organic compounds
Tris[(6S)-6-hydroxy-4-epi-shikimic acid] monohydrate: an enantiomerically pure hydroxylated shikimic acid derived from methyl shikimate
aDepartment of Chemistry, University of Cologne, Greinstr. 4, 50939 Koeln, Germany
*Correspondence e-mail: griesbeck@uni-koeln.de
The title compound, 3C7H10O6·H2O, is the enantiomerically pure product of a multi-step synthesis from the enantiomerically pure natural shikimic acid. The contains three molecules of the acid and one molecule of water. The cyclohexene rings of the acids have half-chair conformations. The carboxylate, the four hydroxide groups and the additional water molecule form a complex three-dimensional hydrogen-bonding network.
Related literature
A series of antitumor-active marine natural carbasugars has been isolated in the last two decades with a cyclohexene-1-carboxylate core structure and four contiguous stereogenic centers (Numata et al., 1997). The of these compounds, the pericosines, has been a matter of debate since the first reports on the isolation (Usami et al., 2008, 2009). By means of detailed NMR analysis of the natural compound pericosine D0 and comparison with the NMR data published for the 6-hydroxy-5-epishikimic acid described herein, the absolute and was established (Usami et al., 2006, 2011). This reveals the importance of this X-ray crystallographic determination that finally proves the assignments that resulted from spectroscopic analyses. For the synthesis, see: Griesbeck et al. (2007).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: COLLECT (Hooft 1998); cell DENZO (Otwinowski & Minor 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SCHAKAL99 (Keller 1999); software used to prepare material for publication: PLATON (Spek 2009).
Supporting information
10.1107/S1600536812041256/gg2099sup1.cif
contains datablocks global, I. DOI:Supporting information file. DOI: 10.1107/S1600536812041256/gg2099Isup2.cdx
Structure factors: contains datablock I. DOI: 10.1107/S1600536812041256/gg2099Isup3.hkl
By means of a 7-step synthetic procedure (Fig. 2), the acetal 2 was synthesized starting from
shikimic acid (Griesbeck et al., 2007) by a sequence of 1) esterification (methanol, camphorsulfonic acid), 2) acetalization (dimethoxypropane, camphorsulfonic acid), 3) trifluoromethanesulfonate formation (trifluoromethanesulfonic anhydride, pyridine), 4) dehydration (caesium carbonate, dimethylformamide), 5) singlet oxygenation (rose bengal, visible light, oxygen atmosphere, tetrachloromethane), 6) reduction (potassium iodide, water-acetic acid), and 7) saponification of the methyl ester(lithium hydroxide, water). The acetal 2 was hydrolyzed by the following procedure: To a solution of 60 mg (0.26 mmol) of 2 in 2.5 ml of water and 2.5 ml of methanol was added 2 drops of concentrated HCl under vigorous stirring at room temperature. The reaction mixture was stirred overnight and the solvent evaporated under reduced pressure. The residue was repeatedly dissolved in ethanol and the solvent evaporated to give 45 mg (91%) of the title compound 1 as a colorless product. Recrystallization from ethanol resulted in fine colorless needles, m.p. 140–141°C.Crystals of 1 are monoclinic;
P21 was chosen as the acid component used was sikimic acid and the was set by reference to the known of the acid employed.The hydrogen atoms of the hydroxy groups and the water molecule are partially disordered. Only one possible orientation was refined. The positions are constrained and treated as riding atoms with distances O—H = 0.84 Å. All other hydrogen atoms were placed in geometrically idealized positions and refined with using riding model with C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C) for CH, C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for C=CH.
