Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104001659/fr1452sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104001659/fr1452IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104001659/fr1452IIIsup3.hkl |
CCDC references: 235349; 235350
To a solution of (I) (2.12 g, 5.00 mmol) in dry benzene (15 ml) in a 100 ml Schlenk tube, was added bis(tributyltin)oxide [(Bu3Sn)2O, 0.38 ml, 0.75 mmol], PhSiH3 (0.31 ml, 2.50 mmol), EtOH (0.585 ml, 2.00 mmol) and 2,2'-azobisisobutyronitrile (AIBN, 90 mg, 0.548 mmol) in benzene (2.0 ml). The vessel was sealed, shaken and placed in an oil bath at 353–358 K. After 12 h, thin-layer chromatography analysis indicated that all of the starting material had been consumed. The mixture was allowed to cool to room temperature, and tetrabutylammonium fluoride (30.0 ml of a 1.0 M solution in tetrahydrofuran, 30.0 mmol) was added with stirring for 2 h, at the end of which time 2 M HCl (15 ml) was added. The reaction mixture was extracted with CH2Cl2 (3 × 50 ml), and the combined organic extracts were dried (MgSO4), filtered, and concentrated. The residue was purified by flash chromatography (eluting with 3:1:0.01 CH2Cl2–EtOAc–MeOH) to give 827 mg (69%) of compound (II) in the nonsolvated form. Analysis: [α]D22 78.3° (c 0.48, CHCl3); HREIMS, calculated for C24H27NO6: 425.1838; found: m/z 425.1842. Compound (III) was obtained as 30% of the final product. Analysis: [α]D22 −104.2° (c 1.0, CHCl3)l; HREIMS, calculated for C24H27NO6: 425.1838; found: m/z 425.1842. Single crystals of (II) as the actone solvate and (III) were obtained from 2:1 acetone–MeOH solutions after partial evaporation. The crystal of (II) was shown to be a racemic mixture, a fact that indicates that either the ring closure of (I) to (II) is accompanied by racemization, or that the starting material, (I), was partially racemized.
Most H atoms were introduced at calculated positions and refined by applying a riding model [C—H = 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C), and O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O)]. The hydroxyl H atoms in (III) were located in the difference Fourier maps and refined with contraints on their positions and Ueq. Friedel equivalents were merged before the final refinement.
For both compounds, data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
C24H27NO6·C3H6O | F(000) = 1032 |
Mr = 483.54 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3948 reflections |
a = 11.579 (1) Å | θ = 2.2–22.1° |
b = 17.4011 (15) Å | µ = 0.09 mm−1 |
c = 13.0453 (11) Å | T = 295 K |
β = 110.488 (2)° | Block, colorless |
V = 2462.2 (4) Å3 | 0.50 × 0.20 × 0.15 mm |
Z = 4 |
Bruker SMART 1000 CCD area-detector diffractometer | 5059 independent reflections |
Radiation source: fine-focus sealed tube | 2927 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: not measured pixels mm-1 | θmax = 26.4°, θmin = 1.9° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −21→21 |
Tmin = 0.881, Tmax = 0.986 | l = −16→16 |
24264 measured 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) = 0.127 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0429P)2 + 0.9647P] where P = (Fo2 + 2Fc2)/3 |
5059 reflections | (Δ/σ)max < 0.001 |
323 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C24H27NO6·C3H6O | V = 2462.2 (4) Å3 |
Mr = 483.54 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.579 (1) Å | µ = 0.09 mm−1 |
b = 17.4011 (15) Å | T = 295 K |
c = 13.0453 (11) Å | 0.50 × 0.20 × 0.15 mm |
β = 110.488 (2)° |
Bruker SMART 1000 CCD area-detector diffractometer | 5059 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2927 reflections with I > 2σ(I) |
Tmin = 0.881, Tmax = 0.986 | Rint = 0.053 |
24264 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.18 e Å−3 |
5059 reflections | Δρmin = −0.19 e Å−3 |
323 parameters |
Experimental. Data were collected using a Bruker AXS SMART 1000 diffractometer equipped with a CCD area detector and graphite monochromated Mo source. Data were measured using phi–omega scans of 0.3 degrees with an integration time of 20 s. A total of 2424 frames were collected, with the initial 606 frames recollected in the final run. |
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. 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 | ||
C1 | 0.1543 (2) | −0.01425 (14) | 0.10333 (19) | 0.0604 (7) | |
H1A | 0.0819 | 0.0165 | 0.0914 | 0.091* | |
H1B | 0.1309 | −0.0630 | 0.0677 | 0.091* | |
H1C | 0.2089 | 0.0116 | 0.0738 | 0.091* | |
C2 | 0.3529 (2) | −0.06856 (13) | 0.53935 (19) | 0.0512 (6) | |
H2A | 0.4352 | −0.0490 | 0.5721 | 0.077* | |
H2B | 0.3532 | −0.1231 | 0.5501 | 0.077* | |
H2C | 0.3003 | −0.0447 | 0.5729 | 0.077* | |
C3 | 0.25460 (19) | 0.03781 (12) | 0.28201 (17) | 0.0406 (5) | |
C4 | 0.30507 (19) | 0.02331 (12) | 0.39474 (18) | 0.0405 (5) | |
C5 | 0.34822 (19) | 0.08446 (12) | 0.46480 (18) | 0.0400 (5) | |
H5A | 0.3797 | 0.0754 | 0.5398 | 0.048* | |
C6 | 0.34609 (17) | 0.15991 (11) | 0.42657 (16) | 0.0338 (5) | |
C7 | 0.40326 (18) | 0.22438 (12) | 0.50131 (16) | 0.0351 (5) | |
C8 | 0.49298 (19) | 0.21275 (13) | 0.60472 (17) | 0.0413 (5) | |
H8 | 0.5175 | 0.1629 | 0.6280 | 0.050* | |
C9 | 0.54587 (19) | 0.27339 (13) | 0.67293 (17) | 0.0427 (5) | |
C10 | 0.6539 (2) | 0.19243 (15) | 0.8237 (2) | 0.0653 (7) | |
H10A | 0.5795 | 0.1747 | 0.8328 | 0.098* | |
H10B | 0.7186 | 0.1952 | 0.8939 | 0.098* | |
H10C | 0.6771 | 0.1574 | 0.7775 | 0.098* | |
C11 | 0.5103 (2) | 0.34864 (13) | 0.63814 (18) | 0.0438 (6) | |
C12 | 0.5331 (3) | 0.48237 (14) | 0.6793 (2) | 0.0772 (9) | |
H12A | 0.5465 | 0.4939 | 0.6123 | 0.116* | |
H12B | 0.5812 | 0.5166 | 0.7358 | 0.116* | |
H12C | 0.4473 | 0.4886 | 0.6686 | 0.116* | |
C13 | 0.42294 (19) | 0.36036 (12) | 0.53622 (17) | 0.0412 (5) | |
H13 | 0.3992 | 0.4104 | 0.5131 | 0.049* | |
C14 | 0.36895 (18) | 0.29957 (12) | 0.46665 (17) | 0.0366 (5) | |
C15 | 0.27294 (18) | 0.31329 (11) | 0.35567 (16) | 0.0346 (5) | |
H15 | 0.2857 | 0.3651 | 0.3320 | 0.041* | |
C16 | 0.28947 (18) | 0.25572 (11) | 0.27239 (16) | 0.0348 (5) | |
H16 | 0.3706 | 0.2657 | 0.2673 | 0.042* | |
C17 | 0.29183 (18) | 0.17365 (11) | 0.31445 (16) | 0.0337 (5) | |
C18 | 0.24728 (19) | 0.11188 (12) | 0.24380 (18) | 0.0391 (5) | |
