The reduction of (1R,8R,11R)-3,3,11-trimethyl-6,6-ethylenedioxybicyclo[6.3.0]undecan-2-one, C16H26O3, (I), gave exclusively an alcohol, C16H28O3, (II). The stereochemistry of the hydroxyl group in (II) was shown as R. The conformation around the eight-membered carbocycle in (I) differs markedly from that in (II).
Supporting information
CCDC references: 150400; 150401
(1R,8R,11R)-3,11,11-Trimethylbicyclo[6.3.0]undecane-2,6-dione (Maeda & Inouye, 1997) was treated with tert-butyldimethylsilyl trifluoromethanesulfonate and 1,2-bis(trimethylsilyloxy)ethane at 203 K for 2 h, followed by a further 2 h at room temperature. The solution was filtered through a short silica-gel column with chloroform. After evaporating the solvent, the residue was chromatographed on alumina (benzene) to give (I) in 94% yield. (I) was reduced with LiAlH4 in dry tetrahydrofuran at 273 K to afford (II) in 96% yield. Compound (I): m.p. 361–362 K (from hexane); found: C 72.35, H 9.67%; calculated for C16H26O3: C 72.14, H 9.84%. Compound (2): m.p. 418–420 K (from hexane); found: C 71.76, H 10.66%; calculated for C16H28O3: C 71.60, H 10.52%.
In (II), atoms C17B and C17C (0.50:0.50) were disordered. The positions of all the H atoms, except methyl H and disordered methylene H atoms, were refined in the final calculations. The methyl and the methylene H atoms were calculated geometrically. Friedel pairs were not measured for (I) and a few (229) for (II). Refinement of the absolute structure parameter is meaningless for this combination of chemical composition and X-ray wavelength; the absolute configurations are deduced from those of the chemical precursors.
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).
(I) (1
R,8
R,11
R)-3,3,11-Trimethyl-6,6-ethylenedioxybicyclo[6.3.0]undecan-2-one
top
Crystal data top
C16H26O3 | Dx = 1.184 Mg m−3 |
Mr = 266.37 | Melting point = 361–362 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 15.594 (3) Å | Cell parameters from 25 reflections |
b = 16.837 (2) Å | θ = 10.0–13.6° |
c = 5.6919 (8) Å | µ = 0.08 mm−1 |
V = 1494.4 (4) Å3 | T = 293 K |
Z = 4 | Needle, colourless |
F(000) = 584 | 0.50 × 0.20 × 0.20 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 30.5°, θmin = 1.8° |
Graphite monochromator | h = 0→22 |
ω–2θ scans | k = 0→24 |
2616 measured reflections | l = 0→8 |
2616 independent reflections | 3 standard reflections every 120 min |
1316 reflections with I > 2σ(I) | intensity decay: 5.1% |
Refinement top
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1375P)2] where P = (Fo2 + 2Fc2)/3 |
2616 reflections | (Δ/σ)max = 0.005 |
243 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
C16H26O3 | V = 1494.4 (4) Å3 |
Mr = 266.37 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 15.594 (3) Å | µ = 0.08 mm−1 |
b = 16.837 (2) Å | T = 293 K |
c = 5.6919 (8) Å | 0.50 × 0.20 × 0.20 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | Rint = 0.000 |
2616 measured reflections | 3 standard reflections every 120 min |
2616 independent reflections | intensity decay: 5.1% |
1316 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.44 e Å−3 |
2616 reflections | Δρmin = −0.42 e Å−3 |
243 parameters | |
Special details top
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 on F2 for ALL reflections except for 0 with very negative F2 or 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 _refine_ls_R_factor_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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0939 (3) | 0.1546 (2) | 0.0449 (8) | 0.0401 (9) | |
H1 | 0.079 (3) | 0.174 (2) | −0.093 (9) | 0.033 (11)* | |
C2 | 0.0153 (3) | 0.1583 (3) | 0.2012 (7) | 0.0434 (9) | |
C3 | −0.0642 (3) | 0.2008 (3) | 0.1090 (8) | 0.0497 (11) | |
C4 | −0.0418 (4) | 0.2782 (3) | −0.0232 (10) | 0.0616 (13) | |
H4A | −0.003 (4) | 0.269 (3) | −0.183 (12) | 0.076 (17)* | |
H4B | −0.106 (5) | 0.298 (4) | −0.062 (15) | 0.11 (2)* | |
C5 | 0.0053 (5) | 0.3437 (4) | 0.1119 (12) | 0.076 (2) | |
H5A | −0.018 (4) | 0.350 (3) | 0.290 (13) | 0.073 (16)* | |
H5B | −0.013 (4) | 0.390 (5) | 0.060 (15) | 0.11 (2)* | |
C6 | 0.1029 (4) | 0.3440 (3) | 0.1102 (9) | 0.0613 (14) | |
C7 | 0.1445 (4) | 0.2828 (3) | 0.2711 (10) | 0.0585 (13) | |
H7A | 0.194 (4) | 0.307 (3) | 0.289 (12) | 0.074 (17)* | |
H7B | 0.108 (3) | 0.275 (3) | 0.426 (10) | 0.053 (13)* | |
C8 | 0.1673 (3) | 0.2030 (3) | 0.1597 (9) | 0.0502 (11) | |
H8 | 0.200 (3) | 0.207 (3) | 0.039 (10) | 0.048 (13)* | |
C9 | 0.2080 (4) | 0.1444 (4) | 0.3337 (12) | 0.071 (2) | |
H9A | 0.182 (4) | 0.151 (3) | 0.499 (14) | 0.079 (18)* | |
H9B | 0.266 (4) | 0.151 (3) | 0.354 (11) | 0.074 (17)* | |