Data collection: COLLECT (Hooft 1998); cell
DENZO (Otwinowski & Minor 1997); data reduction: DENZO (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SCHAKAL99 (Keller 1999); software used to prepare material for publication: PLATON (Spek 2009).Fig. 1. A view of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius. | |
Fig. 2. Synthesis of the title compound | |
Fig. 3. Double layer formed from two independent acid molecules (stereodrawing parallel view). | |
Fig. 4. Layer formed from one independent molecule acid and water. | |
Fig. 5. Two connected Layers. |
3C7H10O6·H2O | F(000) = 620 |
Mr = 588.47 | Dx = 1.614 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 5629 reflections |
a = 11.2561 (17) Å | θ = 2.3–27.0° |
b = 7.7049 (11) Å | µ = 0.15 mm−1 |
c = 13.9688 (14) Å | T = 100 K |
β = 91.672 (8)° | Prism, colourless |
V = 1211.0 (3) Å3 | 0.20 × 0.10 × 0.05 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 1399 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.085 |
Graphite monochromator | θmax = 27.0°, θmin = 2.3° |
ϕ and ω scans | h = −6→14 |
5629 measured reflections | k = −8→9 |
2786 independent reflections | l = −14→17 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0326P)2] where P = (Fo2 + 2Fc2)/3 |
2786 reflections | (Δ/σ)max < 0.001 |
371 parameters | Δρmax = 0.27 e Å−3 |
3 restraints | Δρmin = −0.28 e Å−3 |
3C7H10O6·H2O | V = 1211.0 (3) Å3 |
Mr = 588.47 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.2561 (17) Å | µ = 0.15 mm−1 |
b = 7.7049 (11) Å | T = 100 K |
c = 13.9688 (14) Å | 0.20 × 0.10 × 0.05 mm |
β = 91.672 (8)° |
Nonius KappaCCD diffractometer | 1399 reflections with I > 2σ(I) |
5629 measured reflections | Rint = 0.085 |
2786 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 3 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | Δρmax = 0.27 e Å−3 |
2786 reflections | Δρmin = −0.28 e Å−3 |
371 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against all reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on all data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.3102 (4) | −0.2913 (5) | −0.2574 (2) | 0.0246 (12) | |
O2 | −0.3049 (4) | −0.4950 (5) | −0.3725 (2) | 0.0237 (11) | |
H2 | −0.2943 | −0.5608 | −0.3251 | 0.036* | |
O3 | −0.4164 (4) | −0.2120 (5) | −0.6636 (2) | 0.0235 (11) | |
H3 | −0.4002 | −0.1782 | −0.7189 | 0.035* | |
O4 | −0.3797 (4) | 0.1684 (5) | −0.6388 (2) | 0.0211 (11) | |
H4 | −0.4069 | 0.2653 | −0.6226 | 0.032* | |
O5 | −0.2179 (4) | 0.1329 (5) | −0.4720 (2) | 0.0199 (11) | |
H5 | −0.1998 | 0.1762 | −0.5249 | 0.030* | |
O6 | −0.4911 (4) | −0.0313 (5) | −0.3704 (2) | 0.0226 (11) | |
H6 | −0.5149 | 0.0667 | −0.3527 | 0.034* | |
C1 | −0.3322 (5) | −0.2021 (8) | −0.4214 (4) | 0.0133 (14) | |
C2 | −0.3220 (5) | −0.2449 (8) | −0.5113 (4) | 0.0181 (16) | |
H2AA | −0.3016 | −0.3617 | −0.5251 | 0.022* | |
