Two new polymorphic forms of combretastatin A-4 {systematic name: 2-methoxy-5-[(E)-2-(3,4,5-trimethoxyphenyl)ethenyl]phenol, C18H20O5, CA-4}, an inhibitor of tubulin polymerization at the colchicine binding site, were identified. A number of crystallization attempts led to the orthorhombic form, with two molecules in the asymmetric part of the unit cell; obtaining a different form required the experiment to be moved to another laboratory. None of the attempts resulted in the monoclinic form described earlier. The three different forms contain molecules of significantly different geometries, which can be related to conformational freedom, postulated as the result of biological studies. In addition, the packing modes in all three forms are basically different. The structural differences at both the molecular and the supramolecular level have also been studied via calculations of energies and a topological analysis of the electron density. The results confirm the role of weak interactions in the determination of crystal architecture and additionally hint at an explanation for the results of crystallization attempts: the new monoclinic form has significantly lower energy than the form reported earlier.
Supporting information
CCDC references: 2030953; 2030952
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020).
2-Methoxy-5-[(
E)-2-(3,4,5-trimethoxyphenyl)ethenyl]phenol (1)
top
Crystal data top
C18H20O5 | F(000) = 672 |
Mr = 316.34 | Dx = 1.318 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9167 (5) Å | Cell parameters from 1286 reflections |
b = 6.9587 (5) Å | θ = 3.9–25.2° |
c = 23.2803 (15) Å | µ = 0.10 mm−1 |
β = 96.988 (6)° | T = 295 K |
V = 1594.58 (17) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.2 × 0.1 mm |
Data collection top
Rigaku Xcalibur EosS2 diffractometer | 3277 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 1952 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 16.0338 pixels mm-1 | θmax = 27.7°, θmin = 3.4° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −7→8 |
Tmin = 0.793, Tmax = 1.000 | l = −30→12 |
5526 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0355P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.108 | (Δ/σ)max = 0.001 |
S = 1.00 | Δρmax = 0.15 e Å−3 |
3277 reflections | Δρmin = −0.17 e Å−3 |
289 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0030 (6) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.64520 (19) | 0.5250 (3) | 0.66822 (8) | 0.0417 (5) | |
C2 | 0.6923 (2) | 0.3847 (3) | 0.63298 (8) | 0.0447 (5) | |
H2 | 0.6367 (19) | 0.280 (3) | 0.6220 (7) | 0.046 (6)* | |
C3 | 0.8193 (2) | 0.4025 (3) | 0.61426 (8) | 0.0444 (5) | |
O3 | 0.87314 (15) | 0.2769 (2) | 0.57784 (6) | 0.0630 (4) | |
C31 | 0.7950 (3) | 0.1154 (4) | 0.55791 (13) | 0.0676 (7) | |
H31A | 0.851 (3) | 0.051 (4) | 0.5314 (10) | 0.089 (8)* | |
H31B | 0.708 (3) | 0.155 (3) | 0.5380 (10) | 0.084 (9)* | |
H31C | 0.779 (2) | 0.034 (4) | 0.5893 (10) | 0.084 (9)* | |
C4 | 0.90185 (19) | 0.5578 (3) | 0.63217 (8) | 0.0417 (5) | |
O4 | 1.03300 (13) | 0.5646 (2) | 0.61755 (6) | 0.0521 (4) | |
C41 | 1.0506 (3) | 0.6887 (4) | 0.57004 (12) | 0.0637 (7) | |
H41A | 0.994 (3) | 0.652 (4) | 0.5350 (11) | 0.104 (10)* | |
H41B | 1.144 (3) | 0.681 (4) | 0.5616 (11) | 0.109 (10)* | |
H41C | 1.032 (2) | 0.829 (4) | 0.5808 (10) | 0.092 (9)* | |
C5 | 0.85588 (19) | 0.6977 (3) | 0.66787 (8) | 0.0408 (5) | |
O5 | 0.94493 (13) | 0.8433 (2) | 0.68289 (6) | 0.0518 (4) | |
C51 | 0.9053 (3) | 0.9916 (4) | 0.71985 (11) | 0.0559 (6) | |
H51A | 0.818 (3) | 1.057 (3) | 0.7021 (10) | 0.089 (8)* | |
H51B | 0.983 (2) | 1.080 (3) | 0.7234 (9) | 0.075 (7)* | |
H51C | 0.890 (2) | 0.939 (3) | 0.7587 (9) | 0.073 (7)* | |
C6 | 0.7269 (2) | 0.6821 (3) | 0.68547 (8) | 0.0429 (5) | |
H6 | 0.6927 (19) | 0.786 (3) | 0.7105 (8) | 0.059 (6)* | |
C7 | 0.5106 (2) | 0.5001 (3) | 0.68909 (9) | 0.0492 (5) | |
H7 | 0.500 (2) | 0.373 (3) | 0.7085 (8) | 0.060 (6)* | |
C8 | 0.4057 (2) | 0.6211 (3) | 0.68502 (9) | 0.0487 (5) | |
