Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101013336/gd1172sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013336/gd1172IIIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013336/gd1172IVsup3.hkl |
CCDC references: 173943; 173945
For related literature, see: Allen & Kennard (1993); Chen & Chang (1996); Donkervoort et al. (1996); Ford et al. (2000); Karlsson et al. (1973); Kennedy et al. (2000); Kerr et al. (2001); Khan et al. (1985).
The syntheses and spectroscopic characterizations of compounds (IIIa) and (IV) are described in detail by Kerr et al. (2001). Crystals of both compounds were grown by slow recrystallization from petroleum ether/diethyl ether mixtures at room temperature.
All H atoms were treated as riding, with C—H = 0.93–1.00 Å. For compound (IV), the Freidel equivalents were merged prior to the final refinement.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (IIIa); DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (IV). Cell refinement: MSC/AFC Diffractometer Control Software for (IIIa); DENZO and COLLECT for (IV). Data reduction: TEXSAN (Molecular Structure Corporation, 1992) for (IIIa); DENZO and COLLECT for (IV). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (IIIa); SHELXS97 (Sheldrick, 1990) for (IV). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C16H22O3 | F(000) = 568 |
Mr = 262.34 | Dx = 1.248 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 6.0402 (13) Å | Cell parameters from 21 reflections |
b = 31.423 (4) Å | θ = 7.1–10.7° |
c = 7.7111 (13) Å | µ = 0.09 mm−1 |
β = 107.469 (15)° | T = 295 K |
V = 1396.1 (4) Å3 | Tabular, colourless |
Z = 4 | 0.50 × 0.40 × 0.15 mm |
Rigaku AFC-7S diffractometer | Rint = 0.061 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.6° |
Graphite monochromator | h = 0→7 |
ω/2θ scans | k = 0→38 |
2977 measured reflections | l = −9→9 |
2721 independent reflections | 3 standard reflections every 150 reflections |
1522 reflections with I > 2σ(I) | intensity decay: 3.0% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.1589P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2721 reflections | Δρmax = 0.18 e Å−3 |
176 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
C16H22O3 | V = 1396.1 (4) Å3 |
Mr = 262.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.0402 (13) Å | µ = 0.09 mm−1 |
b = 31.423 (4) Å | T = 295 K |
c = 7.7111 (13) Å | 0.50 × 0.40 × 0.15 mm |
β = 107.469 (15)° |
Rigaku AFC-7S diffractometer | Rint = 0.061 |
2977 measured reflections | 3 standard reflections every 150 reflections |
2721 independent reflections | intensity decay: 3.0% |
1522 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.18 e Å−3 |
2721 reflections | Δρmin = −0.15 e Å−3 |
176 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 | ||
O1 | 0.4059 (3) | −0.01602 (5) | 0.7178 (2) | 0.0581 (5) | |
O2 | 0.2944 (4) | 0.21646 (5) | 0.7625 (3) | 0.0761 (6) | |
O3 | 0.1227 (4) | 0.19061 (6) | 0.9653 (3) | 0.0815 (7) | |
C1 | 0.3382 (4) | 0.02062 (7) | 0.7164 (3) | 0.0398 (5) | |
C2 | 0.3508 (4) | 0.05474 (7) | 0.5890 (3) | 0.0413 (5) | |
H2 | 0.4117 | 0.0521 | 0.4921 | 0.050* | |
C3 | 0.2608 (3) | 0.08994 (6) | 0.6353 (3) | 0.0334 (5) | |
C4 | 0.2031 (4) | 0.08565 (6) | 0.8116 (3) | 0.0338 (5) | |
C5 | 0.2010 (4) | 0.03721 (6) | 0.8395 (3) | 0.0373 (5) | |
H5 | 0.2807 | 0.0300 | 0.9665 | 0.045* | |
C6 | −0.0401 (4) | 0.01703 (7) | 0.7789 (4) | 0.0539 (7) | |