C3 | −0.3400 (6) | −0.1242 (8) | −0.5937 (4) | 0.0170 (15) | |
H3AA | −0.2616 | −0.0992 | −0.6227 | 0.020* | |
C4 | −0.3972 (6) | 0.0455 (8) | −0.5639 (4) | 0.0195 (16) | |
H4AA | −0.4844 | 0.0266 | −0.5567 | 0.023* | |
C5 | −0.3437 (6) | 0.1095 (8) | −0.4700 (4) | 0.0167 (15) | |
H5AA | −0.3817 | 0.2224 | −0.4532 | 0.020* | |
C6 | −0.3652 (5) | −0.0227 (8) | −0.3891 (4) | 0.0166 (15) | |
H6AA | −0.3188 | 0.0098 | −0.3297 | 0.020* | |
C7 | −0.3140 (5) | −0.3311 (8) | −0.3425 (4) | 0.0175 (15) | |
O1A | 0.3146 (4) | 0.7830 (5) | 0.2305 (3) | 0.0250 (12) | |
O2A | 0.2868 (4) | 0.9807 (5) | 0.1148 (2) | 0.0272 (12) | |
H2A | 0.2832 | 1.0478 | 0.1620 | 0.041* | |
O3A | 0.4144 (4) | 0.7044 (5) | −0.1699 (2) | 0.0261 (12) | |
H3A | 0.3921 | 0.6804 | −0.2262 | 0.039* | |
O4A | 0.3839 (4) | 0.3234 (5) | −0.1463 (2) | 0.0213 (11) | |
H4A | 0.4305 | 0.2398 | −0.1364 | 0.032* | |
O5A | 0.2219 (4) | 0.3483 (5) | 0.0099 (2) | 0.0235 (11) | |
H5A | 0.2113 | 0.2508 | −0.0159 | 0.035* | |
O6A | 0.4887 (4) | 0.5260 (5) | 0.1274 (2) | 0.0221 (11) | |
H6A | 0.5103 | 0.4374 | 0.1584 | 0.033* | |
C1A | 0.3275 (5) | 0.6941 (8) | 0.0687 (4) | 0.0159 (15) | |
C2A | 0.3199 (5) | 0.7380 (8) | −0.0230 (4) | 0.0186 (16) | |
H2A1 | 0.2996 | 0.8547 | −0.0383 | 0.022* | |
C3A | 0.3412 (6) | 0.6154 (8) | −0.1043 (4) | 0.0189 (16) | |
H3A1 | 0.2633 | 0.5876 | −0.1371 | 0.023* | |
C4A | 0.3988 (6) | 0.4488 (7) | −0.0705 (3) | 0.0175 (16) | |
H4A1 | 0.4857 | 0.4701 | −0.0591 | 0.021* | |
C5A | 0.3472 (6) | 0.3813 (8) | 0.0213 (3) | 0.0186 (16) | |
H5A1 | 0.3884 | 0.2709 | 0.0399 | 0.022* | |
C6A | 0.3646 (6) | 0.5122 (7) | 0.1018 (4) | 0.0172 (15) | |
H6A1 | 0.3184 | 0.4767 | 0.1586 | 0.021* | |
C7A | 0.3083 (6) | 0.8202 (8) | 0.1454 (4) | 0.0187 (16) | |
O1B | −0.0345 (4) | −0.3888 (5) | −0.4150 (3) | 0.0299 (12) | |
O2B | −0.0513 (4) | −0.4555 (5) | −0.2592 (3) | 0.0285 (12) | |
H2B | −0.0715 | −0.5529 | −0.2813 | 0.043* | |
O3B | 0.1426 (4) | 0.0421 (5) | −0.0919 (2) | 0.0225 (11) | |
H3B | 0.1045 | 0.0246 | −0.0419 | 0.034* | |
O4B | 0.1501 (4) | 0.3201 (5) | −0.2274 (2) | 0.0251 (11) | |
H4B | 0.2020 | 0.3209 | −0.1830 | 0.038* | |
O5B | −0.0695 (4) | 0.2162 (5) | −0.3176 (2) | 0.0231 (11) | |
H5B | −0.1197 | 0.1992 | −0.3623 | 0.035* | |
O6B | 0.1309 (4) | −0.0858 (5) | −0.4331 (2) | 0.0246 (12) | |
H6B | 0.1225 | −0.0478 | −0.4893 | 0.037* | |
C1B | 0.0130 (6) | −0.1703 (8) | −0.2996 (4) | 0.0208 (16) | |
C2B | 0.0253 (6) | −0.1288 (8) | −0.2070 (4) | 0.0265 (18) | |
H2B1 | 0.0105 | −0.2157 | −0.1606 | 0.032* | |
C3B | 0.0617 (6) | 0.0501 (8) | −0.1727 (4) | 0.0238 (17) | |
H3B1 | −0.0107 | 0.1167 | −0.1549 | 0.029* | |
C4B | 0.1225 (6) | 0.1430 (8) | −0.2535 (4) | 0.0227 (17) | |
H4B1 | 0.1979 | 0.0807 | −0.2679 | 0.027* | |
C5B | 0.0418 (6) | 0.1435 (8) | −0.3425 (4) | 0.0198 (16) | |
