Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113019021/fn3140sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113019021/fn3140IIsup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270113019021/fn3140sup3.pdf |
CCDC reference: 964769
The freeze-tolerant Alaskan beetle, Upis ceramboides, adapts to its cold environment by expressing an antifreeze glycolipid (AFGL) that possesses thermal hysteresis properties comparable to those of the most active antifreeze proteins (Walters et al., 2009, 2011). The AFGL is primarily located on the cell membrane and appears to function to prevent the lethal spread of extracellular ice into the cytoplasm. NMR studies indicate that this glycolipid is constructed from a βManp(1→4)-βXylp repeating subunit that may contain other branch points. Some forms of the AFGL may also contain a lipid component, but the structure of the lipid and its mode of attachment to the saccharide backbone remain unclear.
As part of ongoing studies of the relationship between AFGL structure and biological function, we have undertaken structural studies of its constituent βManp-(1→4)-βXylp and βXylp-(1→4)-βManp O-glycosidic linkages. In a recent report (Zhang, Oliver, Vu et al., 2012), the crystal structure of one of these core disaccharides, methyl β-D-mannopyranosyl-(1→4)-β-D-xylopyranoside, (I), was determined. In the solid state, disaccharide (I) exists in two crystallographic forms distinguished mainly by differences in their βManp exocyclic hydroxymethyl (CH2OH) conformations and in the conformations of their internal O-glycosidic linkages. We describe herein the crystal structure of the second AFGL core disaccharide, methyl β-D-xylopyranosyl-(1→4)-β-D-mannopyranoside, (II). This work extends prior crystal structure studies of other biologically relevant β-(1→4)-linked disaccharides, which include methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside, (III) (Stenutz et al., 1999), methyl β-D-galactopyranosyl-(1→4)-β-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), methyl β-D-galactopyranosyl-(1→4)-β-D-allopyranoside, (VII) (Zhang et al., 2010), and methyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside, (VIII) (Zhang, Oliver & Serianni, 2012).
The crystal structure of (II) was determined on a sample prepared chemically by the nine-step synthesis described in the Supplementary materials (Dennison & McGilary, 1951; Schmidt & Michel, 1985; Ning et al., 2003; Angyal et al., 1979). Disaccharide (II) was crystallized from a methanol–water solvent system to yield colorless block-like crystals suitable for diffraction studies.
Crystal data, data collection and structure refinement details are summarized in Table 1. Aliphatic H atoms were included in geometrically calculated positions, with C—H distances constrained to 0.98–1.00 Å. Displacement parameters were set at UisoH = 1.5UeqC for methyl H atoms and UisoH = 1.2UeqC for methine and methylene H atoms. Hydroxy H atoms were located from a difference Fourier map and allowed to refine freely.
The absolute configuration of the compound was known from the synthesis. This was confirmed by comparison of intensities of Friedel pairs of reflections. The Flack x parameter refined to 0.03 (5) based on 1029 reflections (Parsons & Flack, 2004). The Bayesian analysis yielded a Hooft y parameter of 0.01 (3) on 984 reflections (Hooft et al., 2008). Both are indicative of the correct enantiomorph of the space group and hence handedness of the molecule.
Methyl β-D-xylopyranosyl-(1→4)-β-D-mannopyranoside, (II) (Fig. 1), was prepared by a chemical route (see Supplementary materials for the synthetic details). After purification by chromatography, (II) was crystallized from a methanol–water solvent system to give crystals devoid of solvent. In this report, the crystal structure of (II) is compared to the two crystal forms [denoted (IA) and (IB)] of methyl β-D-mannopyranosyl-(1→4)-β-D-xylopyranoside, (I) (Zhang, Oliver, Vu et al., 2012), and to methyl β-D-xylopyranoside, (IX) (Takagi & Jeffrey, 1977).
