PMCID: PMC30997654-Formyl&#x000phenyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyran&#x000oside,a,‡ ,a ,a ,a and
a,*Correspondence e-mail: ‡Additional correspondence author, e-mail: heidelberg@um.edu.my.
This article has been
other articles in PMC.The pyran&#x000oside ring in the title compound, C21H24O11, has a chair conformation with the substituted benzene ring occupying an equatorial position. The crystal packing is dominated by C—HO inter&#x000actions that lead to the formation of supra&#x000molecular layers in the ab plane.For synthesis, see: Bao et al. (2004); Hongu et al. (1999); Patil & Ravindranathan Kartha (2008). For the natural anti-oxidant glucosyl&#x000ated resveratrol, see: La Torre et al. (2004). For the biological activity of related structures, see: Wen et al. (2008); Yan et al. (2009). For the structure of the isomeric allopyran&#x000oside and galactose derivatives, see: Ye et al. (2009); Hussen et al. (2011). For conformational analysis, see: Cremer & Pople (1975).
Crystal data
r = 452.40Triclinic,
a = 5.7868 (2) Å
b = 8.9166 (3) Å
c = 11.4716 (3) Åα = 102.473 (3)°β = 93.481 (2)°γ = 102.780 (3)°
V = 559.96 (3) Å3
Z = 1Cu Kα radiation&#x003 = 0.94 mm−1
T = 100 K0.30 × 0.30 × 0.20 mm
Data collection
Agilent Supernova Dual diffractometer with an Atlas detectorAbsorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010) T
min = 0.919, T
max = 1.0007392 measured reflections4097 independent reflections4087 reflections with I > 2σ(I)
int = 0.021
Refinement
2 > 2σ(F
2)] = 0.041
2) = 0.115
S = 1.074097 reflections293 parameters3 restraintsH-atom parameters constrainedΔρmax = 0.27 e Å−3
Δρmin = &#x e Å−3
Absolute structure: Flack (1983), 1855 Friedel pairsFlack parameter: -0.02(12)
Data collection: CrysAlis PRO (Agilent Technologies, 2010); cell refinement: 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 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Hydrogen-bond geometry (Å, °)Crystal structure: contains datablocks global, I. DOI:
(23K, cif)Structure factors: contains datablocks I. DOI:
(201K, hkl)Additional supplementary materials: ; ;
This study was supported by the University of Malaya under research grant No. FS306/2007 C. The authors are also grateful to the University of Malaya for support of the crystallographic facility.
Experimental
2,3,4,6-Tetra-O-acetyl-α-D-gluctopyranosyl bromide (4.0 g) and
4-hydroxybenzaldehyde (3.0 g) were dissolved in chloroform (30 ml) and the
mixture treated with a solution of aqueous solution (15 ml) of sodium
carbonate (2.7 g) and tetrabutylammonium bromide (0.7 g). The mixture was
heated to reflux under vigorous stirring overnight, after which ethyl acetate
was added and the organic layer was washed three times with sodium hydroxide
solution (1 N) to remove remaining phenols. After drying the solution over
magnesium sulfate and evaporation of the solvent, the target product (2.0 g,
45%) was obtained by crystallization from ethanol. Better crystals were
obtained from 2-propanol.1H NMR (400 MHz, CDCl3): δ 9.92 (s; CHO), 7.85 &#x0 (AB aromatic
4H), 5.34&#x &#x0&#x (2 m, 2 x 2H; H1–H4), 4.27 ( H6a),
4.16 ( H6b), 3.92 ( H5), 2.05&#x (3 s, 12H; Ac); 3J4,5 = 10.0 Hz, 3J5,6a = 5.0 Hz, 3J5,6 b = 2.5 Hz and 2J6 = 12.0 Hz.