C10 | 0.1874 (4) | 0.0618 (4) | 0.2433 (13) | 0.071 (2) | |
H10A | 0.235 (5) | 0.031 (4) | 0.240 (15) | 0.10 (2)* | |
H10B | 0.157 (4) | 0.038 (3) | 0.353 (11) | 0.061 (17)* | |
C11 | 0.1350 (3) | 0.0721 (3) | 0.0209 (9) | 0.0509 (11) | |
H11 | 0.176 (2) | 0.078 (2) | −0.107 (8) | 0.025 (9)* | |
O12 | 0.0156 (2) | 0.1274 (2) | 0.3950 (6) | 0.0616 (10) | |
C13 | −0.1064 (4) | 0.1418 (4) | −0.0611 (10) | 0.0699 (15) | |
H13A | −0.1597 | 0.1634 | −0.1164 | 0.105* | |
H13B | −0.1170 | 0.0926 | 0.0189 | 0.105* | |
H13C | −0.0689 | 0.1326 | −0.1920 | 0.105* | |
C14 | −0.1266 (3) | 0.2166 (4) | 0.3179 (10) | 0.072 (2) | |
H14A | −0.1777 | 0.2417 | 0.2603 | 0.108* | |
H14B | −0.0993 | 0.2507 | 0.4304 | 0.108* | |
H14C | −0.1413 | 0.1671 | 0.3915 | 0.108* | |
O15 | 0.1365 (3) | 0.3371 (2) | −0.1187 (6) | 0.0677 (11) | |
C16 | 0.1498 (5) | 0.4130 (4) | −0.2090 (12) | 0.069 (2) | |
H16A | 0.108 (3) | 0.428 (3) | −0.311 (11) | 0.059 (15)* | |
H16B | 0.203 (5) | 0.406 (4) | −0.272 (13) | 0.08 (2)* | |
C17 | 0.1468 (6) | 0.4677 (4) | −0.0039 (14) | 0.085 (2) | |
H17A | 0.212 (6) | 0.480 (5) | 0.027 (18) | 0.14 (3)* | |
H17B | 0.136 (5) | 0.512 (5) | 0.032 (17) | 0.12 (3)* | |
O18 | 0.1318 (4) | 0.4204 (2) | 0.1927 (7) | 0.090 (2) | |
C19 | 0.0740 (4) | 0.0043 (3) | −0.0378 (13) | 0.074 (2) | |
H19A | 0.0462 | 0.0150 | −0.1850 | 0.112* | |
H19B | 0.0316 | −0.0003 | 0.0837 | 0.112* | |
H19C | 0.1057 | −0.0444 | −0.0491 | 0.112* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.042 (2) | 0.042 (2) | 0.036 (2) | 0.005 (2) | 0.003 (2) | 0.008 (2) |
C2 | 0.048 (2) | 0.049 (2) | 0.034 (2) | 0.004 (2) | 0.001 (2) | 0.003 (2) |
C3 | 0.047 (2) | 0.072 (3) | 0.030 (2) | 0.011 (2) | 0.000 (2) | 0.000 (2) |
C4 | 0.067 (3) | 0.071 (3) | 0.047 (3) | 0.028 (3) | −0.004 (3) | 0.006 (3) |
C5 | 0.113 (5) | 0.052 (3) | 0.063 (4) | 0.027 (3) | 0.002 (4) | −0.003 (3) |
C6 | 0.101 (4) | 0.044 (2) | 0.039 (2) | −0.003 (2) | 0.012 (3) | −0.008 (2) |
C7 | 0.068 (3) | 0.060 (3) | 0.047 (3) | −0.007 (3) | 0.009 (3) | −0.003 (2) |
C8 | 0.048 (2) | 0.057 (3) | 0.046 (3) | −0.003 (2) | 0.002 (2) | 0.003 (2) |
C9 | 0.045 (3) | 0.089 (4) | 0.080 (4) | 0.011 (3) | −0.009 (3) | 0.009 (4) |
C10 | 0.071 (4) | 0.069 (4) | 0.072 (4) | 0.021 (3) | −0.005 (3) | 0.017 (3) |
C11 | 0.053 (2) | 0.045 (2) | 0.054 (3) | 0.010 (2) | 0.011 (2) | 0.009 (2) |
O12 | 0.055 (2) | 0.086 (2) | 0.044 (2) | 0.013 (2) | 0.013 (2) | 0.023 (2) |
C13 | 0.057 (3) | 0.099 (4) | 0.054 (3) | 0.003 (3) | −0.011 (2) | −0.010 (3) |
C14 | 0.051 (3) | 0.114 (4) | 0.050 (3) | 0.028 (3) | 0.003 (2) | −0.005 (3) |
O15 | 0.110 (3) | 0.052 (2) | 0.042 (2) | −0.010 (2) | 0.019 (2) | −0.003 (2) |
C16 | 0.094 (5) | 0.061 (3) | 0.054 (3) | 0.000 (3) | 0.004 (4) | 0.012 (3) |
C17 | 0.132 (6) | 0.049 (3) | 0.075 (4) | −0.021 (4) | 0.001 (5) | 0.002 (3) |
O18 | 0.173 (5) | 0.048 (2) | 0.050 (2) | −0.020 (3) | 0.000 (3) | −0.010 (2) |
C19 | 0.088 (4) | 0.048 (3) | 0.087 (4) | 0.003 (2) | 0.012 (4) | −0.003 (3) |
Geometric parameters (Å, º) top
C1—C2 | 1.515 (6) | C9—H9A | 1.03 (8) |
C1—C11 | 1.537 (6) | C9—H9B | 0.91 (6) |
C1—C8 | 1.550 (7) | C10—C11 | 1.516 (8) |
C1—H1 | 0.88 (5) | C10—H10A | 0.90 (7) |
C2—O12 | 1.220 (5) | C10—H10B | 0.88 (6) |
C2—C3 | 1.524 (6) | C11—C19 | 1.522 (8) |
C3—C13 | 1.535 (7) | C11—H11 | 0.97 (4) |
C3—C4 | 1.545 (7) | C13—H13A | 0.96 |
C3—C14 | 1.559 (7) | C13—H13B | 0.96 |
C4—C5 | 1.531 (9) | C13—H13C | 0.96 |
C4—H4A | 1.11 (6) | C14—H14A | 0.96 |
C4—H4B | 1.08 (7) | C14—H14B | 0.96 |
C5—C6 | 1.521 (9) | C14—H14C | 0.96 |
C5—H5A | 1.08 (7) | O15—C16 | 1.393 (7) |
C5—H5B | 0.88 (8) | C16—C17 | 1.487 (10) |
C6—O15 | 1.410 (6) | C16—H16A | 0.91 (6) |
C6—O18 | 1.441 (6) | C16—H16B | 0.91 (7) |
C6—C7 | 1.525 (8) | C17—O18 | 1.393 (8) |
C7—C8 | 1.528 (7) | C17—H17A | 1.05 (9) |
C7—H7A | 0.88 (6) | C17—H17B | 0.79 (8) |
C7—H7B | 1.06 (5) | C19—H19A | 0.96 |
C8—C9 | 1.535 (8) | C19—H19B | 0.96 |
C8—H8 | 0.86 (5) | C19—H19C | 0.96 |
C9—C10 | 1.517 (9) | | |
| | | |
C2—C1—C11 | 115.3 (4) | C10—C9—H9B | 111 (3) |
C2—C1—C8 | 109.2 (4) | C8—C9—H9B | 115 (4) |
C11—C1—C8 | 101.8 (4) | H9A—C9—H9B | 105 (6) |
C2—C1—H1 | 107 (3) | C11—C10—C9 | 107.1 (5) |
C11—C1—H1 | 111 (3) | C11—C10—H10A | 119 (6) |
C8—C1—H1 | 112 (3) | C9—C10—H10A | 111 (4) |
O12—C2—C1 | 120.7 (4) | C11—C10—H10B | 110 (4) |
O12—C2—C3 | 121.0 (4) | C9—C10—H10B | 107 (4) |
C1—C2—C3 | 118.4 (4) | H10A—C10—H10B | 102 (6) |
C2—C3—C13 | 105.2 (4) | C10—C11—C19 | 115.8 (5) |
C2—C3—C4 | 112.3 (4) | C10—C11—C1 | 104.7 (4) |
C13—C3—C4 | 109.6 (4) | C19—C11—C1 | 115.9 (4) |
C2—C3—C14 | 109.0 (4) | C10—C11—H11 | 107 (2) |
C13—C3—C14 | 108.9 (4) | C19—C11—H11 | 109 (2) |
C4—C3—C14 | 111.6 (4) | C1—C11—H11 | 105 (2) |
