organic compounds
Pallidol hexaacetate ethyl acetate monosolvate
aSchool of Agriculture, Food and Wine, The University of Adelaide, Waite Campus, PMB 1, Glen Osmond, SA 5064, Australia, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: edward.tiekink@gmail.com
The entire molecule of pallidol hexaacetate {systematic name: (±)-(4bR,5R,9bR,10R)-5,10-bis[4-(acetyloxy)phenyl]-4b,5,9b,10-tetrahydroindeno[2,1-a]indene-1,3,6,8-tetrayl tetraacetate} is completed by the application of twofold rotational symmetry in the title ethyl acetate solvate, C40H34O12·C4H8O2. The ethyl acetate molecule was highly disordered and was treated with the SQUEEZE routine [Spek (2009). Acta Cryst. D65, 148–155]; the crystallographic data take into account the presence of the solvent. In pallidol hexaacetate, the dihedral angle between the fused five-membered rings (r.m.s. deviation = 0.100 Å) is 54.73 (6)°, indicating a significant fold in the molecule. Significant twists between residues are also evident as seen in the dihedral angle of 80.70 (5)° between the five-membered ring and the pendent benzene ring to which it is attached. Similarly, the acetate residues are twisted with respect to the benzene ring to which they are attached [C—O(carboxy)—C—C torsion angles = −70.24 (14), −114.43 (10) and −72.54 (13)°]. In the crystal, a three-dimensional architecture is sustained by C—H⋯O interactions which encompass channels in which the disordered ethyl acetate molecules reside.
Related literature
For synthetic protocols, see: Takaya et al. (2005); Moss et al. (2013). For the spectroscopic characteristics of pallidol hexaacetate, see: Khan et al. (1986).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2013); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S160053681301708X/su2614sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681301708X/su2614Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S160053681301708X/su2614Isup3.cml
To a stirred solution of trans-resveratrol (500 mg) and K2CO3 (245 mg) in MeOH (120 ml) at ambient temperature was slowly added an aqueous solution of K3Fe(CN)6 (575 mg in 10 ml) over 5 minutes and the mixture stirred for a further 30 minutes. The mixture was then concentrated in vacuo and loaded directly onto a flash ε-viniferin pentaacetate and trans-δ-viniferin pentaacetate (120 mg, 1:2). Recrystallization of the pallidol hexaacetate from neat EtOAc afforded pure material as a colourless crystalline solid. Melting point 486.0–488.4 K; 1H NMR (600 MHz, CDCl3): δ 7.15 (4H, d, J = 8.4 Hz), 7.05 (4H, d, J = 8.4 Hz), 6.88 (2H, d, J = 1.8 Hz), 6.76 (2H, d, J = 1.8 Hz), 4.45 (2H, dd, J = 3.0, 3.0 Hz), 4.17 (2H, dd, J = 3.0, 3.0 Hz), 2.30 (6H, 2 x OAc), 2.28 (6H, 2 x OAc), 1.69 (6H, 2 x OAc). 13C NMR (600 MHz, CDCl3): δ 169.46, 169.01 and 167.82 (3 x COCH3), 150.9, 149.5, 147.9, 147.4, 140.6, 133.6, 128.7, 121.8, 115.4, 115.1, 61.2, 55.7, 21.11, 21.09 and 19.95 (3 x COCH3). All other spectral data are identical to those previously reported by Khan et al. (1986).
