Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112046689/cu3015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112046689/cu3015Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270112046689/cu3015sup3.pdf |
CCDC reference: 915105
For related literature, see: Cremer & Pople (1975); Flack (1983); Hooft et al. (2008); Hu et al. (2010); Nadanaka & Kitagawa (2008); Pan et al. (2005, 2006); Parsons & Flack (2004); Stenutz et al. (1999); Takagi & Jeffrey (1977, 1979); Walters et al. (2009, 2011); Zhang et al. (2010, 2012).
The crystal structure of (I) was determined from a sample prepared chemically by the six-step synthesis described in the Supplementary materials. Disaccharide (I) was crystallized from a water solution to give colorless needle-like crystals.
Aliphatic H atoms were included in geometrically constrained positions, with C—H = 0.98–1.0 Å. Hydroxy H atoms were initially located from a difference Fourier map and were subsequently refined with a riding model, allowing for rotation to minimize the electron-density contribution of the hydrogen; O—H = 0.84 Å. Methyl and hydroxy H-atom displacement parameters were tied to 1.5Ueq of the atom to which they are bonded, and all other C-bound H atoms were refined with Uiso(H) = 1.2Ueq(C).
The absolute stereochemistry was determined by comparison with the known configuration of the compound, by comparison of intensities of Friedel pairs of reflections and by a Bayesian analysis of Bijvoet pairs. The Friedel pairs analysis yielded a Flack x parameter of 0.05 (12) based on 2045 Friedel opposites (Flack, 1983). The Hooft y parameter is -0.03 (6) with P2(true) and P3(true) values of 1.000 and 1.000 (Hooft et al., 2008). Further anaylsis using Parsons' quotients yields a Flack x parameter of -0.03 (6) (Parsons & Flack, 2004). The analytical methods are in excellent agreement with the known configuration of the compound and the correct configuration is depicted.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008; data reduction: SAINT (Bruker, 2008; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: POV-RAY (Cason, 2003), DIAMOND (Brandenburg, 2009) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).
C12H22O10 | F(000) = 696 |
Mr = 326.30 | Dx = 1.506 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2yb | Cell parameters from 7736 reflections |
a = 13.1578 (6) Å | θ = 3.4–69.3° |
b = 4.6755 (2) Å | µ = 1.15 mm−1 |
c = 23.4908 (11) Å | T = 120 K |
β = 95.112 (2)° | Rod, colourless |
V = 1439.39 (11) Å3 | 0.46 × 0.09 × 0.09 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 5062 independent reflections |
Radiation source: fine-focus sealed tube | 4884 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 8.33 pixels mm-1 | θmax = 69.8°, θmin = 1.9° |
ω– and ϕ scans | h = −15→15 |
Absorption correction: numerical (SADABS; Sheldrick, 2008) | k = −5→5 |
Tmin = 0.701, Tmax = 0.940 | l = −28→28 |
14354 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0454P)2 + 0.4307P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
5062 reflections | Δρmax = 0.18 e Å−3 |
411 parameters | Δρmin = −0.25 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 2045 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.05 (12) |
C12H22O10 | V = 1439.39 (11) Å3 |
Mr = 326.30 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 13.1578 (6) Å | µ = 1.15 mm−1 |
b = 4.6755 (2) Å | T = 120 K |
c = 23.4908 (11) Å | 0.46 × 0.09 × 0.09 mm |
β = 95.112 (2)° |
Bruker APEXII CCD area-detector diffractometer | 5062 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008) | 4884 reflections with I > 2σ(I) |
Tmin = 0.701, Tmax = 0.940 | Rint = 0.023 |
14354 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.079 | Δρmax = 0.18 e Å−3 |
S = 1.04 | Δρmin = −0.25 e Å−3 |
5062 reflections | Absolute structure: Flack (1983), with 2045 Friedel pairs |
411 parameters | Absolute structure parameter: 0.05 (12) |
1 restraint |