H5B1 | 0.0782 | 0.2171 | −0.3928 | 0.024* | |
C6B | 0.0283 (6) | −0.0423 (8) | −0.3797 (4) | 0.0242 (17) | |
H6B1 | −0.0434 | −0.0479 | −0.4236 | 0.029* | |
C7B | −0.0249 (6) | −0.3495 (8) | −0.3313 (4) | 0.0224 (17) | |
O1W | −0.0108 (6) | 0.0088 (8) | 0.0523 (4) | 0.0444 (14) | |
H1W1 | −0.071 (5) | −0.047 (10) | 0.031 (5) | 0.08 (4)* | |
H1W2 | −0.003 (9) | −0.010 (15) | 0.113 (2) | 0.15 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.039 (3) | 0.018 (3) | 0.017 (2) | −0.003 (2) | 0.004 (2) | −0.001 (2) |
O2 | 0.040 (3) | 0.012 (3) | 0.019 (2) | 0.000 (2) | −0.0037 (19) | 0.0025 (19) |
O3 | 0.039 (3) | 0.016 (3) | 0.016 (2) | −0.006 (2) | 0.002 (2) | 0.0002 (19) |
O4 | 0.034 (3) | 0.013 (3) | 0.016 (2) | −0.001 (2) | 0.0000 (19) | −0.0002 (19) |
O5 | 0.021 (3) | 0.020 (3) | 0.019 (2) | −0.003 (2) | −0.0026 (19) | 0.0009 (18) |
O6 | 0.026 (3) | 0.010 (3) | 0.032 (2) | −0.003 (2) | 0.006 (2) | 0.000 (2) |
C1 | 0.013 (4) | 0.008 (4) | 0.019 (3) | 0.001 (3) | −0.003 (3) | −0.001 (3) |
C2 | 0.017 (4) | 0.009 (4) | 0.028 (4) | −0.006 (3) | −0.001 (3) | 0.001 (3) |
C3 | 0.014 (4) | 0.016 (4) | 0.021 (3) | −0.005 (3) | −0.003 (3) | −0.004 (3) |
C4 | 0.025 (4) | 0.015 (4) | 0.018 (3) | 0.003 (3) | −0.002 (3) | 0.006 (3) |
C5 | 0.022 (5) | 0.006 (3) | 0.022 (3) | −0.003 (3) | 0.002 (3) | 0.003 (3) |
C6 | 0.016 (4) | 0.015 (4) | 0.018 (3) | −0.004 (3) | 0.000 (3) | −0.003 (3) |
C7 | 0.007 (4) | 0.017 (4) | 0.029 (4) | 0.003 (3) | 0.001 (3) | 0.005 (3) |
O1A | 0.033 (3) | 0.023 (3) | 0.019 (2) | 0.002 (2) | 0.002 (2) | 0.002 (2) |
O2A | 0.049 (4) | 0.011 (3) | 0.022 (2) | 0.005 (2) | 0.000 (2) | −0.006 (2) |
O3A | 0.039 (3) | 0.021 (3) | 0.019 (2) | −0.008 (2) | 0.000 (2) | 0.002 (2) |
O4A | 0.024 (3) | 0.020 (3) | 0.020 (2) | 0.002 (2) | −0.0007 (19) | −0.0047 (19) |
O5A | 0.022 (3) | 0.019 (3) | 0.029 (2) | −0.002 (2) | −0.001 (2) | −0.0075 (19) |
O6A | 0.027 (3) | 0.013 (3) | 0.026 (2) | −0.003 (2) | −0.0100 (19) | 0.0020 (19) |
C1A | 0.013 (4) | 0.019 (4) | 0.016 (3) | −0.009 (3) | −0.002 (3) | 0.001 (3) |
C2A | 0.016 (4) | 0.016 (4) | 0.024 (3) | 0.001 (3) | 0.002 (3) | 0.003 (3) |
C3A | 0.021 (4) | 0.018 (4) | 0.018 (3) | −0.002 (3) | 0.000 (3) | 0.002 (3) |
C4A | 0.023 (5) | 0.016 (4) | 0.013 (3) | −0.002 (3) | −0.001 (3) | −0.008 (3) |
C5A | 0.016 (4) | 0.019 (4) | 0.020 (3) | 0.005 (3) | −0.009 (3) | −0.002 (3) |
C6A | 0.023 (4) | 0.008 (4) | 0.021 (3) | −0.002 (3) | 0.000 (3) | 0.000 (3) |
C7A | 0.014 (4) | 0.010 (4) | 0.033 (4) | −0.002 (3) | 0.006 (3) | 0.002 (3) |
O1B | 0.047 (4) | 0.023 (3) | 0.020 (2) | −0.006 (2) | −0.001 (2) | −0.004 (2) |
O2B | 0.035 (3) | 0.021 (3) | 0.029 (2) | −0.004 (2) | 0.001 (2) | −0.004 (2) |
O3B | 0.030 (3) | 0.020 (3) | 0.017 (2) | −0.003 (2) | −0.0082 (19) | −0.0005 (18) |
O4B | 0.035 (3) | 0.016 (3) | 0.024 (2) | −0.002 (2) | −0.0052 (19) | −0.001 (2) |