column and the organics eluted with EtOAc. The fraction containing the crude dimers was concentrated in vacuo and then dissolved in CH2Cl2 (60 ml) and DMSO (10 ml). Ac2O (0.83 ml) and Et3N (1.23 ml) were then added and the reaction mixture kept at ambient temperature for 24 h. The reaction was then quenched with NaHCO3 (30 ml) and the organics extracted with EtOAc (3 x 30 ml). The combined organics were washed with water (20 ml), dried (MgSO4) and the volatiles removed in vacuo. The acetates were then separated by flash (increasing polarity from 20% to 50% ethylacetate in petroleum spirit) to afford pallidol hexaacetate (150 mg) along with several other dimers identified as trans-C-bound H-atoms were placed in calculated positions and were included in the
in the riding model approximation: C—H = 0.95 to 0.98 Å, with Uiso(H) =1.5Ueq(C-methyl) and = 1.2Ueq(C) for other H atoms. The heavily disordered ethyl acetate molecule, lying on a 2-fold rotation axis, was removed by using the SQUEEZE option in PLATON (Spek, 2009).The synthesis of pallidol hexaacetate was achieved by employing a modified procedure to that reported by Takaya et al. (2005) as outlined by Moss et al. (2013) which involved the oxidation of trans-resveratrol with K3Fe(CN)6. Herein, the
determination of pallidol hexaacetate, isolated as its ethylacetate solvate, (I), is described.The pallidol hexaacetate molecule is disposed about a two-fold rotation axis, Fig. 1. The central five-membered ring is approximately planar with a r.m.s. deviation of 0.100 Å. The maximum deviations = 0.086 (1) Å for the C10 atom and -0.081 (1) Å for the C9 atom, indicating a small twist about the C9—C10 bond. The dihedral angle between the mean planes of the fused five-membered rings is 54.73 (6)°, indicating significant curvature in the molecule. The pendent benzene ring is nearly perpendicular to the mean plane of the five-membered ring to which it is attached, forming a dihedral angle of 80.70 (5)°. None of the acetate residues are co-planar with the benzene ring to which they are attached as seen in the values of the C2—O1—C3—C4 [-70.24 (14)°], C17—O3—C16—C11 [-114.43 (10)°] and C19—O5—C14—C13 [-72.54 (13)°] torsion angles.
In the crystal, molecules assemble into a three-dimensional architecture via C—H···O interactions, Fig. 2 and Table 1. In so doing, they define channels in which, presumably, reside the disordered ethylacetate molecules.
For synthetic protocols, see: Takaya et al. (2005); Moss et al. (2013). For the spectroscopic characteristics of pallidol hexaacetate, see: Khan et al. (1986).
Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Unlabelled atoms are related by the symmetry operation 1 - x, y, 1/2 - z. The disordered ethylacetate molecule is omitted. | |