Experimental. Methyl 4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2,3-O-isopropylidene-β-D-xylopyranoside (1) was prepared as described previously (Zhang, W., Oliver, A. G. & Serianni, A. S. (2012) Acta Cryst. C68, o7–o11). Methyl 4-O-β-D-galactopyranosyl-2,3-O-isopropylidene-β-D-xylopyranoside (2). Compound 1 (1.00 g, 1.87 mmol) was dissolved in methanol (20 ml) and the solution was saturated with NH3 (g). The reaction solution was stirred overnight at room temperature, concentrated, and the product purified on a silica-gel column [2.5 × 30 cm, eluted with ethyl acetate–methanol (6:1)] to afford 2 (0.64 g, 1.75 mmol, 94%). Methyl 4-O-(3,6-di-O-pivaloyl-β-D-galactopyranosyl)-2,3-O-isopropylidene-β-D-xylopyranoside (3). To a solution of 2 (0.64 g, 1.75 mmol) in dry pyridine (10 ml) at -20 °C, pivaloyl chloride (0.45 ml, 3.68 mmol) was added dropwise. The reaction mixture was stirred overnight at room temperature, diluted with CH2Cl2 (30 ml), and washed with aqueous HCl (1 N) and distilled water. The organic layer was dried over anhydrous Na2SO4, concentrated under vacuum, and the residue was applied to a silica-gel column [2.5 × 30 cm, eluted with hexane–ethyl acetate (2:1)] to afford 3 as a white foam (0.77 g, 1.44 mmol, 82%) (Jiang, L. & Chan, T. (1998). J. Org. Chem., 63, 6035–6038). Methyl 4-O-(2,4-di-O-trifluoromethanesulfonyl-3,6-di-O-pivaloyl-β-D-galactopyranosyl)-2,3-O-isopropylidene-β-D-xylopyranoside (4). Compound 3 (0.55 g, 1.03 mmol) was dissolved in a mixed solvent (dry CH2Cl2, 2 ml, and dry pyridine, 10 ml) and trifluoromethanesulfonic anhydride (0.69 ml, 4.12 mmol) was added slowly at -20 °C. The mixture was stirred overnight at room temperature, diluted with CH2Cl2 (30 ml) and washed with distilled water. The organic layer was dried over anhydrous Na2SO4 and concentrated under vacuum, and the residue was applied to a silica-gel column [2.5 × 30 cm, eluted with hexane–ethyl acetate (6:1)] to give product 4 as a white foam (0.74 g, 0.93 mmol, 90%). Methyl 4-O-(2,4-di-O-acetyl-3,6-di-O-pivaloyl-β-D-mannopyranosyl)-2,3-O-isopropylidene-β-D-xylopyranoside (5). A mixture of compound 4 (638 mg, 0.80 mmol), caesium acetate (614 mg, 3.20 mmol) and 18-crown-6 (845 mg, 3.20 mmol) was dried under vacuum and then dry toluene (15 ml) was added. The reaction mixture was stirred for 2 h at 90 °C. The reaction solution was diluted with CH2Cl2 (30 ml) and washed with aqueous NaHCO3 solution (1 N), followed by distilled water. The organic layer was dried over anhydrous Na2SO4, concentrated under vacuum, and the residue applied to a silica-gel column [1.5 × 40 cm, eluted with hexane–ethyl acetate (3:1)] to obtain product 5 (330 mg, 0.53 mmol, 66%) (Sato, K. & Yoshitomo, A. (1995). Chem. Lett. pp. 39–40). Methyl 4-O-β-D-mannopyranosyl-β-D-xylopyranoside (6, I). Compound 5 (330 mg, 0.53 mmol) was dissolved in methanol (10 ml), and acetyl chloride (10 ml) was added at 0 °C. After stirring for 2 h at room temperature, the reaction solution was saturated with NH3 (g) and stirred for 3 d at 50 °C. The reaction mixture was dried at 30 °C in vacuo. The residue was dissolved in 0.5 ml of distilled water and the solution was applied to a column (2.5 × 100 cm) containing Dowex 50 × 8 (200–400 mesh) ion-exchange resin in the Ca2+ form (Angyal, S., Bethell, G. S. & Beveridge, R. (1979). Carbohydr. Res. 73, 9–18). The column was eluted with distilled decarbonated water at 1.5 ml min-1, and fractions containing pure product were collected and concentrated at 30 °C in vacuo to give 6 (I) (135 mg, 0.41 mmol, 78%). |
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 | ||
O1A | 0.18592 (10) | 0.6246 (4) | 1.04913 (5) | 0.0286 (3) | |
O2A | 0.37438 (9) | 0.8998 (3) | 1.05197 (5) | 0.0222 (3) | |
H2B | 0.4308 | 0.9688 | 1.0449 | 0.033* | |
O3A | 0.46822 (9) | 0.8234 (3) | 0.94716 (5) | 0.0213 (3) | |
H3B | 0.4914 | 0.8995 | 0.9186 | 0.032* | |
O5A | 0.16205 (10) | 0.6702 (3) | 0.95259 (5) | 0.0231 (3) | |
O1'A | 0.31724 (9) | 0.9551 (3) | 0.84521 (5) | 0.0170 (3) | |
O2'A | 0.36087 (9) | 1.2392 (3) | 0.74799 (5) | 0.0175 (3) | |
H2'C | 0.3180 | 1.2832 | 0.7208 | 0.026* | |
O3'A | 0.44273 (10) | 0.9042 (3) | 0.65839 (5) | 0.0191 (3) | |
H3'C | 0.4266 | 1.0773 | 0.6542 | 0.029* | |
O4'A | 0.64208 (9) | 0.8568 (3) | 0.71565 (5) | 0.0196 (3) | |
H4'C | 0.6755 | 0.9961 | 0.7046 | 0.029* | |
O5'A | 0.48841 (9) | 0.9691 (3) | 0.83634 (5) | 0.0161 (2) | |
O6'A | 0.68409 (9) | 1.2524 (3) | 0.83909 (5) | 0.0174 (3) | |
H6'E | 0.6736 | 1.3187 | 0.8713 | 0.026* | |
C1A | 0.21275 (14) | 0.7882 (5) | 1.00357 (7) | 0.0215 (4) | |
H1A | 0.1926 | 0.9925 | 1.0083 | 0.026* | |
C2A | 0.32794 (13) | 0.7619 (4) | 1.00222 (7) | 0.0175 (4) | |
H2A | 0.3470 | 0.5548 | 1.0035 | 0.021* | |
C3A | 0.36309 (12) | 0.8943 (4) | 0.94791 (7) | 0.0163 (4) | |
H3A | 0.3567 | 1.1069 | 0.9505 | 0.020* | |
C4A | 0.29819 (13) | 0.7910 (4) | 0.89495 (7) | 0.0175 (4) | |
H4A | 0.3128 | 0.5845 | 0.8881 | 0.021* | |
C5A | 0.18578 (14) | 0.8287 (5) | 0.90346 (7) | 0.0224 (4) | |
H5A | 0.1706 | 1.0338 | 0.9088 | 0.027* | |
H5B | 0.1435 | 0.7596 | 0.8693 | 0.027* | |
C6A | 0.08504 (16) | 0.6818 (7) | 1.06467 (9) | 0.0411 (6) | |
H6A | 0.0730 | 0.5721 | 1.0990 | 0.062* | |