O5B | 0.024 (3) | 0.018 (3) | 0.027 (2) | 0.000 (2) | −0.003 (2) | −0.001 (2) |
O6B | 0.030 (3) | 0.024 (3) | 0.021 (2) | 0.002 (2) | 0.007 (2) | 0.0008 (19) |
C1B | 0.030 (5) | 0.016 (4) | 0.017 (3) | 0.003 (3) | −0.003 (3) | 0.000 (3) |
C2B | 0.034 (5) | 0.023 (4) | 0.022 (3) | −0.003 (4) | 0.002 (3) | 0.000 (3) |
C3B | 0.033 (5) | 0.015 (4) | 0.023 (3) | 0.000 (3) | −0.004 (3) | −0.001 (3) |
C4B | 0.031 (5) | 0.019 (4) | 0.018 (3) | 0.004 (3) | −0.001 (3) | −0.002 (3) |
C5B | 0.017 (4) | 0.015 (4) | 0.027 (3) | 0.002 (3) | 0.002 (3) | 0.004 (3) |
C6B | 0.028 (5) | 0.021 (4) | 0.023 (3) | −0.003 (3) | 0.001 (3) | −0.001 (3) |
C7B | 0.021 (5) | 0.021 (4) | 0.026 (4) | 0.002 (3) | −0.001 (3) | 0.004 (3) |
O1W | 0.048 (4) | 0.053 (4) | 0.032 (3) | −0.011 (3) | −0.001 (3) | −0.008 (3) |
O1—C7 | 1.226 (6) | C1A—C6A | 1.530 (8) |
O2—C7 | 1.336 (7) | C2A—C3A | 1.502 (8) |
O2—H2 | 0.8400 | C2A—H2A1 | 0.9500 |
O3—C3 | 1.449 (7) | C3A—C4A | 1.508 (8) |
O3—H3 | 0.8400 | C3A—H3A1 | 1.0000 |
O4—C4 | 1.429 (6) | C4A—C5A | 1.515 (7) |
O4—H4 | 0.8400 | C4A—H4A1 | 1.0000 |
O5—C5 | 1.429 (7) | C5A—C6A | 1.518 (7) |
O5—H5 | 0.8400 | C5A—H5A1 | 1.0000 |
O6—C6 | 1.450 (6) | C6A—H6A1 | 1.0000 |
O6—H6 | 0.8400 | O1B—C7B | 1.210 (6) |
C1—C2 | 1.307 (7) | O2B—C7B | 1.337 (6) |
C1—C7 | 1.494 (8) | O2B—H2B | 0.8400 |
C1—C6 | 1.504 (8) | O3B—C3B | 1.431 (7) |
C2—C3 | 1.490 (8) | O3B—H3B | 0.8400 |
C2—H2AA | 0.9500 | O4B—C4B | 1.444 (7) |
C3—C4 | 1.521 (8) | O4B—H4B | 0.8400 |
C3—H3AA | 1.0000 | O5B—C5B | 1.425 (7) |
C4—C5 | 1.510 (7) | O5B—H5B | 0.8400 |
C4—H4AA | 1.0000 | O6B—C6B | 1.433 (6) |
C5—C6 | 1.546 (7) | O6B—H6B | 0.8400 |
C5—H5AA | 1.0000 | C1B—C2B | 1.336 (7) |
C6—H6AA | 1.0000 | C1B—C6B | 1.506 (7) |
O1A—C7A | 1.223 (6) | C1B—C7B | 1.507 (9) |
O2A—C7A | 1.329 (7) | C2B—C3B | 1.512 (8) |
O2A—H2A | 0.8400 | C2B—H2B1 | 0.9500 |
O3A—C3A | 1.426 (6) | C3B—C4B | 1.516 (8) |
O3A—H3A | 0.8400 | C3B—H3B1 | 1.0000 |
O4A—C4A | 1.440 (6) | C4B—C5B | 1.519 (8) |
O4A—H4A | 0.8400 | C4B—H4B1 | 1.0000 |
O5A—C5A | 1.437 (7) | C5B—C6B | 1.529 (8) |
O5A—H5A | 0.8400 | C5B—H5B1 | 1.0000 |
O6A—C6A | 1.436 (6) | C6B—H6B1 | 1.0000 |
O6A—H6A | 0.8400 | O1W—H1W1 | 0.85 (2) |
C1A—C2A | 1.324 (7) | O1W—H1W2 | 0.86 (2) |
C1A—C7A | 1.467 (8) | ||
C7—O2—H2 | 109.5 | O4A—C4A—H4A1 | 108.6 |
C3—O3—H3 | 109.5 | C3A—C4A—H4A1 | 108.6 |
C4—O4—H4 | 109.5 | C5A—C4A—H4A1 | 108.6 |
C5—O5—H5 | 109.5 | O5A—C5A—C4A | 111.5 (4) |
C6—O6—H6 | 109.5 | O5A—C5A—C6A | 107.8 (5) |
C2—C1—C7 | 121.8 (5) | C4A—C5A—C6A | 110.7 (5) |
C2—C1—C6 | 123.4 (5) | O5A—C5A—H5A1 | 108.9 |
C7—C1—C6 | 114.8 (5) | C4A—C5A—H5A1 | 108.9 |
C1—C2—C3 | 124.9 (6) | C6A—C5A—H5A1 | 108.9 |
C1—C2—H2AA | 117.6 | O6A—C6A—C5A | 109.7 (5) |
C3—C2—H2AA | 117.6 | O6A—C6A—C1A | 105.3 (5) |
O3—C3—C2 | 107.1 (5) | C5A—C6A—C1A | 110.9 (4) |