C5—C4—C3 | 118.1 (5) | C3—C13—H13A | 109.5 |
C5—C4—H4A | 105 (3) | C3—C13—H13B | 109.5 |
C3—C4—H4A | 114 (3) | H13A—C13—H13B | 109.5 |
C5—C4—H4B | 109 (4) | C3—C13—H13C | 109.5 |
C3—C4—H4B | 99 (4) | H13A—C13—H13C | 109.5 |
H4A—C4—H4B | 113 (5) | H13B—C13—H13C | 109.5 |
C6—C5—C4 | 118.6 (5) | C3—C14—H14A | 109.5 |
C6—C5—H5A | 110 (3) | C3—C14—H14B | 109.5 |
C4—C5—H5A | 113 (3) | H14A—C14—H14B | 109.5 |
C6—C5—H5B | 108 (5) | C3—C14—H14C | 109.5 |
C4—C5—H5B | 108 (5) | H14A—C14—H14C | 109.5 |
H5A—C5—H5B | 97 (6) | H14B—C14—H14C | 109.5 |
O15—C6—O18 | 105.0 (4) | C16—O15—C6 | 108.7 (4) |
O15—C6—C5 | 112.2 (5) | O15—C16—C17 | 105.9 (5) |
O18—C6—C5 | 108.3 (5) | O15—C16—H16A | 113 (3) |
O15—C6—C7 | 109.9 (4) | C17—C16—H16A | 108 (3) |
O18—C6—C7 | 106.0 (5) | O15—C16—H16B | 100 (4) |
C5—C6—C7 | 114.8 (5) | C17—C16—H16B | 115 (4) |
C6—C7—C8 | 116.4 (4) | H16A—C16—H16B | 116 (5) |
C6—C7—H7A | 98 (4) | O18—C17—C16 | 106.4 (5) |
C8—C7—H7A | 104 (4) | O18—C17—H17A | 98 (5) |
C6—C7—H7B | 111 (3) | C16—C17—H17A | 103 (6) |
C8—C7—H7B | 111 (3) | O18—C17—H17B | 107 (7) |
H7A—C7—H7B | 116 (5) | C16—C17—H17B | 143 (7) |
C7—C8—C9 | 113.2 (5) | H17A—C17—H17B | 89 (7) |
C7—C8—C1 | 117.7 (4) | C17—O18—C6 | 107.5 (4) |
C9—C8—C1 | 103.9 (4) | C11—C19—H19A | 109.5 |
C7—C8—H8 | 114 (3) | C11—C19—H19B | 109.5 |
C9—C8—H8 | 108 (3) | H19A—C19—H19B | 109.5 |
C1—C8—H8 | 98 (3) | C11—C19—H19C | 109.5 |
C10—C9—C8 | 106.4 (5) | H19A—C19—H19C | 109.5 |
C10—C9—H9A | 109 (3) | H19B—C19—H19C | 109.5 |
C8—C9—H9A | 111 (4) | | |
| | | |
C11—C1—C2—O12 | 47.5 (6) | C2—C1—C8—C7 | −42.0 (5) |
C8—C1—C2—O12 | −66.2 (5) | C11—C1—C8—C7 | −164.3 (4) |
C11—C1—C2—C3 | −131.8 (4) | C2—C1—C8—C9 | 83.9 (5) |
C8—C1—C2—C3 | 114.4 (4) | C11—C1—C8—C9 | −38.3 (5) |
O12—C2—C3—C13 | −101.2 (5) | C7—C8—C9—C10 | 153.0 (5) |
C1—C2—C3—C13 | 78.1 (5) | C1—C8—C9—C10 | 24.3 (6) |
O12—C2—C3—C4 | 139.6 (5) | C8—C9—C10—C11 | −0.3 (7) |
C1—C2—C3—C4 | −41.1 (5) | C9—C10—C11—C19 | −152.9 (5) |
O12—C2—C3—C14 | 15.4 (6) | C9—C10—C11—C1 | −24.0 (6) |
C1—C2—C3—C14 | −165.3 (4) | C2—C1—C11—C10 | −79.6 (5) |
C2—C3—C4—C5 | −60.3 (6) | C8—C1—C11—C10 | 38.4 (5) |
C13—C3—C4—C5 | −176.9 (5) | C2—C1—C11—C19 | 49.2 (7) |
C14—C3—C4—C5 | 62.4 (6) | C8—C1—C11—C19 | 167.2 (5) |
C3—C4—C5—C6 | 90.5 (7) | O18—C6—O15—C16 | −25.2 (7) |
C4—C5—C6—O15 | 49.6 (8) | C5—C6—O15—C16 | 92.2 (6) |
C4—C5—C6—O18 | 165.0 (5) | C7—C6—O15—C16 | −138.8 (5) |
C4—C5—C6—C7 | −76.8 (7) | C6—O15—C16—C17 | 15.9 (8) |
O15—C6—C7—C8 | −34.4 (7) | O15—C16—C17—O18 | −0.1 (9) |
O18—C6—C7—C8 | −147.3 (5) | C16—C17—O18—C6 | −15.2 (8) |
C5—C6—C7—C8 | 93.2 (6) | O15—C6—O18—C17 | 24.9 (7) |
C6—C7—C8—C9 | −179.4 (5) | C5—C6—O18—C17 | −95.1 (7) |
C6—C7—C8—C1 | −58.1 (6) | C7—C6—O18—C17 | 141.2 (6) |
(II) (1
R,2
R,8
R,11
R)-3,3,11-Trimethyl-6,6-ethylenedioxybicyclo[6.3.0]undecan-2-ol
top
Crystal data top
C16H28O3 | Dx = 1.153 Mg m−3 |
Mr = 268.38 | Melting point = 418–420 K |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.368 (3) Å | Cell parameters from 25 reflections |
b = 16.3349 (14) Å | θ = 11.6–14.0° |
c = 10.211 (3) Å | µ = 0.08 mm−1 |
β = 116.614 (12)° | T = 293 K |
V = 1546.1 (7) Å3 | Needle, colourless |
Z = 4 | 0.70 × 0.30 × 0.20 mm |
F(000) = 592 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.2° |
Graphite monochromator | h = −14→13 |
ω–2θ scans | k = 0→22 |
4876 measured reflections | l = 0→14 |
4647 independent reflections | 3 standard reflections every 120 min |
3562 reflections with I > 2σ(I) | intensity decay: 3.0% |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0713P)2 + 0.0858P] where P = (Fo2 + 2Fc2)/3 |
4647 reflections | (Δ/σ)max = −0.001 |
503 parameters | Δρmax = 0.22 e Å−3 |
1 restraint | Δρmin = −0.15 e Å−3 |
Crystal data top
C16H28O3 | V = 1546.1 (7) Å3 |
Mr = 268.38 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.368 (3) Å | µ = 0.08 mm−1 |
b = 16.3349 (14) Å | T = 293 K |
c = 10.211 (3) Å | 0.70 × 0.30 × 0.20 mm |
β = 116.614 (12)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.013 |
4876 measured reflections | 3 standard reflections every 120 min |
4647 independent reflections | intensity decay: 3.0% |
3562 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 1 restraint |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.22 e Å−3 |
4647 reflections | Δρmin = −0.15 e Å−3 |
503 parameters | |
Special details top
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 on F2 for ALL reflections except for 2 with very negative F2 or 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 _refine_ls_R_factor_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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1A | 0.2767 (2) | 0.1517 (2) | 1.0441 (3) | 0.0381 (5) | |