H6B | 0.0350 | 0.6258 | 1.0332 | 0.062* | |
H6C | 0.0781 | 0.8865 | 1.0724 | 0.062* | |
C1'A | 0.39359 (12) | 0.8499 (4) | 0.81309 (7) | 0.0155 (3) | |
H1'A | 0.3964 | 0.6367 | 0.8161 | 0.019* | |
C2'A | 0.37092 (13) | 0.9365 (4) | 0.75088 (7) | 0.0166 (4) | |
H2'A | 0.3062 | 0.8441 | 0.7346 | 0.020* | |
C3'A | 0.45944 (13) | 0.8402 (4) | 0.71753 (7) | 0.0160 (3) | |
H3'A | 0.4636 | 0.6272 | 0.7209 | 0.019* | |
C4'A | 0.55968 (12) | 0.9590 (4) | 0.74504 (7) | 0.0158 (3) | |
H4'A | 0.5581 | 1.1728 | 0.7438 | 0.019* | |
C5'A | 0.57246 (13) | 0.8576 (4) | 0.80732 (7) | 0.0161 (3) | |
H5'A | 0.5689 | 0.6440 | 0.8077 | 0.019* | |
C6'A | 0.67154 (13) | 0.9488 (4) | 0.83941 (7) | 0.0182 (4) | |
H6'A | 0.6732 | 0.8812 | 0.8794 | 0.022* | |
H6'B | 0.7291 | 0.8583 | 0.8218 | 0.022* | |
O1B | 0.36657 (10) | 0.5788 (3) | 0.49266 (5) | 0.0256 (3) | |
O2B | 0.39334 (9) | 0.4124 (3) | 0.60806 (5) | 0.0170 (3) | |
H2AB | 0.4208 | 0.5599 | 0.6229 | 0.026* | |
O3B | 0.21660 (9) | 0.4482 (3) | 0.66456 (5) | 0.0188 (3) | |
H3AB | 0.1662 | 0.3888 | 0.6807 | 0.028* | |
O5B | 0.19851 (9) | 0.4634 (3) | 0.48731 (5) | 0.0209 (3) | |
O1'B | 0.02359 (9) | 0.2668 (3) | 0.59163 (5) | 0.0164 (3) | |
O2'B | −0.14996 (10) | 0.0227 (3) | 0.62938 (5) | 0.0177 (3) | |
H2'D | −0.1687 | −0.0145 | 0.5951 | 0.026* | |
O3'B | −0.27955 (9) | 0.3559 (3) | 0.68864 (5) | 0.0190 (3) | |
H3'D | −0.3127 | 0.4993 | 0.6981 | 0.028* | |
O4'B | −0.14285 (9) | 0.4549 (3) | 0.79355 (5) | 0.0215 (3) | |
H4'D | −0.1976 | 0.3858 | 0.8033 | 0.032* | |
O5'B | 0.03231 (9) | 0.2582 (3) | 0.68901 (5) | 0.0166 (3) | |
O6'B | 0.16455 (10) | 0.3821 (4) | 0.78868 (6) | 0.0294 (3) | |
H6'F | 0.2099 | 0.2620 | 0.7992 | 0.044* | |
C1B | 0.29791 (12) | 0.4042 (4) | 0.51630 (7) | 0.0179 (4) | |
H1AA | 0.3165 | 0.1984 | 0.5121 | 0.022* | |
C2B | 0.29761 (13) | 0.4853 (4) | 0.57908 (7) | 0.0153 (3) | |
H2AA | 0.2887 | 0.6972 | 0.5816 | 0.018* | |
C3B | 0.21105 (12) | 0.3423 (4) | 0.60761 (7) | 0.0156 (4) | |
H3AA | 0.2216 | 0.1305 | 0.6083 | 0.019* | |
C4B | 0.11014 (12) | 0.4120 (4) | 0.57287 (7) | 0.0161 (3) | |
H4AA | 0.0981 | 0.6232 | 0.5736 | 0.019* | |
C5B | 0.11795 (13) | 0.3149 (4) | 0.51131 (7) | 0.0194 (4) | |
H5AA | 0.1310 | 0.1065 | 0.5106 | 0.023* | |
H5AB | 0.0527 | 0.3530 | 0.4883 | 0.023* | |
C6B | 0.40707 (16) | 0.4658 (6) | 0.44231 (8) | 0.0350 (5) | |
H6AA | 0.4606 | 0.5934 | 0.4307 | 0.053* | |
H6AB | 0.3523 | 0.4515 | 0.4113 | 0.053* | |
H6AC | 0.4359 | 0.2756 | 0.4507 | 0.053* | |
C1'B | −0.01894 (12) | 0.3872 (4) | 0.63890 (7) | 0.0157 (3) | |
H1'B | −0.0079 | 0.5989 | 0.6397 | 0.019* | |
C2'B | −0.13223 (13) | 0.3206 (4) | 0.63555 (7) | 0.0158 (4) | |
H2'B | −0.1676 | 0.4230 | 0.6021 | 0.019* | |
C3'B | −0.17417 (12) | 0.4270 (4) | 0.69036 (7) | 0.0157 (3) | |
H3'B | −0.1683 | 0.6403 | 0.6911 | 0.019* | |
C4'B | −0.11458 (13) | 0.3106 (4) | 0.74415 (7) | 0.0169 (4) | |
H4'B | −0.1255 | 0.0999 | 0.7476 | 0.020* | |
C5'B | −0.00191 (13) | 0.3766 (4) | 0.74098 (7) | 0.0176 (4) | |
H5'B | 0.0073 | 0.5888 | 0.7404 | 0.021* | |
C6'B | 0.06706 (14) | 0.2542 (5) | 0.78974 (7) | 0.0224 (4) | |
H6'C | 0.0389 | 0.2953 | 0.8266 | 0.027* | |
H6'D | 0.0725 | 0.0442 | 0.7855 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0210 (7) | 0.0496 (9) | 0.0158 (6) | −0.0093 (7) | 0.0043 (5) | 0.0057 (7) |
O2A | 0.0203 (6) | 0.0321 (8) | 0.0144 (5) | −0.0079 (6) | 0.0029 (5) | −0.0023 (6) |
O3A | 0.0163 (6) | 0.0328 (8) | 0.0152 (5) | 0.0009 (6) | 0.0033 (5) | 0.0042 (6) |
O5A | 0.0186 (6) | 0.0378 (8) | 0.0131 (6) | −0.0080 (6) | 0.0022 (5) | 0.0025 (6) |
O1'A | 0.0180 (6) | 0.0196 (6) | 0.0135 (5) | 0.0008 (5) | 0.0031 (4) | 0.0021 (5) |
O2'A | 0.0198 (6) | 0.0174 (6) | 0.0146 (6) | 0.0023 (5) | −0.0031 (5) | 0.0008 (5) |
O3'A | 0.0287 (6) | 0.0171 (7) | 0.0115 (5) | 0.0003 (6) | 0.0019 (5) | −0.0010 (5) |
O4'A | 0.0200 (6) | 0.0183 (6) | 0.0220 (6) | 0.0009 (5) | 0.0098 (5) | −0.0008 (6) |
O5'A | 0.0158 (6) | 0.0196 (6) | 0.0128 (5) | −0.0001 (5) | 0.0021 (4) | −0.0010 (5) |
O6'A | 0.0196 (6) | 0.0193 (6) | 0.0136 (5) | −0.0017 (5) | 0.0028 (5) | −0.0016 (5) |
C1A | 0.0214 (9) | 0.0300 (10) | 0.0133 (8) | −0.0041 (8) | 0.0024 (7) | −0.0006 (8) |
C2A | 0.0201 (9) | 0.0215 (9) | 0.0111 (7) | −0.0006 (7) | 0.0021 (6) | −0.0004 (8) |
C3A | 0.0141 (8) | 0.0193 (9) | 0.0156 (8) | 0.0004 (7) | 0.0019 (6) | 0.0006 (8) |
C4A | 0.0198 (9) | 0.0193 (9) | 0.0136 (8) | −0.0020 (7) | 0.0026 (6) | 0.0013 (7) |
C5A | 0.0202 (9) | 0.0337 (11) | 0.0133 (8) | −0.0036 (8) | 0.0018 (6) | 0.0027 (8) |
C6A | 0.0243 (11) | 0.0760 (19) | 0.0241 (10) | −0.0105 (12) | 0.0091 (8) | 0.0006 (12) |