H8 | 0.326 (2) | 0.585 (3) | 0.7048 (8) | 0.057 (6)* | |
C9 | 0.38408 (18) | 0.8059 (3) | 0.65414 (8) | 0.0409 (5) | |
C10 | 0.2861 (2) | 0.9306 (3) | 0.67065 (8) | 0.0446 (5) | |
H10 | 0.2391 (18) | 0.902 (3) | 0.7030 (7) | 0.046 (5)* | |
C11 | 0.25260 (19) | 1.1000 (3) | 0.64108 (8) | 0.0439 (5) | |
O11 | 0.15689 (16) | 1.2179 (2) | 0.65950 (7) | 0.0642 (5) | |
H11 | 0.140 (3) | 1.323 (4) | 0.6358 (10) | 0.101 (10)* | |
C12 | 0.31594 (19) | 1.1449 (3) | 0.59253 (8) | 0.0424 (5) | |
O12 | 0.27104 (14) | 1.3122 (2) | 0.56505 (6) | 0.0598 (4) | |
C121 | 0.3414 (3) | 1.3783 (5) | 0.51988 (12) | 0.0691 (8) | |
H12A | 0.331 (3) | 1.278 (4) | 0.4871 (11) | 0.101 (10)* | |
H12B | 0.440 (3) | 1.401 (4) | 0.5346 (11) | 0.109 (10)* | |
H12C | 0.301 (2) | 1.501 (4) | 0.5090 (9) | 0.083 (8)* | |
C13 | 0.4142 (2) | 1.0231 (3) | 0.57612 (8) | 0.0464 (5) | |
H13 | 0.4551 (18) | 1.055 (3) | 0.5417 (7) | 0.053 (6)* | |
C14 | 0.4478 (2) | 0.8562 (3) | 0.60633 (8) | 0.0459 (5) | |
H14 | 0.513 (2) | 0.774 (3) | 0.5935 (8) | 0.052 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0379 (11) | 0.0417 (13) | 0.0455 (11) | 0.0045 (10) | 0.0049 (9) | 0.0074 (10) |
C2 | 0.0387 (12) | 0.0405 (13) | 0.0535 (12) | −0.0002 (10) | 0.0004 (10) | −0.0026 (11) |
C3 | 0.0435 (12) | 0.0426 (13) | 0.0465 (11) | 0.0101 (10) | 0.0029 (9) | −0.0029 (10) |
O3 | 0.0575 (10) | 0.0585 (10) | 0.0746 (10) | 0.0022 (8) | 0.0146 (8) | −0.0248 (8) |
C31 | 0.083 (2) | 0.0533 (18) | 0.0665 (17) | 0.0064 (16) | 0.0074 (17) | −0.0138 (15) |
C4 | 0.0326 (10) | 0.0467 (13) | 0.0457 (11) | 0.0055 (10) | 0.0050 (9) | 0.0035 (10) |
O4 | 0.0393 (8) | 0.0574 (10) | 0.0617 (9) | 0.0074 (7) | 0.0151 (7) | 0.0053 (7) |
C41 | 0.0594 (17) | 0.074 (2) | 0.0603 (16) | −0.0001 (16) | 0.0178 (14) | 0.0075 (15) |
C5 | 0.0391 (11) | 0.0383 (12) | 0.0447 (11) | 0.0001 (10) | 0.0036 (9) | 0.0005 (9) |
O5 | 0.0440 (8) | 0.0514 (9) | 0.0620 (9) | −0.0086 (7) | 0.0145 (7) | −0.0107 (7) |
C51 | 0.0640 (16) | 0.0519 (16) | 0.0537 (14) | −0.0091 (14) | 0.0146 (13) | −0.0105 (12) |
C6 | 0.0404 (11) | 0.0420 (13) | 0.0474 (11) | 0.0018 (10) | 0.0096 (9) | 0.0002 (10) |
C7 | 0.0443 (12) | 0.0456 (14) | 0.0590 (13) | −0.0027 (11) | 0.0118 (10) | 0.0066 (11) |
C8 | 0.0394 (12) | 0.0539 (14) | 0.0551 (12) | −0.0032 (11) | 0.0150 (10) | 0.0031 (11) |
C9 | 0.0333 (10) | 0.0465 (13) | 0.0432 (10) | −0.0023 (10) | 0.0061 (9) | −0.0026 (9) |
C10 | 0.0373 (11) | 0.0550 (14) | 0.0438 (11) | −0.0001 (10) | 0.0149 (9) | 0.0008 (10) |
C11 | 0.0369 (11) | 0.0507 (13) | 0.0462 (11) | 0.0038 (10) | 0.0130 (9) | −0.0030 (10) |
O11 | 0.0664 (10) | 0.0659 (11) | 0.0672 (10) | 0.0260 (9) | 0.0356 (8) | 0.0132 (9) |
C12 | 0.0385 (11) | 0.0493 (13) | 0.0397 (10) | 0.0024 (10) | 0.0064 (9) | 0.0017 (10) |
O12 | 0.0615 (9) | 0.0644 (10) | 0.0577 (9) | 0.0174 (8) | 0.0241 (7) | 0.0183 (8) |
C121 | 0.073 (2) | 0.069 (2) | 0.0689 (17) | 0.0104 (17) | 0.0256 (15) | 0.0271 (16) |
C13 | 0.0421 (12) | 0.0598 (15) | 0.0395 (11) | 0.0025 (11) | 0.0139 (9) | 0.0000 (11) |
C14 | 0.0404 (12) | 0.0530 (15) | 0.0463 (12) | 0.0073 (11) | 0.0133 (10) | −0.0052 (10) |
Geometric parameters (Å, º) top
C1—C6 | 1.391 (3) | C51—H51C | 1.00 (2) |
C1—C2 | 1.392 (3) | C6—H6 | 1.01 (2) |
C1—C7 | 1.485 (3) | C7—C8 | 1.332 (3) |
C2—C3 | 1.388 (3) | C7—H7 | 1.01 (2) |
C2—H2 | 0.933 (19) | C8—C9 | 1.477 (3) |
C3—O3 | 1.370 (2) | C8—H8 | 0.99 (2) |
C3—C4 | 1.388 (3) | C9—C14 | 1.390 (3) |
O3—C31 | 1.411 (3) | C9—C10 | 1.391 (3) |
C31—H31A | 0.99 (3) | C10—C11 | 1.385 (3) |
C31—H31B | 0.96 (2) | C10—H10 | 0.954 (18) |
C31—H31C | 0.95 (2) | C11—O11 | 1.363 (2) |
C4—O4 | 1.385 (2) | C11—C12 | 1.394 (3) |
C4—C5 | 1.392 (3) | O11—H11 | 0.92 (3) |
O4—C41 | 1.431 (3) | C12—O12 | 1.376 (2) |
C41—H41A | 0.97 (3) | C12—C13 | 1.380 (3) |
C41—H41B | 0.97 (3) | O12—C121 | 1.408 (3) |
C41—H41C | 1.03 (3) | C121—H12A | 1.03 (3) |
C5—O5 | 1.361 (2) | C121—H12B | 1.01 (3) |
C5—C6 | 1.394 (3) | C121—H12C | 0.97 (3) |
O5—C51 | 1.429 (2) | C13—C14 | 1.377 (3) |