H1A | 0.345 (3) | 0.1231 (17) | 1.128 (3) | 0.034 (6)* | |
C2A | 0.1284 (2) | 0.1114 (2) | 1.0032 (2) | 0.0390 (5) | |
H2A | 0.087 (3) | 0.1371 (17) | 1.062 (3) | 0.039 (7)* | |
C3A | 0.1291 (2) | 0.0197 (2) | 1.0409 (3) | 0.0430 (5) | |
C4A | 0.1874 (3) | −0.0392 (2) | 0.9622 (3) | 0.0479 (6) | |
H4A1 | 0.129 (3) | −0.034 (2) | 0.855 (4) | 0.049 (8)* | |
H4A2 | 0.169 (4) | −0.090 (2) | 0.996 (4) | 0.053 (8)* | |
C5A | 0.3478 (3) | −0.0326 (2) | 0.9962 (3) | 0.0473 (6) | |
H5A1 | 0.394 (3) | −0.086 (2) | 1.008 (3) | 0.049 (8)* | |
H5A2 | 0.407 (4) | 0.001 (2) | 1.085 (4) | 0.055 (8)* | |
C6A | 0.3724 (2) | 0.0056 (2) | 0.8741 (3) | 0.0442 (5) | |
C7A | 0.2950 (3) | 0.0855 (2) | 0.8140 (3) | 0.0445 (6) | |
H7A1 | 0.323 (4) | 0.103 (2) | 0.741 (4) | 0.058 (9)* | |
H7A2 | 0.195 (4) | 0.077 (2) | 0.766 (3) | 0.049 (8)* | |
C8A | 0.3275 (3) | 0.1558 (2) | 0.9224 (3) | 0.0414 (5) | |
H8A | 0.430 (3) | 0.161 (2) | 0.970 (3) | 0.049 (8)* | |
C9A | 0.2675 (4) | 0.2378 (2) | 0.8426 (4) | 0.0623 (8) | |
H9A1 | 0.176 (5) | 0.227 (3) | 0.746 (5) | 0.087 (13)* | |
H9A2 | 0.342 (4) | 0.265 (3) | 0.837 (4) | 0.075 (11)* | |
C10A | 0.2209 (5) | 0.2881 (2) | 0.9383 (4) | 0.0665 (8) | |
H10A | 0.254 (4) | 0.344 (3) | 0.949 (4) | 0.066 (10)* | |
H10B | 0.111 (6) | 0.285 (3) | 0.892 (6) | 0.108 (16)* | |
C11A | 0.2841 (3) | 0.2438 (2) | 1.0862 (3) | 0.0509 (6) | |
H11A | 0.390 (4) | 0.255 (2) | 1.134 (4) | 0.066 (10)* | |
O12A | 0.0348 (2) | 0.12714 (14) | 0.8513 (2) | 0.0519 (5) | |
H12A | −0.037 (4) | 0.142 (2) | 0.855 (4) | 0.069 (11)* | |
C13A | 0.2118 (3) | 0.0090 (2) | 1.2071 (3) | 0.0549 (7) | |
H13A | 0.2024 | −0.0465 | 1.2325 | 0.082* | |
H13B | 0.1730 | 0.0454 | 1.2543 | 0.082* | |
H13C | 0.3119 | 0.0214 | 1.2387 | 0.082* | |
C14A | −0.0289 (3) | −0.0053 (2) | 0.9942 (4) | 0.0601 (7) | |
H14A | −0.0323 | −0.0613 | 1.0208 | 0.090* | |
H14B | −0.0836 | 0.0008 | 0.8901 | 0.090* | |
H14C | −0.0693 | 0.0291 | 1.0427 | 0.090* | |
O15A | 0.5262 (2) | 0.01540 (14) | 0.9269 (2) | 0.0536 (5) | |
C16A | 0.5639 (3) | −0.0118 (3) | 0.8181 (4) | 0.0613 (8) | |
H16A | 0.605 (5) | 0.036 (3) | 0.787 (5) | 0.090 (13)* | |
H16B | 0.644 (6) | −0.040 (4) | 0.845 (5) | 0.099 (15)* | |
C17A | 0.4330 (5) | −0.0531 (4) | 0.7049 (6) | 0.095 (2) | |
H17A | 0.438 (5) | −0.103 (3) | 0.667 (5) | 0.079 (12)* | |
H17B | 0.403 (14) | 0.007 (9) | 0.615 (14) | 0.29 (6)* | |
O18A | 0.3308 (2) | −0.0520 (2) | 0.7568 (2) | 0.0604 (6) | |
C19A | 0.2211 (4) | 0.2682 (2) | 1.1883 (4) | 0.0714 (9) | |
H19A | 0.2571 | 0.2323 | 1.2715 | 0.107* | |
H19B | 0.1179 | 0.2643 | 1.1377 | 0.107* | |
H19C | 0.2484 | 0.3235 | 1.2206 | 0.107* | |
C1B | 0.8496 (2) | 0.05100 (15) | 0.4742 (2) | 0.0352 (4) | |
H1B | 0.929 (3) | 0.0828 (17) | 0.547 (3) | 0.034 (6)* | |
C2B | 0.8042 (2) | 0.0891 (2) | 0.3213 (2) | 0.0364 (5) | |
H2B | 0.863 (3) | 0.0630 (18) | 0.278 (3) | 0.038 (7)* | |
C3B | 0.8361 (2) | 0.1816 (2) | 0.3177 (2) | 0.0403 (5) | |
C4B | 0.7575 (3) | 0.2393 (2) | 0.3773 (3) | 0.0427 (5) | |
H4B1 | 0.651 (4) | 0.236 (2) | 0.318 (3) | 0.052 (8)* | |
H4B2 | 0.777 (3) | 0.294 (2) | 0.354 (3) | 0.053 (8)* | |
C5B | 0.7951 (3) | 0.2336 (2) | 0.5407 (3) | 0.0427 (5) | |
H5B1 | 0.880 (3) | 0.2019 (19) | 0.592 (3) | 0.042 (7)* | |
H5B2 | 0.804 (3) | 0.290 (2) | 0.573 (3) | 0.043 (7)* | |
C6B | 0.6788 (2) | 0.1936 (2) | 0.5709 (2) | 0.0386 (5) | |
C7B | 0.6218 (2) | 0.1128 (2) | 0.4952 (3) | 0.0394 (5) | |
H7B1 | 0.555 (3) | 0.096 (2) | 0.533 (3) | 0.055 (9)* | |
H7B2 | 0.571 (3) | 0.1220 (19) | 0.392 (4) | 0.044 (7)* | |
C8B | 0.7320 (2) | 0.04458 (15) | 0.5283 (2) | 0.0375 (5) | |
H8B | 0.785 (4) | 0.040 (2) | 0.634 (4) | 0.055 (8)* | |
C9B | 0.6574 (3) | −0.0389 (2) | 0.4705 (4) | 0.0530 (6) | |
H9B1 | 0.554 (5) | −0.027 (3) | 0.383 (5) | 0.075 (11)* | |
H9B2 | 0.640 (4) | −0.064 (2) | 0.535 (4) | 0.052 (9)* | |
C10B | 0.7557 (4) | −0.0884 (2) | 0.4278 (4) | 0.0616 (8) | |
H10C | 0.775 (4) | −0.145 (3) | 0.471 (4) | 0.063 (9)* | |
H10D | 0.711 (5) | −0.088 (3) | 0.309 (6) | 0.097 (15)* | |
C11B | 0.8970 (3) | −0.0400 (2) | 0.4857 (3) | 0.0476 (6) | |
H11B | 0.950 (3) | −0.0518 (19) | 0.596 (3) | 0.043 (7)* | |
O12B | 0.6550 (2) | 0.07068 (13) | 0.2301 (2) | 0.0474 (4) | |
H12B | 0.652 (4) | 0.060 (2) | 0.151 (4) | 0.059 (9)* | |
C13B | 0.9995 (3) | 0.1953 (2) | 0.3979 (3) | 0.0544 (7) | |
H13D | 1.0327 | 0.1870 | 0.5010 | 0.082* | |
H13E | 1.0213 | 0.2502 | 0.3807 | 0.082* | |
H13F | 1.0468 | 0.1572 | 0.3621 | 0.082* | |
C14B | 0.7856 (4) | 0.2053 (2) | 0.1564 (3) | 0.0576 (7) | |
H14D | 0.8257 | 0.1678 | 0.1121 | 0.086* | |
H14E | 0.8173 | 0.2599 | 0.1511 | 0.086* | |