H6A | −0.1156 | 0.0241 | 0.6540 | 0.081* | |
H6B | −0.1303 | 0.0276 | 0.8530 | 0.081* | |
H6C | −0.0258 | −0.0133 | 0.7917 | 0.081* | |
C7 | 0.1624 (4) | 0.13113 (7) | 0.5391 (3) | 0.0422 (6) | |
C8 | 0.0592 (4) | 0.15198 (7) | 0.6824 (3) | 0.0452 (6) | |
H8 | −0.0763 | 0.1694 | 0.6212 | 0.054* | |
C9 | −0.0155 (4) | 0.11313 (7) | 0.7733 (3) | 0.0466 (6) | |
H9A | −0.0491 | 0.1209 | 0.8844 | 0.056* | |
H9B | −0.1493 | 0.0990 | 0.6918 | 0.056* | |
C10 | 0.3924 (4) | 0.10675 (7) | 0.9690 (3) | 0.0453 (6) | |
H10A | 0.3417 | 0.1068 | 1.0771 | 0.054* | |
H10B | 0.5332 | 0.0899 | 0.9952 | 0.054* | |
C11 | 0.4463 (5) | 0.15231 (7) | 0.9267 (3) | 0.0556 (7) | |
H11A | 0.5296 | 0.1664 | 1.0392 | 0.067* | |
H11B | 0.5470 | 0.1517 | 0.8497 | 0.067* | |
C12 | 0.2313 (5) | 0.17780 (7) | 0.8331 (3) | 0.0541 (7) | |
C13 | −0.0380 (5) | 0.11880 (8) | 0.3683 (3) | 0.0651 (8) | |
H13A | 0.0226 | 0.1025 | 0.2874 | 0.098* | |
H13B | −0.1107 | 0.1441 | 0.3077 | 0.098* | |
H13C | −0.1502 | 0.1021 | 0.4037 | 0.098* | |
C14 | 0.3359 (5) | 0.15733 (8) | 0.4728 (4) | 0.0634 (8) | |
H14A | 0.4644 | 0.1655 | 0.5750 | 0.095* | |
H14B | 0.2605 | 0.1824 | 0.4114 | 0.095* | |
H14C | 0.3913 | 0.1405 | 0.3904 | 0.095* | |
C15 | 0.1855 (8) | 0.25013 (10) | 0.8219 (6) | 0.1173 (16) | |
H15A | 0.0919 | 0.2664 | 0.7188 | 0.141* | |
H15B | 0.3003 | 0.2690 | 0.8995 | 0.141* | |
C16 | 0.0364 (8) | 0.23152 (10) | 0.9246 (6) | 0.1047 (13) | |
H16A | 0.0494 | 0.2476 | 1.0346 | 0.126* | |
H16B | −0.1249 | 0.2309 | 0.8509 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0723 (12) | 0.0379 (9) | 0.0643 (12) | 0.0130 (8) | 0.0209 (10) | 0.0006 (8) |
O2 | 0.1065 (16) | 0.0297 (9) | 0.0880 (14) | −0.0054 (10) | 0.0232 (12) | −0.0001 (9) |
O3 | 0.1281 (19) | 0.0504 (11) | 0.0743 (13) | 0.0276 (12) | 0.0430 (13) | −0.0070 (10) |
C1 | 0.0383 (12) | 0.0361 (12) | 0.0404 (12) | 0.0000 (10) | 0.0048 (10) | −0.0029 (9) |
C2 | 0.0458 (13) | 0.0441 (13) | 0.0378 (12) | −0.0002 (10) | 0.0183 (11) | −0.0026 (10) |
C3 | 0.0332 (11) | 0.0343 (11) | 0.0314 (11) | −0.0045 (9) | 0.0077 (9) | −0.0011 (8) |
C4 | 0.0365 (12) | 0.0321 (11) | 0.0322 (11) | −0.0005 (9) | 0.0092 (9) | −0.0002 (9) |
C5 | 0.0403 (13) | 0.0347 (11) | 0.0336 (11) | −0.0018 (9) | 0.0063 (10) | 0.0030 (9) |
C6 | 0.0526 (16) | 0.0475 (14) | 0.0625 (16) | −0.0104 (12) | 0.0189 (13) | 0.0029 (12) |
C7 | 0.0503 (14) | 0.0355 (12) | 0.0387 (12) | −0.0018 (10) | 0.0104 (10) | 0.0037 (9) |
C8 | 0.0410 (13) | 0.0379 (12) | 0.0535 (14) | 0.0111 (10) | 0.0090 (11) | 0.0061 (10) |
C9 | 0.0421 (13) | 0.0473 (13) | 0.0530 (14) | 0.0069 (11) | 0.0179 (11) | 0.0037 (11) |
C10 | 0.0527 (14) | 0.0402 (12) | 0.0371 (12) | 0.0031 (10) | 0.0047 (11) | −0.0053 (9) |
C11 | 0.0612 (17) | 0.0396 (13) | 0.0524 (14) | −0.0023 (12) | −0.0034 (12) | −0.0089 (11) |
C12 | 0.0733 (18) | 0.0336 (12) | 0.0555 (16) | 0.0061 (12) | 0.0195 (14) | −0.0032 (11) |
C13 | 0.076 (2) | 0.0574 (16) | 0.0448 (14) | 0.0011 (14) | −0.0082 (14) | 0.0067 (12) |
C14 | 0.080 (2) | 0.0524 (15) | 0.0622 (17) | −0.0088 (14) | 0.0287 (15) | 0.0100 (13) |
C15 | 0.181 (5) | 0.0385 (18) | 0.131 (4) | 0.018 (2) | 0.046 (3) | 0.001 (2) |
C16 | 0.144 (4) | 0.058 (2) | 0.110 (3) | 0.041 (2) | 0.035 (3) | −0.0116 (19) |
O1—C1 | 1.221 (2) | C8—C12 | 1.538 (3) |
O2—C15 | 1.394 (4) | C8—C9 | 1.541 (3) |
O2—C12 | 1.429 (3) | C8—H8 | 0.980 |
O3—C16 | 1.387 (3) | C9—H9A | 0.970 |
