 3.363 (4) | H28C···F3iii | 2.5972 |
C13···O5 | 3.010 (4) | H28C···O7 | 2.6033 |
C13···O1 | 3.129 (4) | H28C···H32B | 2.4516 |
C15···F2 | 3.036 (4) | H30A···F1vii | 2.6608 |
C17···C33vi | 3.572 (5) | H30A···O6 | 2.7171 |
C18···O1 | 3.218 (4) | H30A···C38iii | 2.9517 |
C18···O5 | 3.184 (4) | H30A···H32A | 2.5795 |
C19···C1 | 3.492 (5) | H30A···H34C | 2.5636 |
C19···O4viii | 3.155 (5) | H30A···H38iii | 2.3121 |
C22···O4 | 2.802 (4) | H30B···O6 | 2.5714 |
C22···C34ix | 3.528 (5) | H30B···O10viii | 2.8981 |
C23···C41 | 3.522 (5) | H30B···H34A | 2.3479 |
C23···O8 | 3.131 (4) | H30B···H43Cviii | 2.5837 |
C23···F4 | 3.092 (4) | H31···C26viii | 2.7929 |
C24···O8 | 3.108 (4) | H31···C27viii | 2.9991 |
C26···O8 | 3.026 (4) | H31···C42viii | 2.9123 |
C27···O8 | 3.069 (4) | H31···H33A | 2.5073 |
C28···O7 | 2.703 (4) | H32A···H30A | 2.5795 |
C28···F4 | 3.249 (4) | H32A···H34C | 2.5020 |
C33···C17viii | 3.572 (5) | H32A···H43Axvi | 2.3663 |
C34···C22x | 3.528 (5) | H32B···F3iii | 2.6851 |
C35···O6 | 3.153 (4) | H32B···O7 | 2.5167 |
C35···O10 | 3.013 (4) | H32B···C28 | 3.0749 |
C37···F3 | 3.125 (4) | H32B···H28C | 2.4516 |
C40···O6 | 3.259 (4) | H33A···H18viii | 2.4870 |
C40···O10 | 3.173 (4) | H33A···H31 | 2.5073 |
C41···C23 | 3.522 (5) | H33B···H44Cxvi | 2.5964 |
C41···O9viii | 3.160 (4) | H33C···C34 | 2.8115 |
C43···F2xi | 3.323 (5) | H33C···H34B | 2.3085 |
C44···O9 | 2.814 (4) | H34A···C22x | 2.8434 |
C4···H10Bvi | 2.8863 | H34A···H22Bx | 2.2834 |
C5···H10Bvi | 2.9272 | H34A···H25viii | 2.4405 |
C6···H10A | 2.9596 | H34A···H30B | 2.3479 |
C7···H6C | 3.0545 | H34B···C33 | 2.7807 |
C7···H21Aviii | 2.9847 | H34B···C37xvi | 3.0191 |
C7···H16v | 3.0426 | H34B···C38xvi | 3.0981 |
C8···H16v | 3.0470 | H34B···H33C | 2.3085 |
C11···H39xii | 2.9129 | H34C···H30A | 2.5636 |
C11···H12B | 2.7749 | H34C···H32A | 2.5020 |
C12···H21Civ | 2.9830 | H37···F3 | 2.5651 |
C12···H11C | 2.8300 | H37···O7v | 2.8616 |
C14···H11Cxiii | 3.0563 | H37···C41 | 2.7383 |
C15···H19 | 2.9023 | H38···O6v | 2.8406 |
C15···H9iii | 2.9593 | H38···C29v | 3.0610 |
C19···H15 | 2.7798 | H38···C30v | 3.0856 |
