The novel bicyclic and tricyclic systems dimethyl (4aS*,6S*)-6-methoxy-7-oxo-4a,5,6,7,8,9-hexahydro-2H-benzocycloheptene-3,4-dicarboxylate, C16H20O6, (I), dimethyl (4aS*,6R*)-6-methoxy-7-oxo-4a,5,6,7,8,9-hexahydro-2H-benzocycloheptene-3,4-dicarboxylate, C16H20O6, (II), (3aS*,9R*,10aS*,10bR*)-9-methoxy-2-oxa-1,3a,4,6,7,8,9,10,10a,10b-decahydro-3H-cyclohepta[e]indene-1,3,8-trione, C14H16O5, (III), and (1S*,2R*,9S*,10aR*)-9-methoxy-8-oxo-1,2,3,5,6,7,8,9,10,10a-decahydrobenzocyclooctene-1,2-dicarboxylic acid, C15H20O6, (IV), have been crystallographically characterized, allowing the determination of the relative configuration of the stereogenic centres. The poor quality of the dicarboxylic acid crystals necessitated the use of synchrotron radiation.
Supporting information
CCDC references: 175095; 175096; 175097; 175098
The synthesis of (I), (II) and (III) has been described elsewhere (Clark et
al., 2001). The Diels-Alder adducts (I) and (II) were each dissolved in
the minimum quantity of warm diethyl ether; adducts (III) and (IV) were each
dissolved in the minimum quantity of warm ethyl acetate. In each case, the
solution was allowed to cool to room temperature and then hexane was added
until slight turbidity was observed. The solutions of the Diels-Alder adducts
were allowed to evaporate slowly at room temperature over several days to
afford crystals suitable for X-ray analysis.
Due to very weak diffraction at high angles, data above θ = 26° for (IV) were
excluded from the final cycles of refinement. In all cases, H atoms were
placed geometrically, except for OH and Me, which were located from circular
difference Fourier syntheses. Geometrically placed H atoms were refined riding
on their carrier atoms, while those from the difference Fourier syntheses were
refined as part of rigid groups allowed to rotate about the local C—O or
C—C vector. The methine, methylene and methyl C—H distances were
constrained to 1.00, 0.99 and 0.98 Å, respectively, and the O—H distance
to 0.84 Å. H-atom displacement parameters were related to those of their
carrier atoms by Uiso(H) = xUeq(C,O), where x
= 1.5 for OH and methyl H atoms, and 1.2 for all other CH. The Daresbury
Laboratory SRS was the radiation source for compound (IV). SADABS
(Sheldrick, 1996) was used to correct for the beam decay at the synchrotron.
For all compounds, data collection: SMART (Bruker, 1999). Cell refinement: SAINT (Bruker, 2000) for (I), (II), (III); SAINT (Bruker, 1998) for (IV). For all compounds, data reduction: SAINT and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL. Software used to prepare material for publication: SHELXTL for (I), (II), (III); SHELXL97 and PLATON (Spek, 2001) for (IV).
(I) Dimethyl (4aS*,6
S*)-6-methoxy-7-oxo-4a,5,6,7,8,9-hexahydro-2
H-
benzocycloheptene-3,4-dicarboxylate
top
Crystal data top
C16H20O6 | Z = 2 |
Mr = 308.32 | F(000) = 328 |
Triclinic, P1 | Dx = 1.320 Mg m−3 |
a = 7.4878 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.1793 (12) Å | Cell parameters from 5947 reflections |
c = 11.0220 (13) Å | θ = 2.4–28.7° |
α = 69.955 (2)° | µ = 0.10 mm−1 |
β = 83.957 (2)° | T = 150 K |
γ = 79.806 (2)° | Block, colourless |
V = 775.85 (16) Å3 | 0.5 × 0.3 × 0.3 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3148 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 28.7°, θmin = 2.0° |
ω scans | h = −9→9 |
9181 measured reflections | k = −13→13 |
3597 independent reflections | l = −14→14 |
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)] = 0.035 | Hydrogen site location: geometrically placed, Me from delta-F |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.1526P] where P = (Fo2 + 2Fc2)/3 |
3597 reflections | (Δ/σ)max = 0.001 |
202 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C16H20O6 | γ = 79.806 (2)° |
Mr = 308.32 | V = 775.85 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.4878 (9) Å | Mo Kα radiation |
b = 10.1793 (12) Å | µ = 0.10 mm−1 |
c = 11.0220 (13) Å | T = 150 K |
α = 69.955 (2)° | 0.5 × 0.3 × 0.3 mm |
β = 83.957 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3148 reflections with I > 2σ(I) |
9181 measured reflections | Rint = 0.024 |
3597 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.34 e Å−3 |
3597 reflections | Δρmin = −0.20 e Å−3 |
202 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 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.65089 (14) | −0.13152 (10) | 0.83490 (9) | 0.0201 (2) | |
C2 | 0.80308 (14) | −0.14744 (11) | 0.89538 (10) | 0.0215 (2) | |
C3 | 0.94629 (15) | −0.05316 (12) | 0.84004 (11) | 0.0294 (2) | |
H3A | 0.9429 | 0.0107 | 0.8910 | 0.035* | |
H3B | 1.0674 | −0.1123 | 0.8482 | 0.035* | |
C4a | 0.77001 (14) | 0.05129 (10) | 0.63967 (10) | 0.0207 (2) | |
C4 | 0.92117 (14) | 0.03402 (11) | 0.70076 (11) | 0.0251 (2) | |
H4 | 1.0191 | 0.0798 | 0.6531 | 0.030* | |
C5 | 0.75280 (14) | 0.13882 (11) | 0.49805 (10) | 0.0236 (2) | |
H5A | 0.6749 | 0.0967 | 0.4588 | 0.028* | |
H5B | 0.8745 | 0.1345 | 0.4535 | 0.028* | |
C6 | 0.67159 (14) | 0.29555 (11) | 0.47509 (10) | 0.0255 (2) | |
H6A | 0.7713 | 0.3500 | 0.4689 | 0.031* | |
H6B | 0.6118 | 0.3342 | 0.3915 | 0.031* | |
O7 | 0.54631 (12) | 0.39702 (8) | 0.63726 (8) | 0.0324 (2) | |
C7 | 0.53540 (14) | 0.31555 (11) | 0.58072 (10) | 0.0229 (2) | |
C8 | 0.38436 (14) | 0.22350 (11) | 0.62452 (10) | 0.0222 (2) | |
H8 | 0.2759 | 0.2789 | 0.6549 | 0.027* | |
C9 | 0.44706 (14) | 0.09198 (11) | 0.73858 (10) | 0.0224 (2) | |
H9A | 0.3417 | 0.0419 | 0.7752 | 0.027* | |
H9B | 0.4853 | 0.1232 | 0.8063 | 0.027* | |
C9a | 0.60482 (13) | −0.01491 (10) | 0.70789 (9) | 0.0194 (2) | |
H9 | 0.5589 | −0.0578 | 0.6503 | 0.023* | |
O10 | 0.89137 (11) | −0.22613 (9) | 1.11288 (7) | 0.02906 (19) | |
C10 | 0.84307 (13) | −0.25517 (11) | 1.02548 (10) | 0.0215 (2) | |
O11 | 0.82751 (11) | −0.38646 (8) | 1.03209 (7) | 0.02792 (19) | |
C12 | 0.85284 (18) | −0.49222 (12) | 1.15919 (11) | 0.0332 (3) | |
H12A | 0.9768 | −0.4998 | 1.1846 | 0.050* | |
H12B | 0.8331 | −0.5839 | 1.1567 | 0.050* | |
H12C | 0.7657 | −0.4644 | 1.2221 | 0.050* | |