H14F | 0.6822 | 0.2030 | 0.1054 | 0.086* | |
O15B | 0.7346 (2) | 0.18407 (12) | 0.7278 (2) | 0.0481 (4) | |
C16B | 0.6475 (6) | 0.2286 (3) | 0.7742 (4) | 0.090 (2) | |
H16C | 0.659 (7) | 0.228 (4) | 0.856 (7) | 0.13 (2)* | |
H16D | 0.750 (7) | 0.264 (5) | 0.817 (7) | 0.14 (2)* | |
C17B | 0.5121 (10) | 0.2504 (7) | 0.6323 (9) | 0.068 (2) | 0.50 |
H17C | 0.4361 | 0.2105 | 0.6113 | 0.082* | 0.50 |
H17D | 0.4762 | 0.3043 | 0.6391 | 0.082* | 0.50 |
C17C | 0.5746 (10) | 0.2893 (5) | 0.6584 (9) | 0.064 (2) | 0.50 |
H17E | 0.4812 | 0.3039 | 0.6519 | 0.077* | 0.50 |
H17F | 0.6325 | 0.3385 | 0.6759 | 0.077* | 0.50 |
O18B | 0.5595 (2) | 0.24882 (14) | 0.5293 (2) | 0.0574 (5) | |
C19B | 0.9960 (4) | −0.0632 (2) | 0.4180 (5) | 0.0716 (9) | |
H19D | 1.0746 | −0.0251 | 0.4491 | 0.107* | |
H19E | 0.9428 | −0.0619 | 0.3132 | 0.107* | |
H19F | 1.0332 | −0.1174 | 0.4490 | 0.107* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0290 (9) | 0.0473 (13) | 0.0330 (10) | −0.0007 (9) | 0.0094 (8) | 0.0014 (9) |
C2A | 0.0277 (9) | 0.0536 (14) | 0.0335 (10) | 0.0033 (9) | 0.0116 (8) | 0.0014 (10) |
C3A | 0.0327 (10) | 0.0537 (15) | 0.0424 (12) | −0.0064 (10) | 0.0167 (9) | 0.0006 (10) |
C4A | 0.0438 (13) | 0.0471 (15) | 0.056 (2) | −0.0088 (11) | 0.0247 (12) | −0.0043 (12) |
C5A | 0.0406 (12) | 0.052 (2) | 0.0476 (14) | 0.0037 (11) | 0.0185 (11) | 0.0009 (12) |
C6A | 0.0324 (10) | 0.0580 (15) | 0.0411 (12) | −0.0045 (10) | 0.0155 (9) | −0.0117 (11) |
C7A | 0.0361 (11) | 0.062 (2) | 0.0336 (11) | −0.0019 (11) | 0.0145 (9) | −0.0003 (11) |
C8A | 0.0341 (11) | 0.0485 (13) | 0.0408 (12) | −0.0025 (10) | 0.0160 (9) | 0.0013 (10) |
C9A | 0.077 (2) | 0.058 (2) | 0.058 (2) | 0.004 (2) | 0.036 (2) | 0.0116 (15) |
C10A | 0.083 (2) | 0.049 (2) | 0.067 (2) | 0.006 (2) | 0.033 (2) | 0.0043 (15) |
C11A | 0.0503 (14) | 0.0496 (15) | 0.0503 (14) | −0.0060 (12) | 0.0203 (12) | −0.0064 (12) |
O12A | 0.0283 (8) | 0.0784 (14) | 0.0392 (9) | 0.0078 (8) | 0.0064 (7) | 0.0082 (9) |
C13A | 0.0550 (15) | 0.070 (2) | 0.0433 (13) | 0.0036 (14) | 0.0253 (12) | 0.0108 (13) |
C14A | 0.0410 (14) | 0.073 (2) | 0.069 (2) | −0.0137 (13) | 0.0275 (13) | −0.001 (2) |
O15A | 0.0294 (8) | 0.0804 (14) | 0.0493 (10) | −0.0035 (9) | 0.0162 (7) | −0.0167 (10) |
C16A | 0.0472 (15) | 0.082 (2) | 0.063 (2) | −0.002 (2) | 0.0324 (14) | −0.014 (2) |
C17A | 0.071 (2) | 0.125 (4) | 0.111 (3) | −0.034 (2) | 0.059 (2) | −0.072 (3) |
O18A | 0.0477 (10) | 0.0784 (14) | 0.0571 (12) | −0.0143 (10) | 0.0252 (9) | −0.0283 (11) |
C19A | 0.089 (2) | 0.064 (2) | 0.069 (2) | −0.007 (2) | 0.042 (2) | −0.019 (2) |
C1B | 0.0299 (9) | 0.0408 (12) | 0.0291 (10) | −0.0001 (8) | 0.0080 (8) | −0.0018 (9) |
C2B | 0.0312 (9) | 0.0483 (13) | 0.0277 (9) | −0.0016 (9) | 0.0114 (8) | −0.0035 (9) |
C3B | 0.0389 (11) | 0.0518 (14) | 0.0294 (10) | −0.0050 (10) | 0.0145 (9) | 0.0014 (10) |
C4B | 0.0473 (13) | 0.0392 (12) | 0.0414 (12) | 0.0007 (10) | 0.0197 (10) | 0.0053 (10) |
C5B | 0.0457 (12) | 0.0409 (13) | 0.0403 (12) | −0.0030 (11) | 0.0181 (10) | −0.0060 (10) |
C6B | 0.0366 (10) | 0.0476 (13) | 0.0296 (9) | 0.0101 (10) | 0.0130 (8) | 0.0013 (9) |
C7B | 0.0321 (10) | 0.0508 (14) | 0.0347 (11) | −0.0011 (10) | 0.0144 (9) | 0.0003 (10) |
C8B | 0.0375 (11) | 0.0424 (12) | 0.0300 (11) | −0.0028 (9) | 0.0130 (9) | −0.0001 (9) |
C9B | 0.055 (2) | 0.0473 (15) | 0.061 (2) | −0.0119 (13) | 0.0292 (14) | −0.0013 (13) |
C10B | 0.064 (2) | 0.041 (2) | 0.077 (2) | −0.0031 (13) | 0.028 (2) | −0.0061 (15) |
C11B | 0.0471 (13) | 0.0478 (14) | 0.0436 (13) | 0.0095 (11) | 0.0165 (11) | 0.0041 (11) |
O12B | 0.0360 (8) | 0.0693 (12) | 0.0277 (8) | −0.0102 (8) | 0.0060 (6) | −0.0073 (8) |
C13B | 0.0448 (13) | 0.069 (2) | 0.052 (2) | −0.0164 (13) | 0.0244 (12) | −0.0037 (14) |
C14B | 0.068 (2) | 0.070 (2) | 0.0390 (13) | −0.002 (2) | 0.0278 (13) | 0.0116 (13) |
O15B | 0.0483 (9) | 0.0645 (12) | 0.0296 (8) | 0.0146 (9) | 0.0158 (7) | 0.0010 (8) |
C16B | 0.120 (4) | 0.106 (3) | 0.052 (2) | 0.056 (3) | 0.045 (2) | 0.009 (2) |
C17B | 0.072 (5) | 0.075 (5) | 0.070 (5) | 0.032 (4) | 0.043 (4) | 0.008 (4) |
C17C | 0.076 (5) | 0.054 (4) | 0.065 (4) | 0.023 (4) | 0.033 (4) | −0.008 (3) |
O18B | 0.0507 (10) | 0.0700 (13) | 0.0475 (10) | 0.0277 (10) | 0.0184 (8) | 0.0086 (9) |
C19B | 0.070 (2) | 0.070 (2) | 0.082 (2) | 0.026 (2) | 0.040 (2) | 0.006 (2) |
Geometric parameters (Å, º) top
C1A—C2A | 1.547 (3) | C1B—C11B | 1.554 (4) |
C1A—C8A | 1.554 (3) | C1B—H1B | 0.97 (3) |
C1A—C11A | 1.557 (4) | C2B—O12B | 1.435 (3) |
C1A—H1A | 0.96 (3) | C2B—C3B | 1.552 (4) |
C2A—O12A | 1.437 (3) | C2B—H2B | 1.00 (3) |
C2A—C3A | 1.546 (4) | C3B—C13B | 1.532 (4) |
C2A—H2A | 0.98 (3) | C3B—C14B | 1.537 (3) |