O3—C12 | 1.426 (3) | C9—H9B | 0.970 |
C1—C2 | 1.471 (3) | C10—C11 | 1.525 (3) |
C1—C5 | 1.527 (3) | C10—H10A | 0.970 |
C2—C3 | 1.328 (3) | C10—H10B | 0.970 |
C2—H2 | 0.930 | C11—C12 | 1.512 (3) |
C3—C4 | 1.508 (3) | C11—H11A | 0.970 |
C3—C7 | 1.521 (3) | C11—H11B | 0.970 |
C4—C9 | 1.531 (3) | C13—H13A | 0.960 |
C4—C5 | 1.538 (3) | C13—H13B | 0.960 |
C4—C10 | 1.545 (3) | C13—H13C | 0.960 |
C5—C6 | 1.527 (3) | C14—H14A | 0.960 |
C5—H5 | 0.980 | C14—H14B | 0.960 |
C6—H6A | 0.960 | C14—H14C | 0.960 |
C6—H6B | 0.960 | C15—C16 | 1.486 (6) |
C6—H6C | 0.960 | C15—H15A | 0.970 |
C7—C14 | 1.536 (3) | C15—H15B | 0.970 |
C7—C13 | 1.547 (3) | C16—H16A | 0.970 |
C7—C8 | 1.566 (3) | C16—H16B | 0.970 |
C15—O2—C12 | 108.3 (3) | C8—C9—H9B | 112 |
C16—O3—C12 | 108.8 (2) | H9A—C9—H9B | 109.4 |
O1—C1—C2 | 127.5 (2) | C11—C10—C4 | 112.96 (18) |
O1—C1—C5 | 124.0 (2) | C11—C10—H10A | 109 |
C2—C1—C5 | 108.22 (18) | C4—C10—H10A | 109 |
C3—C2—C1 | 108.7 (2) | C11—C10—H10B | 109 |
C3—C2—H2 | 126 | C4—C10—H10B | 109 |
C1—C2—H2 | 126 | H10A—C10—H10B | 107.8 |
C2—C3—C4 | 113.09 (18) | C12—C11—C10 | 113.0 (2) |
C2—C3—C7 | 135.2 (2) | C12—C11—H11A | 109 |
C4—C3—C7 | 110.71 (17) | C10—C11—H11A | 109 |
C3—C4—C9 | 101.24 (17) | C12—C11—H11B | 109 |
C3—C4—C5 | 103.21 (16) | C10—C11—H11B | 109 |
C9—C4—C5 | 122.85 (18) | H11A—C11—H11B | 108 |
C3—C4—C10 | 110.70 (18) | O3—C12—O2 | 105.36 (19) |
C9—C4—C10 | 107.54 (18) | O3—C12—C11 | 108.7 (2) |
C5—C4—C10 | 110.52 (16) | O2—C12—C11 | 110.1 (2) |
C6—C5—C1 | 108.28 (17) | O3—C12—C8 | 109.7 (2) |
C6—C5—C4 | 114.56 (18) | O2—C12—C8 | 110.98 (19) |
C1—C5—C4 | 102.83 (16) | C11—C12—C8 | 111.72 (18) |
C6—C5—H5 | 110 | C7—C13—H13A | 110 |
C1—C5—H5 | 110 | C7—C13—H13B | 110 |
C4—C5—H5 | 110 | H13A—C13—H13B | 110 |
C5—C6—H6A | 110 | C7—C13—H13C | 110 |
C5—C6—H6B | 110 | H13A—C13—H13C | 110 |
H6A—C6—H6B | 110 | H13B—C13—H13C | 110 |
C5—C6—H6C | 110 | C7—C14—H14A | 110 |
H6A—C6—H6C | 110 | C7—C14—H14B | 110 |
H6B—C6—H6C | 110 | H14A—C14—H14B | 110 |
C3—C7—C14 | 114.4 (2) | C7—C14—H14C | 110 |
C3—C7—C13 | 107.07 (17) | H14A—C14—H14C | 110 |
C14—C7—C13 | 106.8 (2) | H14B—C14—H14C | 110 |
C3—C7—C8 | 101.06 (16) | O2—C15—C16 | 107.3 (3) |
C14—C7—C8 | 117.81 (19) | O2—C15—H15A | 110 |
C13—C7—C8 | 109.3 (2) | C16—C15—H15A | 110 |
C12—C8—C9 | 107.34 (19) | O2—C15—H15B | 110 |
C12—C8—C7 | 115.6 (2) | C16—C15—H15B | 110 |
C9—C8—C7 | 102.85 (17) | H15A—C15—H15B | 108.5 |
C12—C8—H8 | 110 | O3—C16—C15 | 103.8 (3) |
C9—C8—H8 | 110 | O3—C16—H16A | 111 |
C7—C8—H8 | 110 | C15—C16—H16A | 111 |
C4—C9—C8 | 100.46 (18) | O3—C16—H16B | 111 |
C4—C9—H9A | 112 | C15—C16—H16B | 111 |
C8—C9—H9A | 112 | H16A—C16—H16B | 109 |
C4—C9—H9B | 112 | ||
O1—C1—C2—C3 | −179.2 (2) | C14—C7—C8—C9 | −157.1 (2) |
C5—C1—C2—C3 | 6.5 (2) | C13—C7—C8—C9 | 80.9 (2) |
C1—C2—C3—C4 | 7.0 (3) | C3—C4—C9—C8 | −43.9 (2) |
C1—C2—C3—C7 | −160.0 (2) | C5—C4—C9—C8 | −157.83 (18) |
C2—C3—C4—C9 | −145.19 (19) | C10—C4—C9—C8 | 72.2 (2) |
C7—C3—C4—C9 | 25.0 (2) | C12—C8—C9—C4 | −74.5 (2) |
C2—C3—C4—C5 | −17.3 (2) | C7—C8—C9—C4 | 47.9 (2) |
C7—C3—C4—C5 | 152.94 (16) | C3—C4—C10—C11 | 51.4 (3) |
C2—C3—C4—C10 | 101.0 (2) | C9—C4—C10—C11 | −58.3 (3) |
C7—C3—C4—C10 | −88.8 (2) | C5—C4—C10—C11 | 165.16 (19) |
O1—C1—C5—C6 | −69.3 (3) | C4—C10—C11—C12 | 42.2 (3) |
C2—C1—C5—C6 | 105.2 (2) | C16—O3—C12—O2 | 24.0 (3) |
O1—C1—C5—C4 | 169.1 (2) | C16—O3—C12—C11 | 141.9 (3) |
C2—C1—C5—C4 | −16.5 (2) | C16—O3—C12—C8 | −95.6 (3) |