Fig. 2. A view in projection down the c axis of the unit-cell contents of (I). The C—H···O interactions are shown as blue dashed lines. The disordered ethylacetate molecules are omitted but, presumably lie in the occupied channels. |
C40H34O12·C4H8O2 | F(000) = 1672 |
Mr = 794.78 | Dx = 1.321 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -C 2yc | Cell parameters from 19786 reflections |
a = 13.1495 (1) Å | θ = 3.7–74.3° |
b = 12.7439 (1) Å | µ = 0.83 mm−1 |
c = 24.0386 (2) Å | T = 100 K |
β = 97.186 (1)° | Prism, colourless |
V = 3996.65 (5) Å3 | 0.30 × 0.10 × 0.10 mm |
Z = 4 |
Agilent SuperNova Dual diffractometer with an Atlas detector | 4029 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 3714 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.022 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 74.4°, θmin = 3.7° |
ω scan | h = −16→15 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = 0→15 |
Tmin = 0.790, Tmax = 0.922 | l = 0→29 |
27173 measured reflections |
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) = 0.095 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0505P)2 + 2.699P] where P = (Fo2 + 2Fc2)/3 |
4029 reflections | (Δ/σ)max = 0.001 |
238 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C40H34O12·C4H8O2 | V = 3996.65 (5) Å3 |
Mr = 794.78 | Z = 4 |
Monoclinic, C2/c | Cu Kα radiation |
a = 13.1495 (1) Å | µ = 0.83 mm−1 |
b = 12.7439 (1) Å | T = 100 K |
c = 24.0386 (2) Å | 0.30 × 0.10 × 0.10 mm |
β = 97.186 (1)° |
Agilent SuperNova Dual diffractometer with an Atlas detector | 4029 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | 3714 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.922 | Rint = 0.022 |
27173 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.21 e Å−3 |
4029 reflections | Δρmin = −0.22 e Å−3 |
238 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.23221 (6) | 0.46511 (7) | 0.48061 (3) | 0.0295 (2) | |
O2 | 0.35408 (8) | 0.41673 (8) | 0.54965 (4) | 0.0408 (2) | |
O3 | 0.56127 (6) | 0.19610 (6) | 0.42147 (3) | 0.02298 (17) | |
O4 | 0.63350 (6) | 0.31813 (7) | 0.48240 (3) | 0.02886 (19) | |
O5 | 0.88454 (6) | 0.23900 (7) | 0.35088 (3) | 0.02608 (19) | |
O6 | 0.86993 (7) | 0.10847 (7) | 0.28727 (4) | 0.0331 (2) | |
C1 | 0.20807 (11) | 0.51331 (11) | 0.57260 (5) | 0.0374 (3) | |
H1A | 0.2441 | 0.5165 | 0.6108 | 0.056* | |
H1B | 0.1442 | 0.4737 | 0.5727 | 0.056* | |
H1C | 0.1924 | 0.5846 | 0.5589 | 0.056* | |
C2 | 0.27454 (9) | 0.46003 (9) | 0.53515 (5) | 0.0287 (3) | |
C3 | 0.28958 (8) | 0.41950 (9) | 0.44109 (4) | 0.0244 (2) | |
C4 | 0.37948 (8) | 0.46632 (9) | 0.42947 (4) | 0.0238 (2) | |
H4 | 0.4048 | 0.5278 | 0.4489 | 0.029* | |
C5 | 0.43189 (8) | 0.42139 (8) | 0.38878 (4) | 0.0215 (2) | |
H5 | 0.4939 | 0.4526 | 0.3805 | 0.026* | |
C6 | 0.39535 (8) | 0.33136 (8) | 0.35982 (4) | 0.0194 (2) | |
C7 | 0.30498 (8) | 0.28622 (9) | 0.37288 (4) | 0.0238 (2) | |
