Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106036900/sk3047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106036900/sk3047Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106036900/sk3047IIsup3.hkl |
CCDC references: 625701; 625702
The syntheses of compounds (I) and (II) are described by Li & Lundquist (1997). Crystals of (I) (m.p. 401 K) and (II) (m.p. 381–382 K) were obtained from ethanol.
H atoms were refined isotropically and were constrained to the ideal geometry using an appropriate riding model. For methyl groups, the C—H distances (0.98 Å) and C–C–H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting position based on the threefold averaged circular Fourier synthesis. For other H atoms, C—H = 0.95–1.00 Å. For (I), Uiso(H) values were fixed at 1.2 or 1.5 times Ueq(C). Please check added text.
For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.
C23H26O7 | F(000) = 880 |
Mr = 414.44 | Dx = 1.365 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 7078 reflections |
a = 14.4281 (5) Å | θ = 2.5–32.1° |
b = 18.8386 (7) Å | µ = 0.10 mm−1 |
c = 9.0887 (3) Å | T = 173 K |
β = 125.285 (1)° | Prism, colourless |
V = 2016.52 (12) Å3 | 0.42 × 0.22 × 0.18 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 3639 independent reflections |
Radiation source: fine-focus sealed tube | 3193 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 33.2°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −21→21 |
Tmin = 0.608, Tmax = 0.982 | k = −28→28 |
18037 measured 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.072P)2 + 0.020P] where P = (Fo2 + 2Fc2)/3 |
3639 reflections | (Δ/σ)max < 0.001 |
274 parameters | Δρmax = 0.32 e Å−3 |
2 restraints | Δρmin = −0.18 e Å−3 |
C23H26O7 | V = 2016.52 (12) Å3 |
Mr = 414.44 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 14.4281 (5) Å | µ = 0.10 mm−1 |
b = 18.8386 (7) Å | T = 173 K |
c = 9.0887 (3) Å | 0.42 × 0.22 × 0.18 mm |
β = 125.285 (1)° |
Siemens SMART CCD area-detector diffractometer | 3639 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3193 reflections with I > 2σ(I) |
Tmin = 0.608, Tmax = 0.982 | Rint = 0.034 |
18037 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 2 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.32 e Å−3 |
3639 reflections | Δρmin = −0.18 e Å−3 |
274 parameters |
Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003a). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 7078 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003b). |
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 | 0.05273 (12) | 0.98417 (7) | 0.28979 (18) | 0.0336 (3) | |
O2 | 0.18225 (12) | 0.91853 (7) | 0.59272 (16) | 0.0340 (3) | |
O3 | 0.35467 (12) | 0.71243 (6) | 0.46411 (18) | 0.0336 (3) | |
O4 | 0.39322 (12) | 0.67530 (6) | 0.21211 (19) | 0.0327 (3) | |
O5 | 0.72969 (10) | 0.88301 (7) | 0.24914 (16) | 0.0293 (2) | |
O6 | 0.62968 (10) | 0.83612 (6) | 0.42010 (14) | 0.0239 (2) | |
O7 | 0.56041 (10) | 0.95177 (6) | 0.31418 (15) | 0.0276 (2) | |
C1 | 0.24632 (12) | 0.81536 (8) | 0.3156 (2) | 0.0227 (3) | |
C2 | 0.18137 (13) | 0.85382 (8) | 0.1563 (2) | 0.0252 (3) | |
H2 | 0.1821 | 0.8411 | 0.0558 | 0.030* | |
C3 | 0.11515 (14) | 0.91087 (9) | 0.1425 (2) | 0.0277 (3) | |
H3 | 0.0700 | 0.9363 | 0.0324 | 0.033* | |
C4 | 0.11537 (13) | 0.93045 (8) | 0.2897 (2) | 0.0257 (3) | |
C5 | 0.18502 (13) | 0.89333 (8) | 0.4551 (2) | 0.0250 (3) | |
C6 | 0.24838 (13) | 0.83617 (8) | 0.4662 (2) | 0.0241 (3) | |
H6 | 0.2937 | 0.8107 | 0.5761 | 0.029* | |
C7 | −0.02777 (16) | 1.01764 (10) | 0.1194 (3) | 0.0355 (4) | |
H7A | 0.0126 | 1.0397 | 0.0738 | 0.053* | |
H7B | −0.0698 | 1.0541 | 0.1351 | 0.053* | |
H7C | −0.0809 | 0.9820 | 0.0330 | 0.053* | |
C8 | 0.24673 (18) | 0.88047 (11) | 0.7592 (2) | 0.0375 (4) | |
H8A | 0.2203 | 0.8312 | 0.7392 | 0.056* | |
H8B | 0.2369 | 0.9028 | 0.8467 | 0.056* | |
H8C | 0.3272 | 0.8814 | 0.8058 | 0.056* | |
C9 | 0.31515 (14) | 0.75263 (8) | 0.3367 (2) | 0.0246 (3) | |
C10 | 0.34295 (13) | 0.74188 (8) | 0.2022 (2) | 0.0247 (3) | |
H10 | 0.2917 | 0.7643 | 0.0808 | 0.030* | |
C11 | 0.46590 (13) | 0.73650 (8) | 0.2785 (2) | 0.0243 (3) | |
H11 | 0.5192 | 0.7405 | 0.4126 | 0.029* | |
C12 | 0.51144 (13) | 0.76015 (8) | 0.1763 (2) | 0.0235 (3) | |