C20···H8Avi | 2.9377 | H38···H30Av | 2.3121 |
C20···H22A | 2.8970 | H39···C11xv | 2.9129 |
C20···H22C | 3.0718 | H39···H11Bxv | 2.3101 |
C22···H34Aix | 2.8434 | H40···H11Bxv | 2.2376 |
C26···H31vi | 2.7929 | H40···H25 | 2.2977 |
C27···H31vi | 2.9991 | H41···O9viii | 2.2372 |
C28···H32B | 3.0749 | H41···C37 | 2.7932 |
C29···H43Cviii | 3.0990 | H43A···O9 | 2.6129 |
C29···H38iii | 3.0610 | H43A···H32Axiv | 2.3663 |
C29···H28A | 3.0265 | H43B···F2xi | 2.5600 |
C30···H38iii | 3.0856 | H43C···O6vi | 2.8853 |
C33···H17viii | 2.8782 | H43C···O9 | 2.5737 |
C33···H34B | 2.7807 | H43C···C29vi | 3.0990 |
C34···H33C | 2.8115 | H43C···H30Bvi | 2.5837 |
C34···H22Bx | 2.9873 | H44A···O9 | 2.6162 |
C37···H34Bxiv | 3.0191 | H44A···C42 | 2.9982 |
C37···H41 | 2.7932 | H44A···H28Avi | 2.5209 |
C38···H34Bxiv | 3.0981 | H44B···H2 | 2.0631 |
C38···H30Av | 2.9517 | H44B···H12Cvi | 2.5724 |
C39···H11Bxv | 2.8478 | H44C···O9 | 2.5681 |
C40···H11Bxv | 2.8245 | H44C···C42 | 2.9652 |
C41···H37 | 2.7383 | H44C···H33Bxiv | 2.5964 |
C7—O2—C8 | 117.5 (2) | H22B—C22—H22C | 109.47 |
C14—O3—C19 | 114.7 (3) | C5—C22—H22A | 109.52 |
C20—O5—C21 | 116.0 (3) | C5—C22—H22B | 109.41 |
C29—O7—C30 | 117.3 (2) | C5—C22—H22C | 109.44 |
C36—O8—C41 | 114.6 (2) | H22A—C22—H22B | 109.49 |
C42—O10—C43 | 116.5 (3) | H22A—C22—H22C | 109.50 |
C1—N1—C5 | 124.3 (3) | N2—C23—C24 | 118.9 (3) |
C1—N1—H1 | 122 (3) | C24—C23—C28 | 128.2 (3) |
C5—N1—H1 | 113 (3) | N2—C23—C28 | 112.9 (3) |
C23—N2—C27 | 124.7 (3) | C23—C24—C29 | 124.4 (3) |
C27—N2—H2 | 115 (3) | C23—C24—C25 | 121.3 (3) |
C23—N2—H2 | 120 (3) | C25—C24—C29 | 114.3 (3) |
C2—C1—C6 | 128.1 (3) | C24—C25—C35 | 111.9 (3) |
N1—C1—C2 | 119.0 (3) | C24—C25—C26 | 111.5 (2) |
N1—C1—C6 | 112.9 (3) | C26—C25—C35 | 112.2 (2) |
C1—C2—C7 | 125.1 (3) | C27—C26—C42 | 120.8 (3) |
C1—C2—C3 | 121.2 (3) | C25—C26—C27 | 121.0 (3) |
C3—C2—C7 | 113.6 (2) | C25—C26—C42 | 118.2 (3) |
C4—C3—C13 | 111.6 (3) | N2—C27—C44 | 113.6 (3) |
C2—C3—C13 | 112.2 (3) | N2—C27—C26 | 119.6 (3) |
C2—C3—C4 | 111.8 (3) | C26—C27—C44 | 126.8 (3) |
C5—C4—C20 | 120.6 (3) | O6—C29—C24 | 123.4 (3) |