Refinement
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 1.00 Å) and were included in the refinement in the riding model approximation,
with Uiso(H) set to 1.2 to 1.5Uequiv(C).Figures Molecular structure, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.A view in projection down the a axis of the unit-cell contents highlighting the stacking of layers. The C—H···O interactions are shown as orange dashed lines.Crystal data C21H24O11Z = 1Mr = 452.40F(000) = 238Triclinic, P1Dx = 1.342 Mg m−3Hall symbol:
P 1Cu Kα radiation, &#x003 = 1.54184 Åa = 5.7868 (2) ÅCell parameters from 7285 reflectionsb = 8.9166 (3) Åθ = 4.0&#x°c = 11.4716 (3) ŵ = 0.94 mm−1α = 102.473 (3)°T = 100 Kβ = 93.481 (2)°Block, colourlessγ = 102.780 (3)°0.30 × 0.30 × 0.20 mmV = 559.96 (3)
Å3Data collection Agilent Supernova Dual diffractometer with an Atlas detector4097 independent reflectionsRadiation source: SuperNova (Cu) X-ray Source4087 reflections with I > 2σ(I)MirrorRint = 0.021Detector resolution: 10.4041 pixels mm-1θmax = 74.3°, θmin = 4.0°ω scansh = −7→7Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010)k = −9→10Tmin = 0.919, Tmax = 1.000l = −13→147392 measured reflectionsRefinement Refinement on F2Secondary atom site location: difference Fourier mapLeast-squares matrix: fullHydrogen site location: inferred from neighbouring sitesR[F2 > 2σ(F2)] = 0.041H-atom parameters constrainedwR(F2) = 0.115w = 1/[σ2(Fo2) + (0.0908P)2 + 0.072P]
where P = (Fo2 + 2Fc2)/3S = 1.07(Δ/σ)max = 0.0014097 reflectionsΔρmax = 0.27 e Å−3293 parametersΔρmin = &#x e Å−33 restraintsAbsolute structure:
Flack (1983), 1855 Friedel pairsPrimary atom site location: structure-invariant direct methodsSpecial details 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
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) xyzUiso*/UeqO10.9987 (2)0.49931 (15)0.49910 (11)0.0174 (3)O21.0120 (2)0.81529 (16)0.57609 (11)0.0218 (3)O30.7432 (3)0.95346 (19)0.63881 (14)0.0305 (3)O40.7892 (2)0.55996 (15)0.20730 (10)0.0167 (3)O50.4356 (2)0.59974 (16)0.26001 (12)0.0208 (3)O60.7723 (2)0.23423 (15)0.15960 (11)0.0192 (3)O71.0136 (3)0.2794 (2)0.01679 (14)0.0385 (4)O81.1640 (2)0.17486 (15)0.30105 (11)0.0196 (3)O90.8768 (3)&#x04 (17)0.28892 (15)0.0297 (3)O101.1933 (2)0.31718 (15)0.54454 (11)0.0204 (3)O112.0808 (3)0.73176 (19)0.92751 (14)0.0330 (4)C10.9617 (3)0.5930 (2)0.41525 (15)0.0166 (3)H11.11900.64600.39370.020*C20.8116 (3)0.4800 (2)0.30264 (15)0.0155 (3)H20.65030.43160.32250.019*C30.9368 (3)0.3515 (2)0.25138 (15)0.0163 (3)H31.08170.39800.21590.020*C41.0071 (3)0.2710 (2)0.34749 (16)0.0171 (3)H40.86240.20510.37120.021*C51.1452 (3)0.3968 (2)0.45629 (15)0.0168 (3)H51.29680.45720.43430.020*C60.8401 (3)0.7168 (2)0.47781 (16)0.0187 (3)H6A0.79790.77990.42220.022*H6B0.69300.66650.50800.022*C70.9388 (3)0.9279 (2)0.65168 (16)0.0220 (4)C81.1278 (4)1.0105 (3)0.75474 (18)0.0291 (4)H8A1.11381.11930.78450.044*H8B1.28551.01190.72770.044*H8C1.10770.95430.81940.044*C90.5824 (3)0.6053 (2)0.19069 (15)0.0163 (3)C100.5674 (3)0.6549 (3)0.07482 (17)0.0234 (4)H10A0.42870.70010.06850.035*H10B0.55070.56270.00770.035*H10C0.71280.73440.07210.035*C110.8311 (4)0.2113 (2)0.04513 (17)0.0250 (4)C120.6319 (5)0.0922 (3)&#x1 (2)0.0428 (6)H12A0.67470.0749&#x50.064*H12B0.48660.1315&#x00.064*H12C0.6041&#x8&#x70.064*C131.0775 (3)0.0158 (2)0.27726 (16)0.0214 (4)C141.2625 (4)&#x9 (3)0.2328 (3)0.0385 (5)H14A1.1877&#x20.19900.058*H14B1.3833&#x30.29970.058*H14C1.3381&#x20.17060.058*C151.3937 (3)0.3914 (2)0.62530 (15)0.0185 (4)C161.5446 (4)0.2974 (3)0.64956 (18)0.0230 (4)H161.50950.18830.61040.028*C171.7455 (4)0.3644 (3)0.73110 (18)0.0249 (4)H171.84900.30080.74820.030*C181.7984 (3)0.5252 (2)0.78886 (16)0.0229 (4)C191.6452 (3)0.6178 (2)0.76354 (15)0.0216 (4)H191.68030.72680.80280.026*C201.4427 (3)0.5528 (2)0.68196 (16)0.0209 (4)H201.33900.61620.66470.025*C212.0148 (4)0.5937 (3)0.87497 (18)0.0279 (4)H212.10990.52440.89050.034*Atomic displacement parameters (Å2) U11U22U33U12U13U23O10.0207 (6)0.0178 (6)0.0153 (5)0.0077 (5)0.0026 (4)0.0040 (5)O20.0222 (6)0.0195 (7)0.0197 (6)0.0055 (5)&#x5 (5)&#x0 (5)O30.0332 (8)0.0268 (8)0.0305 (7)0.0149 (6)0.0023 (6)&#x2 (6)O40.0163 (6)0.0200 (6)0.0160 (5)0.0071 (4)0.0020 (4)0.0061 (4)O50.0175 (6)0.0221 (7)0.0231 (6)0.0063 (5)0.0035 (5)0.0043 (5)O60.0202 (6)0.0176 (6)0.0160 (6)0.0022 (5)&#x7 (5)&#x6 (5)O70.0419 (9)0.0422 (9)0.0211 (7)&#x8 (7)0.0091 (6)&#x8 (6)O80.0178 (6)0.0166 (6)0.0245 (6)0.0057 (5)0.0023 (5)0.0034 (5)O90.0278 (7)0.0171 (7)0.0435 (8)0.0040 (5)0.0079 (6)0.0062 (6)O100.0231 (6)0.0186 (7)0.0203 (6)0.0041 (5)&#x0 (5)0.0083 (5)O110.0293 (7)0.0380 (9)0.0279 (7)0.0037 (6)&#x4 (6)0.0066 (6)C10.0191 (8)0.0156 (9)0.0157 (8)0.0049 (6)0.0017 (6)0.0041 (6)C20.0167 (7)0.0166 (9)0.0148 (7)0.0051 (6)0.0034 (6)0.0054 (6)C30.0162 (8)0.0156 (8)0.0150 (7)0.0027 (6)&#x6 (6)0.0013 (6)C40.0170 (8)0.0148 (8)0.0189 (8)0.0043 (6)0.0022 (6)0.0022 (6)C50.0183 (8)0.0166 (9)0.0164 (7)0.0052 (6)0.0010 (6)0.0048 (6)C60.0189 (8)0.0167 (8)0.0182 (8)0.0039 (6)0.0004 (6)0.0000 (6)C70.0286 (10)0.0169 (9)0.0206 (9)0.0073 (7)0.0045 (7)0.0024 (7)C80.0365 (11)0.0227 (10)0.0228 (9)0.0043 (8)&#x8 (8)&#x4 (7)C90.0154 (8)0.0147 (8)0.0176 (8)0.0043 (6)&#x1 (6)0.0012 (6)C100.0244 (9)0.0298 (10)0.0189 (8)0.0116 (7)0.0008 (6)0.0075 (7)C110.0334 (10)0.0234 (10)0.0172 (8)0.0073 (8)0.0028 (7)0.0017 (7)C120.0504 (14)0.0434 (14)0.0206 (10)&#x2 (11)&#x4 (9)&#x4 (9)C130.0243 (9)0.0171 (9)0.0224 (8)0.0046 (7)&#x1 (7)0.0048 (7)C140.0350 (11)0.0218 (11)0.0614 (16)0.0118 (9)0.0152 (10)0.0073 (10)C150.0191 (8)0.0225 (10)0.0161 (8)0.0054 (7)0.0032 (6)0.0084 (6)C160.0263 (9)0.0229 (9)0.0238 (8)0.0090 (7)0.0049 (7)0.0102 (7)C170.0243 (9)0.0309 (11)0.0258 (9)0.0124 (8)0.0043 (7)0.0139 (8)C180.0228 (9)0.0310 (11)0.0175 (8)0.0068 (7)0.0035 (7)0.0101 (7)C190.0254 (9)0.0233 (10)0.0160 (8)0.0065 (7)0.0019 (7)0.0041 (7)C200.0240 (9)0.0229 (10)0.0180 (8)0.0085 (7)0.0014 (7)0.0070 (7)C210.0223 (9)0.0400 (13)0.0235 (9)0.0075 (8)0.0010 (7)0.0120 (9)Geometric parameters (Å, °) O1—C51.413 (2)C7—C81.499 (3)O1—C11.439 (2)C8—H8A0.9800O2—C71.340 (2)C8—H8B0.9800O2—C61.443 (2)C8—H8C0.9800O3—C71.210 (3)C9—C101.492 (2)O4—C91.361 (2)C10—H10A0.9800O4—C21.443 (2)C10—H10B0.9800O5—C91.199 (2)C10—H10C0.9800O6—C111.360 (2)C11—C121.497 (3)O6—C31.4389 (19)C12—H12A0.9800O7—C111.197 (3)C12—H12B0.9800O8—C131.356 (2)C12—H12C0.9800O8—C41.431 (2)C13—C141.489 (3)O9—C131.199 (3)C14—H14A0.9800O10—C151.381 (2)C14—H14B0.9800O10—C51.404 (2)C14—H14C0.9800O11—C211.212 (3)C15—C161.391 (3)C1—C61.513 (2)C15—C201.403 (3)C1—C21.534 (2)C16—C171.380 (3)C1—H11.0000C16—H160.9500C2—C31.521 (2)C17—C181.400 (3)C2—H21.0000C17—H170.9500C3—C41.520 (2)C18—C191.396 (3)C3—H31.0000C18—C211.472 (3)C4—C51.527 (2)C19—C201.384 (3)C4—H41.0000C19—H190.9500C5—H51.0000C20—H200.9500C6—H6A0.9900C21—H210.9500C6—H6B0.9900C5—O1—C1111.07 (12)H8B—C8—H8C109.5C7—O2—C6116.65 (14)O5—C9—O4122.82 (15)C9—O4—C2117.18 (13)O5—C9—C10127.05 (16)C11—O6—C3117.74 (14)O4—C9—C10110.10 (14)C13—O8—C4117.05 (14)C9—C10—H10A109.5C15—O10—C5115.77 (13)C9—C10—H10B109.5O1—C1—C6106.88 (13)H10A—C10—H10B109.5O1—C1—C2107.27 (13)C9—C10—H10C109.5C6—C1—C2113.52 (14)H10A—C10—H10C109.5O1—C1—H1109.7H10B—C10—H10C109.5C6—C1—H1109.7O7—C11—O6124.08 (17)C2—C1—H1109.7O7—C11—C12126.49 (19)O4—C2—C3104.57 (13)O6—C11—C12109.41 (17)O4—C2—C1111.42 (13)C11—C12—H12A109.5C3—C2—C1110.19 (13)C11—C12—H12B109.5O4—C2—H2110.2H12A—C12—H12B109.5C3—C2—H2110.2C11—C12—H12C109.5C1—C2—H2110.2H12A—C12—H12C109.5O6—C3—C2107.91 (13)H12B—C12—H12C109.5O6—C3—C4108.09 (14)O9—C13—O8123.37 (18)C2—C3—C4111.16 (13)O9—C13—C14125.80 (19)O6—C3—H3109.9O8—C13—C14110.81 (17)C2—C3—H3109.9C13—C14—H14A109.5C4—C3—H3109.9C13—C14—H14B109.5O8—C4—C3108.55 (14)H14A—C14—H14B109.5O8—C4—C5107.52 (13)C13—C14—H14C109.5C3—C4—C5109.22 (14)H14A—C14—H14C109.5O8—C4—H4110.5H14B—C14—H14C109.5C3—C4—H4110.5O10—C15—C16116.66 (17)C5—C4—H4110.5O10—C15—C20122.13 (16)O10—C5—O1109.38 (13)C16—C15—C20121.21 (17)O10—C5—C4106.87 (14)C17—C16—C15119.31 (19)O1—C5—C4108.50 (13)C17—C16—H16120.3O10—C5—H5110.7C15—C16—H16120.3O1—C5—H5110.7C16—C17—C18120.59 (17)C4—C5—H5110.7C16—C17—H17119.7O2—C6—C1105.19 (14)C18—C17—H17119.7O2—C6—H6A110.7C19—C18—C17119.37 (17)C1—C6—H6A110.7C19—C18—C21121.21 (18)O2—C6—H6B110.7C17—C18—C21119.42 (18)C1—C6—H6B110.7C20—C19—C18120.91 (18)H6A—C6—H6B108.8C20—C19—H19119.5O3—C7—O2123.64 (17)C18—C19—H19119.5O3—C7—C8125.73 (18)C19—C20—C15118.61 (17)O2—C7—C8110.58 (16)C19—C20—H20120.7C7—C8—H8A109.5C15—C20—H20120.7C7—C8—H8B109.5O11—C21—C18124.9 (2)H8A—C8—H8B109.5O11—C21—H21117.5C7—C8—H8C109.5C18—C21—H21117.5H8A—C8—H8C109.5C5—O1—C1—C6&#x (13)C3—C4—C5—O158.77 (17)C5—O1—C1—C267.38 (15)C7—O2—C6—C1&#x (14)C9—O4—C2—C3140.73 (14)O1—C1—C6—O264.96 (16)C9—O4—C2—C1&#x (16)C2—C1—C6—O2&#x (13)O1—C1—C2—O4&#x (13)C6—O2—C7—O3&#x (3)C6—C1—C2—O469.16 (17)C6—O2—C7—C8174.88 (15)O1—C1—C2—C3&#x (16)C2—O4—C9—O59.6 (2)C6—C1—C2—C3&#x (13)C2—O4—C9—C10&#x (15)C11—O6—C3—C2117.13 (16)C3—O6—C11—O72.1 (3)C11—O6—C3—C4&#x (16)C3—O6—C11—C12&#x (19)O4—C2—C3—O6&#x (15)C4—O8—C13—O92.9 (3)C1—C2—C3—O6170.17 (13)C4—O8—C13—C14&#x (17)O4—C2—C3—C4171.65 (13)C5—O10—C15—C16&#x (17)C1—C2—C3—C451.81 (18)C5—O10—C15—C2046.8 (2)C13—O8—C4—C3&#x (16)O10—C15—C16—C17&#x (15)C13—O8—C4—C5131.85 (15)C20—C15—C16—C170.2 (3)O6—C3—C4—O873.14 (16)C15—C16—C17—C18&#x (3)C2—C3—C4—O8&#x (13)C16—C17—C18—C190.2 (3)O6—C3—C4—C5&#x (13)C16—C17—C18—C21&#x (17)C2—C3—C4—C5&#x (18)C17—C18—C19—C20&#x (3)C15—O10—C5—O1&#x (17)C21—C18—C19—C20179.63 (17)C15—O10—C5—C4152.99 (14)C18—C19—C20—C150.2 (3)C1—O1—C5—O10175.14 (12)O10—C15—C20—C19178.82 (15)C1—O1—C5—C4&#x (16)C16—C15—C20—C19&#x (3)O8—C4—C5—O10&#x (16)C19—C18—C21—O11&#x (3)C3—C4—C5—O10176.62 (13)C17—C18—C21—O11177.97 (19)O8—C4—C5—O1176.37 (13)Hydrogen-bond geometry (Å, °) D—H···AD—HH···AD···AD—H···AC1—H1···O5i1.002.513.356 (2)143C3—H3···O5i1.002.353.207 (2)143C6—H6A···O9ii0.992.403.324 (2)155C8—H8C···O11iii0.982.543.475 (3)160Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) x−1, y, z.Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ).Agilent Technologies (2010). CrysAlis PRO Agilent Technologies, Yarnton, Oxfordshire, England.Bao, C., Lu, R., Jin, M., Xue, P., Tan, C., Zhao, Y. & Liu, G. (2004). Carbohydr. Res.
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[]Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography&}