C13 | 0.50841 (14) | −0.22576 (11) | 0.88904 (10) | 0.0219 (2) | |
O13 | 0.43812 (13) | −0.27538 (10) | 0.82533 (8) | 0.0391 (2) | |
O14 | 0.46497 (11) | −0.24372 (9) | 1.01364 (7) | 0.02925 (19) | |
C15 | 0.34015 (17) | −0.34413 (15) | 1.07634 (12) | 0.0359 (3) | |
H15A | 0.2379 | −0.3259 | 1.0212 | 0.054* | |
H15B | 0.2947 | −0.3335 | 1.1597 | 0.054* | |
H15C | 0.4037 | −0.4406 | 1.0904 | 0.054* | |
O16 | 0.33115 (10) | 0.18194 (8) | 0.52459 (7) | 0.02434 (17) | |
C17 | 0.22164 (16) | 0.29506 (12) | 0.43400 (11) | 0.0300 (2) | |
H17A | 0.1121 | 0.3275 | 0.4792 | 0.045* | |
H17B | 0.1868 | 0.2617 | 0.3676 | 0.045* | |
H17C | 0.2909 | 0.3735 | 0.3931 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0219 (5) | 0.0182 (5) | 0.0205 (5) | −0.0042 (4) | 0.0006 (4) | −0.0065 (4) |
C2 | 0.0225 (5) | 0.0196 (5) | 0.0215 (5) | −0.0038 (4) | −0.0006 (4) | −0.0053 (4) |
C3 | 0.0246 (5) | 0.0301 (6) | 0.0298 (6) | −0.0106 (4) | −0.0068 (4) | −0.0006 (4) |
C4a | 0.0220 (5) | 0.0175 (4) | 0.0214 (5) | −0.0031 (4) | 0.0020 (4) | −0.0057 (4) |
C4 | 0.0227 (5) | 0.0234 (5) | 0.0267 (5) | −0.0074 (4) | 0.0006 (4) | −0.0036 (4) |
C5 | 0.0240 (5) | 0.0249 (5) | 0.0204 (5) | −0.0056 (4) | 0.0018 (4) | −0.0057 (4) |
C6 | 0.0250 (5) | 0.0230 (5) | 0.0252 (5) | −0.0073 (4) | −0.0004 (4) | −0.0024 (4) |
O7 | 0.0501 (5) | 0.0218 (4) | 0.0270 (4) | −0.0074 (3) | −0.0083 (4) | −0.0073 (3) |
C7 | 0.0279 (5) | 0.0166 (5) | 0.0213 (5) | −0.0021 (4) | −0.0060 (4) | −0.0019 (4) |
C8 | 0.0222 (5) | 0.0216 (5) | 0.0218 (5) | −0.0013 (4) | 0.0000 (4) | −0.0075 (4) |
C9 | 0.0213 (5) | 0.0221 (5) | 0.0213 (5) | −0.0031 (4) | 0.0017 (4) | −0.0049 (4) |
C9a | 0.0199 (5) | 0.0189 (5) | 0.0192 (4) | −0.0045 (4) | −0.0007 (4) | −0.0053 (4) |
O10 | 0.0325 (4) | 0.0313 (4) | 0.0243 (4) | −0.0079 (3) | −0.0035 (3) | −0.0082 (3) |
C10 | 0.0169 (4) | 0.0231 (5) | 0.0226 (5) | −0.0028 (4) | 0.0004 (4) | −0.0057 (4) |
O11 | 0.0372 (4) | 0.0216 (4) | 0.0229 (4) | −0.0053 (3) | −0.0029 (3) | −0.0037 (3) |
C12 | 0.0443 (7) | 0.0243 (5) | 0.0246 (5) | −0.0063 (5) | −0.0020 (5) | 0.0005 (4) |
C13 | 0.0217 (5) | 0.0205 (5) | 0.0217 (5) | −0.0040 (4) | −0.0019 (4) | −0.0039 (4) |
O13 | 0.0505 (5) | 0.0475 (5) | 0.0262 (4) | −0.0316 (4) | 0.0005 (4) | −0.0095 (4) |
O14 | 0.0284 (4) | 0.0378 (5) | 0.0230 (4) | −0.0147 (3) | 0.0040 (3) | −0.0086 (3) |
C15 | 0.0308 (6) | 0.0475 (7) | 0.0260 (6) | −0.0194 (5) | 0.0027 (4) | −0.0025 (5) |
O16 | 0.0248 (4) | 0.0225 (4) | 0.0256 (4) | −0.0024 (3) | −0.0052 (3) | −0.0073 (3) |
C17 | 0.0275 (5) | 0.0294 (6) | 0.0301 (6) | −0.0022 (4) | −0.0082 (4) | −0.0051 (5) |
Geometric parameters (Å, º) top
C1—C2 | 1.3379 (15) | C8—H8 | 1.000 |
C1—C13 | 1.5001 (13) | C9—C9a | 1.5514 (14) |
C1—C9a | 1.5184 (13) | C9—H9A | 0.990 |
C2—C10 | 1.4982 (14) | C9—H9B | 0.990 |
C2—C3 | 1.5060 (14) | C9a—H9 | 1.000 |
C3—C4 | 1.4992 (15) | O10—C10 | 1.2052 (13) |
C3—H3A | 0.990 | C10—O11 | 1.3385 (13) |
C3—H3B | 0.990 | O11—C12 | 1.4516 (13) |
C4a—C4 | 1.3320 (15) | C12—H12A | 0.980 |
C4a—C5 | 1.5150 (14) | C12—H12B | 0.980 |
C4a—C9a | 1.5170 (13) | C12—H12C | 0.980 |
C4—H4 | 0.950 | C13—O13 | 1.2002 (13) |
C5—C6 | 1.5464 (15) | C13—O14 | 1.3342 (13) |
C5—H5A | 0.990 | O14—C15 | 1.4538 (13) |
C5—H5B | 0.990 | C15—H15A | 0.980 |
C6—C7 | 1.5085 (15) | C15—H15B | 0.980 |
C6—H6A | 0.990 | C15—H15C | 0.980 |
C6—H6B | 0.990 | O16—C17 | 1.4301 (13) |
O7—C7 | 1.2132 (13) | C17—H17A | 0.980 |
C7—C8 | 1.5297 (14) | C17—H17B | 0.980 |
C8—O16 | 1.4221 (12) | C17—H17C | 0.980 |
C8—C9 | 1.5301 (14) | | |
| | | |
C2—C1—C13 | 122.60 (9) | C8—C9—C9a | 116.03 (8) |
C2—C1—C9a | 123.21 (9) | C8—C9—H9A | 108 |
C13—C1—C9a | 114.18 (8) | C9a—C9—H9A | 108 |
C1—C2—C10 | 123.55 (9) | C8—C9—H9B | 108 |
C1—C2—C3 | 122.35 (9) | C9a—C9—H9B | 108 |
C10—C2—C3 | 114.05 (9) | H9A—C9—H9B | 107 |
C4—C3—C2 | 112.70 (9) | C4a—C9a—C1 | 111.93 (8) |
C4—C3—H3A | 109 | C4a—C9a—C9 | 113.80 (8) |
C2—C3—H3A | 109 | C1—C9a—C9 | 106.99 (8) |
C4—C3—H3B | 109 | C4a—C9a—H9 | 108 |
C2—C3—H3B | 109 | C1—C9a—H9 | 108 |
H3A—C3—H3B | 108 | C9—C9a—H9 | 108 |
C4—C4a—C5 | 121.90 (9) | O10—C10—O11 | 123.98 (10) |
C4—C4a—C9a | 122.00 (9) | O10—C10—C2 | 122.84 (9) |
C5—C4a—C9a | 116.10 (9) | O11—C10—C2 | 113.12 (9) |
C4a—C4—C3 | 124.04 (9) | C10—O11—C12 | 114.69 (8) |
C4a—C4—H4 | 118 | O11—C12—H12A | 110 |
C3—C4—H4 | 118 | O11—C12—H12B | 110 |
C4a—C5—C6 | 113.52 (9) | H12A—C12—H12B | 110 |
C4a—C5—H5A | 109 | O11—C12—H12C | 110 |
C6—C5—H5A | 109 | H12A—C12—H12C | 110 |
C4a—C5—H5B | 109 | H12B—C12—H12C | 110 |
C6—C5—H5B | 109 | O13—C13—O14 | 124.22 (10) |
H5A—C5—H5B | 108 | O13—C13—C1 | 123.17 (9) |
C7—C6—C5 | 113.01 (8) | O14—C13—C1 | 112.57 (8) |
C7—C6—H6A | 109 | C13—O14—C15 | 115.85 (9) |
C5—C6—H6A | 109 | O14—C15—H15A | 110 |
C7—C6—H6B | 109 | O14—C15—H15B | 110 |
C5—C6—H6B | 109 | H15A—C15—H15B | 110 |
H6A—C6—H6B | 108 | O14—C15—H15C | 110 |
O7—C7—C6 | 122.44 (10) | H15A—C15—H15C | 110 |
O7—C7—C8 | 118.34 (10) | H15B—C15—H15C | 110 |
C6—C7—C8 | 119.10 (9) | C8—O16—C17 | 112.14 (8) |
O16—C8—C7 | 113.30 (8) | O16—C17—H17A | 110 |
O16—C8—C9 | 109.61 (8) | O16—C17—H17B | 110 |
C7—C8—C9 | 109.19 (8) | H17A—C17—H17B | 110 |
O16—C8—H8 | 108 | O16—C17—H17C | 110 |
C7—C8—H8 | 108 | H17A—C17—H17C | 110 |
C9—C8—H8 | 108 | H17B—C17—H17C | 110 |
| | | |
C13—C1—C2—C10 | −3.19 (16) | C4—C4a—C9a—C9 | 105.06 (11) |
C9a—C1—C2—C10 | 175.18 (9) | C5—C4a—C9a—C9 | −74.67 (11) |
C13—C1—C2—C3 | 179.53 (10) | C2—C1—C9a—C4a | 16.91 (13) |
C9a—C1—C2—C3 | −2.11 (16) | C13—C1—C9a—C4a | −164.60 (8) |
C1—C2—C3—C4 | −13.44 (16) | C2—C1—C9a—C9 | −108.39 (11) |
C10—C2—C3—C4 | 169.04 (9) | C13—C1—C9a—C9 | 70.10 (10) |
C5—C4a—C4—C3 | −179.04 (10) | C8—C9—C9a—C4a | 52.83 (12) |
C9a—C4a—C4—C3 | 1.25 (17) | C8—C9—C9a—C1 | 177.00 (8) |
C2—C3—C4—C4a | 13.99 (16) | C1—C2—C10—O10 | −130.12 (11) |
C4—C4a—C5—C6 | −92.00 (12) | C3—C2—C10—O10 | 47.37 (14) |
C9a—C4a—C5—C6 | 87.73 (11) | C1—C2—C10—O11 | 52.72 (13) |
C4a—C5—C6—C7 | −32.42 (12) | C3—C2—C10—O11 | −129.80 (10) |
C5—C6—C7—O7 | 127.29 (11) | O10—C10—O11—C12 | 6.96 (15) |
C5—C6—C7—C8 | −48.80 (12) | C2—C10—O11—C12 | −175.91 (9) |