The crystal conformations of (IA), (IB) and (II) are defined mainly by the conformations of their internal O-glycosidic linkages and their exocyclic hydroxymethyl groups. A comparison of these conformational features shows that ϕ' (O5'—C1'—O1'—C4 torsion angle) differs by ~11° between (IA) and (II), and by ~12° between (IB) and (II), with ϕ' shifted towards a more staggered conformation in (II). This shift may be reflected in the magnitude of rC1',O1', which is smallest [1.3940 (19) Å] in (II) (more staggered) and longest [1.405 (2) Å] in (IB) (least staggered). In contrast, ψ' (C1'—O1'—C4—C5 torsion angle) differs by ~10° between (IA) and (II), and by ~21° between (IB) and (II), with ψ' shifted to a more eclipsed conformation in (II). The most staggered geometry about ψ' also corresponds with the smallest rC4,O1' (1.429 (2) Å in (IB)).
The internal O-glycosidic linkage conformation of (II) more closely resembles that of (IA) than of (IB). On the other hand, exocyclic hydroxymethyl group conformation in the βManp constituents, denoted by ω or ω' (O5—C5—C6—O6 torsion angle), is gg in (IA), gt in (IB), and gt in (II), so in this respect, (II) resembles (IB) more than (IA). Hydroxymethyl group conformation is also more perfectly staggered in (IA) than in (II), with (IB) falling between them. The slightly longer C5—C6 bond in the βManp residue of (II) [1.516 (2) Å] relative to those in (IA) and (IB) [1.508 (2) Å and 1.509 (2) Å, respectively] may also reflect the shift of ω' to a less staggered conformation in (II).
The external O-glycosidic linkages in (IA), (IB) and (II) differ conformationally, with ϕ (C2—C1—O1—CH3 torsion angle) more nearly staggered when the βManp residue is involved [173.64 (14)° in (II)] than when a βXylp residue is involved [165.60 (17)° for (IA) and 156.37 (16)° for (IB)]. This torsion angle is 169.7° in (IX), which more closely resembles the value in (IA) than in (IB).
A major structural difference between the βXylp and βManp residues of (IA), (IB) and (II) lies in their C2—O2 bond orientations, being equatorial in βXylp and axial in βManp. An inspection of rC2,O2 values (Table 2), however, shows no significant dependence of bond length on C—O bond orientation, giving an average length of 1.422 (3) Å in βXylp and 1.421 (3) Å in βManp. As reported previously, however, rC5,C6 values in aldohexopyranosyl rings such as βManp are shorter than rC,C values involving ring C atoms; from data in Table 2 for (IA), (IB) and (II), the former bond lengths average 1.511 (4) Å and the latter 1.525 (5) Å, indicating an exocyclic C—C bond shorter by more than 0.01 Å. Values of rC4,C5 also appear larger in βManp than in βXylp residues, giving an average of 1.522 (6) Å for βXylp and 1.530 (6) Å for βManp.
The internal O-glycosidic linkages in (IA), (IB) and (II) are associated with larger C—O—C valence bond angles than are the terminal linkages, with data in Table 2 giving an average 116.3 (7)° for the former and 114.0 (7)° for the latter, consistent with prior observations.
Structures (IA) and (IB) contain an inter-residue intramolecular hydrogen bond between O3 (donor) of the βXylp moiety and O5 (acceptor) of the βManp moiety. In (IA), rO3,O5' is 2.7268 (6) Å, and in (IB) rO3,O5' is 2.6920 (17) Å. In (II), where βManp contributes the donor and βXylp contributes the acceptor, rO3,O5' is 2.690 (2) Å, an O—O distance closer to that found in (IB) than in (IA). Since ϕ', ψ', the C1'—O1'—C4 valence bond angle, and the C3—O3 bond torsion collectively determine this internuclear distance, and thus the strength of the interaction, no simple structural pattern emerges to interpret these differences.
Cremer–Pople puckering parameters for the aldopyranosyl rings of (IA), (IB), (II) and (IX) are shown in Table 3. Values of θ for the βManp residues in (IA), (IB) and (II) are very similar (3.76–4.42°), indicating similar degrees of distortion from the pure 4C1 chair conformation. In contrast, θ values vary more widely for the βXylp residues (4.34–8.15°) and average nearly twofold larger than θ for the βManp residues, suggesting that the β-xylopyranosyl ring can tolerate greater ring distortion than the β-mannopyranosyl ring. In a similar vein, the range of ϕ values for the βManp and βXylp residues differs significantly, with the former bracketed by values of 305 and 4° (total range of ~59°) and the latter by 268 and 36° (range of ~128°). The behaviors of θ and ϕ indicate that βXylp rings can accommodate greater overall distortion (embodied in θ) and a wider range of distorted ring forms (embodied in ϕ) than βManp rings. This flexibility presumably evolves from the absence of a conformation-stabilizing exocyclic –CH2OH group in the βXylp structure.