C13 | 0.47217 (14) | 0.73067 (9) | 0.0081 (2) | 0.0285 (3) | |
H13 | 0.4147 | 0.6953 | −0.0436 | 0.034* | |
C14 | 0.51799 (15) | 0.75361 (10) | −0.0817 (2) | 0.0308 (3) | |
H14 | 0.4911 | 0.7343 | −0.1965 | 0.037* | |
C15 | 0.60361 (14) | 0.80494 (9) | −0.0048 (2) | 0.0291 (3) | |
H15 | 0.6348 | 0.8199 | −0.0674 | 0.035* | |
C16 | 0.64375 (13) | 0.83445 (8) | 0.1628 (2) | 0.0249 (3) | |
C17 | 0.59533 (12) | 0.81245 (8) | 0.25264 (19) | 0.0223 (3) | |
C18 | 0.77905 (17) | 0.90537 (10) | 0.1583 (3) | 0.0332 (3) | |
H18A | 0.8079 | 0.8639 | 0.1315 | 0.050* | |
H18B | 0.8417 | 0.9382 | 0.2356 | 0.050* | |
H18C | 0.7214 | 0.9293 | 0.0456 | 0.050* | |
C19 | 0.64536 (13) | 0.91141 (8) | 0.4610 (2) | 0.0242 (3) | |
H19 | 0.7209 | 0.9260 | 0.4901 | 0.029* | |
C20 | 0.64751 (13) | 0.91913 (8) | 0.62880 (19) | 0.0254 (3) | |
H20A | 0.7009 | 0.8840 | 0.7198 | 0.030* | |
H20B | 0.6754 | 0.9671 | 0.6803 | 0.030* | |
C21 | 0.53056 (15) | 0.90814 (8) | 0.5887 (2) | 0.0265 (3) | |
H21A | 0.5328 | 0.9190 | 0.6974 | 0.032* | |
H21B | 0.5068 | 0.8581 | 0.5548 | 0.032* | |
C22 | 0.44625 (14) | 0.95694 (9) | 0.4349 (2) | 0.0272 (3) | |
H22A | 0.3689 | 0.9484 | 0.4028 | 0.033* | |
H22B | 0.4664 | 1.0071 | 0.4728 | 0.033* | |
C23 | 0.44844 (14) | 0.94287 (9) | 0.2723 (2) | 0.0269 (3) | |
H23A | 0.4220 | 0.8938 | 0.2291 | 0.032* | |
H23B | 0.3954 | 0.9758 | 0.1740 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0385 (6) | 0.0346 (6) | 0.0312 (6) | 0.0122 (5) | 0.0221 (5) | 0.0050 (5) |
O2 | 0.0454 (7) | 0.0376 (6) | 0.0264 (6) | 0.0100 (5) | 0.0250 (5) | 0.0029 (5) |
O3 | 0.0435 (7) | 0.0277 (5) | 0.0370 (6) | 0.0059 (5) | 0.0276 (6) | 0.0062 (5) |
O4 | 0.0409 (7) | 0.0207 (5) | 0.0454 (7) | −0.0031 (4) | 0.0300 (6) | −0.0069 (5) |
O5 | 0.0326 (6) | 0.0352 (6) | 0.0282 (5) | −0.0041 (5) | 0.0222 (5) | −0.0029 (4) |
O6 | 0.0293 (5) | 0.0250 (5) | 0.0199 (4) | 0.0009 (4) | 0.0157 (4) | −0.0010 (4) |
O7 | 0.0343 (6) | 0.0271 (5) | 0.0266 (5) | 0.0032 (4) | 0.0207 (5) | 0.0053 (4) |
C1 | 0.0241 (6) | 0.0226 (6) | 0.0248 (6) | −0.0020 (5) | 0.0162 (5) | −0.0015 (5) |
C2 | 0.0271 (7) | 0.0281 (7) | 0.0226 (6) | −0.0009 (5) | 0.0156 (5) | −0.0020 (5) |
C3 | 0.0294 (7) | 0.0302 (7) | 0.0237 (7) | 0.0043 (6) | 0.0154 (6) | 0.0028 (5) |
C4 | 0.0260 (7) | 0.0260 (7) | 0.0268 (7) | 0.0023 (5) | 0.0162 (6) | 0.0018 (5) |
C5 | 0.0276 (7) | 0.0280 (7) | 0.0229 (6) | 0.0001 (5) | 0.0167 (6) | 0.0000 (5) |
C6 | 0.0258 (6) | 0.0255 (6) | 0.0223 (6) | −0.0004 (5) | 0.0146 (5) | 0.0011 (5) |
C7 | 0.0332 (8) | 0.0374 (8) | 0.0388 (9) | 0.0122 (7) | 0.0224 (7) | 0.0118 (7) |
C8 | 0.0478 (10) | 0.0424 (9) | 0.0253 (7) | 0.0047 (8) | 0.0228 (7) | 0.0012 (7) |
C9 | 0.0267 (7) | 0.0226 (6) | 0.0274 (7) | −0.0029 (5) | 0.0172 (6) | −0.0030 (5) |
C10 | 0.0265 (7) | 0.0227 (6) | 0.0271 (7) | −0.0013 (5) | 0.0167 (6) | −0.0040 (5) |
C11 | 0.0262 (7) | 0.0223 (6) | 0.0268 (7) | 0.0012 (5) | 0.0166 (6) | −0.0011 (5) |
C12 | 0.0232 (6) | 0.0256 (6) | 0.0221 (6) | 0.0031 (5) | 0.0133 (5) | −0.0008 (5) |
C13 | 0.0275 (7) | 0.0316 (7) | 0.0248 (7) | 0.0004 (6) | 0.0142 (6) | −0.0055 (6) |
C14 | 0.0329 (8) | 0.0374 (8) | 0.0219 (7) | 0.0054 (6) | 0.0158 (6) | −0.0032 (6) |
C15 | 0.0334 (8) | 0.0354 (8) | 0.0234 (7) | 0.0049 (6) | 0.0191 (6) | 0.0005 (6) |
C16 | 0.0257 (7) | 0.0289 (7) | 0.0233 (6) | 0.0044 (5) | 0.0160 (6) | 0.0008 (5) |
C17 | 0.0231 (6) | 0.0261 (6) | 0.0199 (6) | 0.0034 (5) | 0.0136 (5) | −0.0005 (5) |
C18 | 0.0386 (9) | 0.0379 (8) | 0.0354 (8) | −0.0035 (7) | 0.0284 (7) | −0.0017 (7) |
C19 | 0.0265 (7) | 0.0253 (6) | 0.0228 (6) | −0.0013 (5) | 0.0154 (6) | −0.0024 (5) |
C20 | 0.0289 (7) | 0.0273 (7) | 0.0190 (6) | 0.0003 (5) | 0.0133 (6) | −0.0018 (5) |
C21 | 0.0355 (8) | 0.0260 (7) | 0.0251 (6) | 0.0001 (5) | 0.0217 (6) | 0.0004 (5) |
C22 | 0.0313 (8) | 0.0279 (7) | 0.0274 (7) | 0.0019 (5) | 0.0199 (6) | −0.0009 (5) |
C23 | 0.0289 (7) | 0.0295 (7) | 0.0231 (6) | 0.0041 (5) | 0.0156 (6) | 0.0022 (5) |
C1—C9 | 1.483 (2) | C8—H8B | 0.9800 |
O3—C9 | 1.215 (2) | C8—H8C | 0.9800 |
C9—C10 | 1.504 (2) | C10—H10 | 1.0000 |
C10—C11 | 1.489 (2) | C11—H11 | 1.0000 |
O4—C10 | 1.4256 (19) | C12—C17 | 1.395 (2) |
O4—C11 | 1.4359 (19) | C12—C13 | 1.401 (2) |