O7—C7—C8—O16 | 153.63 (9) | C2—C1—C13—O13 | −134.76 (12) |
C6—C7—C8—O16 | −30.12 (12) | C9a—C1—C13—O13 | 46.75 (14) |
O7—C7—C8—C9 | −83.90 (11) | C2—C1—C13—O14 | 47.41 (13) |
C6—C7—C8—C9 | 92.34 (11) | C9a—C1—C13—O14 | −131.09 (9) |
O16—C8—C9—C9a | 57.17 (11) | O13—C13—O14—C15 | 7.69 (16) |
C7—C8—C9—C9a | −67.48 (11) | C1—C13—O14—C15 | −174.50 (9) |
C4—C4a—C9a—C1 | −16.39 (14) | C7—C8—O16—C17 | −75.50 (11) |
C5—C4a—C9a—C1 | 163.88 (8) | C9—C8—O16—C17 | 162.26 (8) |
(II) dimethyl (4aS*,6
R*)-6-methoxy-7-oxo-4a,5,6,7,8,9-hexahydro-2
H-
benzocycloheptene-3,4-dicarboxylate
top
Crystal data top
C16H20O6 | F(000) = 1312 |
Mr = 308.32 | Dx = 1.328 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 27.666 (9) Å | Cell parameters from 885 reflections |
b = 5.066 (2) Å | θ = 3.1–18.1° |
c = 22.793 (7) Å | µ = 0.10 mm−1 |
β = 105.149 (5)° | T = 150 K |
V = 3084 (2) Å3 | Block from hexagonal plate, colourless |
Z = 8 | 0.50 × 0.45 × 0.25 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2967 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.058 |
Graphite monochromator | θmax = 28.7°, θmin = 1.9° |
ω scans | h = −37→35 |
10535 measured reflections | k = −4→6 |
3584 independent reflections | l = −27→29 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0412P)2 + 8.3P] where P = (Fo2 + 2Fc2)/3 |
3584 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C16H20O6 | V = 3084 (2) Å3 |
Mr = 308.32 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.666 (9) Å | µ = 0.10 mm−1 |
b = 5.066 (2) Å | T = 150 K |
c = 22.793 (7) Å | 0.50 × 0.45 × 0.25 mm |
β = 105.149 (5)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2967 reflections with I > 2σ(I) |
10535 measured reflections | Rint = 0.058 |
3584 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.37 e Å−3 |
3584 reflections | Δρmin = −0.19 e Å−3 |
199 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 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.13422 (6) | 0.0558 (3) | 0.23845 (8) | 0.0219 (4) | |
C2 | 0.16556 (6) | −0.1087 (3) | 0.22076 (8) | 0.0227 (4) | |
C3 | 0.20772 (6) | −0.2482 (4) | 0.26506 (9) | 0.0247 (4) | |
H3A | 0.1983 | −0.4352 | 0.2683 | 0.030* | |
H3B | 0.2379 | −0.2445 | 0.2493 | 0.030* | |
C4 | 0.22005 (7) | −0.1257 (4) | 0.32688 (9) | 0.0269 (4) | |
H4A | 0.2512 | −0.1680 | 0.3545 | 0.032* | |
C4a | 0.18963 (6) | 0.0393 (4) | 0.34516 (8) | 0.0246 (4) | |
C5 | 0.20257 (7) | 0.1559 (4) | 0.40837 (9) | 0.0327 (5) | |
H5A | 0.1855 | 0.3283 | 0.4073 | 0.039* | |
H5B | 0.2391 | 0.1873 | 0.4219 | 0.039* | |
C6 | 0.18702 (7) | −0.0257 (5) | 0.45417 (9) | 0.0374 (5) | |
H6A | 0.2119 | −0.1700 | 0.4652 | 0.045* | |
H6B | 0.1885 | 0.0769 | 0.4916 | 0.045* | |
O7 | 0.12693 (6) | −0.3669 (3) | 0.44837 (7) | 0.0400 (4) | |
C7 | 0.13553 (7) | −0.1467 (4) | 0.43262 (8) | 0.0276 (4) | |
C8 | 0.09399 (6) | 0.0128 (4) | 0.38959 (8) | 0.0230 (4) | |
H8A | 0.0982 | 0.2048 | 0.3998 | 0.028* | |
C9a | 0.13862 (6) | 0.1112 (4) | 0.30472 (8) | 0.0217 (4) | |
H9 | 0.1338 | 0.3052 | 0.3090 | 0.026* | |
C9 | 0.09571 (6) | −0.0321 (4) | 0.32386 (8) | 0.0220 (4) | |
H9A | 0.0634 | 0.0261 | 0.2966 | 0.026* | |
H9B | 0.0989 | −0.2240 | 0.3175 | 0.026* | |
C10 | 0.16304 (6) | −0.1652 (4) | 0.15539 (9) | 0.0243 (4) | |
O10 | 0.18388 (5) | −0.0343 (3) | 0.12509 (7) | 0.0341 (3) | |
O11 | 0.13893 (5) | −0.3903 (3) | 0.13737 (6) | 0.0292 (3) | |
C12 | 0.13454 (8) | −0.4625 (4) | 0.07486 (9) | 0.0331 (4) | |
H12A | 0.1163 | −0.6297 | 0.0658 | 0.050* | |
H12B | 0.1680 | −0.4827 | 0.0685 | 0.050* | |
H12C | 0.1163 | −0.3242 | 0.0479 | 0.050* | |
O13 | 0.07926 (5) | 0.1123 (3) | 0.13907 (6) | 0.0288 (3) | |
C13 | 0.09221 (6) | 0.1790 (4) | 0.19162 (9) | 0.0237 (4) | |
O14 | 0.06994 (5) | 0.3708 (3) | 0.21563 (6) | 0.0294 (3) | |
C15 | 0.02879 (7) | 0.5047 (4) | 0.17351 (10) | 0.0342 (5) | |
H15A | 0.0151 | 0.6406 | 0.1953 | 0.051* | |
H15B | 0.0025 | 0.3766 | 0.1557 | 0.051* | |
H15C | 0.0409 | 0.5873 | 0.1412 | 0.051* | |
O16 | 0.04589 (5) | −0.0722 (3) | 0.39226 (6) | 0.0315 (3) | |
C17 | 0.03486 (8) | −0.0094 (5) | 0.44818 (9) | 0.0402 (5) | |
H17A | 0.0013 | −0.0736 | 0.4474 | 0.060* | |
H17B | 0.0362 | 0.1824 | 0.4540 | 0.060* | |
H17C | 0.0595 | −0.0936 | 0.4817 | 0.060* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0220 (8) | 0.0152 (8) | 0.0297 (9) | −0.0028 (6) | 0.0087 (7) | 0.0002 (7) |
C2 | 0.0231 (8) | 0.0157 (8) | 0.0308 (9) | −0.0043 (7) | 0.0100 (7) | −0.0006 (7) |
C3 | 0.0229 (8) | 0.0186 (8) | 0.0347 (10) | 0.0018 (7) | 0.0114 (7) | −0.0009 (8) |
C4 | 0.0201 (8) | 0.0263 (9) | 0.0329 (10) | 0.0012 (7) | 0.0044 (7) | −0.0005 (8) |
C4a | 0.0197 (8) | 0.0220 (9) | 0.0308 (9) | −0.0034 (7) | 0.0042 (7) | −0.0039 (7) |
C5 | 0.0204 (8) | 0.0376 (11) | 0.0367 (11) | −0.0002 (8) | 0.0014 (8) | −0.0144 (9) |
C6 | 0.0277 (10) | 0.0518 (14) | 0.0282 (10) | 0.0071 (9) | −0.0006 (8) | −0.0074 (10) |
O7 | 0.0576 (10) | 0.0290 (8) | 0.0345 (8) | 0.0094 (7) | 0.0143 (7) | 0.0038 (6) |
C7 | 0.0337 (10) | 0.0274 (10) | 0.0217 (9) | 0.0066 (8) | 0.0075 (7) | −0.0048 (7) |
C8 | 0.0208 (8) | 0.0216 (9) | 0.0265 (9) | −0.0007 (7) | 0.0058 (7) | −0.0037 (7) |
C9a | 0.0201 (8) | 0.0152 (8) | 0.0300 (9) | 0.0017 (6) | 0.0068 (7) | −0.0023 (7) |
C9 | 0.0203 (8) | 0.0214 (9) | 0.0239 (8) | −0.0016 (7) | 0.0051 (7) | −0.0012 (7) |
C10 | 0.0239 (8) | 0.0176 (8) | 0.0331 (10) | 0.0005 (7) | 0.0106 (7) | −0.0005 (7) |
O10 | 0.0361 (7) | 0.0318 (8) | 0.0394 (8) | −0.0100 (6) | 0.0188 (6) | 0.0000 (6) |
O11 | 0.0420 (8) | 0.0204 (7) | 0.0282 (7) | −0.0082 (6) | 0.0145 (6) | −0.0037 (5) |
C12 | 0.0470 (12) | 0.0273 (10) | 0.0257 (9) | −0.0047 (9) | 0.0108 (8) | −0.0018 (8) |
O13 | 0.0279 (6) | 0.0263 (7) | 0.0306 (7) | −0.0028 (6) | 0.0046 (5) | −0.0004 (6) |
C13 | 0.0219 (8) | 0.0190 (9) | 0.0315 (9) | −0.0024 (7) | 0.0094 (7) | 0.0027 (7) |
O14 | 0.0293 (7) | 0.0266 (7) | 0.0323 (7) | 0.0094 (6) | 0.0080 (5) | 0.0037 (6) |
C15 | 0.0294 (9) | 0.0324 (11) | 0.0399 (11) | 0.0089 (8) | 0.0077 (8) | 0.0083 (9) |
O16 | 0.0253 (6) | 0.0459 (9) | 0.0250 (7) | −0.0082 (6) | 0.0098 (5) | −0.0067 (6) |
C17 | 0.0311 (10) | 0.0643 (16) | 0.0278 (10) | −0.0006 (10) | 0.0122 (8) | −0.0070 (10) |