H7 | 0.2793 | 0.2248 | 0.3536 | 0.029* | |
C8 | 0.25172 (8) | 0.32971 (10) | 0.41377 (5) | 0.0270 (2) | |
H8 | 0.1904 | 0.2982 | 0.4227 | 0.032* | |
C9 | 0.45295 (8) | 0.28440 (8) | 0.31499 (4) | 0.0184 (2) | |
H9 | 0.4240 | 0.2132 | 0.3052 | 0.022* | |
C10 | 0.44581 (7) | 0.35182 (8) | 0.25998 (4) | 0.0185 (2) | |
H10 | 0.4247 | 0.4252 | 0.2678 | 0.022* | |
C11 | 0.56755 (8) | 0.27379 (8) | 0.33139 (4) | 0.0188 (2) | |
C12 | 0.62362 (8) | 0.30738 (8) | 0.28902 (4) | 0.0191 (2) | |
C13 | 0.72954 (8) | 0.29618 (8) | 0.29446 (4) | 0.0218 (2) | |
H13 | 0.7679 | 0.3192 | 0.2658 | 0.026* | |
C14 | 0.77742 (8) | 0.25032 (9) | 0.34309 (4) | 0.0220 (2) | |
C15 | 0.72490 (8) | 0.21823 (8) | 0.38658 (4) | 0.0218 (2) | |
H15 | 0.7599 | 0.1880 | 0.4197 | 0.026* | |
C16 | 0.61939 (8) | 0.23177 (8) | 0.38003 (4) | 0.0207 (2) | |
C17 | 0.57259 (8) | 0.24896 (9) | 0.47149 (4) | 0.0229 (2) | |
C18 | 0.49717 (9) | 0.20992 (11) | 0.50834 (5) | 0.0318 (3) | |
H18A | 0.5242 | 0.2217 | 0.5477 | 0.048* | |
H18B | 0.4856 | 0.1347 | 0.5019 | 0.048* | |
H18C | 0.4322 | 0.2477 | 0.4996 | 0.048* | |
C19 | 0.92348 (9) | 0.16363 (9) | 0.31875 (4) | 0.0255 (2) | |
C20 | 1.03744 (9) | 0.16233 (11) | 0.32956 (5) | 0.0334 (3) | |
H20A | 1.0641 | 0.1074 | 0.3068 | 0.050* | |
H20B | 1.0589 | 0.1480 | 0.3694 | 0.050* | |
H20C | 1.0643 | 0.2306 | 0.3197 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0263 (4) | 0.0399 (5) | 0.0223 (4) | 0.0058 (3) | 0.0037 (3) | −0.0057 (3) |
O2 | 0.0498 (6) | 0.0482 (6) | 0.0237 (4) | 0.0166 (5) | 0.0015 (4) | 0.0032 (4) |
O3 | 0.0252 (4) | 0.0263 (4) | 0.0168 (3) | −0.0011 (3) | 0.0004 (3) | 0.0028 (3) |
O4 | 0.0302 (4) | 0.0337 (4) | 0.0223 (4) | −0.0028 (3) | 0.0017 (3) | −0.0036 (3) |
O5 | 0.0180 (4) | 0.0374 (5) | 0.0217 (4) | 0.0034 (3) | −0.0021 (3) | −0.0062 (3) |
O6 | 0.0350 (5) | 0.0312 (4) | 0.0323 (4) | 0.0066 (4) | 0.0001 (3) | −0.0058 (4) |
C1 | 0.0450 (7) | 0.0404 (7) | 0.0289 (6) | −0.0006 (6) | 0.0127 (5) | −0.0086 (5) |
C2 | 0.0362 (6) | 0.0282 (6) | 0.0221 (5) | −0.0005 (5) | 0.0055 (5) | −0.0006 (4) |
C3 | 0.0235 (5) | 0.0311 (6) | 0.0185 (5) | 0.0061 (4) | 0.0020 (4) | −0.0013 (4) |
C4 | 0.0260 (5) | 0.0242 (5) | 0.0201 (5) | 0.0012 (4) | −0.0013 (4) | −0.0026 (4) |
C5 | 0.0219 (5) | 0.0220 (5) | 0.0202 (5) | −0.0012 (4) | 0.0013 (4) | 0.0008 (4) |
C6 | 0.0195 (5) | 0.0219 (5) | 0.0159 (5) | 0.0017 (4) | −0.0015 (4) | 0.0018 (4) |
C7 | 0.0221 (5) | 0.0264 (5) | 0.0222 (5) | −0.0031 (4) | −0.0004 (4) | −0.0031 (4) |
C8 | 0.0203 (5) | 0.0359 (6) | 0.0247 (5) | −0.0022 (4) | 0.0025 (4) | −0.0012 (5) |
C9 | 0.0205 (5) | 0.0173 (5) | 0.0167 (5) | −0.0008 (4) | −0.0009 (4) | 0.0004 (4) |
C10 | 0.0205 (5) | 0.0172 (5) | 0.0172 (5) | 0.0009 (4) | 0.0003 (4) | 0.0005 (4) |
C11 | 0.0206 (5) | 0.0165 (5) | 0.0186 (5) | 0.0005 (4) | 0.0002 (4) | −0.0015 (4) |