C3—C4—C5—C6 | −98.0 (2) | C15—O2—C12—O3 | −11.8 (3) |
C9—C4—C5—C6 | 14.9 (3) | C15—O2—C12—C11 | −128.9 (3) |
C10—C4—C5—C6 | 143.6 (2) | C15—O2—C12—C8 | 106.9 (3) |
C3—C4—C5—C1 | 19.22 (19) | C10—C11—C12—O3 | 77.6 (3) |
C9—C4—C5—C1 | 132.2 (2) | C10—C11—C12—O2 | −167.5 (2) |
C10—C4—C5—C1 | −99.2 (2) | C10—C11—C12—C8 | −43.7 (3) |
C2—C3—C7—C14 | −61.0 (3) | C9—C8—C12—O3 | −59.0 (2) |
C4—C3—C7—C14 | 131.8 (2) | C7—C8—C12—O3 | −173.09 (17) |
C2—C3—C7—C13 | 57.0 (3) | C9—C8—C12—O2 | −175.06 (19) |
C4—C3—C7—C13 | −110.2 (2) | C7—C8—C12—O2 | 70.9 (2) |
C2—C3—C7—C8 | 171.3 (2) | C9—C8—C12—C11 | 61.7 (3) |
C4—C3—C7—C8 | 4.2 (2) | C7—C8—C12—C11 | −52.4 (3) |
C3—C7—C8—C12 | 84.9 (2) | C12—O2—C15—C16 | −3.5 (4) |
C14—C7—C8—C12 | −40.5 (3) | C12—O3—C16—C15 | −25.6 (4) |
C13—C7—C8—C12 | −162.46 (19) | O2—C15—C16—O3 | 17.9 (4) |
C3—C7—C8—C9 | −31.8 (2) |
C16H24O3 | F(000) = 288 |
Mr = 264.35 | Dx = 1.284 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3280 (3) Å | Cell parameters from 17654 reflections |
b = 8.3930 (3) Å | θ = 1.0–27.5° |
c = 10.2120 (4) Å | µ = 0.09 mm−1 |
β = 106.696 (2)° | T = 150 K |
V = 683.70 (4) Å3 | Cut fragment, colourless |
Z = 2 | 0.50 × 0.35 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 1579 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 27.5°, θmin = 3.5° |
ϕ + ω scans to fill Ewald sphere | h = −10→10 |
5455 measured reflections | k = −10→10 |
1667 independent reflections | l = −13→13 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.1142P] where P = (Fo2 + 2Fc2)/3 |
1667 reflections | (Δ/σ)max < 0.001 |
175 parameters | Δρmax = 0.19 e Å−3 |
1 restraint | Δρmin = −0.17 e Å−3 |
C16H24O3 | V = 683.70 (4) Å3 |
Mr = 264.35 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.3280 (3) Å | µ = 0.09 mm−1 |
b = 8.3930 (3) Å | T = 150 K |
c = 10.2120 (4) Å | 0.50 × 0.35 × 0.10 mm |
β = 106.696 (2)° |
Nonius KappaCCD area-detector diffractometer | 1579 reflections with I > 2σ(I) |
5455 measured reflections | Rint = 0.030 |
1667 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 1 restraint |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.19 e Å−3 |
1667 reflections | Δρmin = −0.17 e Å−3 |
175 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 | ||
O1 | 0.48780 (17) | −0.38785 (19) | 0.53438 (12) | 0.0344 (3) | |
O2 | −0.39000 (14) | −0.31606 (19) | 0.09467 (12) | 0.0284 (3) | |
O3 | −0.23261 (14) | −0.38265 (16) | −0.04680 (11) | 0.0213 (3) | |
C1 | 0.3698 (2) | −0.3367 (2) | 0.44531 (16) | 0.0228 (4) | |
C2 | 0.2414 (2) | −0.2175 (2) | 0.46290 (17) | 0.0251 (4) | |
H2A | 0.2696 | −0.1084 | 0.4399 | 0.030* | |
H2B | 0.2334 | −0.2184 | 0.5578 | 0.030* | |
C3 | 0.07774 (19) | −0.2755 (2) | 0.36180 (15) | 0.0178 (3) | |
H3 | 0.0257 | −0.3548 | 0.4104 | 0.021* | |
C4 | 0.12928 (19) | −0.3659 (2) | 0.24538 (15) | 0.0162 (3) | |
C5 | 0.32299 (19) | −0.3867 (2) | 0.29559 (16) | 0.0196 (3) | |
H5 | 0.3718 | −0.3053 | 0.2466 | 0.024* | |
C6 | 0.3965 (2) | −0.5464 (3) | 0.27365 (18) | 0.0280 (4) | |
H6A | 0.3591 | −0.6284 | 0.3267 | 0.042* | |
H6B | 0.5191 | −0.5400 | 0.3037 | 0.042* | |
H6C | 0.3587 | −0.5741 | 0.1764 | 0.042* | |
C7 | −0.0616 (2) | −0.1534 (2) | 0.28849 (16) | 0.0203 (3) | |
C8 | −0.1065 (2) | −0.2061 (2) | 0.13533 (16) | 0.0182 (3) | |
H8 | −0.1520 | −0.1138 | 0.0740 | 0.022* | |
C9 | 0.06617 (19) | −0.2550 (2) | 0.12185 (15) | 0.0173 (3) | |
H9A | 0.0559 | −0.3118 | 0.0349 | 0.021* | |