Geometric parameters (Å, º) top
C1—C2 | 1.338 (2) | C8—H8A | 1.000 |
C1—C13 | 1.494 (3) | C9a—C9 | 1.548 (2) |
C1—C9a | 1.510 (2) | C9a—H9 | 1.000 |
C2—C10 | 1.501 (3) | C9—H9A | 0.990 |
C2—C3 | 1.504 (3) | C9—H9B | 0.990 |
C3—C4 | 1.495 (3) | C10—O10 | 1.207 (2) |
C3—H3A | 0.990 | C10—O11 | 1.331 (2) |
C3—H3B | 0.990 | O11—C12 | 1.445 (2) |
C4—C4a | 1.328 (3) | C12—H12A | 0.980 |
C4—H4A | 0.950 | C12—H12B | 0.980 |
C4a—C5 | 1.511 (3) | C12—H12C | 0.980 |
C4a—C9a | 1.515 (2) | O13—C13 | 1.205 (2) |
C5—C6 | 1.535 (3) | C13—O14 | 1.342 (2) |
C5—H5A | 0.990 | O14—C15 | 1.451 (2) |
C5—H5B | 0.990 | C15—H15A | 0.980 |
C6—C7 | 1.510 (3) | C15—H15B | 0.980 |
C6—H6A | 0.990 | C15—H15C | 0.980 |
C6—H6B | 0.990 | O16—C17 | 1.422 (2) |
O7—C7 | 1.214 (3) | C17—H17A | 0.980 |
C7—C8 | 1.532 (3) | C17—H17B | 0.980 |
C8—O16 | 1.415 (2) | C17—H17C | 0.980 |
C8—C9 | 1.528 (2) | | |
| | | |
C2—C1—C13 | 119.29 (17) | C1—C9a—C4a | 112.51 (14) |
C2—C1—C9a | 121.86 (16) | C1—C9a—C9 | 109.12 (14) |
C13—C1—C9a | 118.80 (15) | C4a—C9a—C9 | 112.15 (15) |
C1—C2—C10 | 123.51 (17) | C1—C9a—H9 | 108 |
C1—C2—C3 | 122.67 (17) | C4a—C9a—H9 | 108 |
C10—C2—C3 | 113.80 (15) | C9—C9a—H9 | 108 |
C4—C3—C2 | 112.56 (15) | C8—C9—C9a | 115.40 (14) |
C4—C3—H3A | 109 | C8—C9—H9A | 108 |
C2—C3—H3A | 109 | C9a—C9—H9A | 108 |
C4—C3—H3B | 109 | C8—C9—H9B | 108 |
C2—C3—H3B | 109 | C9a—C9—H9B | 108 |
H3A—C3—H3B | 108 | H9A—C9—H9B | 108 |
C4a—C4—C3 | 123.34 (17) | O10—C10—O11 | 124.75 (18) |
C4a—C4—H4A | 118 | O10—C10—C2 | 123.93 (17) |
C3—C4—H4A | 118 | O11—C10—C2 | 111.05 (15) |
C4—C4a—C5 | 122.24 (17) | C10—O11—C12 | 115.30 (15) |
C4—C4a—C9a | 121.77 (17) | O11—C12—H12A | 110 |
C5—C4a—C9a | 115.92 (15) | O11—C12—H12B | 110 |
C4a—C5—C6 | 112.05 (17) | H12A—C12—H12B | 110 |
C4a—C5—H5A | 109 | O11—C12—H12C | 110 |
C6—C5—H5A | 109 | H12A—C12—H12C | 110 |
C4a—C5—H5B | 109 | H12B—C12—H12C | 110 |
C6—C5—H5B | 109 | O13—C13—O14 | 124.02 (17) |
H5A—C5—H5B | 108 | O13—C13—C1 | 124.53 (17) |
C7—C6—C5 | 115.50 (16) | O14—C13—C1 | 111.44 (16) |
C7—C6—H6A | 108 | C13—O14—C15 | 115.68 (15) |
C5—C6—H6A | 108 | O14—C15—H15A | 110 |
C7—C6—H6B | 108 | O14—C15—H15B | 110 |
C5—C6—H6B | 108 | H15A—C15—H15B | 110 |
H6A—C6—H6B | 108 | O14—C15—H15C | 110 |
O7—C7—C6 | 121.20 (19) | H15A—C15—H15C | 110 |
O7—C7—C8 | 120.12 (18) | H15B—C15—H15C | 110 |
C6—C7—C8 | 118.68 (18) | C8—O16—C17 | 113.25 (15) |
O16—C8—C9 | 105.51 (13) | O16—C17—H17A | 110 |
O16—C8—C7 | 111.62 (16) | O16—C17—H17B | 110 |
C9—C8—C7 | 109.79 (14) | H17A—C17—H17B | 110 |
O16—C8—H8A | 110 | O16—C17—H17C | 110 |
C9—C8—H8A | 110 | H17A—C17—H17C | 110 |
C7—C8—H8A | 110 | H17B—C17—H17C | 110 |
| | | |
C13—C1—C2—C10 | 4.0 (3) | C4—C4a—C9a—C1 | −19.5 (3) |
C9a—C1—C2—C10 | −178.85 (15) | C5—C4a—C9a—C1 | 163.42 (16) |
C13—C1—C2—C3 | −177.85 (15) | C4—C4a—C9a—C9 | 104.0 (2) |
C9a—C1—C2—C3 | −0.7 (3) | C5—C4a—C9a—C9 | −73.1 (2) |
C1—C2—C3—C4 | −17.1 (2) | O16—C8—C9—C9a | 164.57 (15) |
C10—C2—C3—C4 | 161.19 (15) | C7—C8—C9—C9a | −75.0 (2) |
C2—C3—C4—C4a | 16.6 (3) | C1—C9a—C9—C8 | −177.97 (15) |
C3—C4—C4a—C5 | 178.70 (18) | C4a—C9a—C9—C8 | 56.7 (2) |
C3—C4—C4a—C9a | 1.8 (3) | C1—C2—C10—O10 | 87.2 (2) |
C4—C4a—C5—C6 | −86.3 (2) | C3—C2—C10—O10 | −91.1 (2) |
C9a—C4a—C5—C6 | 90.8 (2) | C1—C2—C10—O11 | −98.6 (2) |
C4a—C5—C6—C7 | −44.3 (2) | C3—C2—C10—O11 | 83.14 (18) |
C5—C6—C7—O7 | 146.00 (19) | O10—C10—O11—C12 | −5.8 (3) |
C5—C6—C7—C8 | −33.4 (3) | C2—C10—O11—C12 | −179.95 (16) |
O7—C7—C8—O16 | 23.7 (2) | C2—C1—C13—O13 | 11.8 (3) |
C6—C7—C8—O16 | −156.95 (16) | C9a—C1—C13—O13 | −165.38 (17) |
O7—C7—C8—C9 | −93.0 (2) | C2—C1—C13—O14 | −169.36 (15) |
C6—C7—C8—C9 | 86.4 (2) | C9a—C1—C13—O14 | 13.4 (2) |
C2—C1—C9a—C4a | 18.9 (2) | O13—C13—O14—C15 | −1.7 (3) |
C13—C1—C9a—C4a | −163.99 (15) | C1—C13—O14—C15 | 179.47 (15) |
C2—C1—C9a—C9 | −106.25 (19) | C9—C8—O16—C17 | −171.37 (17) |
C13—C1—C9a—C9 | 70.87 (19) | C7—C8—O16—C17 | 69.4 (2) |
(III) (3aS*,9
R*,10aS*,10bR*)-9-methoxy-1,3a,4,6,7,8,9,10,10
a,10
b-decahydro-2-oxa- 3
H-cyclohepta[
e]inden-1,3,8-trione
top
Crystal data top
C14H16O5 | F(000) = 560 |
Mr = 264.27 | Dx = 1.418 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.1076 (19) Å | Cell parameters from 5832 reflections |
b = 11.3501 (15) Å | θ = 2.3–28.6° |
c = 7.7762 (10) Å | µ = 0.11 mm−1 |
β = 96.280 (2)° | T = 150 K |
V = 1237.7 (3) Å3 | Block, colourless |
Z = 4 | 0.42 × 0.40 × 0.31 mm |
Data collection top
Bruker SMART1000 CCD area-detector diffractometer | 2437 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 28.6°, θmin = 2.3° |
ω scans | h = −18→18 |
10858 measured reflections | k = −14→14 |
3047 independent reflections | l = −10→10 |
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)] = 0.035 | Hydrogen site location: geometrically placed, Me from delta-F |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0563P)2 + 0.2015P] where P = (Fo2 + 2Fc2)/3 |
2896 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C14H16O5 | V = 1237.7 (3) Å3 |
Mr = 264.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.1076 (19) Å | µ = 0.11 mm−1 |
b = 11.3501 (15) Å | T = 150 K |
c = 7.7762 (10) Å | 0.42 × 0.40 × 0.31 mm |
β = 96.280 (2)° | |
Data collection top
Bruker SMART1000 CCD area-detector diffractometer | 2437 reflections with I > 2σ(I) |
10858 measured reflections | Rint = 0.033 |
3047 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.30 e Å−3 |
2896 reflections | Δρmin = −0.16 e Å−3 |
173 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 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.77569 (7) | 0.23368 (8) | −0.02449 (12) | 0.0432 (3) | |
C1 | 0.72962 (9) | 0.29970 (10) | −0.12021 (14) | 0.0275 (2) | |
O2 | 0.63996 (6) | 0.26549 (7) | −0.19201 (11) | 0.0327 (2) | |
C3A | 0.66626 (8) | 0.45603 (10) | −0.30640 (14) | 0.0252 (2) | |
H3A | 0.6851 | 0.4626 | −0.4263 | 0.030* | |
O3 | 0.51962 (6) | 0.34080 (9) | −0.36971 (13) | 0.0414 (2) | |
C3 | 0.59817 (8) | 0.35389 (10) | −0.29958 (15) | 0.0284 (3) | |
C4 | 0.61806 (9) | 0.57142 (10) | −0.25996 (15) | 0.0316 (3) | |
H4A | 0.6543 | 0.6393 | −0.2989 | 0.038* | |