C3A—C13A | 1.530 (4) | C3B—C4B | 1.538 (4) |
C3A—C14A | 1.542 (3) | C4B—C5B | 1.536 (4) |
C3A—C4A | 1.541 (4) | C4B—H4B1 | 1.00 (3) |
C4A—C5A | 1.543 (4) | C4B—H4B2 | 0.97 (4) |
C4A—H4A1 | 0.99 (3) | C5B—C6B | 1.519 (4) |
C4A—H4A2 | 0.95 (4) | C5B—H5B1 | 0.95 (3) |
C5A—C6A | 1.514 (4) | C5B—H5B2 | 0.96 (3) |
C5A—H5A1 | 0.98 (3) | C6B—O18B | 1.432 (3) |
C5A—H5A2 | 1.00 (4) | C6B—O15B | 1.448 (3) |
C6A—O18A | 1.430 (3) | C6B—C7B | 1.510 (4) |
C6A—O15A | 1.445 (3) | C7B—C8B | 1.522 (4) |
C6A—C7A | 1.510 (4) | C7B—H7B1 | 0.97 (3) |
C7A—C8A | 1.525 (4) | C7B—H7B2 | 0.95 (3) |
C7A—H7A1 | 0.95 (3) | C8B—C9B | 1.548 (4) |
C7A—H7A2 | 0.94 (3) | C8B—H8B | 0.97 (3) |
C8A—C9A | 1.546 (4) | C9B—C10B | 1.510 (5) |
C8A—H8A | 0.95 (3) | C9B—H9B1 | 1.06 (4) |
C9A—C10A | 1.511 (5) | C9B—H9B2 | 0.86 (3) |
C9A—H9A1 | 1.03 (5) | C10B—C11B | 1.531 (4) |
C9A—H9A2 | 0.92 (4) | C10B—H10C | 1.00 (4) |
C10A—C11A | 1.532 (5) | C10B—H10D | 1.09 (5) |
C10A—H10A | 0.97 (4) | C11B—C19B | 1.520 (4) |
C10A—H10B | 1.02 (5) | C11B—H11B | 1.03 (3) |
C11A—C19A | 1.511 (4) | O12B—H12B | 0.82 (4) |
C11A—H11A | 1.00 (4) | C13B—H13D | 0.96 |
O12A—H12A | 0.79 (4) | C13B—H13E | 0.96 |
C13A—H13A | 0.96 | C13B—H13F | 0.96 |
C13A—H13B | 0.96 | C14B—H14D | 0.96 |
C13A—H13C | 0.96 | C14B—H14E | 0.96 |
C14A—H14A | 0.96 | C14B—H14F | 0.96 |
C14A—H14B | 0.96 | O15B—C16B | 1.397 (4) |
C14A—H14C | 0.96 | C16B—C17C | 1.468 (9) |
O15A—C16A | 1.405 (3) | C16B—C17B | 1.542 (10) |
C16A—C17A | 1.493 (5) | C16B—H16C | 0.78 (7) |
C16A—H16A | 1.01 (5) | C16B—H16D | 1.11 (7) |
C16A—H16B | 0.88 (6) | C17B—O18B | 1.346 (8) |
C17A—O18A | 1.381 (4) | C17B—H17C | 0.97 |
C17A—H17A | 0.92 (5) | C17B—H17D | 0.97 |
C17A—H17B | 1.28 (14) | C17C—O18B | 1.419 (8) |
C19A—H19A | 0.96 | C17C—H17E | 0.97 |
C19A—H19B | 0.96 | C17C—H17F | 0.97 |
C19A—H19C | 0.96 | C19B—H19D | 0.96 |
C1B—C2B | 1.545 (3) | C19B—H19E | 0.96 |
C1B—C8B | 1.551 (3) | C19B—H19F | 0.96 |
| | | |
C2A—C1A—C8A | 117.0 (2) | C11B—C1B—H1B | 108.7 (16) |
C2A—C1A—C11A | 113.9 (2) | O12B—C2B—C1B | 108.9 (2) |
C8A—C1A—C11A | 100.7 (2) | O12B—C2B—C3B | 111.6 (2) |
C2A—C1A—H1A | 106.1 (16) | C1B—C2B—C3B | 116.4 (2) |
C8A—C1A—H1A | 111.4 (16) | O12B—C2B—H2B | 108.5 (16) |
C11A—C1A—H1A | 107.4 (16) | C1B—C2B—H2B | 108.0 (16) |
O12A—C2A—C3A | 111.5 (2) | C3B—C2B—H2B | 103.1 (16) |
O12A—C2A—C1A | 108.9 (2) | C13B—C3B—C14B | 107.5 (2) |
C3A—C2A—C1A | 116.9 (2) | C13B—C3B—C4B | 110.8 (2) |
O12A—C2A—H2A | 108.5 (16) | C14B—C3B—C4B | 106.4 (2) |
C3A—C2A—H2A | 102.4 (16) | C13B—C3B—C2B | 109.0 (2) |
C1A—C2A—H2A | 108.2 (16) | C14B—C3B—C2B | 107.2 (2) |
C13A—C3A—C14A | 107.6 (2) | C4B—C3B—C2B | 115.5 (2) |
C13A—C3A—C4A | 110.5 (2) | C5B—C4B—C3B | 118.1 (2) |
C14A—C3A—C4A | 106.5 (2) | C5B—C4B—H4B1 | 109.1 (18) |
C13A—C3A—C2A | 109.0 (2) | C3B—C4B—H4B1 | 111.6 (18) |
C14A—C3A—C2A | 107.1 (2) | C5B—C4B—H4B2 | 110.1 (19) |
C4A—C3A—C2A | 115.7 (2) | C3B—C4B—H4B2 | 105.1 (19) |
C3A—C4A—C5A | 118.3 (2) | H4B1—C4B—H4B2 | 102 (3) |
C3A—C4A—H4A1 | 109.5 (19) | C6B—C5B—C4B | 114.1 (2) |
C5A—C4A—H4A1 | 107.7 (18) | C6B—C5B—H5B1 | 106.0 (18) |
C3A—C4A—H4A2 | 100 (2) | C4B—C5B—H5B1 | 110.9 (17) |
C5A—C4A—H4A2 | 111 (2) | C6B—C5B—H5B2 | 107.4 (17) |
H4A1—C4A—H4A2 | 111 (3) | C4B—C5B—H5B2 | 104.7 (17) |
C6A—C5A—C4A | 113.9 (2) | H5B1—C5B—H5B2 | 114 (3) |
C6A—C5A—H5A1 | 102.6 (18) | O18B—C6B—O15B | 105.1 (2) |
C4A—C5A—H5A1 | 112.4 (18) | O18B—C6B—C7B | 108.1 (2) |
C6A—C5A—H5A2 | 105.1 (19) | O15B—C6B—C7B | 110.1 (2) |
C4A—C5A—H5A2 | 113.9 (19) | O18B—C6B—C5B | 109.1 (2) |
H5A1—C5A—H5A2 | 108 (3) | O15B—C6B—C5B | 108.1 (2) |
O18A—C6A—O15A | 104.7 (2) | C7B—C6B—C5B | 115.8 (2) |
O18A—C6A—C7A | 108.8 (2) | C6B—C7B—C8B | 116.4 (2) |
O15A—C6A—C7A | 110.6 (2) | C6B—C7B—H7B1 | 103 (2) |
O18A—C6A—C5A | 108.6 (2) | C8B—C7B—H7B1 | 108 (2) |
O15A—C6A—C5A | 107.6 (2) | C6B—C7B—H7B2 | 108.9 (19) |
C7A—C6A—C5A | 115.9 (2) | C8B—C7B—H7B2 | 110.5 (18) |
C6A—C7A—C8A | 116.8 (2) | H7B1—C7B—H7B2 | 110 (3) |
C6A—C7A—H7A1 | 106 (2) | C7B—C8B—C9B | 111.3 (2) |
C8A—C7A—H7A1 | 107 (2) | C7B—C8B—C1B | 120.2 (2) |
C6A—C7A—H7A2 | 110 (2) | C9B—C8B—C1B | 105.2 (2) |
C8A—C7A—H7A2 | 109 (2) | C7B—C8B—H8B | 107 (2) |
H7A1—C7A—H7A2 | 107 (3) | C9B—C8B—H8B | 107 (2) |
C7A—C8A—C9A | 111.4 (2) | C1B—C8B—H8B | 105.3 (18) |
C7A—C8A—C1A | 120.3 (2) | C10B—C9B—C8B | 107.2 (2) |
C9A—C8A—C1A | 105.0 (2) | C10B—C9B—H9B1 | 114 (2) |
C7A—C8A—H8A | 106 (2) | C8B—C9B—H9B1 | 108 (2) |
C9A—C8A—H8A | 106 (2) | C10B—C9B—H9B2 | 112 (2) |
C1A—C8A—H8A | 107.3 (18) | C8B—C9B—H9B2 | 111 (2) |
C10A—C9A—C8A | 107.4 (3) | H9B1—C9B—H9B2 | 105 (3) |
C10A—C9A—H9A1 | 107 (3) | C9B—C10B—C11B | 105.3 (2) |
C8A—C9A—H9A1 | 110 (3) | C9B—C10B—H10C | 114 (2) |