H9B | 0.1406 | −0.1616 | 0.1282 | 0.021* | |
C10 | 0.0321 (2) | −0.5234 (2) | 0.21179 (16) | 0.0194 (3) | |
H10A | 0.0553 | −0.5729 | 0.1311 | 0.023* | |
H10B | 0.0713 | −0.5976 | 0.2899 | 0.023* | |
C11 | −0.1575 (2) | −0.4974 (2) | 0.18208 (17) | 0.0219 (4) | |
H11A | −0.2170 | −0.5930 | 0.1355 | 0.026* | |
H11B | −0.1845 | −0.4855 | 0.2699 | 0.026* | |
C12 | −0.22193 (19) | −0.3511 (2) | 0.09335 (15) | 0.0189 (3) | |
C13 | 0.0031 (3) | 0.0192 (2) | 0.2963 (2) | 0.0288 (4) | |
H13A | 0.0422 | 0.0527 | 0.3922 | 0.043* | |
H13B | −0.0878 | 0.0895 | 0.2463 | 0.043* | |
H13C | 0.0960 | 0.0251 | 0.2555 | 0.043* | |
C14 | −0.2077 (2) | −0.1542 (3) | 0.35251 (18) | 0.0290 (4) | |
H14A | −0.2968 | −0.0835 | 0.3002 | 0.044* | |
H14B | −0.1678 | −0.1167 | 0.4473 | 0.044* | |
H14C | −0.2515 | −0.2627 | 0.3509 | 0.044* | |
C15 | −0.5019 (2) | −0.3494 (3) | −0.03634 (17) | 0.0279 (4) | |
H15A | −0.5447 | −0.2496 | −0.0857 | 0.034* | |
H15B | −0.5981 | −0.4139 | −0.0282 | 0.034* | |
C16 | −0.3975 (2) | −0.4416 (2) | −0.10943 (17) | 0.0241 (4) | |
H16A | −0.4043 | −0.5577 | −0.0946 | 0.029* | |
H16B | −0.4335 | −0.4193 | −0.2088 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0298 (7) | 0.0395 (8) | 0.0240 (6) | 0.0062 (6) | −0.0083 (5) | −0.0033 (6) |
O2 | 0.0147 (5) | 0.0452 (9) | 0.0235 (6) | 0.0015 (6) | 0.0028 (4) | −0.0075 (6) |
O3 | 0.0173 (5) | 0.0290 (7) | 0.0153 (5) | 0.0005 (5) | 0.0008 (4) | −0.0031 (5) |
C1 | 0.0195 (8) | 0.0238 (9) | 0.0216 (8) | −0.0059 (7) | 0.0002 (6) | −0.0012 (7) |
C2 | 0.0230 (8) | 0.0283 (9) | 0.0199 (8) | −0.0015 (7) | −0.0003 (6) | −0.0072 (7) |
C3 | 0.0181 (7) | 0.0203 (8) | 0.0145 (7) | −0.0012 (6) | 0.0040 (6) | −0.0012 (6) |
C4 | 0.0160 (7) | 0.0172 (8) | 0.0143 (6) | 0.0001 (6) | 0.0025 (5) | −0.0003 (6) |
C5 | 0.0159 (7) | 0.0230 (8) | 0.0181 (7) | −0.0009 (7) | 0.0020 (6) | 0.0008 (6) |
C6 | 0.0212 (8) | 0.0338 (11) | 0.0251 (8) | 0.0082 (8) | 0.0006 (7) | −0.0033 (8) |
C7 | 0.0195 (8) | 0.0232 (9) | 0.0172 (8) | 0.0013 (7) | 0.0039 (6) | −0.0029 (7) |
C8 | 0.0196 (7) | 0.0190 (8) | 0.0153 (7) | 0.0027 (6) | 0.0038 (6) | 0.0004 (6) |
C9 | 0.0176 (7) | 0.0180 (8) | 0.0154 (7) | −0.0010 (6) | 0.0035 (5) | 0.0012 (6) |
C10 | 0.0214 (8) | 0.0166 (8) | 0.0181 (7) | −0.0026 (7) | 0.0023 (6) | −0.0001 (6) |
C11 | 0.0190 (8) | 0.0234 (9) | 0.0214 (8) | −0.0053 (7) | 0.0030 (6) | 0.0011 (7) |
C12 | 0.0143 (7) | 0.0260 (9) | 0.0156 (7) | −0.0002 (7) | 0.0032 (5) | −0.0023 (7) |
C13 | 0.0337 (10) | 0.0208 (9) | 0.0294 (9) | 0.0028 (8) | 0.0052 (7) | −0.0049 (7) |
C14 | 0.0244 (9) | 0.0423 (12) | 0.0212 (8) | 0.0052 (8) | 0.0077 (7) | −0.0069 (8) |
C15 | 0.0170 (7) | 0.0385 (11) | 0.0241 (8) | 0.0002 (8) | −0.0009 (6) | −0.0013 (8) |
C16 | 0.0197 (8) | 0.0268 (9) | 0.0211 (8) | −0.0026 (7) | −0.0016 (6) | −0.0030 (7) |
O1—C1 | 1.210 (2) | C7—C8 | 1.564 (2) |
O2—C15 | 1.421 (2) | C8—C12 | 1.533 (2) |
O2—C12 | 1.4341 (19) | C8—C9 | 1.539 (2) |
O3—C16 | 1.427 (2) | C8—H8 | 1.000 |
O3—C12 | 1.4329 (17) | C9—H9A | 0.990 |
C1—C2 | 1.513 (3) | C9—H9B | 0.990 |
C1—C5 | 1.524 (2) | C10—C11 | 1.536 (2) |
C2—C3 | 1.533 (2) | C10—H10A | 0.990 |
C2—H2A | 0.990 | C10—H10B | 0.990 |
C2—H2B | 0.990 | C11—C12 | 1.529 (2) |
C3—C7 | 1.568 (2) | C11—H11A | 0.990 |
C3—C4 | 1.571 (2) | C11—H11B | 0.990 |
C3—H3 | 1.000 | C13—H13A | 0.980 |
C4—C9 | 1.534 (2) | C13—H13B | 0.980 |
C4—C10 | 1.536 (2) | C13—H13C | 0.980 |