C11—C12 | 1.483 (2) | C13—C14 | 1.384 (3) |
O1—C4 | 1.3574 (19) | C13—H13 | 0.9500 |
O1—C7 | 1.438 (2) | C14—C15 | 1.397 (3) |
O2—C5 | 1.3598 (18) | C14—H14 | 0.9500 |
O2—C8 | 1.429 (2) | C15—C16 | 1.395 (2) |
O5—C16 | 1.366 (2) | C15—H15 | 0.9500 |
O5—C18 | 1.430 (2) | C16—C17 | 1.409 (2) |
O6—C17 | 1.3746 (17) | C18—H18A | 0.9800 |
O6—C19 | 1.4505 (18) | C18—H18B | 0.9800 |
O7—C19 | 1.4042 (19) | C18—H18C | 0.9800 |
O7—C23 | 1.440 (2) | C19—C20 | 1.514 (2) |
C1—C2 | 1.390 (2) | C19—H19 | 1.0000 |
C1—C6 | 1.407 (2) | C20—C21 | 1.521 (2) |
C2—C3 | 1.395 (2) | C20—H20A | 0.9900 |
C2—H2 | 0.9500 | C20—H20B | 0.9900 |
C3—C4 | 1.386 (2) | C21—C22 | 1.522 (2) |
C3—H3 | 0.9500 | C21—H21A | 0.9900 |
C4—C5 | 1.419 (2) | C21—H21B | 0.9900 |
C5—C6 | 1.378 (2) | C22—C23 | 1.519 (2) |
C6—H6 | 0.9500 | C22—H22A | 0.9900 |
C7—H7A | 0.9800 | C22—H22B | 0.9900 |
C7—H7B | 0.9800 | C23—H23A | 0.9900 |
C7—H7C | 0.9800 | C23—H23B | 0.9900 |
C8—H8A | 0.9800 | ||
C1—C9—C10 | 118.37 (13) | C13—C12—C11 | 121.18 (14) |
O3—C9—C1 | 122.03 (14) | C14—C13—C12 | 119.32 (16) |
O3—C9—C10 | 119.47 (14) | C14—C13—H13 | 120.3 |
O4—C10—C9 | 115.59 (13) | C12—C13—H13 | 120.3 |
O4—C10—C11 | 58.99 (10) | C13—C14—C15 | 120.44 (15) |
O4—C11—C10 | 58.31 (10) | C13—C14—H14 | 119.8 |
O4—C11—C12 | 117.26 (13) | C15—C14—H14 | 119.8 |
C10—C11—C12 | 121.84 (14) | C14—C15—C16 | 120.77 (15) |
C4—O1—C7 | 116.74 (14) | C14—C15—H15 | 119.6 |
C5—O2—C8 | 116.84 (13) | C16—C15—H15 | 119.6 |
C10—O4—C11 | 62.71 (10) | O5—C16—C15 | 124.13 (15) |
C16—O5—C18 | 117.05 (13) | O5—C16—C17 | 116.94 (13) |
C17—O6—C19 | 120.29 (12) | C15—C16—C17 | 118.91 (14) |
C19—O7—C23 | 114.72 (12) | O6—C17—C12 | 115.74 (13) |
C2—C1—C6 | 119.37 (14) | O6—C17—C16 | 124.33 (14) |
C2—C1—C9 | 123.25 (13) | C12—C17—C16 | 119.82 (13) |
C6—C1—C9 | 117.38 (13) | O5—C18—H18A | 109.5 |
C1—C2—C3 | 120.67 (14) | O5—C18—H18B | 109.5 |
C1—C2—H2 | 119.7 | H18A—C18—H18B | 109.5 |
C3—C2—H2 | 119.7 | O5—C18—H18C | 109.5 |
C4—C3—C2 | 119.92 (14) | H18A—C18—H18C | 109.5 |
C4—C3—H3 | 120.0 | H18B—C18—H18C | 109.5 |
C2—C3—H3 | 120.0 | O7—C19—O6 | 111.38 (12) |
O1—C4—C3 | 124.68 (14) | O7—C19—C20 | 113.84 (13) |
O1—C4—C5 | 115.52 (13) | O6—C19—C20 | 105.17 (12) |
C3—C4—C5 | 119.80 (14) | O7—C19—H19 | 108.8 |
O2—C5—C6 | 125.19 (14) | O6—C19—H19 | 108.8 |
O2—C5—C4 | 115.06 (13) | C20—C19—H19 | 108.8 |
C6—C5—C4 | 119.75 (13) | C21—C20—C19 | 111.80 (12) |
C5—C6—C1 | 120.41 (14) | C21—C20—H20A | 109.3 |
C5—C6—H6 | 119.8 | C19—C20—H20A | 109.3 |
C1—C6—H6 | 119.8 | C21—C20—H20B | 109.3 |
O1—C7—H7A | 109.5 | C19—C20—H20B | 109.3 |
O1—C7—H7B | 109.5 | H20A—C20—H20B | 107.9 |
H7A—C7—H7B | 109.5 | C20—C21—C22 | 108.97 (12) |
O1—C7—H7C | 109.5 | C20—C21—H21A | 109.9 |
H7A—C7—H7C | 109.5 | C22—C21—H21A | 109.9 |
H7B—C7—H7C | 109.5 | C20—C21—H21B | 109.9 |
O2—C8—H8A | 109.5 | C22—C21—H21B | 109.9 |
O2—C8—H8B | 109.5 | H21A—C21—H21B | 108.3 |
H8A—C8—H8B | 109.5 | C23—C22—C21 | 109.50 (13) |
O2—C8—H8C | 109.5 | C23—C22—H22A | 109.8 |
H8A—C8—H8C | 109.5 | C21—C22—H22A | 109.8 |
H8B—C8—H8C | 109.5 | C23—C22—H22B | 109.8 |
C11—C10—C9 | 115.84 (14) | C21—C22—H22B | 109.8 |
O4—C10—H10 | 117.8 | H22A—C22—H22B | 108.2 |
C11—C10—H10 | 117.8 | O7—C23—C22 | 111.92 (13) |
C9—C10—H10 | 117.8 | O7—C23—H23A | 109.2 |
O4—C11—H11 | 115.7 | C22—C23—H23A | 109.2 |
C10—C11—H11 | 115.7 | O7—C23—H23B | 109.2 |
C12—C11—H11 | 115.7 | C22—C23—H23B | 109.2 |
C17—C12—C13 | 120.69 (14) | H23A—C23—H23B | 107.9 |
C17—C12—C11 | 118.13 (13) | ||
C6—C1—C2—C3 | −2.5 (2) | C10—C11—C12—C17 | 121.61 (16) |
C9—C1—C2—C3 | 177.72 (15) | O4—C11—C12—C13 | 9.1 (2) |
C1—C2—C3—C4 | 1.2 (2) | C10—C11—C12—C13 | −58.8 (2) |
C7—O1—C4—C3 | 6.8 (2) | C17—C12—C13—C14 | 0.4 (2) |
C7—O1—C4—C5 | −173.40 (15) | C11—C12—C13—C14 | −179.17 (15) |
C2—C3—C4—O1 | −178.78 (16) | C12—C13—C14—C15 | 0.9 (3) |
C2—C3—C4—C5 | 1.4 (2) | C13—C14—C15—C16 | −0.6 (3) |
C8—O2—C5—C6 | −2.8 (2) | C18—O5—C16—C15 | 1.3 (2) |
C8—O2—C5—C4 | 176.94 (15) | C18—O5—C16—C17 | 179.94 (14) |
O1—C4—C5—O2 | −2.3 (2) | C14—C15—C16—O5 | 177.70 (15) |
C3—C4—C5—O2 | 177.56 (16) | C14—C15—C16—C17 | −0.9 (2) |
O1—C4—C5—C6 | 177.49 (15) | C19—O6—C17—C12 | −136.15 (14) |
C3—C4—C5—C6 | −2.7 (2) | C19—O6—C17—C16 | 47.8 (2) |
O2—C5—C6—C1 | −178.91 (15) | C13—C12—C17—O6 | −178.22 (14) |