C1'A | 0.0144 (8) | 0.0172 (8) | 0.0151 (8) | 0.0001 (7) | 0.0027 (6) | 0.0006 (7) |
C2'A | 0.0166 (8) | 0.0184 (9) | 0.0147 (8) | −0.0021 (7) | 0.0011 (6) | −0.0011 (7) |
C3'A | 0.0221 (9) | 0.0146 (8) | 0.0114 (7) | −0.0008 (7) | 0.0021 (6) | 0.0011 (7) |
C4'A | 0.0174 (8) | 0.0141 (8) | 0.0163 (8) | 0.0017 (7) | 0.0042 (6) | 0.0003 (7) |
C5'A | 0.0175 (8) | 0.0158 (8) | 0.0153 (8) | 0.0023 (7) | 0.0033 (6) | 0.0004 (7) |
C6'A | 0.0177 (8) | 0.0183 (9) | 0.0189 (8) | 0.0027 (7) | 0.0026 (6) | 0.0008 (8) |
O1B | 0.0215 (7) | 0.0394 (8) | 0.0165 (6) | −0.0057 (6) | 0.0058 (5) | 0.0014 (6) |
O2B | 0.0152 (6) | 0.0195 (7) | 0.0160 (5) | −0.0008 (5) | −0.0010 (4) | −0.0010 (5) |
O3B | 0.0146 (6) | 0.0300 (7) | 0.0119 (5) | −0.0019 (6) | 0.0021 (4) | −0.0009 (6) |
O5B | 0.0167 (6) | 0.0329 (7) | 0.0130 (5) | −0.0003 (6) | 0.0015 (5) | 0.0046 (6) |
O1'B | 0.0146 (6) | 0.0211 (6) | 0.0138 (5) | −0.0014 (5) | 0.0036 (4) | −0.0018 (5) |
O2'B | 0.0218 (6) | 0.0175 (6) | 0.0136 (5) | −0.0017 (5) | 0.0012 (5) | −0.0018 (5) |
O3'B | 0.0149 (6) | 0.0185 (6) | 0.0241 (6) | 0.0007 (5) | 0.0046 (5) | −0.0020 (6) |
O4'B | 0.0180 (6) | 0.0287 (7) | 0.0188 (6) | −0.0022 (6) | 0.0071 (5) | −0.0065 (6) |
O5'B | 0.0146 (6) | 0.0236 (6) | 0.0116 (5) | 0.0038 (5) | 0.0009 (4) | −0.0005 (5) |
O6'B | 0.0151 (6) | 0.0493 (9) | 0.0234 (6) | 0.0013 (6) | −0.0002 (5) | 0.0044 (7) |
C1B | 0.0142 (8) | 0.0255 (10) | 0.0141 (7) | 0.0007 (8) | 0.0016 (6) | −0.0008 (8) |
C2B | 0.0128 (8) | 0.0168 (8) | 0.0164 (8) | 0.0005 (7) | 0.0017 (6) | 0.0000 (7) |
C3B | 0.0175 (8) | 0.0168 (9) | 0.0124 (7) | 0.0013 (7) | 0.0011 (6) | 0.0000 (7) |
C4B | 0.0145 (8) | 0.0193 (9) | 0.0147 (7) | 0.0002 (7) | 0.0024 (6) | 0.0014 (7) |
C5B | 0.0152 (8) | 0.0292 (11) | 0.0137 (8) | −0.0025 (8) | 0.0010 (6) | 0.0003 (8) |
C6B | 0.0254 (10) | 0.0622 (16) | 0.0188 (9) | −0.0011 (11) | 0.0097 (7) | 0.0026 (11) |
C1'B | 0.0172 (8) | 0.0178 (9) | 0.0122 (7) | 0.0014 (7) | 0.0015 (6) | −0.0005 (7) |
C2'B | 0.0169 (8) | 0.0171 (9) | 0.0131 (7) | 0.0021 (7) | 0.0003 (6) | 0.0020 (7) |
C3'B | 0.0126 (8) | 0.0149 (9) | 0.0198 (8) | −0.0015 (7) | 0.0034 (6) | −0.0012 (8) |
C4'B | 0.0185 (9) | 0.0174 (9) | 0.0150 (8) | −0.0006 (7) | 0.0033 (6) | −0.0023 (7) |
C5'B | 0.0173 (8) | 0.0225 (9) | 0.0136 (7) | 0.0008 (7) | 0.0043 (6) | −0.0031 (8) |
C6'B | 0.0210 (9) | 0.0315 (10) | 0.0151 (8) | 0.0028 (8) | 0.0033 (7) | 0.0006 (8) |
O1A—C1A | 1.386 (2) | C5'B—C6'B | 1.509 (2) |
O1A—C6A | 1.433 (2) | O2A—H2B | 0.8400 |
O2A—C2A | 1.424 (2) | O3A—H3B | 0.8400 |
O3A—C3A | 1.424 (2) | O2'A—H2'C | 0.8400 |
O5A—C1A | 1.429 (2) | O3'A—H3'C | 0.8400 |
O5A—C5A | 1.429 (2) | O4'A—H4'C | 0.8400 |
O1'A—C1'A | 1.399 (2) | O6'A—H6'E | 0.8400 |
O1'A—C4A | 1.439 (2) | C1A—H1A | 1.0000 |
O2'A—C2'A | 1.422 (2) | C2A—H2A | 1.0000 |
O3'A—C3'A | 1.4191 (19) | C3A—H3A | 1.0000 |
O4'A—C4'A | 1.419 (2) | C4A—H4A | 1.0000 |
O5'A—C1'A | 1.430 (2) | C5A—H5A | 0.9900 |
O5'A—C5'A | 1.4470 (19) | C5A—H5B | 0.9900 |
O6'A—C6'A | 1.429 (2) | C6A—H6A | 0.9800 |
C1A—C2A | 1.524 (2) | C6A—H6B | 0.9800 |
C2A—C3A | 1.526 (2) | C6A—H6C | 0.9800 |
C3A—C4A | 1.523 (2) | C1'A—H1'A | 1.0000 |
C4A—C5A | 1.520 (2) | C2'A—H2'A | 1.0000 |
C1'A—C2'A | 1.520 (2) | C3'A—H3'A | 1.0000 |
C2'A—C3'A | 1.528 (2) | C4'A—H4'A | 1.0000 |
C3'A—C4'A | 1.521 (2) | C5'A—H5'A | 1.0000 |
C4'A—C5'A | 1.533 (2) | C6'A—H6'A | 0.9900 |
C5'A—C6'A | 1.508 (2) | C6'A—H6'B | 0.9900 |
O1B—C1B | 1.371 (2) | O2B—H2AB | 0.8400 |
O1B—C6B | 1.440 (2) | O3B—H3AB | 0.8400 |
O2B—C2B | 1.419 (2) | O2'B—H2'D | 0.8400 |
O3B—C3B | 1.4224 (19) | O3'B—H3'D | 0.8400 |
O5B—C5B | 1.425 (2) | O4'B—H4'D | 0.8400 |
O5B—C1B | 1.446 (2) | O6'B—H6'F | 0.8400 |
O1'B—C1'B | 1.405 (2) | C1B—H1AA | 1.0000 |
O1'B—C4B | 1.429 (2) | C2B—H2AA | 1.0000 |
O2'B—C2'B | 1.418 (2) | C3B—H3AA | 1.0000 |
O3'B—C3'B | 1.423 (2) | C4B—H4AA | 1.0000 |
O4'B—C4'B | 1.420 (2) | C5B—H5AA | 0.9900 |
O5'B—C1'B | 1.436 (2) | C5B—H5AB | 0.9900 |
O5'B—C5'B | 1.4482 (19) | C6B—H6AA | 0.9800 |
O6'B—C6'B | 1.417 (2) | C6B—H6AB | 0.9800 |
C1B—C2B | 1.523 (2) | C6B—H6AC | 0.9800 |
C2B—C3B | 1.526 (2) | C1'B—H1'B | 1.0000 |
C3B—C4B | 1.530 (2) | C2'B—H2'B | 1.0000 |
C4B—C5B | 1.528 (2) | C3'B—H3'B | 1.0000 |
C1'B—C2'B | 1.518 (2) | C4'B—H4'B | 1.0000 |
C2'B—C3'B | 1.529 (2) | C5'B—H5'B | 1.0000 |
C3'B—C4'B | 1.527 (2) | C6'B—H6'C | 0.9900 |
C4'B—C5'B | 1.523 (2) | C6'B—H6'D | 0.9900 |
C1A—O1A—C6A | 113.53 (17) | O5'B—C5'B—C6'B | 106.49 (14) |
C1A—O5A—C5A | 110.95 (15) | O5'B—C5'B—C4'B | 109.94 (14) |
C1'A—O1'A—C4A | 115.85 (14) | C6'B—C5'B—C4'B | 114.11 (15) |