C4—C5 | 1.556 (2) | C14—H14A | 0.980 |
C5—C6 | 1.517 (3) | C14—H14B | 0.980 |
C5—H5 | 1.000 | C14—H14C | 0.980 |
C6—H6A | 0.980 | C15—C16 | 1.511 (3) |
C6—H6B | 0.980 | C15—H15A | 0.990 |
C6—H6C | 0.980 | C15—H15B | 0.990 |
C7—C14 | 1.538 (2) | C16—H16A | 0.990 |
C7—C13 | 1.539 (3) | C16—H16B | 0.990 |
C15—O2—C12 | 109.17 (12) | C4—C9—H9A | 112 |
C16—O3—C12 | 106.70 (12) | C8—C9—H9A | 112 |
O1—C1—C2 | 126.49 (16) | C4—C9—H9B | 112 |
O1—C1—C5 | 125.11 (17) | C8—C9—H9B | 112 |
C2—C1—C5 | 108.38 (13) | H9A—C9—H9B | 109 |
C1—C2—C3 | 103.41 (14) | C11—C10—C4 | 111.55 (14) |
C1—C2—H2A | 111 | C11—C10—H10A | 109 |
C3—C2—H2A | 111 | C4—C10—H10A | 109 |
C1—C2—H2B | 111 | C11—C10—H10B | 109 |
C3—C2—H2B | 111 | C4—C10—H10B | 109 |
H2A—C2—H2B | 109 | H10A—C10—H10B | 108 |
C2—C3—C7 | 120.43 (15) | C12—C11—C10 | 113.40 (13) |
C2—C3—C4 | 106.24 (13) | C12—C11—H11A | 109 |
C7—C3—C4 | 106.27 (12) | C10—C11—H11A | 109 |
C2—C3—H3 | 108 | C12—C11—H11B | 109 |
C7—C3—H3 | 108 | C10—C11—H11B | 109 |
C4—C3—H3 | 108 | H11A—C11—H11B | 108 |
C9—C4—C10 | 107.72 (12) | O3—C12—O2 | 105.46 (12) |
C9—C4—C5 | 114.65 (13) | O3—C12—C11 | 110.74 (14) |
C10—C4—C5 | 113.99 (14) | O2—C12—C11 | 109.65 (13) |
C9—C4—C3 | 103.05 (13) | O3—C12—C8 | 106.26 (12) |
C10—C4—C3 | 110.11 (13) | O2—C12—C8 | 111.70 (14) |
C5—C4—C3 | 106.73 (12) | C11—C12—C8 | 112.74 (13) |
C6—C5—C1 | 113.18 (14) | C7—C13—H13A | 110 |
C6—C5—C4 | 118.35 (15) | C7—C13—H13B | 110 |
C1—C5—C4 | 104.00 (12) | H13A—C13—H13B | 110 |
C6—C5—H5 | 107 | C7—C13—H13C | 110 |
C1—C5—H5 | 107 | H13A—C13—H13C | 110 |
C4—C5—H5 | 107 | H13B—C13—H13C | 110 |
C5—C6—H6A | 110 | C7—C14—H14A | 110 |
C5—C6—H6B | 110 | C7—C14—H14B | 110 |
H6A—C6—H6B | 110 | H14A—C14—H14B | 110 |
C5—C6—H6C | 110 | C7—C14—H14C | 110 |
H6A—C6—H6C | 110 | H14A—C14—H14C | 110 |
H6B—C6—H6C | 110 | H14B—C14—H14C | 110 |
C14—C7—C13 | 106.84 (16) | O2—C15—C16 | 104.55 (13) |
C14—C7—C8 | 115.64 (14) | O2—C15—H15A | 111 |
C13—C7—C8 | 107.35 (15) | C16—C15—H15A | 111 |
C14—C7—C3 | 111.19 (15) | O2—C15—H15B | 111 |
C13—C7—C3 | 112.97 (14) | C16—C15—H15B | 111 |
C8—C7—C3 | 102.94 (13) | H15A—C15—H15B | 109 |
C12—C8—C9 | 106.87 (13) | O3—C16—C15 | 102.54 (13) |
C12—C8—C7 | 117.07 (13) | O3—C16—H16A | 111 |
C9—C8—C7 | 101.75 (12) | C15—C16—H16A | 111 |
C12—C8—H8 | 110 | O3—C16—H16B | 111 |
C9—C8—H8 | 110 | C15—C16—H16B | 111 |
C7—C8—H8 | 110 | H16A—C16—H16B | 109 |
C4—C9—C8 | 101.33 (12) | ||
O1—C1—C2—C3 | −143.48 (19) | C13—C7—C8—C9 | 82.17 (16) |
C5—C1—C2—C3 | 34.84 (18) | C3—C7—C8—C9 | −37.26 (16) |
C1—C2—C3—C7 | −147.82 (14) | C10—C4—C9—C8 | 74.09 (15) |
C1—C2—C3—C4 | −27.19 (18) | C5—C4—C9—C8 | −157.87 (13) |
C2—C3—C4—C9 | −110.41 (14) | C3—C4—C9—C8 | −42.31 (15) |
C7—C3—C4—C9 | 18.98 (16) | C12—C8—C9—C4 | −73.32 (14) |
C2—C3—C4—C10 | 134.90 (14) | C7—C8—C9—C4 | 49.96 (16) |
C7—C3—C4—C10 | −95.71 (15) | C9—C4—C10—C11 | −59.43 (16) |
C2—C3—C4—C5 | 10.70 (18) | C5—C4—C10—C11 | 172.15 (12) |
C7—C3—C4—C5 | 140.09 (14) | C3—C4—C10—C11 | 52.25 (16) |
O1—C1—C5—C6 | 20.6 (3) | C4—C10—C11—C12 | 42.23 (18) |
C2—C1—C5—C6 | −157.73 (15) | C16—O3—C12—O2 | −27.63 (18) |
O1—C1—C5—C4 | 150.35 (18) | C16—O3—C12—C11 | 90.91 (16) |
C2—C1—C5—C4 | −27.99 (18) | C16—O3—C12—C8 | −146.34 (13) |
C9—C4—C5—C6 | −110.04 (17) | C15—O2—C12—O3 | 8.7 (2) |
C10—C4—C5—C6 | 14.8 (2) | C15—O2—C12—C11 | −110.60 (16) |
C3—C4—C5—C6 | 136.55 (15) | C15—O2—C12—C8 | 123.68 (16) |