H18 | 0.2118 | 0.1210 | 0.1690 | 0.047* | |
C19 | 0.14134 (18) | 0.30933 (11) | 0.35750 (16) | 0.0352 (5) | |
H19 | 0.1276 | 0.2586 | 0.3838 | 0.042* | |
C20 | 0.04680 (19) | 0.32278 (12) | 0.24428 (17) | 0.0389 (5) | |
H20 | 0.0522 | 0.3762 | 0.2226 | 0.047* | |
C21 | 0.19377 (18) | 0.27097 (12) | 0.15938 (17) | 0.0388 (5) | |
H21A | 0.2101 | 0.3203 | 0.1325 | 0.047* | |
H21B | 0.1994 | 0.2315 | 0.1088 | 0.047* | |
C22 | −0.08685 (19) | 0.30454 (14) | 0.23165 (19) | 0.0503 (6) | |
H22A | −0.0900 | 0.2715 | 0.2905 | 0.060* | |
H22B | −0.1322 | 0.3513 | 0.2320 | 0.060* | |
C23 | −0.1396 (2) | 0.26412 (15) | 0.1227 (2) | 0.0546 (6) | |
H23A | −0.1898 | 0.2207 | 0.1279 | 0.066* | |
H23B | −0.1900 | 0.2990 | 0.0670 | 0.066* | |
C24 | −0.0301 (2) | 0.23760 (13) | 0.09567 (18) | 0.0412 (5) | |
C25 | 0.1146 (5) | 0.5531 (2) | 0.2920 (4) | 0.160 (2) | |
H25A | 0.1791 | 0.5893 | 0.3264 | 0.240* | |
H25B | 0.1333 | 0.5050 | 0.3302 | 0.240* | |
H25C | 0.0378 | 0.5724 | 0.2940 | 0.240* | |
C26 | 0.1050 (3) | 0.54174 (18) | 0.1774 (4) | 0.0904 (11) | |
C27 | 0.0418 (5) | 0.6002 (2) | 0.0957 (4) | 0.165 (2) | |
H27A | 0.0305 | 0.5811 | 0.0238 | 0.248* | |
H27B | 0.0907 | 0.6461 | 0.1089 | 0.248* | |
H27C | −0.0370 | 0.6114 | 0.1010 | 0.248* | |
N | 0.07057 (15) | 0.27108 (9) | 0.16496 (13) | 0.0360 (4) | |
O1 | 0.21508 (16) | −0.02587 (8) | 0.21755 (12) | 0.0577 (5) | |
O2 | 0.30827 (16) | −0.05203 (8) | 0.42513 (13) | 0.0558 (5) | |
O3 | 0.63375 (15) | 0.26620 (10) | 0.77504 (13) | 0.0601 (5) | |
O4 | 0.56892 (16) | 0.40553 (9) | 0.71030 (13) | 0.0609 (5) | |
O5 | 0.12789 (14) | 0.36661 (8) | 0.43017 (12) | 0.0469 (4) | |
H5 | 0.0795 | 0.3515 | 0.4591 | 0.070* | |
O6 | −0.03307 (14) | 0.19344 (10) | 0.02046 (13) | 0.0567 (5) | |
O7 | 0.1535 (2) | 0.48566 (13) | 0.1545 (2) | 0.1023 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0808 (18) | 0.0475 (15) | 0.0347 (14) | −0.0087 (13) | −0.0026 (13) | −0.0083 (12) |
C2 | 0.0604 (15) | 0.0434 (14) | 0.0397 (14) | −0.0048 (11) | 0.0052 (11) | 0.0065 (11) |
C3 | 0.0467 (12) | 0.0346 (12) | 0.0330 (13) | −0.0027 (10) | 0.0046 (10) | −0.0061 (10) |
C4 | 0.0456 (12) | 0.0326 (12) | 0.0367 (13) | −0.0003 (9) | 0.0060 (10) | −0.0007 (10) |
C5 | 0.0449 (12) | 0.0408 (13) | 0.0286 (12) | −0.0009 (10) | 0.0057 (10) | −0.0001 (10) |
C6 | 0.0346 (11) | 0.0351 (12) | 0.0292 (11) | −0.0002 (9) | 0.0081 (9) | −0.0016 (9) |
C7 | 0.0368 (11) | 0.0372 (12) | 0.0297 (12) | −0.0037 (9) | 0.0095 (9) | −0.0042 (9) |
C8 | 0.0441 (12) | 0.0390 (12) | 0.0358 (13) | 0.0013 (10) | 0.0076 (10) | −0.0035 (10) |
C9 | 0.0423 (12) | 0.0489 (14) | 0.0311 (13) | −0.0043 (10) | 0.0055 (10) | −0.0044 (11) |
C10 | 0.0575 (16) | 0.0692 (19) | 0.0519 (17) | 0.0082 (14) | −0.0024 (13) | 0.0051 (14) |
C11 | 0.0489 (13) | 0.0421 (14) | 0.0350 (13) | −0.0129 (10) | 0.0079 (11) | −0.0098 (11) |
C12 | 0.107 (2) | 0.0448 (16) | 0.0533 (18) | −0.0236 (16) | −0.0050 (16) | −0.0075 (14) |
C13 | 0.0513 (13) | 0.0341 (12) | 0.0335 (13) | −0.0089 (10) | 0.0089 (11) | −0.0031 (10) |
C14 | 0.0391 (11) | 0.0369 (12) | 0.0322 (12) | −0.0068 (9) | 0.0106 (9) | −0.0027 (10) |
C15 | 0.0431 (11) | 0.0285 (11) | 0.0294 (11) | −0.0066 (9) | 0.0093 (9) | −0.0002 (9) |
C16 | 0.0373 (11) | 0.0370 (12) | 0.0304 (12) | −0.0054 (9) | 0.0119 (9) | −0.0020 (9) |
C17 | 0.0353 (11) | 0.0344 (11) | 0.0308 (12) | −0.0002 (9) | 0.0110 (9) | −0.0028 (9) |
C18 | 0.0449 (12) | 0.0377 (13) | 0.0294 (12) | −0.0004 (10) | 0.0063 (10) | −0.0016 (10) |
C19 | 0.0469 (12) | 0.0276 (11) | 0.0303 (11) | −0.0015 (9) | 0.0126 (10) | −0.0038 (9) |
C20 | 0.0499 (13) | 0.0302 (11) | 0.0331 (12) | 0.0036 (10) | 0.0101 (10) | −0.0008 (9) |
C21 | 0.0481 (12) | 0.0372 (12) | 0.0330 (12) | −0.0059 (10) | 0.0165 (10) | 0.0001 (10) |
C22 | 0.0441 (13) | 0.0568 (15) | 0.0456 (15) | 0.0105 (11) | 0.0101 (11) | −0.0059 (12) |
C23 | 0.0444 (13) | 0.0637 (16) | 0.0489 (16) | 0.0054 (12) | 0.0077 (11) | −0.0059 (13) |
C24 | 0.0449 (12) | 0.0409 (13) | 0.0323 (12) | −0.0007 (10) | 0.0068 (10) | −0.0003 (10) |
C25 | 0.259 (7) | 0.102 (3) | 0.179 (5) | 0.000 (4) | 0.153 (5) | −0.019 (3) |
C26 | 0.107 (3) | 0.0481 (19) | 0.142 (4) | −0.0124 (18) | 0.076 (3) | −0.006 (2) |
C27 | 0.202 (5) | 0.086 (3) | 0.188 (5) | 0.040 (3) | 0.045 (4) | 0.024 (3) |
N | 0.0396 (9) | 0.0365 (10) | 0.0287 (10) | −0.0002 (8) | 0.0080 (8) | −0.0026 (8) |
O1 | 0.0873 (12) | 0.0353 (9) | 0.0343 (9) | −0.0065 (8) | 0.0007 (9) | −0.0053 (7) |
O2 | 0.0818 (12) | 0.0342 (9) | 0.0374 (10) | −0.0036 (8) | 0.0034 (8) | 0.0026 (7) |
O3 | 0.0640 (10) | 0.0525 (11) | 0.0411 (10) | −0.0007 (8) | −0.0100 (8) | −0.0071 (8) |
O4 | 0.0797 (12) | 0.0420 (10) | 0.0419 (10) | −0.0156 (8) | −0.0026 (9) | −0.0095 (8) |
O5 | 0.0600 (10) | 0.0427 (9) | 0.0401 (10) | 0.0009 (7) | 0.0201 (8) | −0.0106 (7) |
O6 | 0.0571 (10) | 0.0644 (11) | 0.0458 (10) | −0.0092 (8) | 0.0145 (8) | −0.0221 (9) |
O7 | 0.138 (2) | 0.0604 (14) | 0.139 (2) | 0.0010 (14) | 0.0865 (18) | 0.0021 (14) |
C1—O1 | 1.422 (3) | C15—C19 | 1.534 (3) |
C1—H1A | 0.9600 | C15—C16 | 1.538 (3) |
C1—H1B | 0.9600 | C15—H15 | 0.9800 |
C1—H1C | 0.9600 | C16—C21 | 1.526 (3) |
C2—O2 | 1.425 (3) | C16—C17 | 1.527 (3) |
C2—H2A | 0.9600 | C16—H16 | 0.9800 |
C2—H2B | 0.9600 | C17—C18 | 1.392 (3) |
C2—H2C | 0.9600 | C18—H18 | 0.9300 |
C3—O1 | 1.369 (2) | C19—O5 | 1.421 (2) |
C3—C18 | 1.374 (3) | C19—C20 | 1.517 (3) |
C3—C4 | 1.402 (3) | C19—H19 | 0.9800 |
C4—O2 | 1.366 (2) | C20—N | 1.468 (3) |
C4—C5 | 1.377 (3) | C20—C22 | 1.531 (3) |
C5—C6 | 1.402 (3) | C20—H20 | 0.9800 |
C5—H5A | 0.9300 | C21—N | 1.454 (3) |
C6—C17 | 1.396 (3) | C21—H21A | 0.9700 |
C6—C7 | 1.482 (3) | C21—H21B | 0.9700 |
C7—C14 | 1.396 (3) | C22—C23 | 1.510 (3) |
C7—C8 | 1.400 (3) | C22—H22A | 0.9700 |
C8—C9 | 1.378 (3) | C22—H22B | 0.9700 |
C8—H8 | 0.9300 | C23—C24 | 1.503 (3) |
C9—O3 | 1.370 (2) | C23—H23A | 0.9700 |
C9—C11 | 1.400 (3) | C23—H23B | 0.9700 |
C10—O3 | 1.415 (3) | C24—O6 | 1.237 (2) |
C10—H10A | 0.9600 | C24—N | 1.333 (3) |
C10—H10B | 0.9600 | C25—C26 | 1.473 (5) |
C10—H10C | 0.9600 | C25—H25A | 0.9600 |
C11—O4 | 1.371 (2) | C25—H25B | 0.9600 |
C11—C13 | 1.375 (3) | C25—H25C | 0.9600 |
C12—O4 | 1.416 (3) | C26—O7 | 1.214 (3) |
C12—H12A | 0.9600 | C26—C27 | 1.469 (5) |