C1'A—O5'A—C5'A | 110.93 (13) | O6'B—C6'B—C5'B | 108.10 (15) |
O1A—C1A—O5A | 107.59 (16) | C2A—O2A—H2B | 109.5 |
O1A—C1A—C2A | 107.08 (15) | C3A—O3A—H3B | 109.5 |
O5A—C1A—C2A | 110.03 (14) | C2'A—O2'A—H2'C | 109.5 |
O2A—C2A—C1A | 107.53 (13) | C3'A—O3'A—H3'C | 109.5 |
O2A—C2A—C3A | 111.24 (15) | C4'A—O4'A—H4'C | 109.5 |
C1A—C2A—C3A | 111.14 (14) | C6'A—O6'A—H6'E | 109.5 |
O3A—C3A—C4A | 112.99 (14) | O1A—C1A—H1A | 110.7 |
O3A—C3A—C2A | 106.43 (13) | O5A—C1A—H1A | 110.7 |
C4A—C3A—C2A | 111.37 (14) | C2A—C1A—H1A | 110.7 |
O1'A—C4A—C5A | 106.67 (14) | O2A—C2A—H2A | 109.0 |
O1'A—C4A—C3A | 111.63 (14) | C1A—C2A—H2A | 109.0 |
C5A—C4A—C3A | 109.70 (14) | C3A—C2A—H2A | 109.0 |
O5A—C5A—C4A | 109.34 (15) | O3A—C3A—H3A | 108.6 |
O1'A—C1'A—H1'A | 109.7 | C4A—C3A—H3A | 108.6 |
O5'A—C1'A—H1'A | 109.7 | C2A—C3A—H3A | 108.6 |
C2'A—C1'A—H1'A | 109.7 | O1'A—C4A—H4A | 109.6 |
O2'A—C2'A—H2'A | 109.8 | C5A—C4A—H4A | 109.6 |
C1'A—C2'A—H2'A | 109.8 | C3A—C4A—H4A | 109.6 |
C3'A—C2'A—H2'A | 109.8 | O5A—C5A—H5A | 109.8 |
O3'A—C3'A—H3'A | 106.9 | C4A—C5A—H5A | 109.8 |
C4'A—C3'A—H3'A | 106.9 | O5A—C5A—H5B | 109.8 |
C2'A—C3'A—H3'A | 106.9 | C4A—C5A—H5B | 109.8 |
O4'A—C4'A—H4'A | 109.7 | H5A—C5A—H5B | 108.3 |
C3'A—C4'A—H4'A | 109.7 | O1A—C6A—H6A | 109.5 |
C5'A—C4'A—H4'A | 109.7 | O1A—C6A—H6B | 109.5 |
O5'A—C5'A—H5'A | 108.5 | H6A—C6A—H6B | 109.5 |
C6'A—C5'A—H5'A | 108.5 | O1A—C6A—H6C | 109.5 |
C4'A—C5'A—H5'A | 108.5 | H6A—C6A—H6C | 109.5 |
O6'A—C6'A—H6'A | 109.2 | H6B—C6A—H6C | 109.5 |
C5'A—C6'A—H6'A | 109.2 | C2B—O2B—H2AB | 109.5 |
O6'A—C6'A—H6'B | 109.2 | C3B—O3B—H3AB | 109.5 |
C5'A—C6'A—H6'B | 109.2 | C2'B—O2'B—H2'D | 109.5 |
H6'A—C6'A—H6'B | 107.9 | C3'B—O3'B—H3'D | 109.5 |
O1'A—C1'A—O5'A | 107.53 (13) | C4'B—O4'B—H4'D | 109.5 |
O1'A—C1'A—C2'A | 109.64 (14) | C6'B—O6'B—H6'F | 109.5 |
O5'A—C1'A—C2'A | 110.68 (14) | O1B—C1B—H1AA | 110.9 |
O2'A—C2'A—C1'A | 108.68 (15) | O5B—C1B—H1AA | 110.9 |
O2'A—C2'A—C3'A | 109.91 (14) | C2B—C1B—H1AA | 110.9 |
C1'A—C2'A—C3'A | 108.72 (14) | O2B—C2B—H2AA | 108.3 |
O3'A—C3'A—C4'A | 113.06 (14) | C1B—C2B—H2AA | 108.3 |
O3'A—C3'A—C2'A | 112.39 (14) | C3B—C2B—H2AA | 108.3 |
C4'A—C3'A—C2'A | 110.26 (14) | O3B—C3B—H3AA | 109.5 |
O4'A—C4'A—C3'A | 109.96 (14) | C2B—C3B—H3AA | 109.5 |
O4'A—C4'A—C5'A | 109.67 (14) | C4B—C3B—H3AA | 109.5 |
C3'A—C4'A—C5'A | 108.04 (14) | O1'B—C4B—H4AA | 109.4 |
O5'A—C5'A—C6'A | 109.01 (14) | C5B—C4B—H4AA | 109.4 |
O5'A—C5'A—C4'A | 108.34 (13) | C3B—C4B—H4AA | 109.4 |
C6'A—C5'A—C4'A | 113.95 (14) | O5B—C5B—H5AA | 109.6 |
O6'A—C6'A—C5'A | 111.92 (15) | C4B—C5B—H5AA | 109.6 |
C1B—O1B—C6B | 114.79 (17) | O5B—C5B—H5AB | 109.6 |
C5B—O5B—C1B | 113.19 (13) | C4B—C5B—H5AB | 109.6 |
C1'B—O1'B—C4B | 115.95 (13) | H5AA—C5B—H5AB | 108.1 |
C1'B—O5'B—C5'B | 111.83 (13) | O1B—C6B—H6AA | 109.5 |
O1B—C1B—O5B | 107.22 (14) | O1B—C6B—H6AB | 109.5 |
O1B—C1B—C2B | 107.60 (14) | H6AA—C6B—H6AB | 109.5 |
O5B—C1B—C2B | 109.14 (13) | O1B—C6B—H6AC | 109.5 |
O2B—C2B—C1B | 109.02 (13) | H6AA—C6B—H6AC | 109.5 |
O2B—C2B—C3B | 110.46 (14) | H6AB—C6B—H6AC | 109.5 |
C1B—C2B—C3B | 112.49 (14) | O1'B—C1'B—H1'B | 110.1 |
O3B—C3B—C2B | 106.42 (14) | O5'B—C1'B—H1'B | 110.1 |
O3B—C3B—C4B | 113.37 (14) | C2'B—C1'B—H1'B | 110.1 |
C2B—C3B—C4B | 108.57 (14) | O2'B—C2'B—H2'B | 109.2 |
O1'B—C4B—C5B | 105.86 (13) | C1'B—C2'B—H2'B | 109.2 |
O1'B—C4B—C3B | 114.31 (14) | C3'B—C2'B—H2'B | 109.2 |
C5B—C4B—C3B | 108.24 (14) | O3'B—C3'B—H3'B | 107.9 |
O5B—C5B—C4B | 110.17 (14) | C4'B—C3'B—H3'B | 107.9 |
O1'B—C1'B—O5'B | 106.76 (14) | C2'B—C3'B—H3'B | 107.9 |
O1'B—C1'B—C2'B | 109.59 (14) | O4'B—C4'B—H4'B | 110.6 |
O5'B—C1'B—C2'B | 110.09 (13) | C5'B—C4'B—H4'B | 110.6 |
O2'B—C2'B—C1'B | 111.02 (14) | C3'B—C4'B—H4'B | 110.6 |
O2'B—C2'B—C3'B | 109.72 (14) | O5'B—C5'B—H5'B | 108.7 |
C1'B—C2'B—C3'B | 108.43 (14) | C6'B—C5'B—H5'B | 108.7 |
O3'B—C3'B—C4'B | 111.56 (13) | C4'B—C5'B—H5'B | 108.7 |
O3'B—C3'B—C2'B | 108.91 (13) | O6'B—C6'B—H6'C | 110.1 |
C4'B—C3'B—C2'B | 112.57 (14) | C5'B—C6'B—H6'C | 110.1 |
O4'B—C4'B—C5'B | 105.71 (13) | O6'B—C6'B—H6'D | 110.1 |
O4'B—C4'B—C3'B | 110.75 (14) | C5'B—C6'B—H6'D | 110.1 |
C5'B—C4'B—C3'B | 108.53 (13) | H6'C—C6'B—H6'D | 108.4 |
C6A—O1A—C1A—O5A | −76.2 (2) | C6B—O1B—C1B—O5B | −86.34 (19) |
C6A—O1A—C1A—C2A | 165.60 (17) | C6B—O1B—C1B—C2B | 156.37 (16) |
C5A—O5A—C1A—O1A | 179.83 (15) | C5B—O5B—C1B—O1B | −174.51 (14) |
C5A—O5A—C1A—C2A | −63.8 (2) | C5B—O5B—C1B—C2B | −58.2 (2) |
O1A—C1A—C2A—O2A | −67.3 (2) | O1B—C1B—C2B—O2B | −67.13 (19) |
O5A—C1A—C2A—O2A | 176.06 (15) | O5B—C1B—C2B—O2B | 176.83 (14) |
O1A—C1A—C2A—C3A | 170.74 (15) | O1B—C1B—C2B—C3B | 169.98 (14) |
O5A—C1A—C2A—C3A | 54.1 (2) | O5B—C1B—C2B—C3B | 53.9 (2) |