C9—C4—C5—C1 | 123.41 (15) | C10—C11—C12—O3 | 76.22 (17) |
C10—C4—C5—C1 | −111.78 (15) | C10—C11—C12—O2 | −167.81 (13) |
C3—C4—C5—C1 | 9.99 (18) | C10—C11—C12—C8 | −42.68 (19) |
C2—C3—C7—C14 | −103.72 (18) | C9—C8—C12—O3 | −62.21 (15) |
C4—C3—C7—C14 | 135.66 (14) | C7—C8—C12—O3 | −175.41 (13) |
C2—C3—C7—C13 | 16.4 (2) | C9—C8—C12—O2 | −176.73 (12) |
C4—C3—C7—C13 | −104.21 (16) | C7—C8—C12—O2 | 70.07 (18) |
C2—C3—C7—C8 | 131.86 (15) | C9—C8—C12—C11 | 59.27 (16) |
C4—C3—C7—C8 | 11.24 (16) | C7—C8—C12—C11 | −53.93 (19) |
C14—C7—C8—C12 | −42.7 (2) | C12—O2—C15—C16 | 12.3 (2) |
C13—C7—C8—C12 | −161.78 (14) | C12—O3—C16—C15 | 34.46 (18) |
C3—C7—C8—C12 | 78.79 (16) | O2—C15—C16—O3 | −28.40 (19) |
C14—C7—C8—C9 | −158.70 (16) |
Experimental details
(IIIa) | (IV) | |
Crystal data | ||
Chemical formula | C16H22O3 | C16H24O3 |
Mr | 262.34 | 264.35 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21 |
Temperature (K) | 295 | 150 |
a, b, c (Å) | 6.0402 (13), 31.423 (4), 7.7111 (13) | 8.3280 (3), 8.3930 (3), 10.2120 (4) |
β (°) | 107.469 (15) | 106.696 (2) |
V (Å3) | 1396.1 (4) | 683.70 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.50 × 0.40 × 0.15 | 0.50 × 0.35 × 0.10 |
Data collection | ||
Diffractometer | Rigaku AFC-7S diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2977, 2721, 1522 | 5455, 1667, 1579 |
Rint | 0.061 | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.142, 1.01 | 0.031, 0.080, 1.07 |
No. of reflections | 2721 | 1667 |
No. of parameters | 176 | 175 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.15 | 0.19, −0.17 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), MSC/AFC Diffractometer Control Software, DENZO and COLLECT, TEXSAN (Molecular Structure Corporation, 1992), SIR92 (Altomare et al., 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
O1—C1 | 1.221 (2) | C2—C3 | 1.328 (3) |
C1—C2 | 1.471 (3) | C3—C4 | 1.508 (3) |
C1—C5 | 1.527 (3) | C3—C7 | 1.521 (3) |
C2—C1—C5 | 108.22 (18) | C9—C4—C5 | 122.85 (18) |
C2—C3—C7 | 135.2 (2) | C6—C5—C4 | 114.56 (18) |
C5—C1—C2—C3 | 6.5 (2) | C3—C4—C5—C1 | 19.22 (19) |
C1—C2—C3—C4 | 7.0 (3) | C4—C3—C7—C8 | 4.2 (2) |
C7—C3—C4—C9 | 25.0 (2) | C3—C7—C8—C9 | −31.8 (2) |
C2—C3—C4—C5 | −17.3 (2) | C3—C4—C9—C8 | −43.9 (2) |
C2—C1—C5—C4 | −16.5 (2) | C7—C8—C9—C4 | 47.9 (2) |
O1—C1 | 1.210 (2) | C3—C7 | 1.568 (2) |
C1—C2 | 1.513 (3) | C3—C4 | 1.571 (2) |
C1—C5 | 1.524 (2) | C4—C5 | 1.556 (2) |
C2—C1—C5 | 108.38 (13) | C9—C4—C5 | 114.65 (13) |
C2—C3—C7 | 120.43 (15) | C6—C5—C4 | 118.35 (15) |
C5—C1—C2—C3 | 34.84 (18) | C3—C4—C5—C1 | 9.99 (18) |
C1—C2—C3—C4 | −27.19 (18) | C4—C3—C7—C8 | 11.24 (16) |
C7—C3—C4—C9 | 18.98 (16) | C3—C7—C8—C9 | −37.26 (16) |
C2—C3—C4—C5 | 10.70 (18) | C3—C4—C9—C8 | −42.31 (15) |
C2—C1—C5—C4 | −27.99 (18) | C7—C8—C9—C4 | 49.96 (16) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
In order to extend and illustrate our endeavours to develop further the efficiency (Kennedy et al., 2000; Ford et al., 2000) and applicability (Donkervoort et al., 1996) of the Khand cyclization reaction, we sought to utilize this annulation process strategically within routes towards the naturally ocurring sesquiterpenes α-cedrene, (Ia), and β-cedrene, (Ib). It was envisaged that use of these organocobalt-mediated methods would establish a direct and efficient pathway for the synthesis of the structurally demanding [5.3.1.01,5] tricyclic carbon skeleton of this family of natural species.