C12—H12B | 0.9600 | C27—H27A | 0.9600 |
C12—H12C | 0.9600 | C27—H27B | 0.9600 |
C13—C14 | 1.392 (3) | C27—H27C | 0.9600 |
C13—H13 | 0.9300 | O5—H5 | 0.8200 |
C14—C15 | 1.504 (3) | ||
O1—C1—H1A | 109.5 | C17—C16—H16 | 107.0 |
O1—C1—H1B | 109.5 | C15—C16—H16 | 107.0 |
H1A—C1—H1B | 109.5 | C18—C17—C6 | 119.22 (19) |
O1—C1—H1C | 109.5 | C18—C17—C16 | 121.90 (18) |
H1A—C1—H1C | 109.5 | C6—C17—C16 | 118.80 (17) |
H1B—C1—H1C | 109.5 | C3—C18—C17 | 121.5 (2) |
O2—C2—H2A | 109.5 | C3—C18—H18 | 119.2 |
O2—C2—H2B | 109.5 | C17—C18—H18 | 119.2 |
H2A—C2—H2B | 109.5 | O5—C19—C20 | 109.32 (16) |
O2—C2—H2C | 109.5 | O5—C19—C15 | 108.68 (16) |
H2A—C2—H2C | 109.5 | C20—C19—C15 | 111.11 (17) |
H2B—C2—H2C | 109.5 | O5—C19—H19 | 109.2 |
O1—C3—C18 | 124.86 (19) | C20—C19—H19 | 109.2 |
O1—C3—C4 | 115.18 (19) | C15—C19—H19 | 109.2 |
C18—C3—C4 | 119.96 (19) | N—C20—C19 | 110.01 (16) |
O2—C4—C5 | 125.6 (2) | N—C20—C22 | 103.23 (16) |
O2—C4—C3 | 115.85 (18) | C19—C20—C22 | 115.49 (18) |
C5—C4—C3 | 118.6 (2) | N—C20—H20 | 109.3 |
C4—C5—C6 | 122.0 (2) | C19—C20—H20 | 109.3 |
C4—C5—H5A | 119.0 | C22—C20—H20 | 109.3 |
C6—C5—H5A | 119.0 | N—C21—C16 | 110.20 (16) |
C17—C6—C5 | 118.61 (18) | N—C21—H21A | 109.6 |
C17—C6—C7 | 119.57 (18) | C16—C21—H21A | 109.6 |
C5—C6—C7 | 121.80 (18) | N—C21—H21B | 109.6 |
C14—C7—C8 | 118.61 (19) | C16—C21—H21B | 109.6 |
C14—C7—C6 | 119.05 (18) | H21A—C21—H21B | 108.1 |
C8—C7—C6 | 122.32 (19) | C23—C22—C20 | 104.98 (18) |
C9—C8—C7 | 121.6 (2) | C23—C22—H22A | 110.8 |
C9—C8—H8 | 119.2 | C20—C22—H22A | 110.8 |
C7—C8—H8 | 119.2 | C23—C22—H22B | 110.8 |
O3—C9—C8 | 124.7 (2) | C20—C22—H22B | 110.8 |
O3—C9—C11 | 115.77 (19) | H22A—C22—H22B | 108.8 |
C8—C9—C11 | 119.56 (19) | C24—C23—C22 | 105.53 (18) |
O3—C10—H10A | 109.5 | C24—C23—H23A | 110.6 |
O3—C10—H10B | 109.5 | C22—C23—H23A | 110.6 |
H10A—C10—H10B | 109.5 | C24—C23—H23B | 110.6 |
O3—C10—H10C | 109.5 | C22—C23—H23B | 110.6 |
H10A—C10—H10C | 109.5 | H23A—C23—H23B | 108.8 |
H10B—C10—H10C | 109.5 | O6—C24—N | 125.7 (2) |
O4—C11—C13 | 125.2 (2) | O6—C24—C23 | 125.8 (2) |
O4—C11—C9 | 115.74 (19) | N—C24—C23 | 108.40 (19) |
C13—C11—C9 | 119.04 (19) | C26—C25—H25A | 109.5 |
O4—C12—H12A | 109.5 | C26—C25—H25B | 109.5 |
O4—C12—H12B | 109.5 | H25A—C25—H25B | 109.5 |
H12A—C12—H12B | 109.5 | C26—C25—H25C | 109.5 |
O4—C12—H12C | 109.5 | H25A—C25—H25C | 109.5 |
H12A—C12—H12C | 109.5 | H25B—C25—H25C | 109.5 |
H12B—C12—H12C | 109.5 | O7—C26—C27 | 122.2 (4) |
C11—C13—C14 | 121.9 (2) | O7—C26—C25 | 118.7 (4) |
C11—C13—H13 | 119.1 | C27—C26—C25 | 119.0 (4) |
C14—C13—H13 | 119.1 | C26—C27—H27A | 109.5 |
C13—C14—C7 | 119.30 (19) | C26—C27—H27B | 109.5 |
C13—C14—C15 | 121.27 (19) | H27A—C27—H27B | 109.5 |
C7—C14—C15 | 119.42 (18) | C26—C27—H27C | 109.5 |
C14—C15—C19 | 112.42 (17) | H27A—C27—H27C | 109.5 |
C14—C15—C16 | 110.11 (17) | H27B—C27—H27C | 109.5 |
C19—C15—C16 | 110.59 (16) | C24—N—C21 | 127.29 (18) |
C14—C15—H15 | 107.9 | C24—N—C20 | 114.24 (17) |
C19—C15—H15 | 107.9 | C21—N—C20 | 117.74 (16) |
C16—C15—H15 | 107.9 | C3—O1—C1 | 117.70 (17) |
C21—C16—C17 | 115.18 (16) | C4—O2—C2 | 117.39 (17) |
C21—C16—C15 | 109.96 (17) | C9—O3—C10 | 117.96 (18) |
C17—C16—C15 | 110.27 (16) | C11—O4—C12 | 117.41 (18) |
C21—C16—H16 | 107.0 | C19—O5—H5 | 109.5 |
O1—C3—C4—O2 | 0.1 (3) | C15—C16—C17—C18 | 148.42 (19) |
C18—C3—C4—O2 | 179.8 (2) | C21—C16—C17—C6 | −160.10 (17) |
O1—C3—C4—C5 | 179.2 (2) | C15—C16—C17—C6 | −34.9 (2) |
C18—C3—C4—C5 | −1.0 (3) | O1—C3—C18—C17 | −178.7 (2) |
O2—C4—C5—C6 | 177.3 (2) | C4—C3—C18—C17 | 1.6 (3) |
C3—C4—C5—C6 | −1.7 (3) | C6—C17—C18—C3 | 0.5 (3) |
C4—C5—C6—C17 | 3.8 (3) | C16—C17—C18—C3 | 177.16 (19) |
C4—C5—C6—C7 | −174.10 (19) | C14—C15—C19—O5 | 60.1 (2) |
C17—C6—C7—C14 | 20.5 (3) | C16—C15—C19—O5 | −176.37 (16) |
C5—C6—C7—C14 | −161.60 (19) | C14—C15—C19—C20 | −179.56 (16) |
C17—C6—C7—C8 | −157.90 (19) | C16—C15—C19—C20 | −56.0 (2) |
C5—C6—C7—C8 | 20.0 (3) | O5—C19—C20—N | 172.00 (16) |
C14—C7—C8—C9 | 1.1 (3) | C15—C19—C20—N | 52.1 (2) |
C6—C7—C8—C9 | 179.53 (19) | O5—C19—C20—C22 | −71.7 (2) |
C7—C8—C9—O3 | 179.8 (2) | C15—C19—C20—C22 | 168.38 (17) |
C7—C8—C9—C11 | −0.6 (3) | C17—C16—C21—N | 71.5 (2) |
O3—C9—C11—O4 | 0.6 (3) | C15—C16—C21—N | −53.8 (2) |
C8—C9—C11—O4 | −179.0 (2) | N—C20—C22—C23 | −18.0 (2) |
O3—C9—C11—C13 | 179.7 (2) | C19—C20—C22—C23 | −138.13 (19) |
C8—C9—C11—C13 | 0.1 (3) | C20—C22—C23—C24 | 18.2 (2) |
O4—C11—C13—C14 | 178.9 (2) | C22—C23—C24—O6 | 169.8 (2) |
C9—C11—C13—C14 | −0.1 (3) | C22—C23—C24—N | −11.5 (3) |
C11—C13—C14—C7 | 0.6 (3) | O6—C24—N—C21 | 8.2 (4) |
C11—C13—C14—C15 | 179.64 (19) | C23—C24—N—C21 | −170.40 (19) |
C8—C7—C14—C13 | −1.1 (3) | O6—C24—N—C20 | 178.2 (2) |
C6—C7—C14—C13 | −179.58 (19) | C23—C24—N—C20 | −0.5 (2) |
C8—C7—C14—C15 | 179.84 (18) | C16—C21—N—C24 | −136.0 (2) |
C6—C7—C14—C15 | 1.4 (3) | C16—C21—N—C20 | 54.4 (2) |
C13—C14—C15—C19 | −93.5 (2) | C19—C20—N—C24 | 135.74 (19) |
C7—C14—C15—C19 | 85.5 (2) | C22—C20—N—C24 | 12.0 (2) |
C13—C14—C15—C16 | 142.73 (19) | C19—C20—N—C21 | −53.3 (2) |
C7—C14—C15—C16 | −38.3 (2) | C22—C20—N—C21 | −177.09 (17) |
C14—C15—C16—C21 | −178.73 (16) | C18—C3—O1—C1 | −4.6 (3) |
C19—C15—C16—C21 | 56.4 (2) | C4—C3—O1—C1 | 175.2 (2) |
C14—C15—C16—C17 | 53.2 (2) | C5—C4—O2—C2 | 4.2 (3) |
C19—C15—C16—C17 | −71.7 (2) | C3—C4—O2—C2 | −176.73 (19) |
C5—C6—C17—C18 | −3.2 (3) | C8—C9—O3—C10 | −13.8 (3) |
C7—C6—C17—C18 | 174.81 (18) | C11—C9—O3—C10 | 166.7 (2) |
C5—C6—C17—C16 | −179.90 (18) | C13—C11—O4—C12 | 2.7 (4) |
C7—C6—C17—C16 | −1.9 (3) | C9—C11—O4—C12 | −178.3 (2) |
C21—C16—C17—C18 | 23.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O6i | 0.82 | 1.92 | 2.737 (2) | Angle |
Symmetry code: (i) x, −y+1/2, z+1/2. |
C24H27NO6 | F(000) = 1808 |
Mr = 425.47 | Dx = 1.355 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8864 reflections |
a = 13.0534 (16) Å | θ = 2.3–25.0° |
b = 14.9664 (18) Å | µ = 0.10 mm−1 |
c = 21.356 (3) Å | T = 293 K |
V = 4172.1 (9) Å3 | Fragment, colorless |
Z = 8 | 0.50 × 0.42 × 0.40 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 5663 independent reflections |
Radiation source: fine-focus sealed tube | 4458 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: not measured pixels mm-1 | θmax = 28.3°, θmin = 1.7° |