O3—C3—C4 | 109.7 (5) | O6A—C6A—H6A1 | 110.3 |
C2—C3—C4 | 112.0 (4) | C5A—C6A—H6A1 | 110.3 |
O3—C3—H3AA | 109.3 | C1A—C6A—H6A1 | 110.3 |
C2—C3—H3AA | 109.3 | O1A—C7A—O2A | 122.4 (5) |
C4—C3—H3AA | 109.3 | O1A—C7A—C1A | 123.3 (6) |
O4—C4—C5 | 111.1 (5) | O2A—C7A—C1A | 114.3 (5) |
O4—C4—C3 | 107.5 (4) | C7B—O2B—H2B | 109.5 |
C5—C4—C3 | 110.9 (5) | C3B—O3B—H3B | 109.5 |
O4—C4—H4AA | 109.1 | C4B—O4B—H4B | 109.5 |
C5—C4—H4AA | 109.1 | C5B—O5B—H5B | 109.5 |
C3—C4—H4AA | 109.1 | C6B—O6B—H6B | 109.5 |
O5—C5—C4 | 113.2 (4) | C2B—C1B—C6B | 123.5 (6) |
O5—C5—C6 | 105.9 (5) | C2B—C1B—C7B | 121.6 (6) |
C4—C5—C6 | 110.7 (5) | C6B—C1B—C7B | 114.8 (5) |
O5—C5—H5AA | 109.0 | C1B—C2B—C3B | 123.0 (6) |
C4—C5—H5AA | 109.0 | C1B—C2B—H2B1 | 118.5 |
C6—C5—H5AA | 109.0 | C3B—C2B—H2B1 | 118.5 |
O6—C6—C1 | 105.3 (5) | O3B—C3B—C2B | 111.8 (5) |
O6—C6—C5 | 109.7 (5) | O3B—C3B—C4B | 108.5 (5) |
C1—C6—C5 | 109.9 (4) | C2B—C3B—C4B | 108.6 (5) |
O6—C6—H6AA | 110.6 | O3B—C3B—H3B1 | 109.3 |
C1—C6—H6AA | 110.6 | C2B—C3B—H3B1 | 109.3 |
C5—C6—H6AA | 110.6 | C4B—C3B—H3B1 | 109.3 |
O1—C7—O2 | 122.7 (5) | O4B—C4B—C3B | 110.9 (4) |
O1—C7—C1 | 123.3 (6) | O4B—C4B—C5B | 108.9 (5) |
O2—C7—C1 | 114.0 (5) | C3B—C4B—C5B | 109.8 (5) |
C7A—O2A—H2A | 109.5 | O4B—C4B—H4B1 | 109.1 |
C3A—O3A—H3A | 109.5 | C3B—C4B—H4B1 | 109.1 |
C4A—O4A—H4A | 109.5 | C5B—C4B—H4B1 | 109.1 |
C5A—O5A—H5A | 109.5 | O5B—C5B—C4B | 108.1 (5) |
C6A—O6A—H6A | 109.5 | O5B—C5B—C6B | 111.8 (5) |
C2A—C1A—C7A | 122.0 (6) | C4B—C5B—C6B | 109.1 (5) |
C2A—C1A—C6A | 122.4 (5) | O5B—C5B—H5B1 | 109.3 |
C7A—C1A—C6A | 115.5 (5) | C4B—C5B—H5B1 | 109.3 |
C1A—C2A—C3A | 124.3 (6) | C6B—C5B—H5B1 | 109.3 |
C1A—C2A—H2A1 | 117.9 | O6B—C6B—C1B | 110.2 (5) |
C3A—C2A—H2A1 | 117.9 | O6B—C6B—C5B | 108.8 (5) |
O3A—C3A—C2A | 106.9 (5) | C1B—C6B—C5B | 111.9 (4) |
O3A—C3A—C4A | 111.0 (5) | O6B—C6B—H6B1 | 108.6 |
C2A—C3A—C4A | 112.0 (5) | C1B—C6B—H6B1 | 108.6 |
O3A—C3A—H3A1 | 108.9 | C5B—C6B—H6B1 | 108.6 |
C2A—C3A—H3A1 | 108.9 | O1B—C7B—O2B | 124.0 (6) |
C4A—C3A—H3A1 | 108.9 | O1B—C7B—C1B | 122.0 (6) |
O4A—C4A—C3A | 107.5 (4) | O2B—C7B—C1B | 114.0 (5) |
O4A—C4A—C5A | 110.7 (5) | H1W1—O1W—H1W2 | 109 (8) |
C3A—C4A—C5A | 112.6 (5) | ||
C7—C1—C2—C3 | 179.4 (6) | O5A—C5A—C6A—O6A | 169.7 (4) |
C6—C1—C2—C3 | 0.7 (10) | C4A—C5A—C6A—O6A | −68.1 (6) |
C1—C2—C3—O3 | −132.5 (6) | O5A—C5A—C6A—C1A | −74.4 (6) |
C1—C2—C3—C4 | −12.2 (9) | C4A—C5A—C6A—C1A | 47.7 (7) |
O3—C3—C4—O4 | −77.6 (6) | C2A—C1A—C6A—O6A | 98.2 (6) |
C2—C3—C4—O4 | 163.7 (5) | C7A—C1A—C6A—O6A | −77.9 (6) |
O3—C3—C4—C5 | 160.8 (5) | C2A—C1A—C6A—C5A | −20.4 (8) |
C2—C3—C4—C5 | 42.0 (7) | C7A—C1A—C6A—C5A | 163.5 (5) |
O4—C4—C5—O5 | −62.3 (6) | C2A—C1A—C7A—O1A | 179.9 (6) |
C3—C4—C5—O5 | 57.2 (6) | C6A—C1A—C7A—O1A | −4.0 (9) |
O4—C4—C5—C6 | 178.9 (5) | C2A—C1A—C7A—O2A | −2.0 (9) |
C3—C4—C5—C6 | −61.6 (6) | C6A—C1A—C7A—O2A | 174.2 (5) |