With respect to intermolecular hydrogen bonding, all hydroxy groups [O2, O2', O3', O4' and O6' in (IA) and (IB); O2, O6, O2', O3' and O4' in (II)] serve as hydrogen-bond donors. Atoms O2, O3, and O3' serve as mono-acceptors in (IA) and (IB), and O1, O2, O3, O6, O2' and O4' serve as monoacceptors in (II). Atoms O2', O4' and O6' serve as mono-acceptors in (IA), but not in (IB). Atoms O1 and O1' in (IA) and (IB), and O1' in (II), do not serve as hydrogen-bond acceptors. Atom O5 serves as a hydrogen-bond acceptor in (IB), but not in (IA) and (II). Thus, (IA) and (II) each participate in a total of 11 intermolecular hydrogen-bonds, while (IB) participates in nine.
Only one of the intermolecular hydrogen bonds is related by the 21 screw axis, from atom O3' to O4'iii. The remaining intermolecular hydrogen bonds are interactions between hydroxy groups related solely by translation along the b or the c axis [O2···O2'i, O6···O1ii, O6···O2ii, O2'···O3ii and O4'···O6iv; symmetry codes: (i) x, y-1, z; (ii) x, y+1, z; (iii) -x+2, y+1/2, -z+3; (iv) x, y, z+1]. The resulting motif is a bilayered two-dimensional sheet of hydrogen bonded molecules of (II) that lies parallel to the bc plane of the lattice (Table 4 and Fig. 2).
Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2012a); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2012b); molecular graphics: POV-RAY (Cason, 2003) and DIAMOND (Brandenburg, 2009); software used to prepare material for publication: enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).
The molecular structure of (II), showing tha atom-labeling scheme. Displacement
ellipsoids are depicted at the 50% probability. H atoms are represented as
spheres of an arbitrary radius. Hydrogen-bonding scheme of (II), viewed along the b axis depicting two-dimensional sheets parallel to the ac plane. Hydrogen bonds are represented by dashed lines. |
C12H22O10 | F(000) = 348 |
Mr = 326.29 | Dx = 1.484 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54184 Å |
a = 8.9763 (9) Å | Cell parameters from 9986 reflections |
b = 7.4575 (7) Å | θ = 4.1–71.4° |
c = 11.0026 (11) Å | µ = 1.13 mm−1 |
β = 97.406 (2)° | T = 120 K |
V = 730.38 (12) Å3 | Block, colorless |
Z = 2 | 0.32 × 0.14 × 0.11 mm |
Bruker APEXII diffractometer | 2571 independent reflections |
Radiation source: Incoatec micro-focus | 2567 reflections with I > 2σ(I) |
Detector resolution: 8.33 pixels mm-1 | Rint = 0.031 |
combination of ω and ϕ scans | θmax = 71.4°, θmin = 4.1° |
Absorption correction: numerical (SADABS; Sheldrick, 2008) | h = −11→10 |
Tmin = 0.909, Tmax = 1.000 | k = −8→9 |
10641 measured reflections | l = −13→13 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0431P)2 + 0.1364P]
where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.069 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.27 e Å−3 |
2571 reflections | Δρmin = −0.21 e Å−3 |
224 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0085 (12) |
Primary atom site location: real-space vector search | Absolute structure: Flack x determined using 1029 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.03 (5) |
C12H22O10 | V = 730.38 (12) Å3 |
Mr = 326.29 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 8.9763 (9) Å | µ = 1.13 mm−1 |
b = 7.4575 (7) Å | T = 120 K |