H4B | 0.5526 | 0.5748 | −0.3203 | 0.038* | |
C5A | 0.68903 (8) | 0.54864 (9) | 0.04225 (14) | 0.0235 (2) | |
C5 | 0.61415 (8) | 0.57905 (10) | −0.06857 (16) | 0.0289 (3) | |
H5 | 0.5575 | 0.6059 | −0.0255 | 0.035* | |
C6 | 0.68550 (8) | 0.55716 (11) | 0.23423 (15) | 0.0295 (3) | |
H6A | 0.6959 | 0.4777 | 0.2855 | 0.035* | |
H6B | 0.6210 | 0.5834 | 0.2562 | 0.035* | |
C7 | 0.76006 (9) | 0.64285 (11) | 0.32640 (15) | 0.0304 (3) | |
H7A | 0.7699 | 0.7105 | 0.2499 | 0.036* | |
H7B | 0.7370 | 0.6734 | 0.4336 | 0.036* | |
O8 | 0.87525 (7) | 0.53754 (9) | 0.51270 (11) | 0.0410 (2) | |
C8 | 0.85214 (8) | 0.57778 (10) | 0.36936 (14) | 0.0272 (2) | |
C9 | 0.91203 (8) | 0.55270 (10) | 0.22123 (14) | 0.0243 (2) | |
H9 | 0.9746 | 0.5191 | 0.2709 | 0.029* | |
C10b | 0.75405 (7) | 0.42122 (9) | −0.18265 (13) | 0.0218 (2) | |
H10B | 0.8099 | 0.4141 | −0.2509 | 0.026* | |
C10 | 0.86242 (8) | 0.46309 (9) | 0.09406 (14) | 0.0233 (2) | |
H10C | 0.8376 | 0.3983 | 0.1617 | 0.028* | |
H10D | 0.9109 | 0.4288 | 0.0258 | 0.028* | |
C10a | 0.77980 (7) | 0.51041 (9) | −0.03285 (13) | 0.0202 (2) | |
H10A | 0.8048 | 0.5823 | −0.0872 | 0.024* | |
O11 | 0.92977 (6) | 0.65651 (7) | 0.12697 (10) | 0.02546 (19) | |
C12 | 0.98894 (8) | 0.73858 (11) | 0.22894 (15) | 0.0289 (3) | |
H12A | 0.9524 | 0.7746 | 0.3154 | 0.043* | |
H12B | 1.0105 | 0.8001 | 0.1538 | 0.043* | |
H12C | 1.0444 | 0.6973 | 0.2874 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0579 (6) | 0.0245 (4) | 0.0426 (5) | −0.0030 (4) | −0.0142 (5) | 0.0061 (4) |
C1 | 0.0338 (6) | 0.0243 (5) | 0.0240 (5) | −0.0022 (4) | 0.0012 (4) | −0.0015 (4) |
O2 | 0.0340 (5) | 0.0278 (4) | 0.0360 (5) | −0.0084 (3) | 0.0021 (4) | 0.0012 (3) |
C3A | 0.0275 (5) | 0.0285 (6) | 0.0190 (5) | −0.0037 (4) | −0.0004 (4) | 0.0015 (4) |
O3 | 0.0274 (5) | 0.0442 (5) | 0.0509 (6) | −0.0045 (4) | −0.0039 (4) | −0.0094 (4) |
C3 | 0.0278 (6) | 0.0304 (6) | 0.0271 (6) | −0.0021 (4) | 0.0033 (4) | −0.0051 (4) |
C4 | 0.0350 (6) | 0.0272 (6) | 0.0299 (6) | 0.0023 (5) | −0.0092 (5) | 0.0039 (5) |
C5A | 0.0248 (5) | 0.0218 (5) | 0.0239 (5) | 0.0013 (4) | 0.0035 (4) | −0.0010 (4) |
C5 | 0.0258 (5) | 0.0264 (6) | 0.0337 (6) | 0.0050 (4) | 0.0006 (5) | −0.0018 (5) |
C6 | 0.0264 (5) | 0.0376 (7) | 0.0255 (5) | 0.0009 (5) | 0.0075 (4) | −0.0021 (5) |
C7 | 0.0356 (6) | 0.0323 (6) | 0.0240 (5) | 0.0014 (5) | 0.0063 (5) | −0.0060 (4) |
O8 | 0.0438 (5) | 0.0540 (6) | 0.0234 (4) | −0.0127 (4) | −0.0042 (4) | 0.0112 (4) |
C8 | 0.0330 (6) | 0.0259 (5) | 0.0216 (5) | −0.0080 (4) | −0.0015 (4) | 0.0002 (4) |
C9 | 0.0250 (5) | 0.0231 (5) | 0.0237 (5) | 0.0007 (4) | −0.0028 (4) | 0.0023 (4) |
C10b | 0.0236 (5) | 0.0228 (5) | 0.0191 (5) | −0.0011 (4) | 0.0027 (4) | 0.0005 (4) |
C10 | 0.0230 (5) | 0.0216 (5) | 0.0247 (5) | 0.0029 (4) | −0.0009 (4) | −0.0005 (4) |
C10a | 0.0215 (5) | 0.0195 (5) | 0.0192 (5) | 0.0001 (4) | 0.0009 (4) | 0.0010 (4) |
O11 | 0.0286 (4) | 0.0260 (4) | 0.0211 (4) | −0.0056 (3) | −0.0006 (3) | 0.0003 (3) |
C12 | 0.0296 (6) | 0.0283 (6) | 0.0279 (6) | −0.0060 (4) | −0.0004 (5) | −0.0038 (4) |
Geometric parameters (Å, º) top
O1—C1 | 1.1967 (14) | C7—C8 | 1.4998 (17) |
C1—O2 | 1.3813 (14) | C7—H7A | 0.990 |
C1—C10b | 1.5144 (15) | C7—H7B | 0.990 |
O2—C3 | 1.3950 (15) | O8—C8 | 1.2156 (14) |
C3A—C3 | 1.5102 (16) | C8—C9 | 1.5280 (16) |
C3A—C10b | 1.5348 (15) | C9—O11 | 1.4242 (13) |
C3A—C4 | 1.5368 (17) | C9—C10 | 1.5332 (15) |
C3A—H3A | 1.000 | C9—H9 | 1.000 |
O3—C3 | 1.1896 (14) | C10b—C10a | 1.5561 (14) |
C4—C5 | 1.4979 (17) | C10b—H10B | 1.000 |
C4—H4A | 0.990 | C10—C10a | 1.5392 (14) |
C4—H4B | 0.990 | C10—H10C | 0.990 |
C5A—C5 | 1.3336 (16) | C10—H10D | 0.990 |
C5A—C6 | 1.5023 (16) | C10a—H10A | 1.000 |
C5A—C10a | 1.5273 (14) | O11—C12 | 1.4311 (13) |
C5—H5 | 0.950 | C12—H12A | 0.980 |
C6—C7 | 1.5495 (17) | C12—H12B | 0.980 |
C6—H6A | 0.990 | C12—H12C | 0.980 |
C6—H6B | 0.990 | | |
| | | |
O1—C1—O2 | 119.10 (11) | H7A—C7—H7B | 108 |
O1—C1—C10b | 129.99 (11) | O8—C8—C7 | 121.88 (11) |
O2—C1—C10b | 110.91 (9) | O8—C8—C9 | 120.42 (11) |
C1—O2—C3 | 110.40 (9) | C7—C8—C9 | 117.43 (9) |
C3—C3A—C10b | 104.66 (9) | O11—C9—C8 | 112.13 (9) |
C3—C3A—C4 | 110.27 (10) | O11—C9—C10 | 108.09 (8) |
C10b—C3A—C4 | 114.81 (9) | C8—C9—C10 | 111.03 (9) |
C3—C3A—H3A | 109 | O11—C9—H9 | 109 |
C10b—C3A—H3A | 109 | C8—C9—H9 | 109 |
C4—C3A—H3A | 109 | C10—C9—H9 | 109 |
O3—C3—O2 | 119.77 (11) | C1—C10b—C3A | 103.84 (9) |
O3—C3—C3A | 130.09 (12) | C1—C10b—C10a | 113.28 (8) |
O2—C3—C3A | 110.15 (9) | C3A—C10b—C10a | 114.09 (9) |
C5—C4—C3A | 110.37 (9) | C1—C10b—H10B | 109 |
C5—C4—H4A | 110 | C3A—C10b—H10B | 109 |
C3A—C4—H4A | 110 | C10a—C10b—H10B | 109 |
C5—C4—H4B | 110 | C9—C10—C10a | 116.25 (9) |
C3A—C4—H4B | 110 | C9—C10—H10C | 108 |
H4A—C4—H4B | 108 | C10a—C10—H10C | 108 |
C5—C5A—C6 | 121.03 (10) | C9—C10—H10D | 108 |
C5—C5A—C10a | 117.67 (10) | C10a—C10—H10D | 108 |
C6—C5A—C10a | 121.24 (9) | H10C—C10—H10D | 107 |
C5A—C5—C4 | 120.96 (11) | C5A—C10a—C10 | 117.50 (9) |
C5A—C5—H5 | 120 | C5A—C10a—C10b | 109.52 (8) |
C4—C5—H5 | 120 | C10—C10a—C10b | 110.57 (8) |
C5A—C6—C7 | 113.92 (10) | C5A—C10a—H10A | 106 |
C5A—C6—H6A | 109 | C10—C10a—H10A | 106 |
C7—C6—H6A | 109 | C10b—C10a—H10A | 106 |
C5A—C6—H6B | 109 | C9—O11—C12 | 112.21 (8) |
C7—C6—H6B | 109 | O11—C12—H12A | 110 |
H6A—C6—H6B | 108 | O11—C12—H12B | 110 |
C8—C7—C6 | 108.76 (10) | H12A—C12—H12B | 110 |
C8—C7—H7A | 110 | O11—C12—H12C | 110 |
C6—C7—H7A | 110 | H12A—C12—H12C | 110 |
C8—C7—H7B | 110 | H12B—C12—H12C | 110 |
C6—C7—H7B | 110 | | |
| | | |
O1—C1—O2—C3 | −179.81 (11) | O1—C1—C10b—C3A | 178.24 (13) |
C10b—C1—O2—C3 | −0.61 (13) | O2—C1—C10b—C3A | −0.86 (12) |
C1—O2—C3—O3 | −178.30 (11) | O1—C1—C10b—C10a | −57.46 (16) |
C1—O2—C3—C3A | 1.88 (13) | O2—C1—C10b—C10a | 123.45 (10) |
C10b—C3A—C3—O3 | 177.88 (12) | C3—C3A—C10b—C1 | 1.84 (11) |
C4—C3A—C3—O3 | 53.89 (16) | C4—C3A—C10b—C1 | 122.87 (10) |
C10b—C3A—C3—O2 | −2.33 (12) | C3—C3A—C10b—C10a | −121.94 (10) |
C4—C3A—C3—O2 | −126.31 (10) | C4—C3A—C10b—C10a | −0.90 (13) |
C3—C3A—C4—C5 | 76.60 (12) | O11—C9—C10—C10a | −45.97 (12) |