C51—H51A | 1.02 (2) | C13—H13 | 0.966 (18) |
C51—H51B | 0.98 (2) | C14—H14 | 0.94 (2) |
| | | |
C6—C1—C2 | 119.73 (19) | C1—C6—C5 | 119.97 (19) |
C6—C1—C7 | 120.83 (18) | C1—C6—H6 | 120.2 (11) |
C2—C1—C7 | 119.38 (19) | C5—C6—H6 | 119.8 (11) |
C3—C2—C1 | 120.3 (2) | C8—C7—C1 | 128.9 (2) |
C3—C2—H2 | 120.9 (12) | C8—C7—H7 | 117.6 (12) |
C1—C2—H2 | 118.8 (12) | C1—C7—H7 | 113.5 (12) |
O3—C3—C2 | 125.01 (19) | C7—C8—C9 | 130.6 (2) |
O3—C3—C4 | 115.01 (18) | C7—C8—H8 | 117.8 (12) |
C2—C3—C4 | 119.98 (19) | C9—C8—H8 | 111.6 (11) |
C3—O3—C31 | 118.2 (2) | C14—C9—C10 | 117.71 (19) |
O3—C31—H31A | 104.0 (15) | C14—C9—C8 | 123.79 (19) |
O3—C31—H31B | 110.6 (15) | C10—C9—C8 | 118.28 (18) |
H31A—C31—H31B | 111 (2) | C11—C10—C9 | 121.79 (19) |
O3—C31—H31C | 111.0 (15) | C11—C10—H10 | 117.2 (11) |
H31A—C31—H31C | 111 (2) | C9—C10—H10 | 121.0 (11) |
H31B—C31—H31C | 108 (2) | O11—C11—C10 | 119.34 (18) |
O4—C4—C3 | 119.29 (17) | O11—C11—C12 | 121.36 (19) |
O4—C4—C5 | 120.57 (18) | C10—C11—C12 | 119.29 (19) |
C3—C4—C5 | 119.98 (18) | C11—O11—H11 | 112.0 (17) |
C4—O4—C41 | 114.67 (17) | O12—C12—C13 | 126.18 (18) |
O4—C41—H41A | 112.3 (16) | O12—C12—C11 | 114.47 (17) |
O4—C41—H41B | 109.5 (16) | C13—C12—C11 | 119.35 (19) |
H41A—C41—H41B | 107 (2) | C12—O12—C121 | 117.51 (18) |
O4—C41—H41C | 110.1 (13) | O12—C121—H12A | 108.4 (15) |
H41A—C41—H41C | 111 (2) | O12—C121—H12B | 110.2 (15) |
H41B—C41—H41C | 107 (2) | H12A—C121—H12B | 111 (2) |
O5—C5—C4 | 115.11 (17) | O12—C121—H12C | 104.8 (14) |
O5—C5—C6 | 124.91 (18) | H12A—C121—H12C | 113.9 (19) |
C4—C5—C6 | 119.98 (19) | H12B—C121—H12C | 108 (2) |
C5—O5—C51 | 118.36 (17) | C14—C13—C12 | 120.7 (2) |
O5—C51—H51A | 111.1 (13) | C14—C13—H13 | 121.0 (11) |
O5—C51—H51B | 103.6 (13) | C12—C13—H13 | 118.2 (11) |
H51A—C51—H51B | 111.9 (19) | C13—C14—C9 | 121.1 (2) |
O5—C51—H51C | 111.0 (13) | C13—C14—H14 | 119.1 (12) |
H51A—C51—H51C | 108.5 (19) | C9—C14—H14 | 119.8 (12) |
H51B—C51—H51C | 110.7 (17) | | |
| | | |
C6—C1—C2—C3 | −1.0 (3) | C4—C5—C6—C1 | 1.2 (3) |
C7—C1—C2—C3 | −178.28 (18) | C6—C1—C7—C8 | 55.8 (3) |
C1—C2—C3—O3 | −177.42 (17) | C2—C1—C7—C8 | −127.0 (2) |
C1—C2—C3—C4 | 2.0 (3) | C1—C7—C8—C9 | 6.9 (4) |
C2—C3—O3—C31 | −0.6 (3) | C7—C8—C9—C14 | 24.8 (3) |
C4—C3—O3—C31 | 179.9 (2) | C7—C8—C9—C10 | −160.8 (2) |
O3—C3—C4—O4 | −6.4 (2) | C14—C9—C10—C11 | −0.3 (3) |
C2—C3—C4—O4 | 174.08 (16) | C8—C9—C10—C11 | −175.11 (18) |
O3—C3—C4—C5 | 178.08 (16) | C9—C10—C11—O11 | −179.29 (18) |
C2—C3—C4—C5 | −1.4 (3) | C9—C10—C11—C12 | 1.7 (3) |
C3—C4—O4—C41 | 101.4 (2) | O11—C11—C12—O12 | −1.6 (3) |
C5—C4—O4—C41 | −83.1 (2) | C10—C11—C12—O12 | 177.38 (17) |
O4—C4—C5—O5 | 4.4 (2) | O11—C11—C12—C13 | 178.74 (18) |
C3—C4—C5—O5 | 179.88 (16) | C10—C11—C12—C13 | −2.3 (3) |
O4—C4—C5—C6 | −175.62 (16) | C13—C12—O12—C121 | −7.7 (3) |
C3—C4—C5—C6 | −0.2 (3) | C11—C12—O12—C121 | 172.7 (2) |
C4—C5—O5—C51 | −179.52 (18) | O12—C12—C13—C14 | −178.10 (18) |
C6—C5—O5—C51 | 0.5 (3) | C11—C12—C13—C14 | 1.6 (3) |
C2—C1—C6—C5 | −0.6 (3) | C12—C13—C14—C9 | −0.2 (3) |
C7—C1—C6—C5 | 176.64 (18) | C10—C9—C14—C13 | −0.5 (3) |
O5—C5—C6—C1 | −178.89 (16) | C8—C9—C14—C13 | 174.00 (18) |
2-Methoxy-5-[(
E)-2-(3,4,5-trimethoxyphenyl)ethenyl]phenol (2)
top
Crystal data top
C18H20O5 | Dx = 1.274 Mg m−3 |
Mr = 316.34 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 6871 reflections |
a = 25.9293 (7) Å | θ = 3.7–26.0° |
b = 8.8657 (3) Å | µ = 0.09 mm−1 |
c = 14.3503 (5) Å | T = 295 K |
V = 3298.87 (18) Å3 | Prism, colourless |
Z = 8 | 0.3 × 0.2 × 0.2 mm |
F(000) = 1344 | |
Data collection top
Xcalibur, Eos diffractometer | 6241 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 5060 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 16.2413 pixels mm-1 | θmax = 27.0°, θmin = 3.1° |
ω scans | h = −32→28 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −11→11 |
Tmin = 0.837, Tmax = 1.000 | l = −16→18 |
19387 measured reflections | |
Refinement top
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0484P)2 + 0.1541P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