C4—C5—C6—C1 | 1.4 (2) | C11—C12—C17—O6 | 1.37 (19) |
C2—C1—C6—C5 | 1.2 (2) | C13—C12—C17—C16 | −1.9 (2) |
C9—C1—C6—C5 | −179.00 (14) | C11—C12—C17—C16 | 177.65 (13) |
C2—C1—C9—O3 | −166.56 (16) | O5—C16—C17—O6 | −0.6 (2) |
C6—C1—C9—O3 | 13.6 (2) | C15—C16—C17—O6 | 178.13 (14) |
C2—C1—C9—C10 | 17.7 (2) | O5—C16—C17—C12 | −176.55 (13) |
C6—C1—C9—C10 | −162.10 (13) | C15—C16—C17—C12 | 2.2 (2) |
C11—O4—C10—C9 | −106.02 (15) | C23—O7—C19—O6 | 67.84 (16) |
O3—C9—C10—O4 | 13.8 (2) | C23—O7—C19—C20 | −50.85 (17) |
C1—C9—C10—O4 | −170.34 (13) | C17—O6—C19—O7 | 39.66 (18) |
O3—C9—C10—C11 | −52.4 (2) | C17—O6—C19—C20 | 163.43 (12) |
C1—C9—C10—C11 | 123.41 (15) | O7—C19—C20—C21 | 50.31 (18) |
C10—O4—C11—C12 | −112.29 (15) | O6—C19—C20—C21 | −71.88 (15) |
C9—C10—C11—O4 | 105.60 (15) | C19—C20—C21—C22 | −52.97 (17) |
O4—C10—C11—C12 | 104.49 (16) | C20—C21—C22—C23 | 56.24 (17) |
C9—C10—C11—C12 | −149.91 (13) | C19—O7—C23—C22 | 54.54 (17) |
O4—C11—C12—C17 | −170.46 (13) | C21—C22—C23—O7 | −57.01 (17) |
C20H22O7 | F(000) = 792 |
Mr = 374.38 | Dx = 1.345 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3556 reflections |
a = 12.7503 (10) Å | θ = 2.5–22.7° |
b = 9.4201 (7) Å | µ = 0.10 mm−1 |
c = 15.4409 (12) Å | T = 173 K |
β = 94.706 (2)° | Needle with an arrow-head end, colorless |
V = 1848.3 (2) Å3 | 0.65 × 0.14 × 0.06 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 3280 independent reflections |
Radiation source: fine-focus sealed tube | 2257 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω scans | θmax = 25.1°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −15→15 |
Tmin = 0.805, Tmax = 0.994 | k = −11→11 |
19850 measured reflections | l = −18→18 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | Only H-atom coordinates refined |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0524P)2 + 0.460P] where P = (Fo2 + 2Fc2)/3 |
3280 reflections | (Δ/σ)max < 0.001 |
270 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C20H22O7 | V = 1848.3 (2) Å3 |
Mr = 374.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7503 (10) Å | µ = 0.10 mm−1 |
b = 9.4201 (7) Å | T = 173 K |
c = 15.4409 (12) Å | 0.65 × 0.14 × 0.06 mm |
β = 94.706 (2)° |
Siemens SMART CCD area-detector diffractometer | 3280 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2257 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 0.994 | Rint = 0.057 |
19850 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.113 | Only H-atom coordinates refined |
S = 1.01 | Δρmax = 0.39 e Å−3 |
3280 reflections | Δρmin = −0.14 e Å−3 |
270 parameters |
Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003a). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 3556 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003b). |
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 | 0.86916 (13) | 0.22744 (16) | 0.37251 (9) | 0.0521 (4) | |
O2 | 0.97263 (12) | 0.16958 (15) | 0.51711 (9) | 0.0473 (4) | |
O3 | 0.90694 (14) | 0.58207 (17) | 0.71809 (10) | 0.0646 (5) | |
O4 | 0.86665 (13) | 0.86795 (16) | 0.70153 (11) | 0.0588 (5) | |
O5 | 0.54610 (11) | 0.81483 (15) | 0.70368 (9) | 0.0453 (4) | |
O6 | 0.52449 (15) | 0.64410 (17) | 0.59345 (10) | 0.0656 (5) | |
O7 | 0.40794 (13) | 1.01620 (17) | 0.64405 (10) | 0.0577 (5) | |
C1 | 0.87274 (16) | 0.5238 (2) | 0.57035 (13) | 0.0377 (5) | |
C2 | 0.92472 (15) | 0.3935 (2) | 0.58090 (13) | 0.0376 (5) | |
H2 | 0.9622 | 0.3713 | 0.6349 | 0.038 (5)* | |
C3 | 0.92223 (16) | 0.2974 (2) | 0.51417 (13) | 0.0384 (5) | |
C4 | 0.86580 (16) | 0.3292 (2) | 0.43418 (13) | 0.0401 (5) | |
C5 | 0.81294 (17) | 0.4567 (2) | 0.42385 (14) | 0.0441 (5) | |
H5 | 0.7739 | 0.4780 | 0.3704 | 0.055 (6)* | |
C6 | 0.81693 (17) | 0.5540 (2) | 0.49191 (13) | 0.0435 (5) | |
H6 | 0.7810 | 0.6421 | 0.4844 | 0.042 (6)* | |
C7 | 1.02743 (18) | 0.1310 (2) | 0.59851 (14) | 0.0468 (6) | |
H7A | 1.0810 | 0.2027 | 0.6151 | 0.050 (6)* | |
H7B | 1.0613 | 0.0385 | 0.5928 | 0.043 (6)* | |
H7C | 0.9774 | 0.1254 | 0.6433 | 0.051 (6)* | |
C8 | 0.8243 (2) | 0.2591 (3) | 0.28698 (14) | 0.0561 (7) | |
H8A | 0.7481 | 0.2717 | 0.2880 | 0.071 (8)* | |
H8B | 0.8384 | 0.1808 | 0.2478 | 0.081 (8)* | |
H8C | 0.8556 | 0.3467 | 0.2664 | 0.060 (7)* | |