ϕ and ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −19→19 |
Tmin = 0.953, Tmax = 0.962 | l = −27→28 |
45934 measured 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
5663 reflections | (Δ/σ)max < 0.001 |
567 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C24H27NO6 | V = 4172.1 (9) Å3 |
Mr = 425.47 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 13.0534 (16) Å | µ = 0.10 mm−1 |
b = 14.9664 (18) Å | T = 293 K |
c = 21.356 (3) Å | 0.50 × 0.42 × 0.40 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 5663 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4458 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 0.962 | Rint = 0.035 |
45934 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.19 e Å−3 |
5663 reflections | Δρmin = −0.18 e Å−3 |
567 parameters |
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. 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 | ||
C1 | −0.38698 (16) | 0.6461 (2) | 0.10355 (14) | 0.0729 (8) | |
H1A | −0.3781 | 0.6981 | 0.1293 | 0.109* | |
H1B | −0.4513 | 0.6183 | 0.1132 | 0.109* | |
H1C | −0.3861 | 0.6634 | 0.0603 | 0.109* | |
C2 | −0.08087 (18) | 0.40862 (17) | 0.14478 (11) | 0.0581 (6) | |
H2A | −0.0294 | 0.4047 | 0.1128 | 0.087* | |
H2B | −0.1106 | 0.3507 | 0.1514 | 0.087* | |
H2C | −0.0503 | 0.4292 | 0.1830 | 0.087* | |
C3 | −0.20793 (13) | 0.61648 (16) | 0.10554 (9) | 0.0450 (5) | |
C4 | −0.12901 (15) | 0.55531 (14) | 0.11359 (10) | 0.0457 (5) | |
C5 | −0.02846 (14) | 0.58458 (14) | 0.10897 (9) | 0.0410 (4) | |
H5 | 0.0246 | 0.5445 | 0.1162 | 0.049* | |
C6 | −0.00527 (13) | 0.67289 (13) | 0.09364 (8) | 0.0361 (4) | |
C7 | 0.10248 (13) | 0.70448 (13) | 0.08994 (8) | 0.0338 (4) | |
C8 | 0.18466 (13) | 0.64392 (13) | 0.09112 (8) | 0.0357 (4) | |
H8 | 0.1711 | 0.5829 | 0.0917 | 0.043* | |
C9 | 0.28480 (13) | 0.67271 (13) | 0.09138 (8) | 0.0335 (4) | |
C10 | 0.35058 (15) | 0.52462 (14) | 0.10445 (10) | 0.0468 (5) | |
H10A | 0.3115 | 0.5169 | 0.1421 | 0.070* | |
H10B | 0.4149 | 0.4941 | 0.1084 | 0.070* | |
H10C | 0.3132 | 0.5004 | 0.0696 | 0.070* | |
C11 | 0.30628 (13) | 0.76456 (13) | 0.08704 (8) | 0.0351 (4) | |
C12 | 0.43643 (15) | 0.87549 (15) | 0.07236 (11) | 0.0503 (5) | |
H12A | 0.4059 | 0.8924 | 0.0332 | 0.075* | |
H12B | 0.5096 | 0.8799 | 0.0691 | 0.075* | |
H12C | 0.4125 | 0.9146 | 0.1049 | 0.075* | |
C13 | 0.22633 (14) | 0.82430 (13) | 0.08444 (8) | 0.0368 (4) | |
H13 | 0.2404 | 0.8851 | 0.0813 | 0.044* | |
C14 | 0.12380 (13) | 0.79549 (13) | 0.08639 (8) | 0.0346 (4) | |
C15 | 0.03773 (13) | 0.86356 (13) | 0.08722 (8) | 0.0364 (4) | |
H15 | 0.0598 | 0.9136 | 0.0609 | 0.044* | |
C16 | −0.05984 (13) | 0.82460 (14) | 0.05676 (8) | 0.0379 (4) | |
H16 | −0.0439 | 0.8168 | 0.0122 | 0.046* | |
C17 | −0.08515 (13) | 0.73258 (14) | 0.08162 (8) | 0.0374 (4) | |
C18 | −0.18580 (14) | 0.70331 (15) | 0.08866 (9) | 0.0429 (4) | |
H18 | −0.2393 | 0.7432 | 0.0818 | 0.051* | |
C19 | 0.01858 (13) | 0.90181 (13) | 0.15334 (9) | 0.0377 (4) | |
H19 | 0.0796 | 0.9352 | 0.1663 | 0.045* | |
C20 | −0.07248 (15) | 0.96574 (14) | 0.15272 (10) | 0.0440 (5) | |
H20 | −0.0539 | 1.0194 | 0.1290 | 0.053* | |
C21 | −0.14634 (15) | 0.89314 (15) | 0.05988 (9) | 0.0439 (5) | |
H21A | −0.1301 | 0.9435 | 0.0330 | 0.053* | |
H21B | −0.2093 | 0.8663 | 0.0448 | 0.053* | |
C22 | −0.11493 (17) | 0.99393 (18) | 0.21682 (11) | 0.0600 (6) | |
H22A | −0.0661 | 0.9805 | 0.2498 | 0.072* | |
H22B | −0.1296 | 1.0575 | 0.2175 | 0.072* | |
C23 | −0.2124 (2) | 0.94022 (18) | 0.22547 (11) | 0.0631 (6) | |
H23A | −0.2008 | 0.8906 | 0.2538 | 0.076* | |
H23B | −0.2665 | 0.9775 | 0.2423 | 0.076* | |
C24 | −0.24051 (16) | 0.90671 (15) | 0.16120 (10) | 0.0503 (5) | |
C25 | 0.12520 (18) | 0.6868 (2) | 0.44443 (15) | 0.0762 (8) | |
H25A | 0.1520 | 0.7465 | 0.4456 | 0.114* | |
H25B | 0.0614 | 0.6847 | 0.4668 | 0.114* | |
H25C | 0.1141 | 0.6693 | 0.4017 | 0.114* | |
C26 | 0.3180 (2) | 0.66777 (19) | 0.58921 (12) | 0.0718 (7) | |
H26A | 0.3681 | 0.7144 | 0.5853 | 0.108* | |
H26B | 0.3104 | 0.6521 | 0.6325 | 0.108* | |
H26C | 0.2536 | 0.6883 | 0.5731 | 0.108* | |
C27 | 0.29411 (15) | 0.62605 (14) | 0.44984 (10) | 0.0460 (5) | |
C28 | 0.37175 (15) | 0.60827 (14) | 0.49247 (10) | 0.0438 (5) | |
C29 | 0.47152 (15) | 0.60509 (14) | 0.47247 (9) | 0.0424 (4) | |
H29 | 0.5228 | 0.5941 | 0.5017 | 0.051* | |
C30 | 0.49892 (14) | 0.61766 (13) | 0.41009 (9) | 0.0386 (4) | |
C31 | 0.60741 (14) | 0.61966 (13) | 0.38919 (9) | 0.0379 (4) | |
C32 | 0.68862 (15) | 0.59450 (14) | 0.42873 (9) | 0.0413 (4) | |
H32 | 0.6739 | 0.5725 | 0.4684 | 0.050* | |
C33 | 0.78939 (14) | 0.60151 (13) | 0.41027 (9) | 0.0410 (4) | |
C34 | 0.8546 (2) | 0.5721 (3) | 0.51190 (12) | 0.0870 (10) | |
H34A | 0.8167 | 0.6224 | 0.5275 | 0.130* | |
H34B | 0.9190 | 0.5682 | 0.5334 | 0.130* | |
H34C | 0.8161 | 0.5184 | 0.5189 | 0.130* | |
C35 | 0.81271 (14) | 0.63127 (14) | 0.34954 (10) | 0.0421 (4) | |
C36 | 0.93900 (18) | 0.6768 (2) | 0.27640 (13) | 0.0731 (8) | |
H36A | 0.9139 | 0.6402 | 0.2428 | 0.110* | |
H36B | 1.0120 | 0.6827 | 0.2729 | 0.110* | |
H36C | 0.9079 | 0.7349 | 0.2741 | 0.110* | |
C37 | 0.73366 (15) | 0.65526 (14) | 0.31023 (9) | 0.0444 (5) | |
H37 | 0.7486 | 0.6746 | 0.2699 | 0.053* | |
C38 | 0.63171 (14) | 0.65119 (14) | 0.32969 (8) | 0.0412 (4) | |
C39 | 0.54856 (14) | 0.68634 (15) | 0.28707 (9) | 0.0455 (5) | |
H39 | 0.5706 | 0.6741 | 0.2441 | 0.055* | |
C40 | 0.44783 (14) | 0.63474 (14) | 0.29714 (9) | 0.0419 (4) | |
H40 | 0.4616 | 0.5728 | 0.2849 | 0.050* | |
C41 | 0.41947 (14) | 0.63212 (13) | 0.36641 (9) | 0.0385 (4) | |
C42 | 0.31890 (15) | 0.63767 (14) | 0.38729 (10) | 0.0455 (5) | |
H42 | 0.2670 | 0.6495 | 0.3586 | 0.055* | |
C43 | 0.53451 (16) | 0.78797 (15) | 0.29227 (10) | 0.0498 (5) | |
H43 | 0.5988 | 0.8156 | 0.2787 | 0.060* | |
C44 | 0.45112 (16) | 0.81881 (16) | 0.24687 (11) | 0.0523 (5) | |
H44 | 0.4756 | 0.8111 | 0.2038 | 0.063* | |
C45 | 0.36677 (16) | 0.66932 (14) | 0.25197 (10) | 0.0469 (5) | |
H45A | 0.3847 | 0.6522 | 0.2096 | 0.056* | |
H45B | 0.3011 | 0.6426 | 0.2620 | 0.056* | |
C46 | 0.4113 (2) | 0.91385 (18) | 0.25493 (15) | 0.0728 (8) | |
H46A | 0.4259 | 0.9358 | 0.2968 | 0.087* | |
H46B | 0.4429 | 0.9536 | 0.2247 | 0.087* | |
C47 | 0.29618 (18) | 0.90797 (16) | 0.24401 (12) | 0.0595 (6) | |