6241 reflections | Δρmax = 0.12 e Å−3 |
431 parameters | Δρmin = −0.13 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.37378 (10) | 0.0390 (3) | 0.4398 (2) | 0.0472 (6) | |
C2A | 0.41006 (10) | 0.0977 (3) | 0.50153 (19) | 0.0475 (6) | |
H2A | 0.4230 | 0.0375 | 0.5492 | 0.057* | |
C3A | 0.42693 (10) | 0.2454 (3) | 0.4922 (2) | 0.0473 (6) | |
O3A | 0.46376 (8) | 0.3119 (2) | 0.54636 (15) | 0.0620 (5) | |
C31A | 0.48146 (14) | 0.2328 (5) | 0.6256 (3) | 0.0835 (11) | |
H31A | 0.4526 | 0.2047 | 0.6637 | 0.125* | |
H31B | 0.5043 | 0.2961 | 0.6607 | 0.125* | |
H31C | 0.4995 | 0.1437 | 0.6061 | 0.125* | |
C4A | 0.40716 (10) | 0.3364 (3) | 0.42173 (19) | 0.0440 (6) | |
O4A | 0.42370 (8) | 0.48385 (19) | 0.41356 (14) | 0.0532 (5) | |
C41A | 0.45741 (14) | 0.5132 (4) | 0.3367 (2) | 0.0696 (9) | |
H41A | 0.4888 | 0.4573 | 0.3446 | 0.104* | |
H41B | 0.4651 | 0.6191 | 0.3342 | 0.104* | |
H41C | 0.4409 | 0.4830 | 0.2798 | 0.104* | |
C5A | 0.36913 (10) | 0.2801 (3) | 0.36276 (19) | 0.0462 (6) | |
O5A | 0.35117 (8) | 0.3797 (2) | 0.29787 (15) | 0.0589 (5) | |
C51A | 0.31995 (13) | 0.3229 (4) | 0.2244 (2) | 0.0696 (9) | |
H51A | 0.3371 | 0.2396 | 0.1951 | 0.104* | |
H51B | 0.3141 | 0.4011 | 0.1794 | 0.104* | |
H51C | 0.2875 | 0.2896 | 0.2492 | 0.104* | |
C6A | 0.35230 (10) | 0.1325 (3) | 0.3724 (2) | 0.0477 (6) | |
H6A | 0.3265 | 0.0958 | 0.3336 | 0.057* | |
C7A | 0.36021 (10) | −0.1226 (3) | 0.4482 (2) | 0.0551 (7) | |
H7A | 0.3618 | −0.1622 | 0.5081 | 0.066* | |
C8A | 0.34598 (10) | −0.2192 (3) | 0.3818 (2) | 0.0566 (7) | |
H8A | 0.3375 | −0.3155 | 0.4026 | 0.068* | |
C9A | 0.34163 (10) | −0.1962 (3) | 0.2804 (2) | 0.0508 (7) | |
C10A | 0.37862 (11) | −0.1136 (3) | 0.2305 (2) | 0.0554 (7) | |
H10A | 0.4077 | −0.0777 | 0.2612 | 0.067* | |
C11A | 0.37257 (11) | −0.0853 (3) | 0.1379 (2) | 0.0570 (7) | |
O11A | 0.40896 (10) | 0.0001 (3) | 0.0928 (2) | 0.0841 (8) | |
H11A | 0.396 (2) | 0.011 (6) | 0.034 (4) | 0.14 (2)* | |
C12A | 0.33059 (11) | −0.1421 (4) | 0.0899 (2) | 0.0591 (7) | |
O12A | 0.32956 (9) | −0.1045 (3) | −0.00288 (18) | 0.0832 (7) | |
C121 | 0.28899 (17) | −0.1595 (7) | −0.0572 (3) | 0.1145 (16) | |
H12D | 0.2867 | −0.2669 | −0.0500 | 0.172* | |
H12E | 0.2952 | −0.1356 | −0.1215 | 0.172* | |
H12F | 0.2573 | −0.1138 | −0.0375 | 0.172* | |
C13A | 0.29515 (11) | −0.2296 (4) | 0.1363 (2) | 0.0650 (8) | |
H13A | 0.2673 | −0.2708 | 0.1043 | 0.078* | |
C14A | 0.30097 (11) | −0.2564 (3) | 0.2316 (2) | 0.0598 (8) | |
H14A | 0.2769 | −0.3160 | 0.2625 | 0.072* | |
C1B | 0.42763 (9) | 0.1464 (3) | 0.87618 (19) | 0.0430 (5) | |
C2B | 0.38647 (10) | 0.1113 (3) | 0.81668 (19) | 0.0469 (6) | |
H2B | 0.3895 | 0.0319 | 0.7747 | 0.056* | |
C3B | 0.34166 (9) | 0.1937 (3) | 0.82019 (19) | 0.0460 (6) | |
O3B | 0.29932 (7) | 0.1659 (2) | 0.76591 (15) | 0.0600 (5) | |
C31B | 0.30430 (13) | 0.0570 (4) | 0.6937 (3) | 0.0731 (10) | |
H31D | 0.3325 | 0.0842 | 0.6538 | 0.110* | |
H31E | 0.2730 | 0.0537 | 0.6579 | 0.110* | |
H31F | 0.3107 | −0.0404 | 0.7205 | 0.110* | |
C4B | 0.33683 (9) | 0.3157 (3) | 0.8817 (2) | 0.0482 (6) | |
O4B | 0.29291 (7) | 0.4038 (2) | 0.87813 (16) | 0.0634 (5) | |
C41B | 0.25780 (13) | 0.3781 (5) | 0.9519 (3) | 0.0887 (12) | |
H41D | 0.2491 | 0.2730 | 0.9541 | 0.133* | |
H41E | 0.2271 | 0.4365 | 0.9418 | 0.133* | |
H41F | 0.2734 | 0.4074 | 1.0098 | 0.133* | |
C5B | 0.37766 (10) | 0.3509 (3) | 0.9396 (2) | 0.0476 (6) | |
O5B | 0.36984 (7) | 0.4737 (2) | 0.99656 (16) | 0.0641 (6) | |
C51B | 0.41135 (13) | 0.5169 (4) | 1.0551 (3) | 0.0841 (12) | |
H51D | 0.4215 | 0.4327 | 1.0929 | 0.126* | |
H51E | 0.4006 | 0.5986 | 1.0945 | 0.126* | |
H51F | 0.4400 | 0.5487 | 1.0175 | 0.126* | |
C6B | 0.42259 (10) | 0.2677 (3) | 0.93711 (19) | 0.0458 (6) | |
H6B | 0.4497 | 0.2928 | 0.9765 | 0.055* | |
C7B | 0.47708 (9) | 0.0655 (3) | 0.8765 (2) | 0.0490 (6) | |
H7B | 0.5028 | 0.1112 | 0.9119 | 0.059* | |
C8B | 0.49146 (10) | −0.0625 (3) | 0.83475 (19) | 0.0496 (6) | |
H8B | 0.5260 | −0.0882 | 0.8417 | 0.059* | |