C3—C4—C20 | 118.8 (3) | O6—C29—O7 | 121.8 (3) |
C3—C4—C5 | 120.6 (3) | O7—C29—C24 | 114.9 (3) |
N1—C5—C22 | 113.1 (3) | O7—C30—C31 | 107.6 (2) |
N1—C5—C4 | 120.0 (3) | C30—C31—C34 | 108.2 (3) |
C4—C5—C22 | 126.9 (3) | C30—C31—C32 | 112.7 (3) |
O1—C7—O2 | 121.8 (3) | C32—C31—C34 | 112.0 (3) |
O2—C7—C2 | 115.1 (3) | C31—C32—C33 | 114.8 (3) |
O1—C7—C2 | 123.1 (3) | C25—C35—C36 | 123.2 (3) |
O2—C8—C9 | 109.5 (2) | C36—C35—C40 | 116.3 (3) |
C8—C9—C12 | 108.8 (3) | C25—C35—C40 | 120.5 (3) |
C8—C9—C10 | 112.7 (3) | O8—C36—C37 | 120.6 (3) |
C10—C9—C12 | 111.5 (3) | C35—C36—C37 | 122.0 (3) |
C9—C10—C11 | 114.7 (4) | O8—C36—C35 | 117.4 (3) |
C14—C13—C18 | 116.3 (3) | C36—C37—C38 | 119.7 (3) |
C3—C13—C14 | 123.6 (3) | C37—C38—C39 | 120.1 (3) |
C3—C13—C18 | 120.2 (3) | C38—C39—C40 | 119.6 (3) |
O3—C14—C13 | 117.6 (3) | C35—C40—C39 | 122.2 (3) |
C13—C14—C15 | 122.1 (3) | F3—C41—O8 | 110.2 (3) |
O3—C14—C15 | 120.2 (3) | F4—C41—O8 | 107.1 (3) |
C14—C15—C16 | 119.7 (3) | F3—C41—F4 | 104.0 (2) |
C15—C16—C17 | 120.0 (3) | O10—C42—C26 | 111.8 (3) |
C16—C17—C18 | 119.5 (3) | O9—C42—O10 | 120.7 (3) |
C13—C18—C17 | 122.4 (3) | O9—C42—C26 | 127.4 (3) |
F1—C19—O3 | 107.8 (3) | C24—C25—H25 | 106.95 |
F2—C19—O3 | 109.8 (3) | C26—C25—H25 | 106.87 |
F1—C19—F2 | 104.0 (2) | C35—C25—H25 | 106.92 |
O4—C20—O5 | 121.0 (3) | C23—C28—H28A | 109.46 |
O5—C20—C4 | 111.9 (3) | C23—C28—H28B | 109.48 |
O4—C20—C4 | 127.1 (3) | C23—C28—H28C | 109.45 |
C13—C3—H3 | 106.95 | H28A—C28—H28B | 109.54 |
C2—C3—H3 | 106.95 | H28A—C28—H28C | 109.42 |
C4—C3—H3 | 107.00 | H28B—C28—H28C | 109.47 |
C1—C6—H6A | 109.47 | O7—C30—H30A | 110.18 |
H6A—C6—H6C | 109.43 | O7—C30—H30B | 110.20 |
H6B—C6—H6C | 109.49 | C31—C30—H30A | 110.20 |
C1—C6—H6C | 109.44 | C31—C30—H30B | 110.17 |
C1—C6—H6B | 109.51 | H30A—C30—H30B | 108.46 |
H6A—C6—H6B | 109.48 | C30—C31—H31 | 107.88 |
O2—C8—H8B | 109.76 | C32—C31—H31 | 107.94 |
O2—C8—H8A | 109.80 | C34—C31—H31 | 107.88 |
C9—C8—H8B | 109.79 | C31—C32—H32A | 108.58 |
H8A—C8—H8B | 108.25 | C31—C32—H32B | 108.54 |
C9—C8—H8A | 109.78 | C33—C32—H32A | 108.56 |
C12—C9—H9 | 107.91 | C33—C32—H32B | 108.63 |