C9 | 0.87822 (17) | 0.6218 (2) | 0.64538 (14) | 0.0446 (5) | |
C10 | 0.84505 (17) | 0.7733 (2) | 0.63022 (15) | 0.0460 (6) | |
H10 | 0.8505 | 0.8126 | 0.5706 | 0.046 (6)* | |
C11 | 0.76023 (16) | 0.8292 (2) | 0.67980 (13) | 0.0414 (5) | |
H11 | 0.7303 | 0.7601 | 0.7203 | 0.053 (6)* | |
C12 | 0.68639 (17) | 0.9407 (2) | 0.64478 (12) | 0.0383 (5) | |
C13 | 0.72199 (19) | 1.0577 (2) | 0.59966 (13) | 0.0460 (6) | |
H13 | 0.7947 | 1.0671 | 0.5915 | 0.042 (6)* | |
C14 | 0.6521 (2) | 1.1588 (2) | 0.56717 (14) | 0.0514 (6) | |
H14 | 0.6769 | 1.2372 | 0.5360 | 0.064 (7)* | |
C15 | 0.5461 (2) | 1.1483 (2) | 0.57917 (13) | 0.0490 (6) | |
H15 | 0.4984 | 1.2186 | 0.5559 | 0.060 (7)* | |
C16 | 0.50976 (18) | 1.0346 (2) | 0.62536 (13) | 0.0432 (5) | |
C17 | 0.58059 (17) | 0.9289 (2) | 0.65674 (12) | 0.0380 (5) | |
C18 | 0.3332 (2) | 1.1197 (3) | 0.61232 (17) | 0.0675 (8) | |
H18A | 0.3530 | 1.2126 | 0.6372 | 0.072 (8)* | |
H18B | 0.2633 | 1.0933 | 0.6291 | 0.092 (10)* | |
H18C | 0.3318 | 1.1245 | 0.5488 | 0.074 (8)* | |
C19 | 0.4761 (2) | 0.7200 (2) | 0.65499 (15) | 0.0534 (6) | |
H19A | 0.4459 | 0.6528 | 0.6955 | 0.048 (6)* | |
H19B | 0.4174 | 0.7754 | 0.6258 | 0.056 (7)* | |
C20 | 0.5818 (3) | 0.5253 (3) | 0.6265 (2) | 0.0781 (9) | |
H20A | 0.6380 | 0.5568 | 0.6693 | 0.119 (13)* | |
H20B | 0.6128 | 0.4760 | 0.5788 | 0.098 (10)* | |
H20C | 0.5346 | 0.4606 | 0.6543 | 0.095 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0728 (11) | 0.0500 (9) | 0.0337 (8) | 0.0179 (8) | 0.0056 (7) | 0.0004 (7) |
O2 | 0.0596 (10) | 0.0448 (9) | 0.0379 (8) | 0.0217 (8) | 0.0071 (7) | 0.0040 (7) |
O3 | 0.0931 (14) | 0.0559 (10) | 0.0424 (10) | 0.0222 (9) | −0.0100 (9) | −0.0048 (8) |
O4 | 0.0560 (11) | 0.0495 (10) | 0.0685 (11) | 0.0028 (8) | −0.0093 (8) | −0.0140 (8) |
O5 | 0.0534 (9) | 0.0447 (9) | 0.0383 (8) | 0.0062 (8) | 0.0078 (7) | 0.0065 (7) |
O6 | 0.1076 (15) | 0.0419 (10) | 0.0487 (10) | −0.0061 (10) | 0.0158 (10) | 0.0015 (8) |
O7 | 0.0522 (10) | 0.0650 (11) | 0.0560 (10) | 0.0233 (9) | 0.0054 (8) | 0.0003 (8) |
C1 | 0.0363 (12) | 0.0374 (12) | 0.0400 (12) | 0.0053 (10) | 0.0060 (9) | 0.0021 (9) |
C2 | 0.0362 (12) | 0.0417 (12) | 0.0352 (11) | 0.0080 (10) | 0.0051 (9) | 0.0060 (10) |
C3 | 0.0417 (13) | 0.0389 (12) | 0.0360 (11) | 0.0110 (10) | 0.0105 (9) | 0.0064 (10) |
C4 | 0.0466 (13) | 0.0414 (12) | 0.0334 (11) | 0.0079 (10) | 0.0106 (10) | 0.0033 (10) |
C5 | 0.0478 (14) | 0.0476 (13) | 0.0367 (12) | 0.0078 (11) | 0.0014 (10) | 0.0068 (10) |
C6 | 0.0457 (13) | 0.0390 (12) | 0.0457 (13) | 0.0133 (10) | 0.0025 (10) | 0.0037 (10) |
C7 | 0.0498 (14) | 0.0454 (14) | 0.0448 (13) | 0.0141 (12) | 0.0023 (11) | 0.0088 (11) |
C8 | 0.0687 (18) | 0.0666 (17) | 0.0327 (12) | 0.0125 (14) | 0.0033 (11) | −0.0018 (12) |
C9 | 0.0431 (13) | 0.0448 (13) | 0.0457 (14) | 0.0075 (10) | 0.0033 (10) | −0.0010 (11) |
C10 | 0.0492 (14) | 0.0452 (13) | 0.0439 (13) | 0.0023 (11) | 0.0043 (10) | −0.0026 (11) |
C11 | 0.0451 (13) | 0.0409 (12) | 0.0377 (12) | 0.0026 (10) | 0.0001 (10) | −0.0047 (10) |
C12 | 0.0553 (14) | 0.0302 (11) | 0.0289 (11) | 0.0053 (10) | 0.0006 (10) | −0.0043 (9) |
C13 | 0.0534 (15) | 0.0390 (13) | 0.0455 (13) | −0.0027 (11) | 0.0027 (11) | −0.0070 (10) |
C14 | 0.0741 (18) | 0.0327 (12) | 0.0466 (14) | 0.0007 (12) | −0.0002 (12) | 0.0026 (11) |
C15 | 0.0733 (18) | 0.0324 (12) | 0.0395 (13) | 0.0135 (12) | −0.0070 (12) | −0.0039 (10) |
C16 | 0.0535 (15) | 0.0395 (13) | 0.0357 (12) | 0.0124 (11) | −0.0014 (10) | −0.0083 (10) |
C17 | 0.0496 (14) | 0.0354 (12) | 0.0291 (11) | 0.0053 (10) | 0.0040 (9) | −0.0028 (9) |
C18 | 0.0658 (19) | 0.0740 (19) | 0.0603 (17) | 0.0344 (15) | −0.0103 (14) | −0.0140 (14) |
C19 | 0.0591 (16) | 0.0463 (14) | 0.0549 (14) | −0.0031 (13) | 0.0053 (12) | 0.0098 (12) |
C20 | 0.112 (3) | 0.0407 (15) | 0.085 (2) | −0.0029 (16) | 0.034 (2) | −0.0058 (15) |
C1—C9 | 1.478 (3) | C7—H7A | 0.9800 |
O3—C9 | 1.211 (2) | C7—H7B | 0.9800 |
C9—C10 | 1.502 (3) | C7—H7C | 0.9800 |
O4—C10 | 1.426 (3) | C8—H8A | 0.9800 |
O4—C11 | 1.418 (3) | C8—H8B | 0.9800 |
C10—C11 | 1.473 (3) | C8—H8C | 0.9800 |
C11—C12 | 1.483 (3) | C10—H10 | 1.0000 |
O1—C4 | 1.354 (2) | C11—H11 | 1.0000 |
O1—C8 | 1.427 (2) | C12—C17 | 1.381 (3) |
O2—C3 | 1.363 (2) | C12—C13 | 1.400 (3) |