H47A | 0.2593 | 0.9432 | 0.2748 | 0.071* | |
H47B | 0.2786 | 0.9293 | 0.2025 | 0.071* | |
C48 | 0.27091 (16) | 0.81063 (15) | 0.25066 (9) | 0.0458 (5) | |
N1 | −0.16062 (12) | 0.92395 (12) | 0.12327 (7) | 0.0421 (4) | |
N2 | 0.35887 (12) | 0.76510 (12) | 0.25583 (7) | 0.0439 (4) | |
O1 | −0.30562 (11) | 0.58452 (12) | 0.11522 (8) | 0.0637 (5) | |
O2 | −0.15729 (11) | 0.46877 (11) | 0.12600 (9) | 0.0654 (5) | |
O3 | 0.36857 (9) | 0.61711 (9) | 0.09430 (6) | 0.0390 (3) | |
O4 | 0.40874 (9) | 0.78597 (9) | 0.08694 (7) | 0.0435 (3) | |
O5 | −0.00081 (10) | 0.83453 (9) | 0.19847 (6) | 0.0439 (3) | |
H5A | 0.0536 | 0.8174 | 0.2135 | 0.050* | |
O6 | −0.32067 (13) | 0.87013 (14) | 0.14628 (10) | 0.0756 (5) | |
O7 | 0.19539 (11) | 0.62821 (13) | 0.47251 (8) | 0.0686 (5) | |
O8 | 0.35066 (11) | 0.59153 (10) | 0.55475 (7) | 0.0510 (4) | |
O9 | 0.87204 (10) | 0.58299 (12) | 0.44724 (7) | 0.0546 (4) | |
O10 | 0.91417 (10) | 0.63643 (11) | 0.33464 (7) | 0.0543 (4) | |
O11 | 0.51549 (13) | 0.81767 (11) | 0.35438 (7) | 0.0601 (4) | |
H11 | 0.4692 | 0.7879 | 0.3698 | 0.050* | |
O12 | 0.18543 (11) | 0.77607 (11) | 0.25114 (7) | 0.0575 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0214 (10) | 0.099 (2) | 0.0983 (19) | −0.0018 (12) | 0.0010 (11) | −0.0131 (17) |
C2 | 0.0551 (14) | 0.0567 (14) | 0.0627 (13) | −0.0126 (12) | 0.0038 (11) | 0.0094 (11) |
C3 | 0.0212 (9) | 0.0612 (14) | 0.0528 (11) | −0.0070 (9) | 0.0000 (8) | −0.0084 (10) |
C4 | 0.0323 (10) | 0.0492 (12) | 0.0555 (11) | −0.0088 (9) | −0.0001 (9) | 0.0017 (9) |
C5 | 0.0250 (9) | 0.0452 (11) | 0.0528 (10) | −0.0002 (8) | −0.0001 (8) | 0.0026 (9) |
C6 | 0.0226 (8) | 0.0457 (11) | 0.0400 (9) | −0.0020 (8) | −0.0008 (7) | −0.0008 (8) |
C7 | 0.0236 (8) | 0.0413 (10) | 0.0366 (8) | −0.0006 (7) | 0.0007 (7) | 0.0014 (8) |
C8 | 0.0251 (8) | 0.0384 (10) | 0.0434 (9) | −0.0020 (7) | 0.0018 (7) | 0.0006 (8) |
C9 | 0.0246 (8) | 0.0418 (10) | 0.0341 (8) | 0.0016 (7) | 0.0004 (7) | −0.0007 (8) |
C10 | 0.0360 (10) | 0.0439 (12) | 0.0607 (12) | 0.0031 (9) | −0.0007 (9) | 0.0026 (9) |
C11 | 0.0223 (8) | 0.0459 (11) | 0.0372 (8) | −0.0047 (7) | 0.0026 (7) | −0.0024 (8) |
C12 | 0.0330 (10) | 0.0484 (12) | 0.0696 (13) | −0.0100 (9) | 0.0052 (9) | 0.0019 (10) |
C13 | 0.0303 (9) | 0.0362 (10) | 0.0438 (9) | −0.0045 (8) | 0.0030 (8) | 0.0008 (8) |
C14 | 0.0247 (8) | 0.0423 (10) | 0.0367 (8) | 0.0013 (7) | 0.0027 (7) | 0.0026 (8) |
C15 | 0.0266 (9) | 0.0399 (10) | 0.0429 (9) | 0.0019 (8) | 0.0010 (7) | 0.0070 (8) |
C16 | 0.0279 (9) | 0.0493 (11) | 0.0365 (8) | 0.0064 (8) | −0.0011 (7) | 0.0008 (8) |
C17 | 0.0270 (9) | 0.0485 (11) | 0.0368 (8) | 0.0014 (8) | −0.0022 (7) | −0.0036 (8) |
C18 | 0.0249 (9) | 0.0546 (13) | 0.0492 (10) | 0.0027 (9) | −0.0039 (8) | −0.0065 (10) |
C19 | 0.0258 (9) | 0.0397 (10) | 0.0476 (10) | 0.0006 (8) | −0.0039 (7) | −0.0006 (8) |
C20 | 0.0341 (10) | 0.0425 (11) | 0.0554 (11) | 0.0045 (9) | −0.0056 (9) | −0.0018 (9) |
C21 | 0.0337 (10) | 0.0547 (13) | 0.0434 (10) | 0.0090 (9) | −0.0082 (8) | 0.0034 (9) |
C22 | 0.0467 (13) | 0.0686 (16) | 0.0649 (13) | 0.0168 (12) | −0.0095 (11) | −0.0198 (12) |
C23 | 0.0658 (16) | 0.0648 (16) | 0.0587 (13) | 0.0116 (13) | 0.0137 (12) | −0.0065 (11) |
C24 | 0.0375 (11) | 0.0511 (13) | 0.0622 (12) | 0.0091 (10) | 0.0049 (9) | −0.0051 (10) |
C25 | 0.0385 (13) | 0.086 (2) | 0.105 (2) | 0.0141 (13) | 0.0020 (14) | 0.0031 (17) |
C26 | 0.0776 (18) | 0.0694 (17) | 0.0683 (15) | 0.0112 (15) | 0.0131 (14) | −0.0075 (14) |
C27 | 0.0317 (10) | 0.0430 (11) | 0.0635 (12) | −0.0003 (9) | 0.0077 (9) | 0.0036 (10) |
C28 | 0.0401 (11) | 0.0385 (11) | 0.0527 (11) | −0.0022 (9) | 0.0077 (9) | 0.0049 (9) |
C29 | 0.0340 (10) | 0.0449 (12) | 0.0484 (10) | −0.0002 (9) | −0.0003 (8) | 0.0043 (8) |
C30 | 0.0311 (9) | 0.0379 (10) | 0.0468 (10) | 0.0006 (8) | 0.0004 (8) | 0.0019 (8) |
C31 | 0.0301 (9) | 0.0401 (11) | 0.0435 (9) | 0.0015 (8) | 0.0014 (7) | 0.0000 (8) |
C32 | 0.0335 (10) | 0.0455 (11) | 0.0449 (10) | 0.0006 (9) | 0.0004 (8) | 0.0075 (8) |
C33 | 0.0327 (10) | 0.0390 (10) | 0.0515 (10) | 0.0033 (8) | −0.0026 (8) | 0.0061 (9) |
C34 | 0.0557 (15) | 0.148 (3) | 0.0571 (14) | 0.0225 (18) | −0.0097 (12) | 0.0239 (17) |
C35 | 0.0315 (10) | 0.0406 (11) | 0.0542 (11) | 0.0028 (8) | 0.0055 (8) | 0.0033 (9) |
C36 | 0.0428 (13) | 0.099 (2) | 0.0777 (16) | 0.0114 (14) | 0.0183 (11) | 0.0373 (15) |
C37 | 0.0348 (10) | 0.0557 (13) | 0.0426 (9) | 0.0060 (9) | 0.0043 (8) | 0.0061 (9) |
C38 | 0.0303 (10) | 0.0512 (12) | 0.0420 (9) | 0.0037 (9) | 0.0004 (8) | 0.0000 (8) |
C39 | 0.0317 (10) | 0.0649 (14) | 0.0399 (9) | 0.0044 (10) | 0.0003 (8) | 0.0019 (9) |
C40 | 0.0354 (10) | 0.0429 (11) | 0.0476 (10) | 0.0039 (9) | −0.0061 (8) | −0.0047 (9) |
C41 | 0.0310 (9) | 0.0345 (10) | 0.0501 (10) | −0.0014 (8) | −0.0019 (8) | −0.0013 (8) |
C42 | 0.0300 (9) | 0.0465 (12) | 0.0600 (12) | −0.0012 (9) | −0.0050 (9) | 0.0037 (10) |
C43 | 0.0338 (10) | 0.0624 (14) | 0.0534 (11) | −0.0101 (10) | −0.0049 (9) | 0.0135 (10) |
C44 | 0.0378 (11) | 0.0618 (14) | 0.0573 (12) | −0.0065 (10) | −0.0060 (10) | 0.0162 (11) |
C45 | 0.0398 (11) | 0.0514 (12) | 0.0494 (10) | 0.0008 (10) | −0.0098 (9) | −0.0061 (9) |
C46 | 0.0626 (16) | 0.0509 (15) | 0.105 (2) | −0.0100 (13) | −0.0250 (15) | 0.0240 (15) |
C47 | 0.0544 (14) | 0.0568 (15) | 0.0674 (14) | 0.0093 (12) | 0.0008 (11) | 0.0082 (12) |
C48 | 0.0388 (11) | 0.0581 (13) | 0.0405 (9) | 0.0054 (10) | −0.0007 (8) | 0.0027 (9) |
N1 | 0.0289 (8) | 0.0509 (10) | 0.0467 (8) | 0.0078 (7) | −0.0052 (7) | −0.0009 (7) |
N2 | 0.0324 (9) | 0.0492 (10) | 0.0501 (9) | 0.0000 (8) | −0.0060 (7) | 0.0039 (8) |
O1 | 0.0230 (7) | 0.0739 (11) | 0.0942 (12) | −0.0110 (7) | 0.0026 (7) | −0.0056 (10) |
O2 | 0.0366 (8) | 0.0562 (10) | 0.1036 (13) | −0.0128 (7) | −0.0026 (8) | 0.0136 (9) |
O3 | 0.0234 (6) | 0.0404 (7) | 0.0530 (7) | 0.0007 (5) | 0.0014 (5) | 0.0005 (6) |
O4 | 0.0228 (6) | 0.0427 (8) | 0.0651 (8) | −0.0053 (5) | 0.0027 (6) | 0.0000 (7) |
O5 | 0.0326 (7) | 0.0552 (8) | 0.0437 (7) | 0.0053 (6) | −0.0018 (5) | 0.0065 (6) |
O6 | 0.0383 (9) | 0.0897 (14) | 0.0987 (13) | −0.0076 (9) | 0.0125 (9) | −0.0221 (11) |
O7 | 0.0326 (8) | 0.0861 (13) | 0.0870 (12) | 0.0080 (8) | 0.0144 (8) | 0.0225 (10) |