O2A—C2A—C3A—O3A | 68.12 (19) | O2B—C2B—C3B—O3B | 61.01 (17) |
C1A—C2A—C3A—O3A | −172.10 (15) | C1B—C2B—C3B—O3B | −176.91 (14) |
O2A—C2A—C3A—C4A | −168.33 (15) | O2B—C2B—C3B—C4B | −176.62 (14) |
C1A—C2A—C3A—C4A | −48.5 (2) | C1B—C2B—C3B—C4B | −54.54 (19) |
C1'A—O1'A—C4A—C5A | −149.22 (15) | C1'B—O1'B—C4B—C5B | −159.98 (14) |
C1'A—O1'A—C4A—C3A | 90.97 (18) | C1'B—O1'B—C4B—C3B | 80.98 (19) |
O3A—C3A—C4A—O1'A | −71.65 (19) | O3B—C3B—C4B—O1'B | −68.1 (2) |
C2A—C3A—C4A—O1'A | 168.62 (14) | C2B—C3B—C4B—O1'B | 173.88 (13) |
O3A—C3A—C4A—C5A | 170.34 (15) | O3B—C3B—C4B—C5B | 174.25 (15) |
C2A—C3A—C4A—C5A | 50.6 (2) | C2B—C3B—C4B—C5B | 56.20 (19) |
C1A—O5A—C5A—C4A | 66.5 (2) | C1B—O5B—C5B—C4B | 63.1 (2) |
O1'A—C4A—C5A—O5A | −179.88 (15) | O1'B—C4B—C5B—O5B | 176.15 (14) |
C3A—C4A—C5A—O5A | −58.8 (2) | C3B—C4B—C5B—O5B | −60.9 (2) |
C4A—O1'A—C1'A—O5'A | −88.38 (17) | C4B—O1'B—C1'B—O5'B | −89.82 (17) |
C4A—O1'A—C1'A—C2'A | 151.23 (15) | C4B—O1'B—C1'B—C2'B | 150.97 (14) |
C5'A—O5'A—C1'A—O1'A | 176.80 (13) | C5'B—O5'B—C1'B—O1'B | 177.20 (13) |
C5'A—O5'A—C1'A—C2'A | −63.47 (18) | C5'B—O5'B—C1'B—C2'B | −63.91 (18) |
O1'A—C1'A—C2'A—O2'A | 55.90 (18) | O1'B—C1'B—C2'B—O2'B | 53.63 (18) |
O5'A—C1'A—C2'A—O2'A | −62.56 (18) | O5'B—C1'B—C2'B—O2'B | −63.51 (18) |
O1'A—C1'A—C2'A—C3'A | 175.52 (14) | O1'B—C1'B—C2'B—C3'B | 174.24 (14) |
O5'A—C1'A—C2'A—C3'A | 57.06 (19) | O5'B—C1'B—C2'B—C3'B | 57.10 (19) |
O2'A—C2'A—C3'A—O3'A | −63.20 (18) | O2'B—C2'B—C3'B—O3'B | −56.39 (18) |
C1'A—C2'A—C3'A—O3'A | 177.95 (14) | C1'B—C2'B—C3'B—O3'B | −177.80 (14) |
O2'A—C2'A—C3'A—C4'A | 63.93 (18) | O2'B—C2'B—C3'B—C4'B | 67.87 (18) |
C1'A—C2'A—C3'A—C4'A | −54.92 (19) | C1'B—C2'B—C3'B—C4'B | −53.54 (19) |
O3'A—C3'A—C4'A—O4'A | −56.24 (19) | O3'B—C3'B—C4'B—O4'B | −68.31 (18) |
C2'A—C3'A—C4'A—O4'A | 177.00 (14) | C2'B—C3'B—C4'B—O4'B | 168.90 (14) |
O3'A—C3'A—C4'A—C5'A | −175.91 (14) | O3'B—C3'B—C4'B—C5'B | 176.07 (14) |
C2'A—C3'A—C4'A—C5'A | 57.34 (18) | C2'B—C3'B—C4'B—C5'B | 53.28 (19) |
C1'A—O5'A—C5'A—C6'A | −170.45 (14) | C1'B—O5'B—C5'B—C6'B | −172.44 (15) |
C1'A—O5'A—C5'A—C4'A | 65.04 (18) | C1'B—O5'B—C5'B—C4'B | 63.47 (19) |
O4'A—C4'A—C5'A—O5'A | 179.04 (13) | O4'B—C4'B—C5'B—O5'B | −175.14 (14) |
C3'A—C4'A—C5'A—O5'A | −61.12 (18) | C3'B—C4'B—C5'B—O5'B | −56.30 (19) |
O4'A—C4'A—C5'A—C6'A | 57.5 (2) | O4'B—C4'B—C5'B—C6'B | 65.3 (2) |
C3'A—C4'A—C5'A—C6'A | 177.37 (15) | C3'B—C4'B—C5'B—C6'B | −175.85 (16) |
O5'A—C5'A—C6'A—O6'A | −64.08 (18) | O5'B—C5'B—C6'B—O6'B | 71.34 (19) |
C4'A—C5'A—C6'A—O6'A | 57.1 (2) | C4'B—C5'B—C6'B—O6'B | −167.19 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2B···O3Ai | 0.84 | 2.12 | 2.8642 (19) | 147 |
O3A—H3B···O5′A | 0.84 | 1.96 | 2.7268 (16) | 152 |
O2′A—H2′C···O3Bii | 0.84 | 1.95 | 2.7814 (17) | 170 |
O3′A—H3′C···O2Bii | 0.84 | 1.93 | 2.7072 (18) | 153 |
O4′A—H4′C···O3′Biii | 0.84 | 1.83 | 2.6510 (19) | 164 |
O6′A—H6′E···O2Ai | 0.84 | 2.00 | 2.8227 (16) | 167 |
O2B—H2AB···O3′A | 0.84 | 1.82 | 2.6403 (18) | 164 |
O3B—H3AB···O5′B | 0.84 | 1.89 | 2.6920 (17) | 159 |
O2′B—H2′D···O5Biv | 0.84 | 1.94 | 2.7724 (17) | 169 |
O3′B—H3′D···O4′Av | 0.84 | 1.83 | 2.6585 (18) | 167 |
O4′B—H4′D···O6′Avi | 0.84 | 1.94 | 2.7677 (17) | 170 |
O6′B—H6′F···O1′Avii | 0.84 | 2.23 | 3.051 (2) | 168 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x, y+1, z; (iii) x+1, y+1, z; (iv) −x, y−1/2, −z+1; (v) x−1, y, z; (vi) x−1, y−1, z; (vii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C12H22O10 |
Mr | 326.30 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 13.1578 (6), 4.6755 (2), 23.4908 (11) |
β (°) | 95.112 (2) |
V (Å3) | 1439.39 (11) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.46 × 0.09 × 0.09 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Numerical (SADABS; Sheldrick, 2008) |
Tmin, Tmax | 0.701, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14354, 5062, 4884 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.079, 1.04 |
No. of reflections | 5062 |
No. of parameters | 411 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.25 |
Absolute structure | Flack (1983), with 2045 Friedel pairs |
Absolute structure parameter | 0.05 (12) |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), POV-RAY (Cason, 2003), DIAMOND (Brandenburg, 2009) and ORTEP-3 (Farrugia, 1997), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2B···O3Ai | 0.84 | 2.12 | 2.8642 (19) | 147.1 |
O3A—H3B···O5'A | 0.84 | 1.96 | 2.7268 (16) | 151.9 |
O2'A—H2'C···O3Bii | 0.84 | 1.95 | 2.7814 (17) | 170.0 |
O3'A—H3'C···O2Bii | 0.84 | 1.93 | 2.7072 (18) | 152.7 |
O4'A—H4'C···O3'Biii | 0.84 | 1.83 | 2.6510 (19) | 164.2 |