C9B | 0.46040 (9) | −0.1688 (3) | 0.77915 (18) | 0.0439 (6) | |
C10B | 0.47509 (10) | −0.2003 (3) | 0.68782 (19) | 0.0464 (6) | |
H10B | 0.5046 | −0.1553 | 0.6634 | 0.056* | |
C11B | 0.44673 (10) | −0.2968 (3) | 0.63325 (19) | 0.0468 (6) | |
O11B | 0.46226 (8) | −0.3222 (3) | 0.54421 (15) | 0.0660 (6) | |
H11B | 0.4434 (19) | −0.401 (6) | 0.525 (4) | 0.129 (17)* | |
C12B | 0.40256 (10) | −0.3655 (3) | 0.6695 (2) | 0.0477 (6) | |
O12B | 0.37597 (8) | −0.4529 (3) | 0.60644 (16) | 0.0677 (6) | |
C122 | 0.33565 (14) | −0.5404 (5) | 0.6377 (3) | 0.0877 (12) | |
H12A | 0.3476 | −0.6055 | 0.6867 | 0.132* | |
H12B | 0.3226 | −0.6003 | 0.5873 | 0.132* | |
H12C | 0.3087 | −0.4765 | 0.6611 | 0.132* | |
C13B | 0.38878 (11) | −0.3395 (3) | 0.7603 (2) | 0.0536 (7) | |
H13B | 0.3600 | −0.3875 | 0.7853 | 0.064* | |
C14B | 0.41767 (10) | −0.2415 (3) | 0.8152 (2) | 0.0531 (7) | |
H14B | 0.4081 | −0.2248 | 0.8768 | 0.064* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0491 (14) | 0.0432 (14) | 0.0492 (16) | 0.0015 (12) | 0.0059 (12) | 0.0023 (12) |
C2A | 0.0525 (14) | 0.0475 (15) | 0.0427 (15) | 0.0012 (12) | 0.0032 (12) | 0.0047 (12) |
C3A | 0.0501 (14) | 0.0499 (15) | 0.0419 (15) | −0.0001 (12) | 0.0015 (12) | −0.0016 (12) |
O3A | 0.0728 (12) | 0.0598 (13) | 0.0533 (12) | −0.0116 (10) | −0.0167 (10) | 0.0052 (9) |
C31A | 0.091 (2) | 0.097 (3) | 0.063 (2) | −0.025 (2) | −0.027 (2) | 0.021 (2) |
C4A | 0.0542 (14) | 0.0351 (13) | 0.0426 (14) | 0.0004 (11) | 0.0040 (12) | −0.0039 (11) |
O4A | 0.0709 (11) | 0.0407 (10) | 0.0480 (11) | −0.0042 (9) | 0.0027 (9) | −0.0042 (8) |
C41A | 0.086 (2) | 0.0601 (19) | 0.063 (2) | −0.0154 (16) | 0.0132 (17) | 0.0016 (15) |
C5A | 0.0526 (14) | 0.0402 (14) | 0.0458 (16) | 0.0064 (11) | −0.0003 (12) | 0.0017 (11) |
O5A | 0.0712 (12) | 0.0427 (10) | 0.0628 (13) | −0.0001 (9) | −0.0200 (10) | 0.0044 (9) |
C51A | 0.083 (2) | 0.065 (2) | 0.062 (2) | −0.0056 (17) | −0.0217 (17) | 0.0086 (16) |
C6A | 0.0483 (13) | 0.0427 (13) | 0.0521 (16) | −0.0009 (11) | −0.0028 (13) | −0.0031 (12) |
C7A | 0.0593 (16) | 0.0469 (17) | 0.0590 (19) | −0.0049 (13) | 0.0030 (14) | 0.0082 (14) |
C8A | 0.0576 (15) | 0.0396 (14) | 0.072 (2) | −0.0050 (12) | 0.0058 (15) | 0.0082 (14) |
C9A | 0.0507 (15) | 0.0368 (14) | 0.0648 (19) | 0.0015 (11) | 0.0062 (13) | −0.0027 (13) |
C10A | 0.0516 (15) | 0.0530 (17) | 0.062 (2) | −0.0059 (13) | 0.0045 (13) | −0.0050 (14) |
C11A | 0.0545 (15) | 0.0520 (17) | 0.064 (2) | −0.0048 (13) | 0.0102 (14) | −0.0046 (14) |
O11A | 0.0778 (16) | 0.107 (2) | 0.0674 (17) | −0.0348 (14) | 0.0092 (13) | 0.0084 (14) |
C12A | 0.0558 (16) | 0.0620 (18) | 0.0594 (19) | 0.0025 (14) | 0.0056 (15) | −0.0078 (15) |
O12A | 0.0787 (14) | 0.109 (2) | 0.0617 (16) | −0.0134 (14) | −0.0012 (12) | −0.0011 (14) |
C121 | 0.102 (3) | 0.168 (5) | 0.074 (3) | −0.032 (3) | −0.022 (2) | 0.004 (3) |
C13A | 0.0535 (16) | 0.067 (2) | 0.074 (2) | −0.0096 (14) | −0.0038 (15) | −0.0146 (17) |
C14A | 0.0598 (17) | 0.0480 (16) | 0.071 (2) | −0.0106 (14) | 0.0084 (15) | −0.0032 (15) |
C1B | 0.0458 (12) | 0.0419 (13) | 0.0412 (14) | −0.0018 (10) | −0.0050 (12) | −0.0021 (11) |
C2B | 0.0486 (14) | 0.0457 (14) | 0.0463 (16) | −0.0015 (11) | −0.0051 (11) | −0.0064 (12) |
C3B | 0.0431 (13) | 0.0489 (15) | 0.0462 (15) | −0.0045 (11) | −0.0057 (12) | −0.0022 (12) |
O3B | 0.0483 (10) | 0.0689 (13) | 0.0628 (13) | 0.0001 (9) | −0.0137 (9) | −0.0130 (10) |
C31B | 0.0688 (19) | 0.077 (2) | 0.073 (2) | −0.0023 (17) | −0.0217 (17) | −0.0240 (18) |
C4B | 0.0439 (13) | 0.0514 (15) | 0.0492 (16) | 0.0019 (11) | 0.0020 (12) | −0.0016 (13) |
O4B | 0.0513 (10) | 0.0742 (14) | 0.0648 (13) | 0.0136 (9) | 0.0008 (10) | −0.0094 (11) |
C41B | 0.0528 (17) | 0.122 (3) | 0.092 (3) | 0.002 (2) | 0.0125 (18) | −0.020 (2) |
C5B | 0.0509 (14) | 0.0452 (15) | 0.0465 (15) | −0.0028 (12) | −0.0002 (12) | −0.0087 (12) |
O5B | 0.0588 (11) | 0.0631 (13) | 0.0704 (15) | 0.0048 (10) | −0.0053 (11) | −0.0291 (11) |
C51B | 0.074 (2) | 0.078 (2) | 0.101 (3) | 0.0065 (18) | −0.020 (2) | −0.050 (2) |