C10b—C3A—C4—C5 | −41.30 (13) | C8—C9—C10—C10a | 77.39 (12) |
C6—C5A—C5—C4 | 179.50 (11) | C5—C5A—C10a—C10 | −173.76 (10) |
C10a—C5A—C5—C4 | 2.29 (16) | C6—C5A—C10a—C10 | 9.04 (14) |
C3A—C4—C5—C5A | 43.06 (15) | C5—C5A—C10a—C10b | −46.54 (13) |
C5—C5A—C6—C7 | −118.78 (12) | C6—C5A—C10a—C10b | 136.25 (10) |
C10a—C5A—C6—C7 | 58.34 (14) | C9—C10—C10a—C5A | −68.11 (12) |
C5A—C6—C7—C8 | −85.84 (12) | C9—C10—C10a—C10b | 165.18 (9) |
C6—C7—C8—O8 | −98.50 (13) | C1—C10b—C10a—C5A | −74.89 (11) |
C6—C7—C8—C9 | 75.50 (12) | C3A—C10b—C10a—C5A | 43.64 (12) |
O8—C8—C9—O11 | −133.25 (11) | C1—C10b—C10a—C10 | 56.13 (11) |
C7—C8—C9—O11 | 52.65 (13) | C3A—C10b—C10a—C10 | 174.66 (9) |
O8—C8—C9—C10 | 105.73 (12) | C8—C9—O11—C12 | 66.33 (11) |
C7—C8—C9—C10 | −68.37 (12) | C10—C9—O11—C12 | −170.97 (9) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···O3i | 0.99 | 2.42 | 3.3900 (16) | 168 |
Symmetry code: (i) −x+1, −y+1, −z. |
(IV) (1
S*,2
R*,9
S*,10aR*)-9-methoxy-8-oxo-1,2,3,5,6,7,8,9,10,10
a-decahydro- benzocyclooctene-1,2-dicarboxylic acid
top
Crystal data top
C15H20O6 | Dx = 1.421 Mg m−3 |
Mr = 296.31 | Synchrotron radiation, λ = 0.6892 Å |
Orthorhombic, Pbca | Cell parameters from 5549 reflections |
a = 14.676 (2) Å | θ = 3.2–29.1° |
b = 9.967 (2) Å | µ = 0.11 mm−1 |
c = 18.937 (3) Å | T = 150 K |
V = 2770.0 (8) Å3 | Tablet, colourless |
Z = 8 | 0.06 × 0.05 × 0.01 mm |
F(000) = 1264 | |
Data collection top
Bruker SMART CCD area-detector on SRS Station 9.8 diffractometer | 1769 reflections with I > 2σ(I) |
Radiation source: synchrotron storage ring | Rint = 0.136 |
Germanium monochromator | θmax = 26.0°, θmin = 2.6° |
0.15 degree ω scans | h = −20→17 |
18905 measured reflections | k = −14→12 |
2715 independent reflections | l = −25→24 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.084 | H-atom parameters constrained |
wR(F2) = 0.231 | w = 1/[σ2(Fo2) + (0.123P)2 + 1.776P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2715 reflections | Δρmax = 0.53 e Å−3 |
192 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | |
Crystal data top
C15H20O6 | V = 2770.0 (8) Å3 |
Mr = 296.31 | Z = 8 |
Orthorhombic, Pbca | Synchrotron radiation, λ = 0.6892 Å |
a = 14.676 (2) Å | µ = 0.11 mm−1 |
b = 9.967 (2) Å | T = 150 K |
c = 18.937 (3) Å | 0.06 × 0.05 × 0.01 mm |
Data collection top
Bruker SMART CCD area-detector on SRS Station 9.8 diffractometer | 1769 reflections with I > 2σ(I) |
18905 measured reflections | Rint = 0.136 |
2715 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.084 | 0 restraints |
wR(F2) = 0.231 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.53 e Å−3 |
2715 reflections | Δρmin = −0.29 e Å−3 |
192 parameters | |
Special details top
Experimental. The Daresbury Laboratory SRS was the X-ray source. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0734 (2) | 0.8207 (3) | 0.69360 (17) | 0.0230 (8) | |
H1 | 0.0091 | 0.8484 | 0.7030 | 0.028* | |
C2 | 0.1182 (2) | 0.9317 (4) | 0.65095 (18) | 0.0264 (8) | |
H2 | 0.1138 | 1.0150 | 0.6802 | 0.032* | |
C3 | 0.2209 (2) | 0.9072 (4) | 0.6379 (2) | 0.0319 (9) | |
H3A | 0.2286 | 0.8571 | 0.5931 | 0.038* | |
H3B | 0.2521 | 0.9947 | 0.6326 | 0.038* | |
C4 | 0.2649 (3) | 0.8303 (4) | 0.6964 (2) | 0.0347 (10) | |
H4 | 0.3283 | 0.8130 | 0.6917 | 0.042* | |
C4a | 0.2247 (2) | 0.7834 (4) | 0.75456 (19) | 0.0291 (9) | |
C5 | 0.2813 (3) | 0.7076 (4) | 0.8080 (2) | 0.0355 (10) | |
H5A | 0.3404 | 0.6851 | 0.7858 | 0.043* | |
H5B | 0.2499 | 0.6220 | 0.8185 | 0.043* | |
C6 | 0.3006 (3) | 0.7775 (5) | 0.8774 (2) | 0.0353 (10) | |
H6A | 0.3115 | 0.8737 | 0.8675 | 0.042* | |
H6B | 0.3577 | 0.7402 | 0.8971 | 0.042* | |
C7 | 0.2260 (3) | 0.7670 (5) | 0.9343 (2) | 0.0346 (10) | |
H7A | 0.2080 | 0.6718 | 0.9396 | 0.042* | |
H7B | 0.2512 | 0.7976 | 0.9800 | 0.042* | |
C8 | 0.1430 (3) | 0.8488 (4) | 0.91697 (17) | 0.0269 (8) | |
O8 | 0.1430 (2) | 0.9700 (3) | 0.92010 (13) | 0.0369 (7) | |
C9 | 0.0597 (2) | 0.7717 (4) | 0.89150 (18) | 0.0275 (8) | |
H9 | 0.0472 | 0.6969 | 0.9254 | 0.033* | |
O9 | −0.01852 (17) | 0.8565 (3) | 0.88839 (13) | 0.0312 (7) | |
C9M | −0.0651 (3) | 0.8631 (4) | 0.95555 (19) | 0.0344 (9) | |
H9M1 | −0.1181 | 0.9224 | 0.9515 | 0.052* | |
H9M2 | −0.0235 | 0.8982 | 0.9915 | 0.052* | |
H9M3 | −0.0854 | 0.7730 | 0.9692 | 0.052* | |
C10 | 0.0754 (3) | 0.7122 (4) | 0.81838 (18) | 0.0271 (8) | |
H10A | 0.0159 | 0.6851 | 0.7983 | 0.033* | |
H10B | 0.1131 | 0.6303 | 0.8232 | 0.033* | |
C10a | 0.1227 (2) | 0.8084 (4) | 0.76623 (17) | 0.0232 (8) | |
H10C | 0.1184 | 0.8994 | 0.7883 | 0.028* | |
C11 | 0.0704 (2) | 0.6916 (4) | 0.65070 (18) | 0.0254 (8) | |
O11 | 0.0998 (2) | 0.6811 (3) | 0.59198 (14) | 0.0397 (7) | |
O12 | 0.0266 (2) | 0.5920 (3) | 0.68351 (15) | 0.0431 (8) | |
H12 | 0.0220 | 0.5261 | 0.6561 | 0.065* | |
C21 | 0.0674 (3) | 0.9599 (4) | 0.58358 (18) | 0.0278 (8) | |
O21 | −0.01638 (18) | 0.9402 (3) | 0.58095 (14) | 0.0363 (7) | |
O22 | 0.11397 (19) | 1.0089 (3) | 0.53182 (13) | 0.0376 (7) | |
H22 | 0.0791 | 1.0245 | 0.4976 | 0.056* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0146 (16) | 0.032 (2) | 0.0221 (17) | 0.0015 (15) | −0.0015 (13) | −0.0038 (14) |
C2 | 0.0232 (19) | 0.035 (2) | 0.0212 (17) | 0.0019 (16) | −0.0003 (14) | −0.0035 (14) |
C3 | 0.0206 (19) | 0.049 (3) | 0.0264 (19) | −0.0043 (17) | −0.0004 (15) | 0.0040 (17) |
C4 | 0.0162 (18) | 0.055 (3) | 0.033 (2) | −0.0004 (18) | 0.0018 (15) | 0.0031 (18) |
C4a | 0.0206 (18) | 0.039 (2) | 0.0281 (19) | −0.0002 (16) | −0.0008 (15) | −0.0003 (16) |
C5 | 0.0169 (18) | 0.052 (3) | 0.038 (2) | 0.0092 (18) | 0.0011 (16) | 0.0073 (18) |
C6 | 0.023 (2) | 0.051 (3) | 0.032 (2) | 0.0015 (18) | −0.0072 (16) | 0.0084 (18) |
C7 | 0.031 (2) | 0.049 (2) | 0.0237 (18) | −0.0066 (19) | −0.0055 (16) | 0.0107 (17) |
C8 | 0.031 (2) | 0.036 (2) | 0.0131 (16) | −0.0027 (16) | 0.0043 (14) | −0.0032 (14) |
O8 | 0.0394 (17) | 0.0408 (19) | 0.0304 (14) | −0.0066 (13) | 0.0042 (12) | −0.0054 (12) |
C9 | 0.0218 (18) | 0.036 (2) | 0.0250 (18) | 0.0003 (16) | 0.0047 (14) | 0.0027 (15) |
O9 | 0.0253 (14) | 0.0441 (16) | 0.0240 (13) | 0.0061 (12) | 0.0036 (10) | 0.0047 (11) |