The cyclization precursors (IIa)/(IIb), prepared as an inseparable 2:1 mixture of geometric isomers, were employed in the key intramolecular Khand cyclization, and the products (IIIa) and (IIIb) were isolated in an excellent optimum combined yield of 95% (Kerr et al., 2001). Following separation, NMR spectroscopic studies could not fully identify each individual product with respect to the methyl group stereochemistry adjacent to the cyclopentenone carbonyl. Accordingly, the major component, (IIIa), was recrystallized and structural elucidation revealed the stereochemistry shown in Fig. 1. As this was not the required isomer, we were able to concentrate our synthetic endeavours on the tricyclic species, (IIIb), which was hydrogenated to give compound (IV), as shown in Fig. 2. In addition to showing the stereochemistry of the methyl group, the structure of (IV) also shows that the H atom introduced at the ring junction is syn to the methyl. Pleasingly, this stereochemical outcome was that desired for the continuation of the total synthesis programme. The crystal structure analyses of compounds (IIIa) and (IV) are presented here. \sch
Both structures (IIIa) and (IV) are comprised of discrete molecules, with all intermolecular distances being equal to at least the sum of van der Waal's radii. Interestingly, (IV) crystallizes in the chiral space group P21, raising the possibility of resolving the racemic mechanical mixture of crystals by utilizing seeding techniques.
The main differences in geometry between the two compounds are, as expected, centred around the double bond found in (IIIa) but not (IV). Not only is this C2—C3 bond shorter in (IIIa), but conjugation to the carbonyl group also causes significant changes to the C1—C2 and C1═O1 distances [1.328 (3), 1.471 (3) and 1.221 (2) Å, respectively, for (IIIa), and 1.533 (2), 1.513 (3) and 1.210 (2) Å, respectively, for (IV)]. The presence of an sp2 hybridized atom at C3 also leads to a shortening of the C3—C4 and C3—C7 bonds. This shortening is more pronounced for C3—C4, which is within the cyclopentene ring, than it is for the aliphatic C3—C7 bond (see Tables 1 and 2). The bond lengths of the acetal group in (IIIa) are artificially shortened by a considerable degree of rotational motion (Fig. 1). A search of the Cambridge Structural Database (Release?; Allen & Kennard, 1993) found no cedrane-based fragments with a double bond such as that in (IIIa). However, several saturated analogues of (IV) were found, though none with a similarly placed ketone functionality. These gave geometric parameters consistent with those found for (IV) (for typical examples see Chen & Chang, 1996; Karlsson et al., 1973; Khan et al., 1985).
The conformation of the cedrene tricyclic skeleton is also affected by the introduction of an sp2 atom at C3. Least changed is the six-membered ring C4/C9/C8/C12/C11/C10, which adopts a chair conformation in both compounds. The planarity forced upon C2, C3, C4 and C7 in (IIIa) by the sp2 atom C3 is not perfect, as C3 lies slightly above the plane of the other three atoms, but it still has a marked effect on the five-membered rings C1/C2/C3/C4/C5 (ring A) and C3/C4/C9/C8/C7 (ring B). In (IIIa), there are two torsion angles around ring A that approach planarity [C1—C2—C3—C4 7.0 (3) and C3—C2—C1—C5 6.5 (2)°], which means that atoms C4 and C5 are twisted furthest from the ring plane. The torsion angles about ring A in (IV) show both an overall greater deviation from planarity (Table 2) and that C1 and C2 are the atoms twisted furthest out of the plane. The torsion angles about ring B for the two structures show that for both (IIIa) and (IV) the C4—C3—C7—C8 angle is flattest, but only for (IIIa) does it truly approach planarity [4.2 (3) and 11.24 (16)°, respectively]. The flattened conformation of (IIIa) leaves the methyl groups of C13 and C14 staggered with respect to C2 [C2—C3—C7—C13 57.0 (3)°], whilst in (IV), the methyl group of C13 approaches an eclipsed position [16.4 (2)°]. The strain inherent in these fused ring systems is shown by some large angular deviations from ideal geometry. Most notable are the widening of the C2—C3—C7 angles [to 135.2 (2) and 120.43 (15)° in (IIIa) and (IV), respectively], and of the C4—C5—C6 angle to 118.35 (15)° in (IV) and the C5—C4—C9 angle to 122.85 (18)° in (IIIa).