O8 | 0.0469 (8) | 0.0520 (9) | 0.0542 (8) | 0.0052 (7) | 0.0150 (7) | 0.0079 (7) |
O9 | 0.0341 (7) | 0.0741 (11) | 0.0557 (8) | 0.0064 (7) | −0.0049 (6) | 0.0161 (8) |
O10 | 0.0307 (7) | 0.0695 (10) | 0.0626 (9) | 0.0063 (7) | 0.0083 (6) | 0.0177 (8) |
O11 | 0.0635 (10) | 0.0515 (9) | 0.0654 (9) | −0.0106 (8) | −0.0102 (8) | 0.0023 (7) |
O12 | 0.0321 (7) | 0.0686 (11) | 0.0716 (10) | 0.0047 (8) | −0.0008 (7) | 0.0020 (8) |
C1—O1 | 1.428 (3) | C25—H25A | 0.9600 |
C1—H1A | 0.9600 | C25—H25B | 0.9600 |
C1—H1B | 0.9600 | C25—H25C | 0.9600 |
C1—H1C | 0.9600 | C26—O8 | 1.423 (3) |
C2—O2 | 1.402 (3) | C26—H26A | 0.9600 |
C2—H2A | 0.9600 | C26—H26B | 0.9600 |
C2—H2B | 0.9600 | C26—H26C | 0.9600 |
C2—H2C | 0.9600 | C27—O7 | 1.377 (2) |
C3—O1 | 1.378 (2) | C27—C42 | 1.385 (3) |
C3—C18 | 1.379 (3) | C27—C28 | 1.388 (3) |
C3—C4 | 1.389 (3) | C28—C29 | 1.371 (3) |
C4—O2 | 1.373 (3) | C28—O8 | 1.381 (2) |
C4—C5 | 1.387 (3) | C29—C30 | 1.392 (3) |
C5—C6 | 1.395 (3) | C29—H29 | 0.9300 |
C5—H5 | 0.9300 | C30—C41 | 1.412 (3) |
C6—C17 | 1.397 (3) | C30—C31 | 1.485 (3) |
C6—C7 | 1.486 (2) | C31—C38 | 1.392 (3) |
C7—C14 | 1.392 (3) | C31—C32 | 1.407 (3) |
C7—C8 | 1.405 (2) | C32—C33 | 1.377 (3) |
C8—C9 | 1.376 (2) | C32—H32 | 0.9300 |
C8—H8 | 0.9300 | C33—O9 | 1.365 (2) |
C9—O3 | 1.375 (2) | C33—C35 | 1.405 (3) |
C9—C11 | 1.406 (3) | C34—O9 | 1.409 (3) |
C10—O3 | 1.421 (2) | C34—H34A | 0.9600 |
C10—H10A | 0.9600 | C34—H34B | 0.9600 |
C10—H10B | 0.9600 | C34—H34C | 0.9600 |
C10—H10C | 0.9600 | C35—O10 | 1.364 (2) |
C11—O4 | 1.375 (2) | C35—C37 | 1.378 (3) |
C11—C13 | 1.375 (3) | C36—O10 | 1.420 (3) |
C12—O4 | 1.422 (3) | C36—H36A | 0.9600 |
C12—H12A | 0.9600 | C36—H36B | 0.9600 |
C12—H12B | 0.9600 | C36—H36C | 0.9600 |
C12—H12C | 0.9600 | C37—C38 | 1.395 (3) |
C13—C14 | 1.407 (2) | C37—H37 | 0.9300 |
C13—H13 | 0.9300 | C38—C39 | 1.511 (3) |
C14—C15 | 1.517 (2) | C39—C43 | 1.536 (3) |
C15—C19 | 1.544 (3) | C39—C40 | 1.540 (3) |
C15—C16 | 1.544 (3) | C39—H39 | 0.9800 |
C15—H15 | 0.9800 | C40—C45 | 1.523 (3) |
C16—C17 | 1.512 (3) | C40—C41 | 1.525 (3) |
C16—C21 | 1.527 (3) | C40—H40 | 0.9800 |
C16—H16 | 0.9800 | C41—C42 | 1.389 (3) |
C17—C18 | 1.393 (3) | C42—H42 | 0.9300 |
C18—H18 | 0.9300 | C43—O11 | 1.421 (3) |
C19—O5 | 1.417 (2) | C43—C44 | 1.529 (3) |
C19—C20 | 1.526 (3) | C43—H43 | 0.9800 |
C19—H19 | 0.9800 | C44—N2 | 1.460 (3) |
C20—N1 | 1.453 (2) | C44—C46 | 1.524 (4) |
C20—C22 | 1.536 (3) | C44—H44 | 0.9800 |
C20—H20 | 0.9800 | C45—N2 | 1.440 (3) |
C21—N1 | 1.442 (2) | C45—H45A | 0.9700 |
C21—H21A | 0.9700 | C45—H45B | 0.9700 |
C21—H21B | 0.9700 | C46—C47 | 1.524 (3) |
C22—C23 | 1.516 (4) | C46—H46A | 0.9700 |
C22—H22A | 0.9700 | C46—H46B | 0.9700 |
C22—H22B | 0.9700 | C47—C48 | 1.500 (3) |
C23—C24 | 1.507 (3) | C47—H47A | 0.9700 |
C23—H23A | 0.9700 | C47—H47B | 0.9700 |
C23—H23B | 0.9700 | C48—O12 | 1.230 (2) |
C24—O6 | 1.223 (3) | C48—N2 | 1.340 (3) |
C24—N1 | 1.345 (3) | O5—H5A | 0.8200 |
C25—O7 | 1.403 (3) | O11—H11 | 0.8200 |
O1—C1—H1A | 109.5 | H26A—C26—H26B | 109.5 |
O1—C1—H1B | 109.5 | O8—C26—H26C | 109.5 |
H1A—C1—H1B | 109.5 | H26A—C26—H26C | 109.5 |
O1—C1—H1C | 109.5 | H26B—C26—H26C | 109.5 |
H1A—C1—H1C | 109.5 | O7—C27—C42 | 123.68 (19) |
H1B—C1—H1C | 109.5 | O7—C27—C28 | 117.22 (19) |
O2—C2—H2A | 109.5 | C42—C27—C28 | 119.07 (18) |
O2—C2—H2B | 109.5 | C29—C28—O8 | 118.87 (19) |
H2A—C2—H2B | 109.5 | C29—C28—C27 | 119.72 (19) |
O2—C2—H2C | 109.5 | O8—C28—C27 | 121.39 (18) |
H2A—C2—H2C | 109.5 | C28—C29—C30 | 122.50 (18) |
H2B—C2—H2C | 109.5 | C28—C29—H29 | 118.7 |
O1—C3—C18 | 124.08 (19) | C30—C29—H29 | 118.7 |
O1—C3—C4 | 116.05 (19) | C29—C30—C41 | 117.66 (17) |
C18—C3—C4 | 119.87 (17) | C29—C30—C31 | 122.36 (17) |
O2—C4—C5 | 124.48 (19) | C41—C30—C31 | 119.93 (17) |
O2—C4—C3 | 116.52 (17) | C38—C31—C32 | 117.84 (17) |
C5—C4—C3 | 119.00 (19) | C38—C31—C30 | 119.89 (17) |
C4—C5—C6 | 121.41 (18) | C32—C31—C30 | 122.20 (17) |
C4—C5—H5 | 119.3 | C33—C32—C31 | 121.85 (18) |
C6—C5—H5 | 119.3 | C33—C32—H32 | 119.1 |
C5—C6—C17 | 119.16 (16) | C31—C32—H32 | 119.1 |
C5—C6—C7 | 121.28 (16) | O9—C33—C32 | 125.01 (18) |
C17—C6—C7 | 119.56 (17) | O9—C33—C35 | 115.28 (16) |
C14—C7—C8 | 118.67 (16) | C32—C33—C35 | 119.70 (17) |
C14—C7—C6 | 120.22 (16) | O9—C34—H34A | 109.5 |
C8—C7—C6 | 121.10 (16) | O9—C34—H34B | 109.5 |
C9—C8—C7 | 121.55 (17) | H34A—C34—H34B | 109.5 |
C9—C8—H8 | 119.2 | O9—C34—H34C | 109.5 |
C7—C8—H8 | 119.2 | H34A—C34—H34C | 109.5 |
O3—C9—C8 | 124.46 (17) | H34B—C34—H34C | 109.5 |
O3—C9—C11 | 115.84 (15) | O10—C35—C37 | 124.76 (18) |
C8—C9—C11 | 119.68 (16) | O10—C35—C33 | 116.34 (17) |
O3—C10—H10A | 109.5 | C37—C35—C33 | 118.88 (17) |
O3—C10—H10B | 109.5 | O10—C36—H36A | 109.5 |
H10A—C10—H10B | 109.5 | O10—C36—H36B | 109.5 |
O3—C10—H10C | 109.5 | H36A—C36—H36B | 109.5 |
H10A—C10—H10C | 109.5 | O10—C36—H36C | 109.5 |
H10B—C10—H10C | 109.5 | H36A—C36—H36C | 109.5 |
O4—C11—C13 | 125.90 (17) | H36B—C36—H36C | 109.5 |
O4—C11—C9 | 114.95 (16) | C35—C37—C38 | 121.42 (17) |
C13—C11—C9 | 119.14 (16) | C35—C37—H37 | 119.3 |
O4—C12—H12A | 109.5 | C38—C37—H37 | 119.3 |
O4—C12—H12B | 109.5 | C31—C38—C37 | 120.26 (17) |
H12A—C12—H12B | 109.5 | C31—C38—C39 | 120.27 (17) |
O4—C12—H12C | 109.5 | C37—C38—C39 | 119.38 (17) |
H12A—C12—H12C | 109.5 | C38—C39—C43 | 112.76 (17) |
H12B—C12—H12C | 109.5 | C38—C39—C40 | 110.77 (17) |
C11—C13—C14 | 121.43 (17) | C43—C39—C40 | 112.62 (17) |
C11—C13—H13 | 119.3 | C38—C39—H39 | 106.7 |
C14—C13—H13 | 119.3 | C43—C39—H39 | 106.7 |
C7—C14—C13 | 119.45 (16) | C40—C39—H39 | 106.7 |
C7—C14—C15 | 120.56 (15) | C45—C40—C41 | 117.04 (16) |
C13—C14—C15 | 119.95 (16) | C45—C40—C39 | 109.54 (17) |
C14—C15—C19 | 112.30 (14) | C41—C40—C39 | 110.83 (15) |
C14—C15—C16 | 110.63 (15) | C45—C40—H40 | 106.2 |
C19—C15—C16 | 113.06 (14) | C41—C40—H40 | 106.2 |
C14—C15—H15 | 106.8 | C39—C40—H40 | 106.2 |
C19—C15—H15 | 106.8 | C42—C41—C30 | 119.44 (18) |
C16—C15—H15 | 106.8 | C42—C41—C40 | 122.62 (17) |
C17—C16—C21 | 115.78 (15) | C30—C41—C40 | 117.80 (16) |
C17—C16—C15 | 112.09 (15) | C27—C42—C41 | 121.52 (18) |
C21—C16—C15 | 109.74 (16) | C27—C42—H42 | 119.2 |
C17—C16—H16 | 106.2 | C41—C42—H42 | 119.2 |
C21—C16—H16 | 106.2 | O11—C43—C44 | 111.91 (19) |