C6B | 0.0454 (13) | 0.0473 (15) | 0.0446 (15) | −0.0040 (12) | −0.0061 (11) | −0.0064 (12) |
C7B | 0.0476 (13) | 0.0523 (15) | 0.0472 (15) | −0.0025 (12) | −0.0106 (13) | −0.0078 (12) |
C8B | 0.0478 (13) | 0.0515 (15) | 0.0494 (16) | 0.0036 (12) | −0.0096 (12) | −0.0039 (13) |
C9B | 0.0477 (13) | 0.0400 (14) | 0.0440 (15) | 0.0050 (11) | −0.0016 (11) | −0.0003 (11) |
C10B | 0.0489 (14) | 0.0418 (14) | 0.0484 (16) | −0.0026 (12) | 0.0014 (12) | −0.0013 (11) |
C11B | 0.0546 (14) | 0.0443 (15) | 0.0415 (15) | −0.0049 (12) | 0.0038 (12) | −0.0044 (11) |
O11B | 0.0718 (13) | 0.0760 (16) | 0.0503 (12) | −0.0270 (12) | 0.0151 (10) | −0.0173 (11) |
C12B | 0.0508 (14) | 0.0412 (14) | 0.0510 (16) | −0.0075 (12) | 0.0029 (12) | −0.0058 (12) |
O12B | 0.0720 (12) | 0.0715 (14) | 0.0596 (14) | −0.0302 (11) | 0.0081 (10) | −0.0132 (11) |
C122 | 0.084 (2) | 0.106 (3) | 0.074 (2) | −0.050 (2) | −0.001 (2) | −0.003 (2) |
C13B | 0.0580 (15) | 0.0469 (16) | 0.0560 (18) | −0.0075 (13) | 0.0120 (14) | −0.0008 (13) |
C14B | 0.0644 (16) | 0.0510 (16) | 0.0439 (16) | −0.0009 (13) | 0.0057 (13) | −0.0057 (13) |
Geometric parameters (Å, º) top
C1A—C6A | 1.390 (4) | C1B—C6B | 1.392 (4) |
C1A—C2A | 1.393 (4) | C1B—C2B | 1.402 (3) |
C1A—C7A | 1.480 (4) | C1B—C7B | 1.469 (3) |
C2A—C3A | 1.387 (4) | C2B—C3B | 1.374 (4) |
C2A—H2A | 0.9300 | C2B—H2B | 0.9300 |
C3A—O3A | 1.365 (3) | C3B—O3B | 1.369 (3) |
C3A—C4A | 1.392 (4) | C3B—C4B | 1.401 (4) |
O3A—C31A | 1.412 (4) | O3B—C31B | 1.423 (4) |
C31A—H31A | 0.9600 | C31B—H31D | 0.9600 |
C31A—H31B | 0.9600 | C31B—H31E | 0.9600 |
C31A—H31C | 0.9600 | C31B—H31F | 0.9600 |
C4A—O4A | 1.381 (3) | C4B—C5B | 1.382 (4) |
C4A—C5A | 1.392 (4) | C4B—O4B | 1.382 (3) |
O4A—C41A | 1.431 (4) | O4B—C41B | 1.415 (4) |
C41A—H41A | 0.9600 | C41B—H41D | 0.9600 |
C41A—H41B | 0.9600 | C41B—H41E | 0.9600 |
C41A—H41C | 0.9600 | C41B—H41F | 0.9600 |
C5A—O5A | 1.365 (3) | C5B—O5B | 1.376 (3) |
C5A—C6A | 1.386 (4) | C5B—C6B | 1.380 (4) |
O5A—C51A | 1.421 (4) | O5B—C51B | 1.418 (4) |
C51A—H51A | 0.9600 | C51B—H51D | 0.9600 |
C51A—H51B | 0.9600 | C51B—H51E | 0.9600 |
C51A—H51C | 0.9600 | C51B—H51F | 0.9600 |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—C8A | 1.333 (4) | C7B—C8B | 1.337 (4) |
C7A—H7A | 0.9300 | C7B—H7B | 0.9300 |
C8A—C9A | 1.474 (4) | C8B—C9B | 1.474 (4) |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C9A—C14A | 1.374 (4) | C9B—C14B | 1.382 (4) |
C9A—C10A | 1.403 (4) | C9B—C10B | 1.393 (4) |
C10A—C11A | 1.361 (4) | C10B—C11B | 1.374 (4) |
C10A—H10A | 0.9300 | C10B—H10B | 0.9300 |
C11A—O11A | 1.372 (4) | C11B—O11B | 1.359 (3) |
C11A—C12A | 1.384 (4) | C11B—C12B | 1.397 (4) |
O11A—H11A | 0.92 (6) | O11B—H11B | 0.89 (5) |
C12A—O12A | 1.373 (4) | C12B—C13B | 1.371 (4) |
C12A—C13A | 1.374 (4) | C12B—O12B | 1.376 (3) |
O12A—C121 | 1.398 (4) | O12B—C122 | 1.377 (4) |
C121—H12D | 0.9600 | C122—H12A | 0.9600 |
C121—H12E | 0.9600 | C122—H12B | 0.9600 |
C121—H12F | 0.9600 | C122—H12C | 0.9600 |
C13A—C14A | 1.396 (5) | C13B—C14B | 1.391 (4) |
C13A—H13A | 0.9300 | C13B—H13B | 0.9300 |
C14A—H14A | 0.9300 | C14B—H14B | 0.9300 |
| | | |
C6A—C1A—C2A | 119.4 (2) | C6B—C1B—C2B | 118.9 (2) |
C6A—C1A—C7A | 122.6 (3) | C6B—C1B—C7B | 117.2 (2) |
C2A—C1A—C7A | 118.0 (2) | C2B—C1B—C7B | 123.9 (2) |
C3A—C2A—C1A | 120.3 (3) | C3B—C2B—C1B | 120.2 (2) |
C3A—C2A—H2A | 119.9 | C3B—C2B—H2B | 119.9 |
C1A—C2A—H2A | 119.9 | C1B—C2B—H2B | 119.9 |
O3A—C3A—C2A | 125.0 (3) | O3B—C3B—C2B | 124.2 (2) |
O3A—C3A—C4A | 114.9 (2) | O3B—C3B—C4B | 115.2 (2) |
C2A—C3A—C4A | 120.1 (2) | C2B—C3B—C4B | 120.6 (2) |
C3A—O3A—C31A | 118.1 (2) | C3B—O3B—C31B | 117.7 (2) |
O3A—C31A—H31A | 109.5 | O3B—C31B—H31D | 109.5 |
O3A—C31A—H31B | 109.5 | O3B—C31B—H31E | 109.5 |
H31A—C31A—H31B | 109.5 | H31D—C31B—H31E | 109.5 |
O3A—C31A—H31C | 109.5 | O3B—C31B—H31F | 109.5 |
H31A—C31A—H31C | 109.5 | H31D—C31B—H31F | 109.5 |
H31B—C31A—H31C | 109.5 | H31E—C31B—H31F | 109.5 |
O4A—C4A—C3A | 119.7 (2) | C5B—C4B—O4B | 121.7 (2) |
O4A—C4A—C5A | 120.6 (2) | C5B—C4B—C3B | 119.0 (2) |