O2—C7 | 1.434 (2) | C13—C14 | 1.371 (3) |
O5—C17 | 1.388 (2) | C13—H13 | 0.9500 |
O5—C19 | 1.432 (3) | C14—C15 | 1.383 (3) |
O6—C19 | 1.375 (3) | C14—H14 | 0.9500 |
O6—C20 | 1.409 (3) | C15—C16 | 1.387 (3) |
O7—C16 | 1.364 (3) | C15—H15 | 0.9500 |
O7—C18 | 1.422 (3) | C16—C17 | 1.404 (3) |
C1—C6 | 1.383 (3) | C18—H18A | 0.9800 |
C1—C2 | 1.398 (3) | C18—H18B | 0.9800 |
C2—C3 | 1.370 (3) | C18—H18C | 0.9800 |
C2—H2 | 0.9500 | C19—H19A | 0.9900 |
C3—C4 | 1.410 (3) | C19—H19B | 0.9900 |
C4—C5 | 1.380 (3) | C20—H20A | 0.9800 |
C5—C6 | 1.393 (3) | C20—H20B | 0.9800 |
C5—H5 | 0.9500 | C20—H20C | 0.9800 |
C6—H6 | 0.9500 | ||
C1—C9—C10 | 118.46 (19) | O4—C10—H10 | 117.1 |
O3—C9—C1 | 121.7 (2) | C11—C10—H10 | 117.1 |
O3—C9—C10 | 119.9 (2) | C9—C10—H10 | 117.1 |
O4—C10—C9 | 116.10 (18) | O4—C11—C10 | 59.07 (13) |
O4—C10—C11 | 58.57 (13) | O4—C11—H11 | 115.2 |
C11—C10—C9 | 117.93 (19) | C12—C11—H11 | 115.2 |
C11—O4—C10 | 62.36 (13) | C10—C11—H11 | 115.2 |
O4—C11—C12 | 118.07 (18) | C17—C12—C13 | 119.33 (19) |
C12—C11—C10 | 122.35 (19) | C17—C12—C11 | 119.52 (19) |
C4—O1—C8 | 117.99 (17) | C13—C12—C11 | 121.1 (2) |
C3—O2—C7 | 116.57 (16) | C14—C13—C12 | 120.1 (2) |
C17—O5—C19 | 114.82 (15) | C14—C13—H13 | 119.9 |
C19—O6—C20 | 114.30 (19) | C12—C13—H13 | 119.9 |
C16—O7—C18 | 117.5 (2) | C13—C14—C15 | 120.9 (2) |
C6—C1—C2 | 119.19 (19) | C13—C14—H14 | 119.5 |
C6—C1—C9 | 123.06 (19) | C15—C14—H14 | 119.5 |
C2—C1—C9 | 117.73 (18) | C16—C15—C14 | 119.7 (2) |
C3—C2—C1 | 120.74 (19) | C16—C15—H15 | 120.1 |
C3—C2—H2 | 119.6 | C14—C15—H15 | 120.1 |
C1—C2—H2 | 119.6 | C15—C16—O7 | 124.8 (2) |
C2—C3—O2 | 125.21 (18) | C15—C16—C17 | 119.5 (2) |
C2—C3—C4 | 119.81 (18) | O7—C16—C17 | 115.67 (19) |
O2—C3—C4 | 114.97 (17) | O5—C17—C12 | 119.12 (18) |
O1—C4—C3 | 114.98 (18) | O5—C17—C16 | 120.48 (19) |
O1—C4—C5 | 125.31 (19) | C12—C17—C16 | 120.3 (2) |
C3—C4—C5 | 119.71 (19) | O7—C18—H18A | 109.5 |
C6—C5—C4 | 119.9 (2) | O7—C18—H18B | 109.5 |
C6—C5—H5 | 120.0 | H18A—C18—H18B | 109.5 |
C4—C5—H5 | 120.0 | O7—C18—H18C | 109.5 |
C5—C6—C1 | 120.63 (19) | H18A—C18—H18C | 109.5 |
C5—C6—H6 | 119.7 | H18B—C18—H18C | 109.5 |
C1—C6—H6 | 119.7 | O6—C19—O5 | 113.1 (2) |
O2—C7—H7A | 109.5 | O6—C19—H19A | 109.0 |
O2—C7—H7B | 109.5 | O5—C19—H19A | 109.0 |
H7A—C7—H7B | 109.5 | O6—C19—H19B | 109.0 |
O2—C7—H7C | 109.5 | O5—C19—H19B | 109.0 |
H7A—C7—H7C | 109.5 | H19A—C19—H19B | 107.8 |
H7B—C7—H7C | 109.5 | O6—C20—H20A | 109.5 |
O1—C8—H8A | 109.5 | O6—C20—H20B | 109.5 |
O1—C8—H8B | 109.5 | H20A—C20—H20B | 109.5 |
H8A—C8—H8B | 109.5 | O6—C20—H20C | 109.5 |
O1—C8—H8C | 109.5 | H20A—C20—H20C | 109.5 |
H8A—C8—H8C | 109.5 | H20B—C20—H20C | 109.5 |
H8B—C8—H8C | 109.5 | ||
C6—C1—C2—C3 | 1.1 (3) | C9—C10—C11—O4 | 105.0 (2) |
C9—C1—C2—C3 | 179.57 (19) | O4—C10—C11—C12 | 105.7 (2) |
C1—C2—C3—O2 | 178.04 (19) | C9—C10—C11—C12 | −149.3 (2) |
C1—C2—C3—C4 | −0.7 (3) | O4—C11—C12—C17 | −152.82 (18) |
C7—O2—C3—C2 | 3.6 (3) | C10—C11—C12—C17 | 137.8 (2) |
C7—O2—C3—C4 | −177.60 (18) | O4—C11—C12—C13 | 27.2 (3) |
C8—O1—C4—C3 | −172.81 (19) | C10—C11—C12—C13 | −42.2 (3) |
C8—O1—C4—C5 | 7.1 (3) | C17—C12—C13—C14 | −0.5 (3) |
C2—C3—C4—O1 | 179.50 (18) | C11—C12—C13—C14 | 179.40 (19) |
O2—C3—C4—O1 | 0.7 (3) | C12—C13—C14—C15 | 0.8 (3) |
C2—C3—C4—C5 | −0.4 (3) | C13—C14—C15—C16 | 0.6 (3) |
O2—C3—C4—C5 | −179.21 (18) | C14—C15—C16—O7 | 177.36 (19) |
O1—C4—C5—C6 | −178.9 (2) | C14—C15—C16—C17 | −2.3 (3) |
C3—C4—C5—C6 | 1.0 (3) | C18—O7—C16—C15 | 1.3 (3) |
C4—C5—C6—C1 | −0.6 (3) | C18—O7—C16—C17 | −179.05 (18) |
C2—C1—C6—C5 | −0.5 (3) | C19—O5—C17—C12 | −116.1 (2) |
C9—C1—C6—C5 | −178.9 (2) | C19—O5—C17—C16 | 66.9 (2) |
C6—C1—C9—O3 | 163.4 (2) | C13—C12—C17—O5 | −178.16 (16) |
C2—C1—C9—O3 | −15.0 (3) | C11—C12—C17—O5 | 1.9 (3) |
C6—C1—C9—C10 | −15.4 (3) | C13—C12—C17—C16 | −1.2 (3) |
C2—C1—C9—C10 | 166.20 (19) | C11—C12—C17—C16 | 178.90 (17) |
C11—O4—C10—C9 | −108.2 (2) | C15—C16—C17—O5 | 179.52 (17) |
O3—C9—C10—O4 | 10.3 (3) | O7—C16—C17—O5 | −0.1 (3) |
C1—C9—C10—O4 | −170.88 (18) | C15—C16—C17—C12 | 2.6 (3) |
O3—C9—C10—C11 | −56.3 (3) | O7—C16—C17—C12 | −177.09 (18) |
C1—C9—C10—C11 | 122.6 (2) | C20—O6—C19—O5 | 80.5 (3) |
C10—O4—C11—C12 | −112.8 (2) | C17—O5—C19—O6 | 68.8 (2) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C23H26O7 | C20H22O7 |