C15—C16—H16 | 106.2 | O11—C43—C39 | 113.46 (16) |
C18—C17—C6 | 118.88 (18) | C44—C43—C39 | 109.76 (18) |
C18—C17—C16 | 122.02 (17) | O11—C43—H43 | 107.1 |
C6—C17—C16 | 118.93 (15) | C44—C43—H43 | 107.1 |
C3—C18—C17 | 121.47 (19) | C39—C43—H43 | 107.1 |
C3—C18—H18 | 119.3 | N2—C44—C46 | 102.59 (18) |
C17—C18—H18 | 119.3 | N2—C44—C43 | 109.74 (17) |
O5—C19—C20 | 108.21 (15) | C46—C44—C43 | 116.9 (2) |
O5—C19—C15 | 112.80 (15) | N2—C44—H44 | 109.1 |
C20—C19—C15 | 110.52 (15) | C46—C44—H44 | 109.1 |
O5—C19—H19 | 108.4 | C43—C44—H44 | 109.1 |
C20—C19—H19 | 108.4 | N2—C45—C40 | 110.61 (17) |
C15—C19—H19 | 108.4 | N2—C45—H45A | 109.5 |
N1—C20—C19 | 110.53 (16) | C40—C45—H45A | 109.5 |
N1—C20—C22 | 102.61 (16) | N2—C45—H45B | 109.5 |
C19—C20—C22 | 116.46 (17) | C40—C45—H45B | 109.5 |
N1—C20—H20 | 109.0 | H45A—C45—H45B | 108.1 |
C19—C20—H20 | 109.0 | C47—C46—C44 | 105.4 (2) |
C22—C20—H20 | 109.0 | C47—C46—H46A | 110.7 |
N1—C21—C16 | 110.56 (14) | C44—C46—H46A | 110.7 |
N1—C21—H21A | 109.5 | C47—C46—H46B | 110.7 |
C16—C21—H21A | 109.5 | C44—C46—H46B | 110.7 |
N1—C21—H21B | 109.5 | H46A—C46—H46B | 108.8 |
C16—C21—H21B | 109.5 | C48—C47—C46 | 105.0 (2) |
H21A—C21—H21B | 108.1 | C48—C47—H47A | 110.8 |
C23—C22—C20 | 105.41 (18) | C46—C47—H47A | 110.8 |
C23—C22—H22A | 110.7 | C48—C47—H47B | 110.8 |
C20—C22—H22A | 110.7 | C46—C47—H47B | 110.8 |
C23—C22—H22B | 110.7 | H47A—C47—H47B | 108.8 |
C20—C22—H22B | 110.7 | O12—C48—N2 | 124.3 (2) |
H22A—C22—H22B | 108.8 | O12—C48—C47 | 127.5 (2) |
C24—C23—C22 | 105.67 (19) | N2—C48—C47 | 108.25 (19) |
C24—C23—H23A | 110.6 | C24—N1—C21 | 127.16 (18) |
C22—C23—H23A | 110.6 | C24—N1—C20 | 115.83 (17) |
C24—C23—H23B | 110.6 | C21—N1—C20 | 116.21 (16) |
C22—C23—H23B | 110.6 | C48—N2—C45 | 124.27 (18) |
H23A—C23—H23B | 108.7 | C48—N2—C44 | 114.58 (18) |
O6—C24—N1 | 126.3 (2) | C45—N2—C44 | 118.79 (18) |
O6—C24—C23 | 126.5 (2) | C3—O1—C1 | 115.97 (19) |
N1—C24—C23 | 107.19 (19) | C4—O2—C2 | 118.02 (16) |
O7—C25—H25A | 109.5 | C9—O3—C10 | 117.70 (14) |
O7—C25—H25B | 109.5 | C11—O4—C12 | 117.84 (16) |
H25A—C25—H25B | 109.5 | C19—O5—H5A | 109.5 |
O7—C25—H25C | 109.5 | C27—O7—C25 | 118.41 (19) |
H25A—C25—H25C | 109.5 | C28—O8—C26 | 114.35 (17) |
H25B—C25—H25C | 109.5 | C33—O9—C34 | 117.53 (17) |
O8—C26—H26A | 109.5 | C35—O10—C36 | 116.73 (17) |
O8—C26—H26B | 109.5 | C43—O11—H11 | 109.5 |
O1—C3—C4—O2 | 4.3 (3) | O9—C33—C35—C37 | −177.09 (19) |
C18—C3—C4—O2 | −175.51 (19) | C32—C33—C35—C37 | 1.8 (3) |
O1—C3—C4—C5 | −175.43 (18) | O10—C35—C37—C38 | −177.6 (2) |
C18—C3—C4—C5 | 4.7 (3) | C33—C35—C37—C38 | 0.5 (3) |
O2—C4—C5—C6 | 177.29 (19) | C32—C31—C38—C37 | 1.4 (3) |
C3—C4—C5—C6 | −3.0 (3) | C30—C31—C38—C37 | 178.49 (19) |
C4—C5—C6—C17 | −1.1 (3) | C32—C31—C38—C39 | −174.95 (19) |
C4—C5—C6—C7 | 178.79 (18) | C30—C31—C38—C39 | 2.1 (3) |
C5—C6—C7—C14 | −167.79 (17) | C35—C37—C38—C31 | −2.1 (3) |
C17—C6—C7—C14 | 12.2 (3) | C35—C37—C38—C39 | 174.29 (19) |
C5—C6—C7—C8 | 11.0 (3) | C31—C38—C39—C43 | 93.4 (2) |
C17—C6—C7—C8 | −169.06 (17) | C37—C38—C39—C43 | −83.0 (2) |
C14—C7—C8—C9 | 2.6 (3) | C31—C38—C39—C40 | −33.8 (3) |
C6—C7—C8—C9 | −176.18 (16) | C37—C38—C39—C40 | 149.73 (19) |
C7—C8—C9—O3 | 178.07 (16) | C38—C39—C40—C45 | −177.94 (16) |
C7—C8—C9—C11 | −3.4 (3) | C43—C39—C40—C45 | 54.7 (2) |
O3—C9—C11—O4 | −0.6 (2) | C38—C39—C40—C41 | 51.4 (2) |
C8—C9—C11—O4 | −179.25 (16) | C43—C39—C40—C41 | −75.9 (2) |
O3—C9—C11—C13 | −179.48 (15) | C29—C30—C41—C42 | 3.2 (3) |
C8—C9—C11—C13 | 1.9 (3) | C31—C30—C41—C42 | −174.55 (18) |
O4—C11—C13—C14 | −178.37 (17) | C29—C30—C41—C40 | −172.81 (18) |
C9—C11—C13—C14 | 0.4 (3) | C31—C30—C41—C40 | 9.5 (3) |
C8—C7—C14—C13 | −0.3 (3) | C45—C40—C41—C42 | 16.6 (3) |
C6—C7—C14—C13 | 178.47 (16) | C39—C40—C41—C42 | 143.2 (2) |
C8—C7—C14—C15 | −177.91 (16) | C45—C40—C41—C30 | −167.56 (18) |
C6—C7—C14—C15 | 0.9 (3) | C39—C40—C41—C30 | −41.0 (2) |
C11—C13—C14—C7 | −1.1 (3) | O7—C27—C42—C41 | −177.9 (2) |
C11—C13—C14—C15 | 176.47 (16) | C28—C27—C42—C41 | −0.1 (3) |
C7—C14—C15—C19 | 96.3 (2) | C30—C41—C42—C27 | −2.4 (3) |
C13—C14—C15—C19 | −81.2 (2) | C40—C41—C42—C27 | 173.34 (19) |
C7—C14—C15—C16 | −31.0 (2) | C38—C39—C43—O11 | −55.3 (2) |
C13—C14—C15—C16 | 151.40 (16) | C40—C39—C43—O11 | 71.0 (2) |
C14—C15—C16—C17 | 48.18 (19) | C38—C39—C43—C44 | 178.70 (16) |
C19—C15—C16—C17 | −78.76 (19) | C40—C39—C43—C44 | −55.0 (2) |
C14—C15—C16—C21 | 178.29 (14) | O11—C43—C44—N2 | −75.4 (2) |
C19—C15—C16—C21 | 51.3 (2) | C39—C43—C44—N2 | 51.5 (2) |
C5—C6—C17—C18 | 3.5 (3) | O11—C43—C44—C46 | 40.8 (3) |
C7—C6—C17—C18 | −176.48 (16) | C39—C43—C44—C46 | 167.73 (19) |
C5—C6—C17—C16 | −171.99 (16) | C41—C40—C45—N2 | 75.6 (2) |
C7—C6—C17—C16 | 8.1 (2) | C39—C40—C45—N2 | −51.6 (2) |
C21—C16—C17—C18 | 19.1 (2) | N2—C44—C46—C47 | −20.2 (3) |
C15—C16—C17—C18 | 146.05 (17) | C43—C44—C46—C47 | −140.3 (2) |
C21—C16—C17—C6 | −165.57 (16) | C44—C46—C47—C48 | 17.4 (3) |
C15—C16—C17—C6 | −38.6 (2) | C46—C47—C48—O12 | 172.9 (2) |
O1—C3—C18—C17 | 177.75 (19) | C46—C47—C48—N2 | −7.4 (3) |
C4—C3—C18—C17 | −2.4 (3) | O6—C24—N1—C21 | −8.9 (4) |
C6—C17—C18—C3 | −1.7 (3) | C23—C24—N1—C21 | 170.71 (19) |
C16—C17—C18—C3 | 173.59 (17) | O6—C24—N1—C20 | −178.1 (2) |
C14—C15—C19—O5 | −55.40 (19) | C23—C24—N1—C20 | 1.4 (2) |
C16—C15—C19—O5 | 70.65 (19) | C16—C21—N1—C24 | −110.3 (2) |
C14—C15—C19—C20 | −176.68 (15) | C16—C21—N1—C20 | 59.0 (2) |
C16—C15—C19—C20 | −50.6 (2) | C19—C20—N1—C24 | 112.71 (19) |
O5—C19—C20—N1 | −72.83 (19) | C22—C20—N1—C24 | −12.1 (2) |
C15—C19—C20—N1 | 51.1 (2) | C19—C20—N1—C21 | −57.8 (2) |
O5—C19—C20—C22 | 43.7 (2) | C22—C20—N1—C21 | 177.37 (17) |
C15—C19—C20—C22 | 167.68 (18) | O12—C48—N2—C45 | 11.0 (3) |
C17—C16—C21—N1 | 74.9 (2) | C47—C48—N2—C45 | −168.61 (18) |
C15—C16—C21—N1 | −53.2 (2) | O12—C48—N2—C44 | 173.31 (19) |
N1—C20—C22—C23 | 17.3 (2) | C47—C48—N2—C44 | −6.3 (2) |
C19—C20—C22—C23 | −103.5 (2) | C40—C45—N2—C48 | −143.59 (19) |
C20—C22—C23—C24 | −17.1 (2) | C40—C45—N2—C44 | 54.8 (2) |
C22—C23—C24—O6 | −170.2 (2) | C46—C44—N2—C48 | 17.1 (2) |
C22—C23—C24—N1 | 10.2 (2) | C43—C44—N2—C48 | 142.10 (19) |
O7—C27—C28—C29 | 179.8 (2) | C46—C44—N2—C45 | −179.54 (19) |
C42—C27—C28—C29 | 1.9 (3) | C43—C44—N2—C45 | −54.6 (3) |
O7—C27—C28—O8 | 1.4 (3) | C18—C3—O1—C1 | 3.2 (3) |