C3A—C4A—C5A | 119.6 (2) | O4B—C4B—C3B | 119.1 (2) |
C4A—O4A—C41A | 115.3 (2) | C4B—O4B—C41B | 114.3 (3) |
O4A—C41A—H41A | 109.5 | O4B—C41B—H41D | 109.5 |
O4A—C41A—H41B | 109.5 | O4B—C41B—H41E | 109.5 |
H41A—C41A—H41B | 109.5 | H41D—C41B—H41E | 109.5 |
O4A—C41A—H41C | 109.5 | O4B—C41B—H41F | 109.5 |
H41A—C41A—H41C | 109.5 | H41D—C41B—H41F | 109.5 |
H41B—C41A—H41C | 109.5 | H41E—C41B—H41F | 109.5 |
O5A—C5A—C6A | 124.8 (2) | O5B—C5B—C6B | 124.3 (2) |
O5A—C5A—C4A | 115.1 (2) | O5B—C5B—C4B | 115.0 (2) |
C6A—C5A—C4A | 120.1 (2) | C6B—C5B—C4B | 120.7 (2) |
C5A—O5A—C51A | 118.1 (2) | C5B—O5B—C51B | 117.0 (2) |
O5A—C51A—H51A | 109.5 | O5B—C51B—H51D | 109.5 |
O5A—C51A—H51B | 109.5 | O5B—C51B—H51E | 109.5 |
H51A—C51A—H51B | 109.5 | H51D—C51B—H51E | 109.5 |
O5A—C51A—H51C | 109.5 | O5B—C51B—H51F | 109.5 |
H51A—C51A—H51C | 109.5 | H51D—C51B—H51F | 109.5 |
H51B—C51A—H51C | 109.5 | H51E—C51B—H51F | 109.5 |
C5A—C6A—C1A | 120.4 (2) | C5B—C6B—C1B | 120.6 (2) |
C5A—C6A—H6A | 119.8 | C5B—C6B—H6B | 119.7 |
C1A—C6A—H6A | 119.8 | C1B—C6B—H6B | 119.7 |
C8A—C7A—C1A | 129.0 (3) | C8B—C7B—C1B | 131.0 (2) |
C8A—C7A—H7A | 115.5 | C8B—C7B—H7B | 114.5 |
C1A—C7A—H7A | 115.5 | C1B—C7B—H7B | 114.5 |
C7A—C8A—C9A | 129.6 (3) | C7B—C8B—C9B | 129.3 (2) |
C7A—C8A—H8A | 115.2 | C7B—C8B—H8B | 115.4 |
C9A—C8A—H8A | 115.2 | C9B—C8B—H8B | 115.4 |
C14A—C9A—C10A | 117.8 (3) | C14B—C9B—C10B | 118.5 (2) |
C14A—C9A—C8A | 120.6 (3) | C14B—C9B—C8B | 122.2 (2) |
C10A—C9A—C8A | 121.6 (3) | C10B—C9B—C8B | 119.2 (2) |
C11A—C10A—C9A | 121.0 (3) | C11B—C10B—C9B | 121.0 (2) |
C11A—C10A—H10A | 119.5 | C11B—C10B—H10B | 119.5 |
C9A—C10A—H10A | 119.5 | C9B—C10B—H10B | 119.5 |
C10A—C11A—O11A | 118.9 (3) | O11B—C11B—C10B | 118.7 (2) |
C10A—C11A—C12A | 120.7 (3) | O11B—C11B—C12B | 121.4 (2) |
O11A—C11A—C12A | 120.4 (3) | C10B—C11B—C12B | 119.9 (3) |
C11A—O11A—H11A | 104 (3) | C11B—O11B—H11B | 105 (3) |
O12A—C12A—C13A | 126.4 (3) | C13B—C12B—O12B | 126.1 (2) |
O12A—C12A—C11A | 114.2 (3) | C13B—C12B—C11B | 119.6 (2) |
C13A—C12A—C11A | 119.3 (3) | O12B—C12B—C11B | 114.3 (2) |
C12A—O12A—C121 | 118.1 (3) | C12B—O12B—C122 | 118.9 (3) |
O12A—C121—H12D | 109.5 | O12B—C122—H12A | 109.5 |
O12A—C121—H12E | 109.5 | O12B—C122—H12B | 109.5 |
H12D—C121—H12E | 109.5 | H12A—C122—H12B | 109.5 |
O12A—C121—H12F | 109.5 | O12B—C122—H12C | 109.5 |
H12D—C121—H12F | 109.5 | H12A—C122—H12C | 109.5 |
H12E—C121—H12F | 109.5 | H12B—C122—H12C | 109.5 |
C12A—C13A—C14A | 119.9 (3) | C12B—C13B—C14B | 120.2 (3) |
C12A—C13A—H13A | 120.1 | C12B—C13B—H13B | 119.9 |
C14A—C13A—H13A | 120.1 | C14B—C13B—H13B | 119.9 |
C9A—C14A—C13A | 121.1 (3) | C9B—C14B—C13B | 120.7 (3) |
C9A—C14A—H14A | 119.5 | C9B—C14B—H14B | 119.6 |
C13A—C14A—H14A | 119.5 | C13B—C14B—H14B | 119.6 |
| | | |
C6A—C1A—C2A—C3A | −3.9 (4) | C6B—C1B—C2B—C3B | −1.3 (4) |
C7A—C1A—C2A—C3A | 175.2 (2) | C7B—C1B—C2B—C3B | −179.3 (3) |
C1A—C2A—C3A—O3A | −177.2 (2) | C1B—C2B—C3B—O3B | −178.9 (3) |
C1A—C2A—C3A—C4A | 0.8 (4) | C1B—C2B—C3B—C4B | 1.3 (4) |
C2A—C3A—O3A—C31A | −8.9 (4) | C2B—C3B—O3B—C31B | −8.0 (4) |
C4A—C3A—O3A—C31A | 173.1 (3) | C4B—C3B—O3B—C31B | 171.7 (3) |
O3A—C3A—C4A—O4A | −2.6 (4) | O3B—C3B—C4B—C5B | 179.5 (3) |
C2A—C3A—C4A—O4A | 179.3 (2) | C2B—C3B—C4B—C5B | −0.7 (4) |
O3A—C3A—C4A—C5A | −179.6 (2) | O3B—C3B—C4B—O4B | −5.1 (4) |
C2A—C3A—C4A—C5A | 2.2 (4) | C2B—C3B—C4B—O4B | 174.7 (2) |
C3A—C4A—O4A—C41A | 106.9 (3) | C5B—C4B—O4B—C41B | −79.8 (4) |
C5A—C4A—O4A—C41A | −76.0 (3) | C3B—C4B—O4B—C41B | 104.9 (3) |
O4A—C4A—C5A—O5A | 1.0 (4) | O4B—C4B—C5B—O5B | 3.7 (4) |
C3A—C4A—C5A—O5A | 178.0 (2) | C3B—C4B—C5B—O5B | 179.0 (2) |
O4A—C4A—C5A—C6A | −179.1 (2) | O4B—C4B—C5B—C6B | −175.3 (3) |
C3A—C4A—C5A—C6A | −2.1 (4) | C3B—C4B—C5B—C6B | 0.0 (4) |
C6A—C5A—O5A—C51A | −11.8 (4) | C6B—C5B—O5B—C51B | 0.8 (5) |
C4A—C5A—O5A—C51A | 168.1 (3) | C4B—C5B—O5B—C51B | −178.1 (3) |
O5A—C5A—C6A—C1A | 178.8 (3) | O5B—C5B—C6B—C1B | −178.9 (3) |
C4A—C5A—C6A—C1A | −1.1 (4) | C4B—C5B—C6B—C1B | 0.0 (4) |
C2A—C1A—C6A—C5A | 4.1 (4) | C2B—C1B—C6B—C5B | 0.7 (4) |