C10—C9—H9 | 107.95 | H32A—C32—H32B | 107.54 |
C8—C9—H9 | 107.84 | C32—C33—H33A | 109.47 |
C9—C10—H10B | 108.63 | C32—C33—H33B | 109.46 |
C11—C10—H10B | 108.62 | C32—C33—H33C | 109.52 |
H10A—C10—H10B | 107.57 | H33A—C33—H33B | 109.40 |
C9—C10—H10A | 108.56 | H33A—C33—H33C | 109.51 |
C11—C10—H10A | 108.56 | H33B—C33—H33C | 109.48 |
C10—C11—H11C | 109.48 | C31—C34—H34A | 109.49 |
H11A—C11—H11B | 109.45 | C31—C34—H34B | 109.52 |
C10—C11—H11A | 109.50 | C31—C34—H34C | 109.47 |
C10—C11—H11B | 109.46 | H34A—C34—H34B | 109.46 |
H11A—C11—H11C | 109.47 | H34A—C34—H34C | 109.44 |
H11B—C11—H11C | 109.46 | H34B—C34—H34C | 109.45 |
C9—C12—H12C | 109.43 | C36—C37—H37 | 120.12 |
H12A—C12—H12C | 109.45 | C38—C37—H37 | 120.13 |
H12B—C12—H12C | 109.49 | C37—C38—H38 | 120.02 |
H12A—C12—H12B | 109.45 | C39—C38—H38 | 119.87 |
C9—C12—H12B | 109.49 | C38—C39—H39 | 120.24 |
C9—C12—H12A | 109.52 | C40—C39—H39 | 120.18 |
C14—C15—H15 | 120.20 | C35—C40—H40 | 118.97 |
C16—C15—H15 | 120.11 | C39—C40—H40 | 118.80 |
C15—C16—H16 | 120.04 | F3—C41—H41 | 111.71 |
C17—C16—H16 | 120.01 | F4—C41—H41 | 111.71 |
C16—C17—H17 | 120.21 | O8—C41—H41 | 111.75 |
C18—C17—H17 | 120.27 | O10—C43—H43A | 109.45 |
C17—C18—H18 | 118.72 | O10—C43—H43B | 109.43 |
C13—C18—H18 | 118.91 | O10—C43—H43C | 109.45 |
O3—C19—H19 | 111.65 | H43A—C43—H43B | 109.54 |
F1—C19—H19 | 111.58 | H43A—C43—H43C | 109.43 |
F2—C19—H19 | 111.65 | H43B—C43—H43C | 109.54 |
O5—C21—H21B | 109.49 | C27—C44—H44A | 109.49 |
H21A—C21—H21C | 109.43 | C27—C44—H44B | 109.43 |
O5—C21—H21A | 109.50 | C27—C44—H44C | 109.44 |
O5—C21—H21C | 109.52 | H44A—C44—H44B | 109.48 |
H21A—C21—H21B | 109.50 | H44A—C44—H44C | 109.53 |
H21B—C21—H21C | 109.39 | H44B—C44—H44C | 109.45 |
C7—O2—C8—C9 | −159.7 (3) | C3—C4—C20—O5 | 2.5 (4) |
O2—C8—C9—C10 | −57.5 (4) | C3—C4—C20—O4 | −179.6 (4) |
C8—C9—C10—C11 | 173.1 (4) | O2—C8—C9—C12 | 178.3 (3) |
C29—O7—C30—C31 | −170.7 (3) | C12—C9—C10—C11 | −64.2 (5) |
O7—C30—C31—C32 | −60.9 (3) | C18—C13—C14—C15 | 3.5 (5) |
C30—C31—C32—C33 | 174.9 (3) | C3—C13—C18—C17 | 178.7 (3) |
C8—O2—C7—O1 | 6.7 (4) | C14—C13—C18—C17 | −1.2 (5) |