C42—C27—C28—O8 | −176.58 (19) | C4—C3—O1—C1 | −176.6 (2) |
O8—C28—C29—C30 | 177.43 (18) | C5—C4—O2—C2 | 10.3 (3) |
C27—C28—C29—C30 | −1.1 (3) | C3—C4—O2—C2 | −169.4 (2) |
C28—C29—C30—C41 | −1.5 (3) | C8—C9—O3—C10 | −7.0 (3) |
C28—C29—C30—C31 | 176.20 (19) | C11—C9—O3—C10 | 174.39 (15) |
C29—C30—C31—C38 | −166.16 (19) | C13—C11—O4—C12 | −11.4 (3) |
C41—C30—C31—C38 | 11.4 (3) | C9—C11—O4—C12 | 169.84 (16) |
C29—C30—C31—C32 | 10.7 (3) | C42—C27—O7—C25 | −34.7 (3) |
C41—C30—C31—C32 | −171.65 (19) | C28—C27—O7—C25 | 147.5 (2) |
C38—C31—C32—C33 | 0.9 (3) | C29—C28—O8—C26 | 110.1 (2) |
C30—C31—C32—C33 | −176.11 (19) | C27—C28—O8—C26 | −71.4 (3) |
C31—C32—C33—O9 | 176.3 (2) | C32—C33—O9—C34 | −12.5 (3) |
C31—C32—C33—C35 | −2.5 (3) | C35—C33—O9—C34 | 166.3 (2) |
O9—C33—C35—O10 | 1.2 (3) | C37—C35—O10—C36 | 5.8 (3) |
C32—C33—C35—O10 | −179.95 (19) | C33—C35—O10—C36 | −172.4 (2) |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | C24H27NO6·C3H6O | C24H27NO6 |
Mr | 483.54 | 425.47 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, P212121 |
Temperature (K) | 295 | 293 |
a, b, c (Å) | 11.579 (1), 17.4011 (15), 13.0453 (11) | 13.0534 (16), 14.9664 (18), 21.356 (3) |
α, β, γ (°) | 90, 110.488 (2), 90 | 90, 90, 90 |
V (Å3) | 2462.2 (4) | 4172.1 (9) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 |
Crystal size (mm) | 0.50 × 0.20 × 0.15 | 0.50 × 0.42 × 0.40 |
Data collection | ||
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.881, 0.986 | 0.953, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24264, 5059, 2927 | 45934, 5663, 4458 |
Rint | 0.053 | 0.035 |
(sin θ/λ)max (Å−1) | 0.626 | 0.667 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.127, 1.01 | 0.033, 0.086, 0.98 |
No. of reflections | 5059 | 5663 |
No. of parameters | 323 | 567 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.19 | 0.19, −0.18 |
Computer programs: SMART (Bruker 1997), SAINT (Bruker 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1997), SHELXTL.
C15—C19 | 1.534 (3) | C19—C20 | 1.517 (3) |
C19—O5 | 1.421 (2) | ||
C5—C6—C7 | 121.80 (18) | C17—C16—C15 | 110.27 (16) |
C8—C7—C6 | 122.32 (19) | C18—C17—C16 | 121.90 (18) |
C14—C15—C16 | 110.11 (17) | O5—C19—C20 | 109.32 (16) |
C21—C16—C17 | 115.18 (16) | O5—C19—C15 | 108.68 (16) |
C5—C6—C7—C8 | 20.0 (3) | C14—C15—C16—C17 | 53.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O6i | 0.82 | 1.92 | 2.737 (2) | Angle |
Symmetry code: (i) x, −y+1/2, z+1/2. |
C15—C19 | 1.544 (3) | C19—C20 | 1.526 (3) |
C19—O5 | 1.417 (2) | ||
C5—C6—C7 | 121.28 (16) | C17—C16—C15 | 112.09 (15) |
C8—C7—C6 | 121.10 (16) | C18—C17—C6 | 118.88 (18) |
C14—C15—C16 | 110.63 (15) | O5—C19—C20 | 108.21 (15) |
C17—C16—C21 | 115.78 (15) | O5—C19—C15 | 112.80 (15) |
C5—C6—C7—C8 | 11.0 (3) | C14—C15—C16—C17 | 48.18 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O12 | 0.82 | 2.00 | 2.818 (2) | 179 |
In a project involving the synthesis and evaluation of a number of phenanthroindolizidine alkaloids (Li et al., 2001) that are of interest as potential cancer chemotherapeutic agents, we have developed a synthetic route (Zhong et al., 2004; see scheme) to this group of alkaloids via a pair of epimeric intermediates, the title compounds, (II) and (III). Reductive ring closure of optically active (I) using free-radical chemistry (Hays & Fu, 1996, 1999) gives the intermediates (II) and (III) in an approximate 2.3:1 ratio. The key issue in this work was the determination of the relative stereochemistries for (II) and (III), as those epimers did not lend themselves to definitive NMR spectral analyses. Compound (III), with its trans H—C—C—OH arrangement which is necessary for the elimination of water, is readily converted to the 14–14a double-bonded intermediate (IV) (compound not analyzed due to instability). Reduction of the amide function and concomitant rearrangement of the double bond in (IV) produces the natural product tylophorine, which is an antitumor agent (Gao et al., 2004). Optical rotation measurements of bulk samples of (II) and (III) indicate that optical activity is maintained, to give the final product as (S)-(+)-tylophorine (Buckley & Rapoport, 1983; Norlander & Njoroge, 1987), having a single chiral center at the 13a-position. However, the crystal of (II) was obtained as a racemate (see Experimental), indicating that at least a portion of the sample had racemized during ring closure or that the starting material, (I), was partially racemized at the outset. The issue of this apparent partial racemization is presently under study. \sch
The structure of the molecule consists of a semiplanar aromatic system that is torsionally distorted, with an azacyclohexane ring in a chair configuration fused cis to atoms C14 and C17 of a dihydrophenanthrene system. The molecular structures of (II) and (III), apart from their epimeric relationship at C19, are very similar.
One major structural difference between (II) and (III) is the torsion angle between the aromatic rings, defined as the angle between the C5—C6 and C7—C8 bonds. For (II), this angle is 20.0 (3)°, whereas in (III), the corresponding value is found to be 11.0 (3)°. The torsion angles between the C14—C15 and C16—C17 bonds are 53.2 (2) and 48.18 (19)° for (II) and (III), respectively. Taken together, these values are in accord with the statistically observed relationship between these two parameters in these types of systems (Allen, 2002; Bruno et al., 2002). Given the difference in unit-cell contents and the inclusion of acetone in the structure of (II), no straightforward comparison of the torsion angles may be made, although the values are not atypical for the dihydrophenanthrenyl ring system. We note that, in the presence of acetone in the lattice, the number of intermolecular contacts is lower, and we speculate that this leads to the lower torsional value.
While the presence of a solvent of crystallization in (II) disturbs the intermolecular contacts, a direct comparison may be made between the interbond angles and lengths of the two structures. Inspection of the structures of (II) and (III) shows that all bond lengths and angles in the two structures are well within the normal reported ranges and are similar in both structures.