C10A—C9A—H9A2 | 107 (3) | C11B—C10B—H10C | 110 (2) |
C8A—C9A—H9A2 | 108 (3) | C9B—C10B—H10D | 108 (3) |
H9A1—C9A—H9A2 | 118 (4) | C11B—C10B—H10D | 106 (3) |
C9A—C10A—C11A | 105.1 (3) | H10C—C10B—H10D | 113 (3) |
C9A—C10A—H10A | 113 (2) | C19B—C11B—C10B | 114.8 (3) |
C11A—C10A—H10A | 111 (2) | C19B—C11B—C1B | 117.4 (3) |
C9A—C10A—H10B | 107 (3) | C10B—C11B—C1B | 104.4 (2) |
C11A—C10A—H10B | 109 (3) | C19B—C11B—H11B | 108.0 (16) |
H10A—C10A—H10B | 111 (4) | C10B—C11B—H11B | 106.2 (16) |
C19A—C11A—C10A | 115.4 (3) | C1B—C11B—H11B | 105.1 (17) |
C19A—C11A—C1A | 117.5 (3) | C2B—O12B—H12B | 104 (3) |
C10A—C11A—C1A | 103.8 (2) | C3B—C13B—H13D | 109.5 |
C19A—C11A—H11A | 110 (2) | C3B—C13B—H13E | 109.5 |
C10A—C11A—H11A | 107 (2) | H13D—C13B—H13E | 109.5 |
C1A—C11A—H11A | 103 (2) | C3B—C13B—H13F | 109.5 |
C2A—O12A—H12A | 101 (3) | H13D—C13B—H13F | 109.5 |
C3A—C13A—H13A | 109.5 | H13E—C13B—H13F | 109.5 |
C3A—C13A—H13B | 109.5 | C3B—C14B—H14D | 109.5 |
H13A—C13A—H13B | 109.5 | C3B—C14B—H14E | 109.5 |
C3A—C13A—H13C | 109.5 | H14D—C14B—H14E | 109.5 |
H13A—C13A—H13C | 109.5 | C3B—C14B—H14F | 109.5 |
H13B—C13A—H13C | 109.5 | H14D—C14B—H14F | 109.5 |
C3A—C14A—H14A | 109.5 | H14E—C14B—H14F | 109.5 |
C3A—C14A—H14B | 109.5 | C16B—O15B—C6B | 108.7 (2) |
H14A—C14A—H14B | 109.5 | O15B—C16B—C17C | 104.8 (4) |
C3A—C14A—H14C | 109.5 | O15B—C16B—C17B | 104.9 (4) |
H14A—C14A—H14C | 109.5 | O15B—C16B—H16C | 123 (5) |
H14B—C14A—H14C | 109.5 | C17C—C16B—H16C | 130 (5) |
C16A—O15A—C6A | 108.8 (2) | C17B—C16B—H16C | 130 (5) |
O15A—C16A—C17A | 106.0 (2) | O15B—C16B—H16D | 76 (4) |
O15A—C16A—H16A | 108 (3) | C17C—C16B—H16D | 91 (4) |
C17A—C16A—H16A | 118 (3) | C17B—C16B—H16D | 124 (4) |
O15A—C16A—H16B | 119 (3) | H16C—C16B—H16D | 85 (5) |
C17A—C16A—H16B | 114 (4) | O18B—C17B—C16B | 103.4 (5) |
H16A—C16A—H16B | 92 (4) | O18B—C17B—H17C | 111.1 |
O18A—C17A—C16A | 106.6 (3) | C16B—C17B—H17C | 111.1 |
O18A—C17A—H17A | 112 (3) | O18B—C17B—H17D | 111.1 |
C16A—C17A—H17A | 122 (3) | C16B—C17B—H17D | 111.1 |
O18A—C17A—H17B | 107 (5) | H17C—C17B—H17D | 109.0 |
C16A—C17A—H17B | 93 (6) | O18B—C17C—C16B | 103.6 (5) |
H17A—C17A—H17B | 115 (6) | O18B—C17C—H17E | 111.0 |
C17A—O18A—C6A | 109.5 (2) | C16B—C17C—H17E | 111.0 |
C11A—C19A—H19A | 109.5 | O18B—C17C—H17F | 111.0 |
C11A—C19A—H19B | 109.5 | C16B—C17C—H17F | 111.0 |
H19A—C19A—H19B | 109.5 | H17E—C17C—H17F | 109.0 |
C11A—C19A—H19C | 109.5 | C17B—O18B—C6B | 110.5 (4) |
H19A—C19A—H19C | 109.5 | C17C—O18B—C6B | 107.3 (3) |
H19B—C19A—H19C | 109.5 | C11B—C19B—H19D | 109.5 |
C2B—C1B—C8B | 117.1 (2) | C11B—C19B—H19E | 109.5 |
C2B—C1B—C11B | 113.9 (2) | H19D—C19B—H19E | 109.5 |
C8B—C1B—C11B | 100.4 (2) | C11B—C19B—H19F | 109.5 |
C2B—C1B—H1B | 109.0 (15) | H19D—C19B—H19F | 109.5 |
C8B—C1B—H1B | 107.2 (16) | H19E—C19B—H19F | 109.5 |
| | | |
C8A—C1A—C2A—O12A | −32.4 (3) | C1B—C2B—C3B—C13B | 62.6 (3) |
C11A—C1A—C2A—O12A | 84.7 (3) | O12B—C2B—C3B—C14B | −55.5 (2) |
C8A—C1A—C2A—C3A | 95.1 (3) | C1B—C2B—C3B—C14B | 178.7 (2) |
C11A—C1A—C2A—C3A | −147.8 (2) | O12B—C2B—C3B—C4B | 62.9 (2) |
O12A—C2A—C3A—C13A | −171.6 (2) | C1B—C2B—C3B—C4B | −62.8 (3) |
C1A—C2A—C3A—C13A | 62.2 (3) | C13B—C3B—C4B—C5B | −59.4 (3) |
O12A—C2A—C3A—C14A | −55.4 (3) | C14B—C3B—C4B—C5B | −176.0 (2) |
C1A—C2A—C3A—C14A | 178.4 (2) | C2B—C3B—C4B—C5B | 65.1 (3) |
O12A—C2A—C3A—C4A | 63.2 (3) | C3B—C4B—C5B—C6B | −106.9 (3) |
C1A—C2A—C3A—C4A | −63.0 (3) | C4B—C5B—C6B—O18B | −72.5 (3) |
C13A—C3A—C4A—C5A | −59.3 (3) | C4B—C5B—C6B—O15B | 173.7 (2) |
C14A—C3A—C4A—C5A | −176.0 (3) | C4B—C5B—C6B—C7B | 49.7 (3) |
C2A—C3A—C4A—C5A | 65.1 (3) | O18B—C6B—C7B—C8B | −178.5 (2) |
C3A—C4A—C5A—C6A | −106.6 (3) | O15B—C6B—C7B—C8B | −64.3 (3) |
C4A—C5A—C6A—O18A | −73.0 (3) | C5B—C6B—C7B—C8B | 58.7 (3) |
C4A—C5A—C6A—O15A | 174.2 (2) | C6B—C7B—C8B—C9B | 168.5 (2) |
C4A—C5A—C6A—C7A | 49.8 (3) | C6B—C7B—C8B—C1B | −68.0 (3) |
O18A—C6A—C7A—C8A | −178.9 (2) | C2B—C1B—C8B—C7B | −38.0 (3) |
O15A—C6A—C7A—C8A | −64.4 (3) | C11B—C1B—C8B—C7B | −161.8 (2) |
C5A—C6A—C7A—C8A | 58.5 (3) | C2B—C1B—C8B—C9B | 88.4 (2) |
C6A—C7A—C8A—C9A | 168.1 (2) | C11B—C1B—C8B—C9B | −35.4 (2) |
C6A—C7A—C8A—C1A | −68.6 (3) | C7B—C8B—C9B—C10B | 148.3 (3) |
C2A—C1A—C8A—C7A | −36.9 (3) | C1B—C8B—C9B—C10B | 16.6 (3) |
C11A—C1A—C8A—C7A | −161.0 (2) | C8B—C9B—C10B—C11B | 9.7 (3) |
C2A—C1A—C8A—C9A | 89.4 (3) | C9B—C10B—C11B—C19B | −162.4 (3) |
C11A—C1A—C8A—C9A | −34.6 (3) | C9B—C10B—C11B—C1B | −32.5 (3) |
C7A—C8A—C9A—C10A | 146.3 (3) | C2B—C1B—C11B—C19B | 44.1 (3) |
C1A—C8A—C9A—C10A | 14.6 (4) | C8B—C1B—C11B—C19B | 170.1 (3) |
C8A—C9A—C10A—C11A | 12.2 (4) | C2B—C1B—C11B—C10B | −84.2 (3) |
C9A—C10A—C11A—C19A | −164.3 (3) | C8B—C1B—C11B—C10B | 41.7 (3) |