Mr | 414.44 | 374.38 |
Crystal system, space group | Monoclinic, Cc | Monoclinic, P21/c |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 14.4281 (5), 18.8386 (7), 9.0887 (3) | 12.7503 (10), 9.4201 (7), 15.4409 (12) |
β (°) | 125.285 (1) | 94.706 (2) |
V (Å3) | 2016.52 (12) | 1848.3 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.42 × 0.22 × 0.18 | 0.65 × 0.14 × 0.06 |
Data collection | ||
Diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.608, 0.982 | 0.805, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18037, 3639, 3193 | 19850, 3280, 2257 |
Rint | 0.034 | 0.057 |
(sin θ/λ)max (Å−1) | 0.769 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.099, 1.01 | 0.044, 0.113, 1.01 |
No. of reflections | 3639 | 3280 |
No. of parameters | 274 | 270 |
No. of restraints | 2 | 0 |
H-atom treatment | H-atom parameters constrained | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.18 | 0.39, −0.14 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT and SADABS (Sheldrick, 2003), SHELXTL (Bruker, 2003), SHELXTL, DIAMOND (Brandenburg, 2005).
Bond | (I) | (II) | Angle | (I) | (II) |
C1-C9 | 1.483 (2) | 1.478 (3) | C1-C9-C10 | 118.37 (13) | 118.46 (19) |
O3-C9 | 1.215 (2) | 1.211 (2) | O3-C9-C1 | 122.03 (14) | 121.7 (2) |
C9-C10 | 1.504 (2) | 1.502 (3) | O3-C9-C10 | 119.47 (14) | 119.9 (2) |
C10-C11 | 1.489 (2) | 1.473 (3) | O4-C10-C9 | 115.59 (13) | 116.10 (18) |
O4-C10 | 1.4256 (19) | 1.426 (3) | O4-C10-C11 | 58.99 (10) | 58.57 (13) |
O4-C11 | 1.4359 (19) | 1.418 (3) | O4-C11-C10 | 58.31 (10) | 59.07 (13) |
C11-C12 | 1.483 (2) | 1.483 (3) | C10-O4-C11 | 62.71 (10) | 62.36 (13) |
O4-C11-C12 | 117.26 (13) | 118.07 (18) | |||
C9-C10-C11 | 115.84 (14) | 117.93 (19) | |||
C10-C11-C12 | 121.84 (14) | 122.35 (19) |
Code | τ1 | τ2 | τ3 | A/B |
(I)a | 147 | 123.41 (15) | -149.91 (13) | 85.44 (9) |
(II)a | 148 | 122.6 (2) | -149.3 (2) | 89.92 (10) |
EXEWOTb | 157 | 122.8 | -154.2 | 107.7 |
EXEWOTc | 149 | 101.5 | -151.1 | 65.3 |
FATQOHd* | 147 | 113.0 | -154.2 | 48.6 |
LIGXUUe | 169 (5) | 112.8 (7) | -151.0 (6) | 99.0 |
LIGXUU01f | 157 (15) | 145 (1) | -149 (1) | 114.5 |
QECFAFg | 148 | 147.4 | -150.5 | 127.3 |
QINFICh | 151 | 143.3 | -150.7 | 144.0 |
SOMHEHi | 106 | 119.9 | -148.4 | 93.9 |
WAMLOMj | 148 | 121.5 | -152.1 | 87.1 |
TECTAXk | 147 | 158.8 | -153.2 | 133.1 |
VAZBOOl* | 150 | 150.0 | -154.6 | 103.8 |
Notes: τ1=H10-C10-C11-H11, τ2=C1-C9-C10-C11, τ3=C9-C10-C11-C12, A/B=angle between the aromatic rings in relation to the oxirane group. (a) this work; (b) Bakó et al. (2004), first molecule; (c) Bakó et al. (2004), second molecule; (d) Shi et al. (2004); (e) Stomberg et al. (1994), monoclinic form; (f) Stomberg et al. (1994), trigonal form; (g) Bakó et al. (1999); (h) Bardet et al. (1999); (i) Baures et al. (1990); (j) Xu et al. (2005); (k) Zhang et al. (2006); (l) Cuthbertson et al. (2005); (*) Racemic crystal - data for the opposite enantiomer are deposited in CSD. |
Label | D—H···A | D—H | H···A | D···A | D—H···A | |
[a] | C3—H3···O1i | 0.95 | 2.56 | 3.415 (2) | 150 | |
[b] | C7—H7A···O2i | 0.98 | 2.48 | 3.396 (2) | 155 | |
[c] | C7—H7B···O4ii | 0.98 | 2.53 | 3.456 (2) | 157 | |
[d] | C14—H14···O3iii | 0.95 | 2.56 | 3.458 (2) | 158 | |
[e] | C18—H18A···O3iv | 0.98 | 2.45 | 3.384 (2) | 158 | |
[f] | C21—H21A···O7v | 0.99 | 2.59 | 3.2139 (19) | 121 |
Symmetry codes: (i) x, 2 − y, z − 1/2; (ii) x − 1/2, 1/2 + y, z; (iii) x, y, z − 1; (iv) 1/2 + x, 3/2 − y, z − 1/2; (v) x, 2 − y, 1/2 + z. |
Label | D—H···A | D—H | H···A | D···A | D—H···A |
[a] | C7—H7C···O3i | 0.98 | 2.53 | 2.923 (3) | 104 |
[b] | C11—H11···O5 | 1.00 | 2.40 | 2.788 (3) | 102 |
[c] | C19—H19B···O7 | 0.99 | 2.29 | 2.924 (3) | 121 |
Symmetry code: (i) −x + 2, y − 1/2, −z + 3/2. |