C9M | 0.028 (2) | 0.048 (2) | 0.0271 (19) | 0.0000 (19) | 0.0097 (16) | 0.0030 (17) |
C10 | 0.0247 (18) | 0.033 (2) | 0.0233 (17) | −0.0033 (16) | 0.0012 (14) | −0.0007 (14) |
C10a | 0.0202 (17) | 0.0314 (19) | 0.0180 (16) | −0.0036 (15) | −0.0021 (13) | −0.0028 (13) |
C11 | 0.0184 (17) | 0.035 (2) | 0.0230 (18) | 0.0000 (16) | −0.0054 (14) | −0.0040 (15) |
O11 | 0.0438 (17) | 0.0438 (17) | 0.0314 (15) | −0.0048 (14) | 0.0123 (13) | −0.0094 (12) |
O12 | 0.056 (2) | 0.0425 (18) | 0.0309 (15) | −0.0190 (15) | 0.0089 (14) | −0.0112 (12) |
C21 | 0.026 (2) | 0.033 (2) | 0.0249 (18) | 0.0011 (16) | 0.0018 (15) | −0.0047 (15) |
O21 | 0.0254 (15) | 0.0487 (18) | 0.0348 (15) | 0.0000 (12) | −0.0026 (11) | 0.0043 (12) |
O22 | 0.0335 (15) | 0.0551 (18) | 0.0243 (13) | 0.0004 (14) | −0.0010 (11) | 0.0096 (13) |
Geometric parameters (Å, º) top
C1—C2 | 1.520 (5) | C7—H7A | 0.990 |
C1—C11 | 1.522 (5) | C7—H7B | 0.990 |
C1—C10a | 1.559 (4) | C8—O8 | 1.210 (5) |
C1—H1 | 1.000 | C8—C9 | 1.523 (5) |
C2—C21 | 1.504 (5) | C9—O9 | 1.427 (4) |
C2—C3 | 1.547 (5) | C9—C10 | 1.524 (5) |
C2—H2 | 1.000 | C9—H9 | 1.000 |
C3—C4 | 1.494 (5) | O9—C9M | 1.445 (4) |
C3—H3A | 0.990 | C9M—H9M1 | 0.980 |
C3—H3B | 0.990 | C9M—H9M2 | 0.980 |
C4—C4a | 1.335 (5) | C9M—H9M3 | 0.980 |
C4—H4 | 0.950 | C10—C10a | 1.541 (5) |
C4a—C5 | 1.512 (5) | C10—H10A | 0.990 |
C4a—C10a | 1.533 (5) | C10—H10B | 0.990 |
C5—C6 | 1.513 (6) | C10a—H10C | 1.000 |
C5—H5A | 0.990 | C11—O11 | 1.197 (4) |
C5—H5B | 0.990 | C11—O12 | 1.336 (5) |
C6—C7 | 1.540 (6) | O12—H12 | 0.840 |
C6—H6A | 0.990 | C21—O21 | 1.247 (5) |
C6—H6B | 0.990 | C21—O22 | 1.291 (4) |
C7—C8 | 1.502 (6) | O22—H22 | 0.840 |
| | | |
C2—C1—C11 | 110.2 (3) | C8—C7—H7B | 109 |
C2—C1—C10a | 109.0 (3) | C6—C7—H7B | 109 |
C11—C1—C10a | 114.7 (3) | H7A—C7—H7B | 108 |
C2—C1—H1 | 108 | O8—C8—C7 | 122.1 (4) |
C11—C1—H1 | 108 | O8—C8—C9 | 121.3 (4) |
C10a—C1—H1 | 108 | C7—C8—C9 | 116.5 (3) |
C21—C2—C1 | 111.9 (3) | O9—C9—C8 | 111.1 (3) |
C21—C2—C3 | 112.1 (3) | O9—C9—C10 | 108.4 (3) |
C1—C2—C3 | 113.0 (3) | C8—C9—C10 | 111.2 (3) |
C21—C2—H2 | 106 | O9—C9—H9 | 109 |
C1—C2—H2 | 106 | C8—C9—H9 | 109 |
C3—C2—H2 | 106 | C10—C9—H9 | 109 |
C4—C3—C2 | 112.6 (3) | C9—O9—C9M | 111.8 (3) |
C4—C3—H3A | 109 | O9—C9M—H9M1 | 110 |
C2—C3—H3A | 109 | O9—C9M—H9M2 | 110 |
C4—C3—H3B | 109 | H9M1—C9M—H9M2 | 110 |
C2—C3—H3B | 109 | O9—C9M—H9M3 | 110 |
H3A—C3—H3B | 108 | H9M1—C9M—H9M3 | 110 |
C4a—C4—C3 | 126.9 (3) | H9M2—C9M—H9M3 | 110 |
C4a—C4—H4 | 117 | C9—C10—C10a | 114.1 (3) |
C3—C4—H4 | 117 | C9—C10—H10A | 109 |
C4—C4a—C5 | 119.0 (3) | C10a—C10—H10A | 109 |
C4—C4a—C10a | 119.6 (3) | C9—C10—H10B | 109 |
C5—C4a—C10a | 121.4 (3) | C10a—C10—H10B | 109 |
C4a—C5—C6 | 117.0 (4) | H10A—C10—H10B | 108 |
C4a—C5—H5A | 108 | C4a—C10a—C10 | 115.5 (3) |
C6—C5—H5A | 108 | C4a—C10a—C1 | 109.8 (3) |
C4a—C5—H5B | 108 | C10—C10a—C1 | 113.9 (3) |
C6—C5—H5B | 108 | C4a—C10a—H10C | 106 |
H5A—C5—H5B | 107 | C10—C10a—H10C | 106 |
C5—C6—C7 | 116.3 (3) | C1—C10a—H10C | 106 |
C5—C6—H6A | 108 | O11—C11—O12 | 122.7 (3) |
C7—C6—H6A | 108 | O11—C11—C1 | 124.0 (3) |
C5—C6—H6B | 108 | O12—C11—C1 | 113.2 (3) |
C7—C6—H6B | 108 | C11—O12—H12 | 110 |
H6A—C6—H6B | 107 | O21—C21—O22 | 123.5 (3) |
C8—C7—C6 | 112.8 (3) | O21—C21—C2 | 119.6 (3) |
C8—C7—H7A | 109 | O22—C21—C2 | 116.9 (3) |
C6—C7—H7A | 109 | C21—O22—H22 | 110 |
| | | |
C11—C1—C2—C21 | 59.8 (4) | O9—C9—C10—C10a | 79.2 (4) |
C10a—C1—C2—C21 | −173.5 (3) | C8—C9—C10—C10a | −43.2 (4) |
C11—C1—C2—C3 | −67.9 (4) | C4—C4a—C10a—C10 | 159.2 (4) |
C10a—C1—C2—C3 | 58.8 (4) | C5—C4a—C10a—C10 | −21.5 (5) |
C21—C2—C3—C4 | −158.2 (3) | C4—C4a—C10a—C1 | 28.7 (5) |
C1—C2—C3—C4 | −30.7 (5) | C5—C4a—C10a—C1 | −152.0 (3) |
C2—C3—C4—C4a | 0.7 (6) | C9—C10—C10a—C4a | 101.7 (4) |
C3—C4—C4a—C5 | −179.9 (4) | C9—C10—C10a—C1 | −129.9 (3) |
C3—C4—C4a—C10a | −0.5 (6) | C2—C1—C10a—C4a | −56.6 (4) |
C4—C4a—C5—C6 | 108.8 (4) | C11—C1—C10a—C4a | 67.5 (4) |
C10a—C4a—C5—C6 | −70.5 (5) | C2—C1—C10a—C10 | 172.2 (3) |
C4a—C5—C6—C7 | 83.6 (5) | C11—C1—C10a—C10 | −63.8 (4) |
C5—C6—C7—C8 | −71.5 (5) | C2—C1—C11—O11 | 0.3 (5) |
C6—C7—C8—O8 | −72.2 (5) | C10a—C1—C11—O11 | −123.1 (4) |
C6—C7—C8—C9 | 104.8 (4) | C2—C1—C11—O12 | −176.0 (3) |
O8—C8—C9—O9 | −12.9 (4) | C10a—C1—C11—O12 | 60.6 (4) |
C7—C8—C9—O9 | 170.1 (3) | C1—C2—C21—O21 | 29.3 (5) |
O8—C8—C9—C10 | 107.9 (4) | C3—C2—C21—O21 | 157.5 (3) |
C7—C8—C9—C10 | −69.1 (4) | C1—C2—C21—O22 | −153.3 (3) |
C8—C9—O9—C9M | −86.3 (3) | C3—C2—C21—O22 | −25.2 (5) |
C10—C9—O9—C9M | 151.2 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O9i | 0.84 | 1.89 | 2.716 (4) | 168 |
O22—H22···O21ii | 0.84 | 1.78 | 2.621 (4) | 174 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, −y+2, −z+1. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C16H20O6 | C16H20O6 | C14H16O5 | C15H20O6 |
Mr | 308.32 | 308.32 | 264.27 | 296.31 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 150 | 150 | 150 | 150 |
a, b, c (Å) | 7.4878 (9), 10.1793 (12), 11.0220 (13) | 27.666 (9), 5.066 (2), 22.793 (7) | 14.1076 (19), 11.3501 (15), 7.7762 (10) | 14.676 (2), 9.967 (2), 18.937 (3) |
α, β, γ (°) | 69.955 (2), 83.957 (2), 79.806 (2) | 90, 105.149 (5), 90 | 90, 96.280 (2), 90 | 90, 90, 90 |
V (Å3) | 775.85 (16) | 3084 (2) | 1237.7 (3) | 2770.0 (8) |
Z | 2 | 8 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Synchrotron, λ = 0.6892 Å |
µ (mm−1) | 0.10 | 0.10 | 0.11 | 0.11 |
Crystal size (mm) | 0.5 × 0.3 × 0.3 | 0.50 × 0.45 × 0.25 | 0.42 × 0.40 × 0.31 | 0.06 × 0.05 × 0.01 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART1000 CCD area-detector diffractometer | Bruker SMART CCD area-detector on SRS Station 9.8 diffractometer |
Absorption correction | – | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9181, 3597, 3148 | 10535, 3584, 2967 | 10858, 3047, 2437 | 18905, 2715, 1769 |
Rint | 0.024 | 0.058 | 0.033 | 0.136 |
(sin θ/λ)max (Å−1) | 0.676 | 0.676 | 0.674 | 0.636 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.100, 1.06 | 0.050, 0.126, 0.98 | 0.035, 0.100, 1.07 | 0.084, 0.231, 1.08 |
No. of reflections | 3597 | 3584 | 2896 | 2715 |