C8—O2—C7—C2 | −173.1 (3) | C3—C13—C14—O3 | 0.1 (5) |
C19—O3—C14—C13 | 126.2 (3) | C3—C13—C14—C15 | −176.4 (3) |
C19—O3—C14—C15 | −57.3 (4) | C18—C13—C14—O3 | 180.0 (3) |
C14—O3—C19—F1 | −157.8 (2) | O3—C14—C15—C16 | 179.9 (3) |
C14—O3—C19—F2 | 89.5 (3) | C13—C14—C15—C16 | −3.7 (5) |
C21—O5—C20—O4 | 3.7 (5) | C14—C15—C16—C17 | 1.5 (5) |
C21—O5—C20—C4 | −178.3 (3) | C15—C16—C17—C18 | 0.7 (5) |
C30—O7—C29—C24 | 173.5 (3) | C16—C17—C18—C13 | −0.8 (5) |
C30—O7—C29—O6 | −6.7 (4) | N2—C23—C24—C25 | −7.4 (5) |
C36—O8—C41—F4 | 152.2 (2) | C28—C23—C24—C29 | −6.2 (6) |
C41—O8—C36—C35 | −128.1 (3) | N2—C23—C24—C29 | 172.7 (3) |
C41—O8—C36—C37 | 53.5 (4) | C28—C23—C24—C25 | 173.7 (3) |
C36—O8—C41—F3 | −95.2 (3) | C29—C24—C25—C35 | 71.1 (3) |
C43—O10—C42—O9 | −4.9 (5) | C23—C24—C29—O6 | −173.2 (3) |
C43—O10—C42—C26 | 176.3 (3) | C23—C24—C29—O7 | 6.7 (5) |
C1—N1—C5—C22 | 171.6 (3) | C25—C24—C29—O6 | 6.9 (5) |
C5—N1—C1—C6 | −172.5 (3) | C25—C24—C29—O7 | −173.2 (3) |
C5—N1—C1—C2 | 6.6 (5) | C23—C24—C25—C26 | 17.9 (4) |
C1—N1—C5—C4 | −8.2 (5) | C23—C24—C25—C35 | −108.8 (4) |
C23—N2—C27—C44 | −171.4 (3) | C29—C24—C25—C26 | −162.2 (3) |
C23—N2—C27—C26 | 8.1 (4) | C24—C25—C26—C42 | 164.8 (3) |
C27—N2—C23—C24 | −6.8 (5) | C35—C25—C26—C27 | 109.9 (3) |
C27—N2—C23—C28 | 172.2 (3) | C35—C25—C26—C42 | −68.7 (3) |
C6—C1—C2—C7 | 5.9 (6) | C24—C25—C35—C36 | 66.4 (4) |
N1—C1—C2—C7 | −173.0 (3) | C24—C25—C35—C40 | −114.7 (3) |
N1—C1—C2—C3 | 7.9 (5) | C26—C25—C35—C36 | −59.9 (4) |
C6—C1—C2—C3 | −173.2 (3) | C24—C25—C26—C27 | −16.6 (4) |
C7—C2—C3—C4 | 162.3 (3) | C26—C25—C35—C40 | 119.0 (3) |
C1—C2—C3—C13 | 107.8 (4) | C42—C26—C27—C44 | 2.9 (5) |
C1—C2—C7—O2 | −4.0 (5) | C25—C26—C42—O9 | 175.2 (3) |
C7—C2—C3—C13 | −71.4 (3) | C42—C26—C27—N2 | −176.5 (3) |
C1—C2—C7—O1 | 176.2 (3) | C27—C26—C42—O9 | −3.4 (5) |
C1—C2—C3—C4 | −18.4 (5) | C27—C26—C42—O10 | 175.3 (3) |
C3—C2—C7—O1 | −4.6 (5) | C25—C26—C42—O10 | −6.1 (4) |
C3—C2—C7—O2 | 175.2 (3) | C25—C26—C27—N2 | 4.9 (4) |
C2—C3—C4—C5 | 16.8 (5) | C25—C26—C27—C44 | −175.7 (3) |
C13—C3—C4—C20 | 70.4 (4) | O7—C30—C31—C34 | 174.7 (3) |