C12 | 0.0215 (5) | 0.0182 (5) | 0.0167 (5) | −0.0010 (4) | −0.0011 (4) | −0.0023 (4) |
C13 | 0.0223 (5) | 0.0251 (5) | 0.0179 (5) | −0.0013 (4) | 0.0017 (4) | −0.0034 (4) |
C14 | 0.0179 (5) | 0.0260 (5) | 0.0209 (5) | 0.0014 (4) | −0.0023 (4) | −0.0058 (4) |
C15 | 0.0242 (5) | 0.0227 (5) | 0.0172 (5) | 0.0032 (4) | −0.0025 (4) | −0.0024 (4) |
C16 | 0.0241 (5) | 0.0202 (5) | 0.0172 (5) | 0.0003 (4) | 0.0012 (4) | −0.0005 (4) |
C17 | 0.0240 (5) | 0.0270 (5) | 0.0166 (5) | 0.0054 (4) | −0.0014 (4) | 0.0028 (4) |
C18 | 0.0305 (6) | 0.0432 (7) | 0.0220 (5) | 0.0002 (5) | 0.0043 (4) | 0.0066 (5) |
C19 | 0.0282 (6) | 0.0289 (6) | 0.0193 (5) | 0.0082 (4) | 0.0026 (4) | 0.0045 (4) |
C20 | 0.0254 (6) | 0.0429 (7) | 0.0321 (6) | 0.0093 (5) | 0.0044 (5) | 0.0073 (5) |
O1—C2 | 1.3603 (14) | C9—C11 | 1.5152 (14) |
O1—C3 | 1.4103 (13) | C9—C10 | 1.5697 (13) |
O2—C2 | 1.1953 (15) | C9—H9 | 1.0000 |
O3—C17 | 1.3700 (13) | C10—C12i | 1.5076 (14) |
O3—C16 | 1.4049 (13) | C10—C10i | 1.560 (2) |
O4—C17 | 1.1978 (14) | C10—H10 | 1.0000 |
O5—C19 | 1.3712 (13) | C11—C16 | 1.3854 (14) |
O5—C14 | 1.4050 (13) | C11—C12 | 1.3972 (14) |
O6—C19 | 1.1955 (14) | C12—C13 | 1.3900 (15) |
C1—C2 | 1.4941 (16) | C12—C10i | 1.5076 (13) |
C1—H1A | 0.9800 | C13—C14 | 1.3857 (15) |
C1—H1B | 0.9800 | C13—H13 | 0.9500 |
C1—H1C | 0.9800 | C14—C15 | 1.3849 (15) |
C3—C8 | 1.3807 (16) | C15—C16 | 1.3873 (15) |
C3—C4 | 1.3835 (16) | C15—H15 | 0.9500 |
C4—C5 | 1.3886 (15) | C17—C18 | 1.4951 (15) |
C4—H4 | 0.9500 | C18—H18A | 0.9800 |
C5—C6 | 1.3957 (15) | C18—H18B | 0.9800 |
C5—H5 | 0.9500 | C18—H18C | 0.9800 |
C6—C7 | 1.3910 (15) | C19—C20 | 1.4886 (16) |
C6—C9 | 1.5158 (14) | C20—H20A | 0.9800 |
C7—C8 | 1.3915 (15) | C20—H20B | 0.9800 |
C7—H7 | 0.9500 | C20—H20C | 0.9800 |
C8—H8 | 0.9500 | ||
C2—O1—C3 | 116.15 (9) | C12i—C10—H10 | 110.1 |
C17—O3—C16 | 117.01 (8) | C10i—C10—H10 | 110.1 |
C19—O5—C14 | 115.82 (8) | C9—C10—H10 | 110.1 |
C2—C1—H1A | 109.5 | C16—C11—C12 | 119.00 (9) |
C2—C1—H1B | 109.5 | C16—C11—C9 | 128.50 (9) |
H1A—C1—H1B | 109.5 | C12—C11—C9 | 112.41 (9) |
C2—C1—H1C | 109.5 | C13—C12—C11 | 120.93 (9) |
H1A—C1—H1C | 109.5 | C13—C12—C10i | 127.87 (9) |
H1B—C1—H1C | 109.5 | C11—C12—C10i | 111.20 (9) |
O2—C2—O1 | 122.74 (11) | C14—C13—C12 | 117.83 (10) |
O2—C2—C1 | 126.19 (11) | C14—C13—H13 | 121.1 |
O1—C2—C1 | 111.06 (10) | C12—C13—H13 | 121.1 |
C8—C3—C4 | 121.86 (10) | C15—C14—C13 | 122.99 (10) |
C8—C3—O1 | 118.07 (10) | C15—C14—O5 | 117.09 (9) |
C4—C3—O1 | 120.05 (10) | C13—C14—O5 | 119.86 (10) |
C3—C4—C5 | 118.44 (10) | C14—C15—C16 | 117.63 (10) |
C3—C4—H4 | 120.8 | C14—C15—H15 | 121.2 |
C5—C4—H4 | 120.8 | C16—C15—H15 | 121.2 |
C4—C5—C6 | 121.34 (10) | C11—C16—C15 | 121.55 (10) |
C4—C5—H5 | 119.3 | C11—C16—O3 | 118.01 (9) |
C6—C5—H5 | 119.3 | C15—C16—O3 | 120.29 (9) |