C7A—C1A—C6A—C5A | −175.0 (3) | C7B—C1B—C6B—C5B | 178.8 (3) |
C6A—C1A—C7A—C8A | 30.6 (4) | C6B—C1B—C7B—C8B | 171.6 (3) |
C2A—C1A—C7A—C8A | −148.6 (3) | C2B—C1B—C7B—C8B | −10.3 (5) |
C1A—C7A—C8A—C9A | 2.9 (5) | C1B—C7B—C8B—C9B | −4.4 (6) |
C7A—C8A—C9A—C14A | −139.2 (3) | C7B—C8B—C9B—C14B | −59.4 (4) |
C7A—C8A—C9A—C10A | 41.2 (4) | C7B—C8B—C9B—C10B | 122.2 (3) |
C14A—C9A—C10A—C11A | 4.4 (4) | C14B—C9B—C10B—C11B | 2.6 (4) |
C8A—C9A—C10A—C11A | −175.9 (3) | C8B—C9B—C10B—C11B | −179.0 (2) |
C9A—C10A—C11A—O11A | 177.9 (3) | C9B—C10B—C11B—O11B | 179.1 (2) |
C9A—C10A—C11A—C12A | −2.4 (4) | C9B—C10B—C11B—C12B | −0.3 (4) |
C10A—C11A—C12A—O12A | −180.0 (3) | O11B—C11B—C12B—C13B | 178.6 (3) |
O11A—C11A—C12A—O12A | −0.3 (4) | C10B—C11B—C12B—C13B | −2.0 (4) |
C10A—C11A—C12A—C13A | −0.8 (4) | O11B—C11B—C12B—O12B | −2.8 (4) |
O11A—C11A—C12A—C13A | 178.8 (3) | C10B—C11B—C12B—O12B | 176.5 (3) |
C13A—C12A—O12A—C121 | −0.3 (5) | C13B—C12B—O12B—C122 | −9.6 (5) |
C11A—C12A—O12A—C121 | 178.8 (4) | C11B—C12B—O12B—C122 | 171.9 (3) |
O12A—C12A—C13A—C14A | −179.0 (3) | O12B—C12B—C13B—C14B | −176.3 (3) |
C11A—C12A—C13A—C14A | 1.9 (5) | C11B—C12B—C13B—C14B | 2.1 (4) |
C10A—C9A—C14A—C13A | −3.3 (4) | C10B—C9B—C14B—C13B | −2.5 (4) |
C8A—C9A—C14A—C13A | 177.0 (3) | C8B—C9B—C14B—C13B | 179.1 (3) |
C12A—C13A—C14A—C9A | 0.2 (5) | C12B—C13B—C14B—C9B | 0.2 (4) |
Relevant geometrical data (Å, °) top | 1 | 2A | 2B | TIJYER | FIYJAY | QESRUC |
C3—C4—O4—C41 | 101.4 (2) | 106.9 (3) | 104.9 (3) | 93.6 | -100.3 | 89.1 |
C5—C4—O4–C41 | -83.2 (2) | -76.0 (3) | -79.8 (4) | -98.3 | 82.5 | -92.7 |
O4—C4—C5—O5 | 4.5 (2) | 1.0 (4) | 3.7 (4) | 12.4 | -2.5 | -2.9 |
C6—C1—C7—C8 | 55.8 (3) | 30.6 (4) | -10.3 (5) | 18.9 | -58.1 | -31.2 |
C2—C1—C7—C8 | -127.0 (2) | -148.6 (3) | 171.6 (3) | 165.3 | 126.7 | 152.1 |
C1—C7—C8—C9 | 6.9 (4) | 2.9 (5) | -4.4 (6) | 9.4 | -6.5 | -7.1 |
C7—C8—C9—C10 | -160.8 (2) | 41.2 (4) | 122.2 (3) | 40.1 | 169.9 | 147.7 |
C7—C8—C9—C14 | 24.8 (3) | -139.2 (3) | -59.4 (4) | -144.0 | -15.8 | -37.2 |
| | | | | | |
A/B | 58.56 (10) | 32.83 (13) | 11.72 (19) | 22.4 | 59.6 | 34.2 |
B/C | 26.47 (15) | 42.40 (15) | 60.99 (12) | 43.2 | 17.5 | 39.0 |
A/C | 65.21 (7) | 41.27 (12) | 61.45 (8) | 53.0 | 66.0 | 52.5 |
A/OMe3 | 1.9 (2) | 8.6 (3) | 1.9 (4) | 8.7 | 2.1 | 9.3 |
A/OMe4 | 80.44 (12) | 74.58 (15) | 77.22 (18) | 87.7 | 80.9 | 87.8 |
A/OMe5 | 0.7 (2) | 11.0 (3) | 8.3 (4) | 7.8 | 2.1 | 34.0 |
Values of torsion angles (°) used to describe conformations for
CA-4 molecule in
crystal structures 1, 2 and TIJYER (X-ray) and optimized at the
MP2/TZ and
M06-2X/TZ level top | X-ray | MP2/TZ | M06-2X/TZ |
| 1 | | |
C8—C7—C1—C6 | 55.8 | 34.7 | 37.2 |
C7—C8–C9—C10 | -160.8 | -129.4 | -139.5 |
| 2A | | |
C8—C7—C1—C6 | 30.5 | 33.3 | 32.6 |
C7–C8–C9—C10 | 41.2 | 44.0 | 37.1 |
| 2B | | |
C8—C7—C1—C6 | -10.4 | -34.7 | -37.2 |
C7—C8–C9—C10 | 122.2 | 129.4 | 139.5 |
| TIJYER | | |
C8—C7—C1—C6 | -18.9 | -33.3 | -32.6 |
C7—C8—C9—C10 | -40.1 | -44.0 | -37.2 |
Calculated relative energies for combretastatin A-4 conformations
(in kcal mol-1) topConformation | MP2/TZ Torsion angles C6—C1—C7—C8/C7—C8—C9—C10 | MP2/TZ Energy | M06-2X/TZ Torsion angles C6—C1—C7—C8/C7—C8—C9—C10 | M06-2X/TZ Energy |
1 | -34.9/129.6 (34.9/-129.6) | 0.00 | -36.7/139.4 (36.7/-139.4) | 0.00 |
2 | 33.3/44.0 (-33.3/-44.0) | 0.15 | 32.6/37.1 (-32.6/-37.2) | 0.15 |
3 | -30.1/-44.1 (30.1/44.1) | 0.27 | -31.5/-37.2 (31.5/37.2) | 0.20 |
4 | 34.7/-129.4 (-34.7/129.4) | 0.20 | 37.2/-139.5 (-37.2/139.5) | 0.23 |
For each of the conformations in the Table, there is its centrosymmetric
counterpart (1′, 2′, etc.) with opposite
signs of the torsion angles and exactly the same energy. |
Hydrogen-bond data (Å, °) topD—H···A | D—H | H···A | D···A | D—H···A |
1 | | | | |
O11—H11···O4i | 0.92 (3) | 2.00 (3) | 2.827 (2) | 148 (2) |
2 | | | | |
O11B—H11B···O4Aii | 0.89 (5) | 1.96 (5) | 2.733 (3) | 143 (5) |
TIJYER | | | | |
O11—H11···O3iii | 0.83 | 2.27 | 2.905 | 134 |
Symmetry codes: (i) x-1, y+1, z;
(ii) x, y-1, z;
(iii) x-1, y, z-1. |