C2—C3—C4—C20 | −163.0 (3) | C34—C31—C32—C33 | −62.7 (4) |
C13—C3—C4—C5 | −109.8 (4) | C40—C35—C36—O8 | 179.6 (3) |
C2—C3—C13—C14 | −66.1 (4) | C25—C35—C36—O8 | −1.4 (5) |
C4—C3—C13—C14 | 60.2 (4) | C25—C35—C36—C37 | 177.0 (3) |
C4—C3—C13—C18 | −119.7 (3) | C36—C35—C40—C39 | 0.7 (5) |
C2—C3—C13—C18 | 114.0 (3) | C40—C35—C36—C37 | −1.9 (5) |
C3—C4—C5—N1 | −4.8 (5) | C25—C35—C40—C39 | −178.3 (3) |
C3—C4—C5—C22 | 175.4 (3) | C35—C36—C37—C38 | 1.5 (5) |
C20—C4—C5—C22 | −4.8 (6) | O8—C36—C37—C38 | 179.9 (3) |
C5—C4—C20—O4 | 0.6 (6) | C36—C37—C38—C39 | 0.3 (5) |
C20—C4—C5—N1 | 175.0 (3) | C37—C38—C39—C40 | −1.6 (5) |
C5—C4—C20—O5 | −177.3 (3) | C38—C39—C40—C35 | 1.1 (5) |
Symmetry codes: (i) x−1, y−1, z+1; (ii) x, y, z+1; (iii) x, y−1, z; (iv) x−1, y+1, z; (v) x, y+1, z; (vi) x+1, y, z; (vii) x, y, z−1; (viii) x−1, y, z; (ix) x+1, y, z+1; (x) x−1, y, z−1; (xi) x+1, y+1, z−1; (xii) x−1, y, z+1; (xiii) x+1, y−1, z; (xiv) x+1, y+1, z; (xv) x+1, y, z−1; (xvi) x−1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6ii | 0.96 (4) | 2.13 (4) | 3.080 (4) | 171 (4) |
N2—H2···O1 | 0.88 (4) | 2.19 (4) | 3.060 (3) | 171 (4) |
C8—H8B···F4 | 0.99 | 2.43 | 3.363 (4) | 157 |
C10—H10A···O2 | 0.99 | 2.48 | 2.894 (5) | 104 |
C15—H15···F2 | 0.95 | 2.48 | 3.036 (4) | 117 |
C19—H19···O4viii | 1.00 | 2.20 | 3.155 (5) | 159 |
C28—H28B···O1 | 0.98 | 2.59 | 3.494 (4) | 153 |
C32—H32B···O7 | 0.99 | 2.52 | 2.906 (4) | 103 |
C41—H41···O9viii | 1.00 | 2.24 | 3.160 (4) | 153 |
Symmetry codes: (ii) x, y, z+1; (viii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C22H27F2NO5 |
Mr | 423.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 8.2340 (16), 8.7827 (18), 14.9145 (18) |
α, β, γ (°) | 89.299 (11), 78.697 (11), 89.906 (7) |
V (Å3) | 1057.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.3 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21160, 4617, 3257 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.095, 1.02 |
No. of reflections | 4617 |
No. of parameters | 549 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.23 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), PLATON.