O6'A—H6'E···O2Ai | 0.84 | 2.00 | 2.8227 (16) | 166.5 |
O2B—H2AB···O3'A | 0.84 | 1.82 | 2.6403 (18) | 163.6 |
O3B—H3AB···O5'B | 0.84 | 1.89 | 2.6920 (17) | 159.0 |
O2'B—H2'D···O5Biv | 0.84 | 1.94 | 2.7724 (17) | 169.4 |
O3'B—H3'D···O4'Av | 0.84 | 1.83 | 2.6585 (18) | 166.7 |
O4'B—H4'D···O6'Avi | 0.84 | 1.94 | 2.7677 (17) | 169.8 |
O6'B—H6'F···O1'Avii | 0.84 | 2.23 | 3.051 (2) | 167.7 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x, y+1, z; (iii) x+1, y+1, z; (iv) −x, y−1/2, −z+1; (v) x−1, y, z; (vi) x−1, y−1, z; (vii) x, y−1, z. |
Parameter | Man-Xyl (IA) | Man-Xyl (IB) | Gal-Xyl (II) | Me β-Galp (VIII) | Me β-Xylp (IX) |
Bond lengths and | |||||
internuclear distances (Å) | |||||
C1—C2 | 1.524 (2) | 1.523 (2) | 1.495 (9) | 1.528 | |
C2—C3 | 1.526 (2) | 1.526 (2) | 1.519 (8) | 1.520 | |
C3—C4 | 1.523 (2) | 1.530 (2) | 1.518 (9) | 1.521 | |
C4—C5 | 1.520 (2) | 1.528 (2) | 1.489 (9) | 1.519 | |
C5—C6 | |||||
C1'—C2' | 1.520 (2) | 1.518 (2) | 1.530 (6) | 1.526 (2) | |
C2'—C3' | 1.528 (2) | 1.529 (2) | 1.529 (6) | 1.523 (2) | |
C3'—C4' | 1.521 (2) | 1.527 (2) | 1.535 (6) | 1.523 (2) | |
C4'—C5' | 1.533 (2) | 1.523 (2) | 1.520 (6) | 1.529 (2) | |
C5'—C6' | 1.508 (2) | 1.509 (2) | 1.516 (7) | 1.515 (2) | |
C1—O1 | 1.386 (2) | 1.371 (2) | 1.373 (9) | 1.381 | |
C1—O5 | 1.429 (2) | 1.446 (2) | 1.444 (8) | 1.427 | |
C2—O2 | 1.424 (2) | 1.419 (2) | 1.413 (8) | 1.416 | |
C3—O3 | 1.424 (2) | 1.4224 (19) | 1.424 (8) | 1.421 | |
C4—O4 | 1.417 | ||||
C5—O5 | 1.429 (2) | 1.425 (2) | 1.443 (8) | 1.421 | |
C6—O6 | |||||
C1'—O1' | 1.399 (2) | 1.405 (2) | 1.406 (5) | 1.389 (2) | |
C1'—O5' | 1.430 (2) | 1.436 (2) | 1.441 (8) | 1.425 (2) | |
C2'—O2' | 1.422 (2) | 1.418 (2) | 1.429 (6) | 1.424 (2) | |
C3'—O3' | 1.4191 (19) | 1.423 (2) | 1.434 (5) | 1.414 (2) | |
C4'—O4' | 1.419 (2) | 1.420 (2) | 1.417 (6) | 1.426 (2) | |
C5'—O5' | 1.4470 (19) | 1.4482 (19) | 1.452 (6) | 1.430 | |
C6'—O6' | 1.429 (2) | 1.417 (2) | 1.439 (5) | 1.418 (3) | |
C4—O1' | 1.439 (2) | 1.429 (2) | 1.443 (7) | ||
O3···O5' | 2.7268 (16) | 2.6920 (17) | 2.729 (5) | ||
O3···O6' | 4.4522 (18) | 3.0694 (17) | 2.978 (6) | ||
Bond angles (°) | |||||
C1—O1—C6 | 113.53 (17) | 114.79 (17) | 118.3 (9) | 113.9 | 113.0 |
C1'—O1'—C4 | 115.85 (14) | 115.95 (13) | 113.6 (7) | ||
Torsion angles (°) | |||||
C2—C1—O1—C6(ϕ) | 165.60 (17) | 156.37 (16) | 164.5 (9) | 163.3 (2) | 169.7 |
O5—C1—O1—C6(ϕ) | -76.2 (2) | -86.34 (19) | -81.4 (11) | -77.1 (2) | -72.1 |
C2'—C1'—O1'—C4(ϕ') | 151.23 (15) | 150.97 (14) | 156.4 (5) | ||
O5'—C1'—O1'—C4(ϕ') | -88.38 (17) | -89.82 (17) | -85.7 (6) | ||
C1'—O1'—C4—C3(ψ') | 90.97 (18) | 80.98 (19) | 94.0 (11) | ||
C1'—O1'—C4—C5(ψ') | -149.22 (15) | -159.98 (14) | -141.6 (8) | ||
H1'—C1'—O1'—C4(ϕ') | 30.79 | 29.69 | 34.3 | ||
C1'—O1'—C4—H4(ψ') | -30.63 | -42.10 | -25.2 | ||
O5'—C5'—C6'—O6'(ω') | -64.08 (18) | 71.34 (19) | 60.7 (5) | 63.5 (2) | |
(gg) | (gt) | (gt) | (gt) |
Notes: (*) only parameters pertaining to the major component are reported here. gg is gauche–gauche and gt is gauche–trans. |
Compound | θ (°) | ϕ (°) | Q (Å) | q2 (Å) | q3 (Å) |
(IA), α-Manp | 3.77 (17) | 305 (3) | 0.6084 (18) | 0.0400 (18) | 0.6071 (18) |
(IA), β-Xylp | 8.07 (18) | 338.4 (14) | 0.5764 (19) | 0.0817 (18) | 0.5707 (19) |
(IB), α-Manp | 3.94 (17) | 4(3) | 0.5849 (18) | 0.0401 (17) | 0.5835 (18) |
(IB), β-Xylp | 3.77 (17) | 305 (3) | 0.6084 (18) | 0.0400 (18) | 0.6071 (18) |
(II), β-Galp | 7.3 (5) | 14 (4) | 0.596 (5) | 0.078 (5) | 0.591 (5) |
(II), β-Xylp | 13.9 (10) | 6(5) | 0.551 (11) | 0.131 (10) | 0.535 (11) |
(VIII), β-Galp | 5.89 | 346.64 | 0.5824 | 0.0597 | 0.5793 |
(IX), β-Xylp | 8.17 | 36.41 | 0.5795 | 0.0824 | 0.5737 |
Note: (*) s.u. values not provided in original text for (VIII) and (IX). |
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Recent studies of the freeze-tolerant Alaskan beetle, Upis ceramboides, have revealed the presence of a unique antifreeze glycolipid (AFGL) that possesses thermal hysteresis properties (the temperature at which an ice crystal grows is lower than the melting point of the crystal) and probably plays a role in the adaptation of this insect (Walters et al., 2009), and other organisms (Walters et al., 2011), to low temperatures. The backbone covalent structure of this glycolipid is comprised of a repeating β-Manp(1→4)β-Xylp unit, although it remains unclear whether this backbone is strictly linear or contains branch points. Likewise, some forms of the AFGL apparently contain a lipid component, but the exact nature of the lipid and its mode of attachment to the saccharide core remain unclear.