C2—C1—C6—O6 | 99.4 (6) | C6B—C1B—C2B—C3B | −3.0 (11) |
C7—C1—C6—O6 | −79.5 (6) | C7B—C1B—C2B—C3B | −179.2 (6) |
C2—C1—C6—C5 | −18.7 (9) | C1B—C2B—C3B—O3B | −140.0 (6) |
C7—C1—C6—C5 | 162.5 (5) | C1B—C2B—C3B—C4B | −20.4 (9) |
O5—C5—C6—O6 | 169.9 (4) | O3B—C3B—C4B—O4B | −63.3 (6) |
C4—C5—C6—O6 | −67.0 (6) | C2B—C3B—C4B—O4B | 175.1 (5) |
O5—C5—C6—C1 | −74.8 (6) | O3B—C3B—C4B—C5B | 176.4 (5) |
C4—C5—C6—C1 | 48.3 (7) | C2B—C3B—C4B—C5B | 54.7 (7) |
C2—C1—C7—O1 | 171.8 (6) | O4B—C4B—C5B—O5B | −67.1 (6) |
C6—C1—C7—O1 | −9.3 (9) | C3B—C4B—C5B—O5B | 54.4 (6) |
C2—C1—C7—O2 | −9.7 (9) | O4B—C4B—C5B—C6B | 171.1 (5) |
C6—C1—C7—O2 | 169.2 (5) | C3B—C4B—C5B—C6B | −67.4 (6) |
C7A—C1A—C2A—C3A | 178.6 (6) | C2B—C1B—C6B—O6B | 113.1 (7) |
C6A—C1A—C2A—C3A | 2.7 (10) | C7B—C1B—C6B—O6B | −70.4 (7) |
C1A—C2A—C3A—O3A | −134.8 (6) | C2B—C1B—C6B—C5B | −8.1 (10) |
C1A—C2A—C3A—C4A | −12.9 (9) | C7B—C1B—C6B—C5B | 168.4 (5) |
O3A—C3A—C4A—O4A | −77.0 (6) | O5B—C5B—C6B—O6B | 160.3 (4) |
C2A—C3A—C4A—O4A | 163.5 (5) | C4B—C5B—C6B—O6B | −80.2 (6) |
O3A—C3A—C4A—C5A | 160.8 (5) | O5B—C5B—C6B—C1B | −77.7 (6) |
C2A—C3A—C4A—C5A | 41.3 (7) | C4B—C5B—C6B—C1B | 41.8 (7) |
O4A—C4A—C5A—O5A | −60.9 (6) | C2B—C1B—C7B—O1B | −178.8 (6) |
C3A—C4A—C5A—O5A | 59.4 (6) | C6B—C1B—C7B—O1B | 4.6 (10) |
O4A—C4A—C5A—C6A | 179.1 (5) | C2B—C1B—C7B—O2B | 3.9 (10) |
C3A—C4A—C5A—C6A | −60.5 (7) | C6B—C1B—C7B—O2B | −172.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1Ai | 0.84 | 1.81 | 2.624 (5) | 164 |
O3—H3···O4Aii | 0.84 | 1.90 | 2.705 (5) | 161 |
O4—H4···O6iii | 0.84 | 1.94 | 2.738 (6) | 157 |
O5—H5···O6Biv | 0.84 | 2.08 | 2.736 (5) | 134 |
O6—H6···O3iii | 0.84 | 1.89 | 2.718 (6) | 169 |
O6A—H6A···O3Av | 0.84 | 1.99 | 2.764 (6) | 153 |
O4A—H4A···O6Av | 0.84 | 1.88 | 2.712 (6) | 168 |
O5B—H5B···O5 | 0.84 | 1.93 | 2.765 (5) | 171 |
O5A—H5A···O3B | 0.84 | 2.06 | 2.882 (5) | 164 |
O2A—H2A···O1vi | 0.84 | 1.84 | 2.664 (5) | 167 |
O6B—H6B···O1Biv | 0.84 | 2.05 | 2.801 (5) | 149 |
O4B—H4B···O4A | 0.84 | 2.10 | 2.835 (6) | 147 |
O2B—H2B···O5Bvii | 0.84 | 1.85 | 2.663 (6) | 163 |
O3B—H3B···O1W | 0.84 | 1.88 | 2.703 (6) | 166 |
O3A—H3A···O4iv | 0.84 | 1.89 | 2.705 (5) | 163 |
O1W—H1W1···O5Aviii | 0.85 (2) | 1.95 (2) | 2.794 (7) | 173 (8) |
O1W—H1W2···O2Bix | 0.86 (2) | 2.16 (5) | 2.967 (6) | 157 (11) |
Symmetry codes: (i) −x, y−3/2, −z; (ii) −x, y−1/2, −z−1; (iii) −x−1, y+1/2, −z−1; (iv) −x, y+1/2, −z−1; (v) −x+1, y−1/2, −z; (vi) −x, y+3/2, −z; (vii) x, y−1, z; (viii) −x, y−1/2, −z; (ix) −x, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | 3C7H10O6·H2O |
Mr | 588.47 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 11.2561 (17), 7.7049 (11), 13.9688 (14) |
β (°) | 91.672 (8) |
V (Å3) | 1211.0 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5629, 2786, 1399 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.102, 0.88 |