C7—C6—C5 | 118.55 (10) | O4—C17—O3 | 123.38 (10) |
C7—C6—C9 | 120.94 (9) | O4—C17—C18 | 126.17 (10) |
C5—C6—C9 | 120.51 (9) | O3—C17—C18 | 110.43 (10) |
C6—C7—C8 | 120.95 (10) | C17—C18—H18A | 109.5 |
C6—C7—H7 | 119.5 | C17—C18—H18B | 109.5 |
C8—C7—H7 | 119.5 | H18A—C18—H18B | 109.5 |
C3—C8—C7 | 118.86 (10) | C17—C18—H18C | 109.5 |
C3—C8—H8 | 120.6 | H18A—C18—H18C | 109.5 |
C7—C8—H8 | 120.6 | H18B—C18—H18C | 109.5 |
C11—C9—C6 | 114.79 (8) | O6—C19—O5 | 122.45 (10) |
C11—C9—C10 | 102.76 (8) | O6—C19—C20 | 127.18 (11) |
C6—C9—C10 | 113.59 (8) | O5—C19—C20 | 110.37 (10) |
C11—C9—H9 | 108.5 | C19—C20—H20A | 109.5 |
C6—C9—H9 | 108.5 | C19—C20—H20B | 109.5 |
C10—C9—H9 | 108.5 | H20A—C20—H20B | 109.5 |
C12i—C10—C10i | 104.29 (9) | C19—C20—H20C | 109.5 |
C12i—C10—C9 | 114.78 (8) | H20A—C20—H20C | 109.5 |
C10i—C10—C9 | 107.37 (8) | H20B—C20—H20C | 109.5 |
C3—O1—C2—O2 | −2.36 (17) | C10—C9—C11—C12 | −11.21 (11) |
C3—O1—C2—C1 | 178.50 (10) | C16—C11—C12—C13 | 1.96 (15) |
C2—O1—C3—C8 | 111.57 (12) | C9—C11—C12—C13 | −174.97 (9) |
C2—O1—C3—C4 | −70.24 (14) | C16—C11—C12—C10i | −179.25 (9) |
C8—C3—C4—C5 | 0.54 (17) | C9—C11—C12—C10i | 3.83 (12) |
O1—C3—C4—C5 | −177.59 (9) | C11—C12—C13—C14 | 0.27 (15) |
C3—C4—C5—C6 | 0.24 (16) | C10i—C12—C13—C14 | −178.31 (10) |
C4—C5—C6—C7 | −0.59 (15) | C12—C13—C14—C15 | −1.81 (16) |
C4—C5—C6—C9 | 179.16 (9) | C12—C13—C14—O5 | −178.90 (9) |
C5—C6—C7—C8 | 0.18 (16) | C19—O5—C14—C15 | 110.20 (11) |
C9—C6—C7—C8 | −179.57 (9) | C19—O5—C14—C13 | −72.54 (13) |
C4—C3—C8—C7 | −0.94 (17) | C13—C14—C15—C16 | 1.04 (16) |
O1—C3—C8—C7 | 177.22 (10) | O5—C14—C15—C16 | 178.20 (9) |
C6—C7—C8—C3 | 0.57 (17) | C12—C11—C16—C15 | −2.79 (15) |
C7—C6—C9—C11 | −133.77 (10) | C9—C11—C16—C15 | 173.58 (10) |
C5—C6—C9—C11 | 46.49 (13) | C12—C11—C16—O3 | −178.43 (9) |
C7—C6—C9—C10 | 108.39 (11) | C9—C11—C16—O3 | −2.06 (16) |
C5—C6—C9—C10 | −71.36 (12) | C14—C15—C16—C11 | 1.32 (16) |
C11—C9—C10—C12i | 129.45 (9) | C14—C15—C16—O3 | 176.87 (9) |
C6—C9—C10—C12i | −105.94 (10) | C17—O3—C16—C11 | −114.43 (10) |
C11—C9—C10—C10i | 14.02 (9) | C17—O3—C16—C15 | 69.87 (13) |
C6—C9—C10—C10i | 138.64 (8) | C16—O3—C17—O4 | −5.04 (15) |
C6—C9—C11—C16 | 48.41 (14) | C16—O3—C17—C18 | 173.34 (9) |
C10—C9—C11—C16 | 172.23 (10) | C14—O5—C19—O6 | −2.25 (15) |
C6—C9—C11—C12 | −135.02 (9) | C14—O5—C19—C20 | 178.01 (9) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O6ii | 1.00 | 2.51 | 3.5053 (14) | 179 |
C15—H15···O4iii | 0.95 | 2.59 | 3.4834 (12) | 158 |
C20—H20A···O6iv | 0.98 | 2.52 | 3.2708 (15) | 133 |
C20—H20B···O2iii | 0.98 | 2.28 | 3.2318 (16) | 162 |
Symmetry codes: (ii) x−1/2, y+1/2, z; (iii) −x+3/2, −y+1/2, −z+1; (iv) −x+2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C40H34O12·C4H8O2 |
Mr | 794.78 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 13.1495 (1), 12.7439 (1), 24.0386 (2) |