No. of parameters | 202 | 199 | 173 | 192 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.20 | 0.37, −0.19 | 0.30, −0.16 | 0.53, −0.29 |
Selected torsion angles (º) for (I) topC1—C2—C10—O10 | −130.12 (11) | C2—C1—C13—O13 | −134.76 (12) |
Selected torsion angles (º) for (II) topC1—C2—C10—O10 | 87.2 (2) | C2—C1—C13—O13 | 11.8 (3) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···O3i | 0.99 | 2.42 | 3.3900 (16) | 168 |
Symmetry code: (i) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O9i | 0.84 | 1.89 | 2.716 (4) | 168 |
O22—H22···O21ii | 0.84 | 1.78 | 2.621 (4) | 174 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, −y+2, −z+1. |
Ring-puckering parameters (Å,°) for compounds (I)-(IV) topCompound | Ring size | q2 | q3 | q4 | ϕ2 | ϕ3 | QT | θ |
(I) | 6 | 0.253 (2) | 0.012 (2) | | 298.6 (4) | | 0.253 (2) | 87.3 (5) |
(I) | 7 | 0.515 (2) | 0.675 (2) | | 253.6 (2) | 144.2 (2) | 0.849 (2) | |
(II) | 6 | 0.214 (1) | 0.015 (1) | | 300.7 (3) | | 0.214 (1) | 86.0 (3) |
(II) | 7 | 0.538 (1) | 0.652 (1) | | 241.6 (1) | 139.4 (1) | 0.845 (1) | |
(III) | 6 | 0.624 (1) | -0.021 (1) | | 59.0 (1) | | 0.624 (1) | 92.0 (1) |
(III) | 7 | 0.382 (1) | 0.699 (1) | | 250.1 (2) | 259.3 (1) | 0.797 (1) | |
(IV) | 6 | 0.404 (4) | -0.309 (4) | | 180.6 (5) | | 0.509 (4) | 127.5 (5) |
(IV) | 8 | 0.869 (4) | 0.739 (4) | 0.272 (4) | 33.3 (3) | 110.7 (3) | 1.173 (4) | |
As part of a broad programme concerning the rapid construction of medium-ring polycyclic units found in natural products, we explored Diels-Alder reactions of vinyl-substituted cycloheptene and cyclooctene systems generated by formal [2,3] rearrangement of carbenoid-derived oxonium ylides. The novel bicyclic and tricyclic systems containing a seven-membered carbocycle, compounds (I), (II) and (III), were prepared by the reaction of dimethylacetylene dicarboxylate or maleic anhydride with 2-methoxy-5-vinyl-cyclohept-4-enone, itself prepared by [2,3]-sigmatropic ring-expansion of catalytically generated cyclic divinyl-substituted oxonium ylides (Scheme). Similarly, a bicyclic compound containing an eight-membered carbocycle, (IV), was prepared by reaction of maleic anhydride with 2-methoxy-5-vinyl-cyclooct-4-enone. \sch
Crystallographic characterization has been an effective method of unambiguously establishing the stereochemical outcome of these Diels-Alder reactions, permitting the relative configuration of the stereogenic centres in each diastereoisomer to be determined. Compounds (I) and (II) form a pair of diastereomers, in which the relative configuration at C8 and C9a has been determined as S*,S* and R*,S*, respectively. Aside from this difference in configuration, the other significant differences in molecular structure are in the orientation of the ester side arms attached at C1 and C2. These differences can be seen in Figs. 1 and 2 and are illustrated by the following interplanar angles, where plane A contains atoms C13/O13/C15/O14, plane B C10/O10/O11/C12 and plane C C13/C1/C2/C10: AB angles are 135.7 and 13.5°, AC 41.2 and 81.6°, and BC 130.7 and 86.5° for (I) and (II), respectively. Similarly, this is shown by the C2—C1—C13—O13 and O10—C10—C2—C1 torsion angles (Table 1). The different orientations have different intramolecular contact distances between the ester arms: the separation between O11 and O14 of 2.835 Å in (I), compared with 4.845 Å in (II), may be due to the formation of dimers in (I) through a weak C—H···O interaction between C4 and O13. In (II), where the two ester groups are almost orthogonal to one another, the closest contact is between O13 and C10 (2.65 Å).
The conformation of the two rings in this pair of structures is almost identical. In both cases, the six-membered ring adopts a nearly ideal boat conformation, with C3 and C9a displaced in the same direction from the plane of the remaining four atoms by 0.165 (2) and 0.205 (2) Å, respectively for (I), and by -0.203 (3) and -0.235 (3) Å, respectively, for (II). The overall ring plane has an r.m.s. deviation of 0.087 Å for (I) and 0.103 Å for (II). The planes through the two half-rings defined by C9a/C1/C2/C3 and C9a/C4a/C4/C3 have deviations of only 0.007 and 0.004 Å, respectively, in (I), and 0.002 and 0.006 Å, respectively, in (II), with a hinge angle about C9a···C3 of 16.79 (9)° in (I) and 19.79 (11)° in (II). The puckering parameters (Cremer & Pople, 1975) for both the six-membered and the irregular seven-membered rings are given in Table 1.
Adduct (III) is a tricyclic compound with four stereogenic centres, at C3a, C9, C10a and C10b, the configuration of which has been determined as S*, R*, S* and R*, respectively (Fig. 3). As in the previous compounds, the six-membered ring adopts a nearly ideal boat conformation, with C4 and C10a displaced in the same direction from the plane of the other four ring atoms by 0.515 (2) and 0.565 (2) Å, respectively. The overall ring plane has an r.m.s. deviation of 0.087 Å, while the planes through the two half-rings, defined by C4/C3A/C10b/C10a and C4/C5/C5a/C10a, have deviations of only 0.004 and 0.008 Å, respectively, with a hinge angle of 46.75 (7)° about C4···C10a. The five-membered ring is planar to within 0.009 Å, but with O1 and O3 displaced in opposite directions from the ring plane by 0.021 (2) and -0.042 (2) Å, respectively.
Compound (IV) is again a bicyclic compound, but in this case containing an eight-membered carbocycle and a six-membered ring (Fig. 4). In this case, the six-membered ring adopts an envelope conformation, with C1 displaced by -0.703 (7) Å from the plane of the other five atoms, which define a plane with an r.m.s. deviation of only 0.003 Å. The puckering parameters for the six-membered ring and the irregular seven-membered ring are given in Table 1. The hydrogen bonding links molecules to form centrosymmetric dimers by inversion through (0, 1, 1/2). These dimers are each linked to four neighbouring dimers related by 21 screw axis operations (Fig. 5). These interactions result in a two-dimensional network structure which is infinite in the bc plane but does not propagate along the a axis.