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Compounds (I) and (II) are obtained on epoxidation of chalcones (Li & Lundquist, 1997). Compound (I) (m.p. 401 K) and a diastereomer (m.p. 370–371 K) are obtained on epoxidation of the chalcone 1-(3,4-dimethoxyphenyl)-3-[3-methoxy-2-(tetrahydropyran-2-yloxy)phenyl] −2-propen-1-one. The epoxidation is accomplished with hydrogen peroxide using a method involving phase-transfer catalysis (Brunow & Lundquist, 1981, 1984). The epoxides can be converted to a lignin model of the phenylcoumaran type (III) in three reaction steps: BF3-catalysed rearrangement, sodium borohydride reduction and acid-catalysed ring closure. The yield of (III) obtained from (II) was low (Li & Lundquist, 1997). Studies of the reactions involved have shown that the outcome of the rearrangement reaction is strongly dependent on the structure of the epoxide and the conditions prevailing during the reaction (Ralph et al., 1987; Li et al., 1993). It should be noted that reduction of the rearrangement product with sodium borohydride under alkaline conditions lowers the yield substantially (Li et al., 1993). The synthesis of the cis isomer corresponding to (III) using (I) as starting material has been described (Li et al., 1997). The lignin model (IV) has also been prepared via a chalcone epoxide (Brunow & Lundquist, 1984); the stereochemistry of (IV) has been established by a crystal structure determination (Stomberg & Lundquist, 1987). Compound (IV) has been used as starting material in the synthesis of neolignans of the phenylcoumaran type (Juhász et al., 2000, 2001). It is notable that a chalcone epoxide of the topical type is an intermediate in a synthesis of the flavonolignan silychristin (Tanaka et al., 1989).
Perspective drawings and the atom-numbering of (I) and (II) are shown in Figs. 1 and 2, respectively. Selected bond distances and bond angles for both compounds are given in Table 1. The crystal structures establish the stereochemistries of (I) and (II) and confirm their molecular structures. Comparison of the 1H NMR spectra (Li & Lundquist, 1997) of (I) and its diastereomer of m.p. 370–371 K suggests that the diastereomers differ with respect to the configuration of the asymmetric carbon in the tetrahydropyranyl group. The substituents at the oxirane rings of (I) and (II) are trans-orientated. Chalcone epoxides described in the literature in general have the trans configuration but chalcone epoxides with the cis configuration are known (Wasserman & Aubrey, 1955; Matano, 1994).
Excepting the C10—C11 and O4—C11 bond lengths and bond angles involving the atoms of the oxirane rings (the C9—C10—C11 angles differ by 2.1º), the bond lengths and bond angles in the central parts of (I) and (II) are, within experimental error, the same (Table 1). The C1—C9—C10—C11 and C9—C10—C11—C12 torsion angles (denoted τ2 and τ3 in Table 2) differ just slightly, by 0.8 and 0.6º, respectively.
Comparison with the crystal structures of related chalcone epoxides was performed after a search of the Cambridge Structural Database (CSD; Version 5.27 of November 2005, plus two updates; Allen, 2002). The substituents at the oxirane ring are trans-orientated in the chalcone epoxides subjected to crystal structure determinations to date. Some pertinent structural data are tabulated in Table 2. It is apparent that torsion angle τ3 is less flexible than torsion angle τ2. The angles between the planes of the aromatic rings differ considerably.
There are weak C—H···O hydrogen bonds present in the crystal structures of both (I) and (II). (For geometrical details and notations of these hydrogen bonds see Tables 3 and 4.) The hydrogen-bonding patterns of (I) and (II) are quite different. For (I), on the first-level graph set, defined by Bernstein et al. (1995) and Grell et al. (1999), the following chains are formed: C(4) by hydrogen bond a, C(5) by f, C(6) by b, C(8) by d, and C(10) by c and e. On the second-level graph set, rings R22(10) (a, b), R22(27) (a, f) and R22(29) (b, f) and chains C21(8) (d, e), C22(8) (a, b), C22(10) (a, c; b, c), C22(14) (a, c), C22(15) (c, d), C22(16) (b, c), C22(17) (c, e), C22(18) (a, d; c, d; d, e), C22(19) (d, f; e, f), C22(20) (a, e; b, d; c, e), C22(22) (b, e), C22(24) (c, f) and C22(29) (b, f) were recognized. For (II), the hydrogen bonds can be descibed just on the first-level graph-set level, viz. chain C(8) for a, and intramolecular strings S(5) for b and S(6) for c. The assignments of graph-set descriptors were performed using PLUTO as described by Motherwell et al. (1999). All the examined chalcone epoxides (Table 2) have different hydrogen-bonding patterns.