β (°) | 97.186 (1) |
V (Å3) | 3996.65 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with an Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2013) |
Tmin, Tmax | 0.790, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27173, 4029, 3714 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.095, 1.02 |
No. of reflections | 4029 |
No. of parameters | 238 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O6i | 1.00 | 2.51 | 3.5053 (14) | 179 |
C15—H15···O4ii | 0.95 | 2.59 | 3.4834 (12) | 158 |
C20—H20A···O6iii | 0.98 | 2.52 | 3.2708 (15) | 133 |
C20—H20B···O2ii | 0.98 | 2.28 | 3.2318 (16) | 162 |
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+3/2, −y+1/2, −z+1; (iii) −x+2, y, −z+1/2. |
Footnotes
‡Additional correspondence author, e-mail: dennis.taylor@adelaide.edu.au.
Acknowledgements
This project was supported in part by the School of Agriculture, Food and Wine, The University of Adelaide, and by Australia's grape-growers and winemakers through their investment body, the Grape and Wine Research and Development Corporation, with matching funds from the Australian Government. QM thanks the Faculty of Science for a PhD scholarship. The authors also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM·C/HIR-MOHE/SC/03).
References
Agilent (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA. Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The synthesis of pallidol hexaacetate was achieved by employing a modified procedure to that reported by Takaya et al. (2005) as outlined by Moss et al. (2013) which involved the oxidation of trans-resveratrol with K3Fe(CN)6. Herein, the crystal structure determination of pallidol hexaacetate, isolated as its ethylacetate solvate, (I), is described.
The pallidol hexaacetate molecule is disposed about a two-fold rotation axis, Fig. 1. The central five-membered ring is approximately planar with a r.m.s. deviation of 0.100 Å. The maximum deviations = 0.086 (1) Å for the C10 atom and -0.081 (1) Å for the C9 atom, indicating a small twist about the C9—C10 bond. The dihedral angle between the mean planes of the fused five-membered rings is 54.73 (6)°, indicating significant curvature in the molecule. The pendent benzene ring is nearly perpendicular to the mean plane of the five-membered ring to which it is attached, forming a dihedral angle of 80.70 (5)°. None of the acetate residues are co-planar with the benzene ring to which they are attached as seen in the values of the C2—O1—C3—C4 [-70.24 (14)°], C17—O3—C16—C11 [-114.43 (10)°] and C19—O5—C14—C13 [-72.54 (13)°] torsion angles.
In the crystal, molecules assemble into a three-dimensional architecture via C—H···O interactions, Fig. 2 and Table 1. In so doing, they define channels in which, presumably, reside the disordered ethylacetate molecules.