N1—C1 | 1.381 (4) | N2—C23 | 1.372 (4) |
N1—C5 | 1.374 (5) | N2—C27 | 1.371 (4) |
C1—C2 | 1.354 (4) | C23—C24 | 1.362 (4) |
C2—C3 | 1.532 (5) | C24—C25 | 1.522 (5) |
C3—C4 | 1.521 (5) | C25—C26 | 1.520 (5) |
C4—C5 | 1.360 (4) | C26—C27 | 1.356 (4) |
C7—O2—C8—C9 | −159.7 (3) | C29—O7—C30—C31 | −170.7 (3) |
O2—C8—C9—C10 | −57.5 (4) | O7—C30—C31—C32 | −60.9 (3) |
C8—C9—C10—C11 | 173.1 (4) | C30—C31—C32—C33 | 174.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6i | 0.96 (4) | 2.13 (4) | 3.080 (4) | 171 (4) |
N2—H2···O1 | 0.88 (4) | 2.19 (4) | 3.060 (3) | 171 (4) |
C19—H19···O4ii | 1.00 | 2.20 | 3.155 (5) | 159 |
C41—H41···O9ii | 1.00 | 2.24 | 3.160 (4) | 153 |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z. |
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In order to investigate the stereochemical course of the Candida rugosa lipase mediated kinetic resolution of 3-acyloxymethyl-4-aryl-1,4-dihydropyridine-3,5-dicarboxylates, a derivative containing a second chiral centre of known configuration was prepared. This would allow the determination of the relative configuration of the chiral centre at C4 (labeled C3 and C25 in the presented structure). The enzymatically prepared carboxylic acid (1) was esterified to (S)-2-methyl-1-butanol, giving the title compound, (2), and its crystal structure was determined. However, since the starting material was not entirely stereochemically pure, there was a risk that the two diastereomers would preferentially crystallize together. This indeed proved to be the case, as is shown in Fig. 1. Later, compound (2) was prepared in stereochemically pure form. Unfortunately, we could not obtain crystals suitable for a structure determination from this material.
The asymmetric unit contains two molecules, which are diastereomers with configuration (R,S) and (S,S) at (C3,C9) and (C25,C31), respectively. These configurations have been assigned with reference to the known (S)-configuration of atoms C9 and C31. The diastereomers have adopted conformations which are related by an inversion operation, with the exception of the 2-methylbutyl moiety. This is illustrated in Fig. 2, which displays a fit of molecule (1) and the inverted molecule (2). In the crystal, the molecules are related by a pseudo-c-glide plane, with exception of the 2-methylbutyl moiety. The unit cell displays a pseudo-monoclinic geometry, with the pseudo-glide plane parallel to the a and c axes. The best-fit between the molecules is obtained by a rotation of -176° over the rotary-inversion axis [-0.018,-1.000,0.042], combined with a shift of 7.226 Å (i.e. 0.48c) in the direction [0.002,-0.096,-1.000]. The unit weight r.m.s. fit is 0.31 Å, with the largest deviations for atoms C9, C10 and C12 of molecule (1).
Addition of the difluoromethoxyphenyl moiety to the dihydropyridine ring results in a slight deformation from planarity towards a sofa conformation in both diastereomers. The relevant asymmetry parameters (Duax & Norton, 1975) are ΔCs[N1] = 2.2 (4)° for molecule (1) and ΔCs[N2] = 1.8 (4)° for molecule (2); all other asymmetry parameters are at least 10°. The total puckering amplitude (Cremer & Pople, 1975) of the dihydropyridine ring is 0.177 (3) Å in molecule (1) and 0.173 (3) Å in molecule (2). The phenyl rings show total puckering amplitudes of 0.029 (3) and 0.019 (3) for molecules (1) and (2), respectively. For these rings, all asymmetry parameters are less then 5°. Hydrogenation of the pyridine N atom apparently has no influence on its hybridization (sp2) or the planarity of this part of the six-membered ring. The bond distances along the dihydropyridine rings indicate delocalization of the formal double bonds of the C═C—N—C═C fragment (see Table 1).
Crystal packing involves the formation of chains, parallel to the c axis, consisting of molecules connected by N—H···O hydrogen bonds (see Fig. 3 and Table 2). Each chain consists of an alternation of both diastereomers. The unitary graph set is DD, the binary graph set is C22[12] (Bernstein et al., 1995). Two neighbouring chains are connected by C—H···O hydrogen bonds linking the F2OCH moiety to the O═C acceptor of the carboxylate moiety. These hydrogen bonds form links between equal stereoisomers. Both types of hydrogen bond together create a two-dimensional network of hydrogen-bonded molecules, with main axes a and c.