No. of reflections | 2786 |
No. of parameters | 371 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.28 |
Computer programs: COLLECT (Hooft 1998), DENZO (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SCHAKAL99 (Keller 1999), PLATON (Spek 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1Ai | 0.84 | 1.81 | 2.624 (5) | 164 |
O3—H3···O4Aii | 0.84 | 1.90 | 2.705 (5) | 161 |
O4—H4···O6iii | 0.84 | 1.94 | 2.738 (6) | 157 |
O5—H5···O6Biv | 0.84 | 2.08 | 2.736 (5) | 134 |
O6—H6···O3iii | 0.84 | 1.89 | 2.718 (6) | 169 |
O6A—H6A···O3Av | 0.84 | 1.99 | 2.764 (6) | 153 |
O4A—H4A···O6Av | 0.84 | 1.88 | 2.712 (6) | 168 |
O5B—H5B···O5 | 0.84 | 1.93 | 2.765 (5) | 171 |
O5A—H5A···O3B | 0.84 | 2.06 | 2.882 (5) | 164 |
O2A—H2A···O1vi | 0.84 | 1.84 | 2.664 (5) | 167 |
O6B—H6B···O1Biv | 0.84 | 2.05 | 2.801 (5) | 149 |
O4B—H4B···O4A | 0.84 | 2.10 | 2.835 (6) | 147 |
O2B—H2B···O5Bvii | 0.84 | 1.85 | 2.663 (6) | 163 |
O3B—H3B···O1W | 0.84 | 1.88 | 2.703 (6) | 166 |
O3A—H3A···O4iv | 0.84 | 1.89 | 2.705 (5) | 163 |
O1W—H1W1···O5Aviii | 0.85 (2) | 1.95 (2) | 2.794 (7) | 173 (8) |
O1W—H1W2···O2Bix | 0.86 (2) | 2.16 (5) | 2.967 (6) | 157 (11) |
Symmetry codes: (i) −x, y−3/2, −z; (ii) −x, y−1/2, −z−1; (iii) −x−1, y+1/2, −z−1; (iv) −x, y+1/2, −z−1; (v) −x+1, y−1/2, −z; (vi) −x, y+3/2, −z; (vii) x, y−1, z; (viii) −x, y−1/2, −z; (ix) −x, y+1/2, −z. |
Acknowledgements
This research was supported by the Deutsche Forschungsgemeinschaft and by University start-up funding (2004–2005).
References
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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 title compound is a enantiomerically pure, highly substituted polyhydroxylated cyclohexane derived from the natural shikimic acid. Polyfunctionalized shikimic acid derivatives, e.g. the drug oseltamivir (tamiflu) lately have become well known as drugs repressing the symptoms of bird flu. Furthermore, the 4-epi-shikimic acid skeleton is present in numerous natural products with interesting biological properties, one example is the (6S)-6-chloro derivative (pericosine A), an antitumour agent from Periconia byssoid (Usami et al., 2006). Synthetic efforts to new and efficient structural modifications of the shikimate skeleton are thus of current and high relevance.
The asymmetric unit contains three molecules of the acid and one molecule water. All three independent acid molecules have the same half chair conformation (Fig. 1). Two molecules of the acid form hydrogen bonded carboxylic acid dimers, which are connected to double layers by hydrogen bonds (Fig. 3). The third molecule of the acid and the water molecule form a second layer structure (Fig. 4). These two different layer structures are connected via additional hydrogen bonds, forming a three dimmensional network (Fig. 5).