C9A—C10A—C11A—C1A | −34.3 (3) | O18B—C6B—O15B—C16B | 2.7 (4) |
C2A—C1A—C11A—C19A | 45.0 (3) | C7B—C6B—O15B—C16B | −113.5 (3) |
C8A—C1A—C11A—C19A | 171.2 (3) | C5B—C6B—O15B—C16B | 119.1 (3) |
C2A—C1A—C11A—C10A | −83.7 (3) | C6B—O15B—C16B—C17C | −21.3 (6) |
C8A—C1A—C11A—C10A | 42.4 (3) | C6B—O15B—C16B—C17B | 13.0 (6) |
O18A—C6A—O15A—C16A | 19.0 (3) | O15B—C16B—C17B—O18B | −24.9 (8) |
C7A—C6A—O15A—C16A | −98.0 (3) | C17C—C16B—C17B—O18B | 69.6 (8) |
C5A—C6A—O15A—C16A | 134.4 (3) | O15B—C16B—C17C—O18B | 31.7 (8) |
C6A—O15A—C16A—C17A | −9.9 (5) | C17B—C16B—C17C—O18B | −62.8 (7) |
O15A—C16A—C17A—O18A | −3.4 (6) | C16B—C17B—O18B—C17C | −63.9 (9) |
C16A—C17A—O18A—C6A | 15.6 (6) | C16B—C17B—O18B—C6B | 27.6 (8) |
O15A—C6A—O18A—C17A | −21.5 (4) | C16B—C17C—O18B—C17B | 70.7 (9) |
C7A—C6A—O18A—C17A | 96.8 (4) | C16B—C17C—O18B—C6B | −30.6 (7) |
C5A—C6A—O18A—C17A | −136.2 (4) | O15B—C6B—O18B—C17B | −20.3 (6) |
C8B—C1B—C2B—O12B | −31.2 (3) | C7B—C6B—O18B—C17B | 97.2 (6) |
C11B—C1B—C2B—O12B | 85.4 (2) | C5B—C6B—O18B—C17B | −136.0 (6) |
C8B—C1B—C2B—C3B | 95.9 (2) | O15B—C6B—O18B—C17C | 17.9 (5) |
C11B—C1B—C2B—C3B | −147.4 (2) | C7B—C6B—O18B—C17C | 135.4 (5) |
O12B—C2B—C3B—C13B | −171.6 (2) | C5B—C6B—O18B—C17C | −97.9 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O12A—H12A···O15Bi | 0.79 (4) | 2.25 (4) | 2.937 (3) | 146 (4) |
O12B—H12B···O15Aii | 0.82 (4) | 2.19 (4) | 2.912 (3) | 148 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x, y, z−1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C16H26O3 | C16H28O3 |
Mr | 266.37 | 268.38 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 15.594 (3), 16.837 (2), 5.6919 (8) | 10.368 (3), 16.3349 (14), 10.211 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 116.614 (12), 90 |
V (Å3) | 1494.4 (4) | 1546.1 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.50 × 0.20 × 0.20 | 0.70 × 0.30 × 0.20 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2616, 2616, 1316 | 4876, 4647, 3562 |
Rint | 0.000 | 0.013 |
(sin θ/λ)max (Å−1) | 0.714 | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.168, 1.07 | 0.045, 0.111, 1.05 |
No. of reflections | 2616 | 4647 |
No. of parameters | 243 | 503 |
No. of restraints | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.42 | 0.22, −0.15 |
Selected torsion angles (º) for (I) topC8—C1—C2—C3 | 114.4 (4) | C4—C5—C6—C7 | −76.8 (7) |
C1—C2—C3—C4 | −41.1 (5) | C5—C6—C7—C8 | 93.2 (6) |
C2—C3—C4—C5 | −60.3 (6) | C6—C7—C8—C1 | −58.1 (6) |
C3—C4—C5—C6 | 90.5 (7) | C2—C1—C8—C7 | −42.0 (5) |
Selected torsion angles (º) for (II) topC8A—C1A—C2A—C3A | 95.1 (3) | C8B—C1B—C2B—C3B | 95.9 (2) |
C1A—C2A—C3A—C4A | −63.0 (3) | C1B—C2B—C3B—C4B | −62.8 (3) |
C2A—C3A—C4A—C5A | 65.1 (3) | C2B—C3B—C4B—C5B | 65.1 (3) |
C3A—C4A—C5A—C6A | −106.6 (3) | C3B—C4B—C5B—C6B | −106.9 (3) |
C4A—C5A—C6A—C7A | 49.8 (3) | C4B—C5B—C6B—C7B | 49.7 (3) |
C5A—C6A—C7A—C8A | 58.5 (3) | C5B—C6B—C7B—C8B | 58.7 (3) |
C6A—C7A—C8A—C1A | −68.6 (3) | C6B—C7B—C8B—C1B | −68.0 (3) |
C2A—C1A—C8A—C7A | −36.9 (3) | C2B—C1B—C8B—C7B | −38.0 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O12A—H12A···O15Bi | 0.79 (4) | 2.25 (4) | 2.937 (3) | 146 (4) |
O12B—H12B···O15Aii | 0.82 (4) | 2.19 (4) | 2.912 (3) | 148 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x, y, z−1. |
During the course of our synthetic studies of precapnelladiene, the terpenoid with an 8-membered carbocycle, we prepared a chiral (1R,8R,11R)-3,3,11-trimethylbicyclo[6.3.0]undecane-2,6-dione (Maeda & Inouye, 1994) as the synthetic intermediate. Because of flexible conformation of an 8-membered ring, it is important to clarify the conformational change of the 8-membered ring during the reaction. We wish to report here crystal structures of (1R,8R,11R)-3,3,11-trimethyl-6,6-ethylenedioxybicyclo[6.3.0]undecan-2-one (I), which was synthesized from the dione, and the corresponding alcohol (II). The stereochemistry of the hydroxyl group in (II) was unequivocally confirmed as R as estimated from its NMR spectrum; the H attached at the alcoholic carbon absorbs at δ 3.56 with J=3.1 Hz. Two independent molecules were found in (II), they differ only in their conformations around an acetal moiety. On the other hand, the conformation of the 8-membered carbocycle differs markedly in (I) and (II). Torsion angles of the model indicate major differences being found at the carbons 4 and 5. Crystal structure of (I) reveals that the Re-side of the carbonyl carbon is protected by the C6-methylene group from an incoming reagent to give an R alcohol exclusively. The resulting alcoholic oxygen in (II) interacts with C6-methylene group giving conformational change at the carbons 4 and 5.