As part of ongoing studies of the relationship between AFGL structure and function, we have undertaken structural studies of its constituent β-Manp(1→4)β-Xylp and β-Xylp(1→4)β-Manp O-glycosidic linkages. In this report, we describe the crystal structure of one of the core disaccharide fragments, namely, methyl β-D-mannopyranosyl-(1→4)-β-D-xylopyranoside, (I), and compare its crystallographic properties with those reported recently for the biologically important methyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside, (II) (Zhang et al., 2012), which contains the O-glycosidic linkage commonly involved in the O-glycosylation of proteoglycans (Nadanaka & Kitagawa, 2008). NMR studies of the solution conformations of (I) and (II) using 13C-labeled isotopomers will be described elsewhere. This work extends our recent crystal structure investigations of other structurally related β-(1→4)-linked disaccharides, including methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside, (III) (Stenutz et al., 1999), methyl β-D-galactopyranosyl-(1→4)-α-D-glucopyranoside, (IV) (Pan et al., 2005), methyl β-L-galactopyranosyl-(1→4)-β-D-glucopyranoside, (V) (Pan et al., 2006), methyl β-D-galactopyranosyl-(1→4)-α-D-mannopyranoside, (VI) (Hu et al., 2010), and methyl β-D-galactopyranosyl-(1→4)-β-D-allopyranoside, (VII) (Zhang et al., 2010).
Compound (I) was prepared by a chemical route (see Supplementary materials for the synthetic details). After purification by chromatography, (I) was crystallized from water to give crystals devoid of water. In this report, the crystal structure of (I) is compared with that of the structurally related methyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside, (II) (Zhang et al., 2012), and with the structures of methyl β-D-galactopyranoside, (VIII) (Takagi & Jeffrey, 1979), and methyl β-D-xylopyranoside, (IX) (Takagi & Jeffrey, 1977).
Unlike (II), the structure of which shows disorder, the structure of (I) is well behaved and yields an asymmetric unit containing two crystallographically independent forms of (I), denoted (IA) and (IB) (Fig. 1). These conformers differ in two respects, namely in the conformation about the internal O-glycoside linkage and in the conformation of the exocyclic hydroxymethyl group in the β-Manp moiety (Fig. 2). The difference in linkage conformation is due mainly to ψ' (C1'—O1'—C4—C5 torsion), which has a value of -149.22 (15)° in molecule (IA) and -159.98 (14)° in molecule (IB), giving a difference of ~10.8°. In contrast, ϕ' (O5'—C1'—O1'—C4 torsion) is -88.38 (17)° in (IA) and -89.82 (17)° in (IB), giving a difference of only ~1.4°. The corresponding values of ϕ' and ψ' in (II) are -85.7 (6) and -141.6 (8)° (Table 1). Thus, the presence of an axial atom O2' in (IA) and (IB) does not exert a major effect on the linkage conformation when (II) is used for the comparison, with ϕ' only slightly affected (5° or less) and ψ' changing by 16° or less. The conformation of the exocyclic hydroxymethyl group in (IA) is gg [O5'—C5'—C6'—O6' = -64.08 (18)°; O6' anti to H5'], whereas this conformation is gt in (IB) [O5'—C5'—C6'—O6' = 71.34 (19)°; O6' anti to C4']. The hydroxymethyl group in the Gal moiety of (II) assumes a gt conformation [O5'—C5'—C6'—O6' = 60.7 (5)°], similar to that found in (IB).
The structures of (IA) and (IB) contain an intramolecular inter-residue hydrogen bond between atom O3 (donor) of the β-Xylp moiety and atom O5 (acceptor) of the β-Manp moiety. In (IA), O3···O5' = 2.7268 (16) Å, and in (IB) this distance is 2.6920 (17) Å. The same distance in (II) is 2.729 (5) Å. Interestingly, the O3···O6' distance in (IA) is 4.4522 (18) Å, which precludes hydrogen bonding between these atoms. This distance is determined by the conformation about the C5'—C6' bond, which is gg in (IA). In contrast, the O3···O6' distance in (IB) is 3.0694 (17) Å, which is similar to that found in (II) [2.978 (6) Å]. The gt conformation about the C5'—C6' bond in (IB) and (II) shortens this distance appreciably and allows hydrogen bonding between these atoms in the structure. It is noteworthy that, although ψ' differs in (IA) and (IB) by ~11°, this rotation exerts little effect on the O3···O5' distance and does not disrupt the inter-residue hydrogen bond.
Cremer–Pople puckering parameters (Cremer & Pople, 1975) for the aldopyranosyl rings of (IA) and (IB) are shown in Table 2. The β-Xylp ring in (IA) is the most distorted from an idealized 4C1 chair conformation, with θ = 8.07°, compared with values below 4° for the remaining three residues. The β-Manp and β-Xylp rings of (IA) and (IB) show different directions of distortion. The β-Manp of (IA) is skewed towards BC2,C5, while that of (IB) is skewed towards C3,O5B. The β-Xylp ring of (IA) is skewed towards 05TBC2, while that of (IB) is skewed towards BC2,C5. The β-Xylp ring of (IX) resembles neither that in (IA) nor that in (IB): while distorted to an extent similar to that in (IA), the direction of distortion differs substantially, being C3TBC1 in (IX) compared with O5TBC2 in (IA) and BC2,C5 in (IB). These findings suggest significant ring plasticity in the β-xylopyranosyl ring configuration in the solid state, with ϕ values ranging over 90° (305° to 36°). Whether this degree of flexibility translates into similar flexibilities in solution, which in turn affect biological function, remains unclear, although the presence of an unsubstituted atom C5 in β-D-xylopyranosyl rings may introduce greater localized (librational) motion than permitted in β-D-glucopyranosyl rings, where the exocyclic CH2OH substituent serves as a conformational anchor. Since the crystal structure of methyl β-D-mannopyranoside has not yet been reported, it is not currently possible to compare its structure with those of the β-Manp residues in (IA) and (IB).
The intermolecular hydrogen bonding in molecules (IA) and (IB) differs, with (IA) involved in more hydrogen bonds as an acceptor than (IB). In both (IA) and (IB), all five hydroxy groups serve as hydrogen-bond donors (O2, O2', O3', O4' and O6'). Atoms O2, O3, and O3' serve as mono-acceptors in (IA) and (IB), while atoms O1 and O1' (glycosidic O atoms) do not serve ashydrogen-bond acceptors in either structure. Atom O5 serves as a hydrogen-bond acceptor in (IB) but not in (IA). Atoms O2', O4' and O6' serve as mono-acceptors in (IA) but not in (IB). The total number of intermolecular hydrogen bonds (donor + acceptor) in (IA) is 11, while in (IB) there are nine. In this regard, structure (IB) might be considered less `solvated' than (IA), which may contribute to their different overall conformations in the crystal structure.
Considering only intermolecular hydrogen-bond interactions, the extended structure consists of hydrogen-bonded helices of molecules (IA) and (IB) (Fig. 3 and Table 3). The (IA) helix is formed by the hydrogen bonds from atom O2A to O3Ai and from atom O6'A to O2Ai, related by the screw axis parallel to the b axis [symmetry code: (i) -x + 1, y + 1/2, -z + 2]. The helix formed by molecules (IB) consists solely of hydrogen bonds from atom O2'B to O5Biv along an alternate 21 axis parallel to the b axis [symmetry code: (iv) -x, y - 1/2, -z + 1]. These helical chains of molecules (IA) and (IB) are bonded via contacts from atom O2B to O3'A within the asymmetric unit and from atom O3'A to O2Bii and from atom O2'A to O3Bii related by translation along the b axis by one unit cell above and below, respectively [symmetry code: (ii) x, y + 1, z]. These paired chains expand into the extended structuree through contacts from atom O4'A to O3'Biii related by translation along the b axis, and from atom O3'B to O4'Av by translation along the a axis [symmetry codes: (iii) x + 1, y + 1, z; (v) x - 1, y, z]. The final inter-helix interactions are via atom O4'B to O6'Avi, related by a diagonally adjacent unit cell, and a hydrogen bond from atom O6'B to O1'Avii in the b direction [symmetry codes: (vi) x - 1, y - 1, z; (vii) x, y - 1, z]. Since the helices also have rotational symmetry, due to the screw axis, the chains extend simultaneously along the c axis. The result is a three-dimensional hydrogen-bonded network.