c = 11.0026 (11) Å | 0.32 × 0.14 × 0.11 mm |
β = 97.406 (2)° |
Bruker APEXII diffractometer | 2571 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008) | 2567 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 1.000 | Rint = 0.031 |
10641 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.069 | Δρmax = 0.27 e Å−3 |
S = 1.06 | Δρmin = −0.21 e Å−3 |
2571 reflections | Absolute structure: Flack x determined using 1029 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). |
224 parameters | Absolute structure parameter: 0.03 (5) |
1 restraint |
Experimental. Synthesis of Methyl β-D-[2-13C]xylopyranosyl-(1→4)-β-D-mannopyranoside (II) (See Accompanying Reaction Scheme) Methyl 4,6-O-benzylidene-β-D-mannopyranoside (2) Methyl β-D-mannopyranoside (1) (2.0 g, 10.3 mmol) was dissolved in dry N,N-dimethylformamide (DMF) (30.0 ml), and benzaldehyde dimethylacetal (1.78 ml, 11.9 mmol) and a catalytic amount of p-toluenesulfonic acid were added. The reaction mixture was stirred at rt overnight and neutralized by adding one drop of triethylamine. The DMF was evaporated and the syrup was dissolved in CH2Cl2, and the resulting solution washed with water. The organic phase was dried over Na2SO4 and evaporated to dryness to give 2 (1.89 g, 6.7 mmol, 65%). Methyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranoside (3) Compound 2 (1.20 g, 4.25 mmol) was dissolved in DMF (30.0 ml) and NaH (90%, 0.85 g, 21.3 mmol) was added to the solution. After stirring at rt for 1 h, benzyl bromide (2.03 ml, 17.0 mmol) was added dropwise at 0 °C and the mixture was kept stirring at rt for 20 h. The mixture was then washed with distilled water and extracted with CH2Cl2. The organic phase was dried over Na2SO4, evaporated to dryness, and purified by flash chromatography on a silica gel column (solvent: hexanes/ethyl acetate, 4:1) to afford 3 (1.76 g, 3.83 mmol, 90%). Methyl 2,3,6-tri-O-benzyl-β-D-mannopyranoside (4) Compound 3 (1.20 g, 1.95 mmol) and sodium cyanoborohydride (1.23 g, 19.50 mmol) were dissolved in anhydrous THF (30.0 ml), and molecular sieves (4 Å, 1.0 g) were added. Hydrogen chloride in diethyl ether (1M, 24.0 ml) was added dropwise and the mixture was stirred for 2 h (Denison & McGilary, 1951). The reaction mixture was diluted with CH2Cl2 and filtered, and the filtrate was washed with distilled water and saturated aqueous NaHCO3 solution. The organic layer was evaporated to dryness and purified by flash chromatography on a silica gel column (solvent: hexanes/ethyl acetate, 3:1) to afford 4 (0.84 g, 1.36 mmol, 70%). 2,3,4-Tri-O-acetyl-α-D-[2-13C]xylopyranosyl trichloroacetimidate (8) D-[2-13C]Xylose 5 (0.60 g, 4.00 mmol) was dissolved in dry pyridine (15 ml) and acetic anhydride (2.25 ml, 24.0 mmol) was added. The reaction mixture was stirred at rt overnight and concentrated in vacuo to afford the per-O-acetylated D-xylopyranose 6. Compound 6 was deacetylated at C1 with benzylamine (0.52 ml, 4.80 mmol) in THF (20.0 ml) to afford 7. After purification, 7 was converted to the corresponding trichloroacetimidate with trichloroacetonitrile and 1,8-diazobicyclo [5.4.0]-undec-7-ene (DBU) as described by Schmidt & Michel (1985), affording 8 (0.94 g, 2.24 mmol, 56%). Methyl 2,3,4-tri-O-acetyl-β-D-[2-13C]xylopyranosyl-(1→4)–2,3,6-tri-O-benzyl-β-D-mannopyranoside (9) The donor 8 (0.96 g, 2.28 mmol) and acceptor 4 (0.96 g, 2.07 mmol) were dissolved in anhydrous CH2Cl2 (20.0 ml) after drying over high vacuum, and the solution was treated with molecular sieves (4 Å, 1.0 g). A catalytic amount of trimethylsilyltriflate (25 ml, 0.13 mmol) was added at 0 °C. The reaction mixture was stirred at rt overnight and neutralized with the addition of triethylamine, and the molecular sieves were removed by filtration. The solution was concentrated and purified by flash chromatography on a silica gel column (solvent: hexanes/ethyl acetate, 3:1) to afford 9 (1.20 g, 1.66 mmol, 73%). Methyl β-D-[2-13C]xylopyranosyl-(1→4)-β-D-mannopyranoside (II) Compound 9 (0.76 g, 1.05 mmol) was dissolved in ethanol (20.0 ml) and treated with Pd/C (10%, 200 mg) and H2 overnight to afford 10. The Pd/C catalyst was removed by filtration and the filtrate was concentrated in vacuo. The residue was dissolved in methanol (20.0 ml) saturated with NH3 (Ning et al., 2003). After 15 h, the reaction mixture was concentrated at 30 °C in vacuo. The residue was dissolved in ~1 ml of distilled water and the solution was applied to a column (2.5 x 100 cm) containing Dowex 50 × 8 (200–400 mesh) ion-exchange resin in the Ca2+ form (Angyal et al., 1979). The column was eluted with distilled, decarbonated water at ~1.5 ml/min, and fractions (10 ml) were collected and assayed by TLC. Fractions containing product were pooled and concentrated at 30 °C in vacuo to give II (0.30 g, 0.92 mmol, 88%). |
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 | 0.62043 (14) | −0.00497 (19) | 0.63442 (11) | 0.0203 (3) | |
O2 | 0.76518 (14) | −0.0690 (2) | 0.85577 (11) | 0.0208 (3) | |
H2 | 0.775 (3) | −0.123 (5) | 0.925 (3) | 0.031 (7)* | |
O3 | 0.66415 (15) | 0.0780 (2) | 1.06503 (11) | 0.0193 (3) | |
H3 | 0.683 (4) | 0.153 (5) | 1.119 (3) | 0.043 (8)* | |
O5 | 0.72002 (13) | 0.25556 (18) | 0.71721 (10) | 0.0158 (3) | |
O6 | 0.77159 (15) | 0.6414 (2) | 0.67367 (11) | 0.0197 (3) | |
H6 | 0.741 (3) | 0.739 (5) | 0.697 (3) | 0.033 (7)* | |
C1 | 0.60745 (19) | 0.1232 (3) | 0.72421 (15) | 0.0161 (4) | |
H1A | 0.5058 | 0.1799 | 0.7101 | 0.019* | |
C2 | 0.62852 (19) | 0.0297 (3) | 0.84834 (15) | 0.0171 (4) | |
H2A | 0.5431 | −0.0547 | 0.8536 | 0.021* | |
C3 | 0.63237 (18) | 0.1699 (3) | 0.95052 (15) | 0.0155 (3) | |
H3A | 0.5302 | 0.2247 | 0.9465 | 0.019* | |
C4 | 0.74467 (18) | 0.3191 (2) | 0.93466 (14) | 0.0142 (3) | |
H4A | 0.8500 | 0.2730 | 0.9505 | 0.017* | |
C5 | 0.71220 (18) | 0.3958 (2) | 0.80448 (14) | 0.0149 (3) | |
H5A | 0.6093 | 0.4495 | 0.7927 | 0.018* | |
C6 | 0.82592 (19) | 0.5370 (2) | 0.77938 (15) | 0.0166 (4) | |
H6A | 0.8466 | 0.6168 | 0.8515 | 0.020* | |
H6B | 0.9213 | 0.4779 | 0.7661 | 0.020* | |
C7 | 0.5867 (2) | 0.0625 (3) | 0.51180 (16) | 0.0249 (4) | |
H7A | 0.5980 | −0.0339 | 0.4532 | 0.037* | |
H7B | 0.6558 | 0.1605 | 0.4992 | 0.037* | |
H7C | 0.4831 | 0.1071 | 0.4992 | 0.037* | |
O1' | 0.72263 (13) | 0.46436 (17) | 1.01656 (10) | 0.0149 (3) | |
O2' | 0.86060 (14) | 0.79277 (19) | 1.09326 (11) | 0.0189 (3) | |
H2' | 0.825 (3) | 0.891 (5) | 1.107 (2) | 0.030 (7)* | |
O3' | 0.84216 (15) | 0.85384 (19) | 1.34740 (11) | 0.0206 (3) | |
H3' | 0.905 (3) | 0.888 (5) | 1.401 (3) | 0.037 (7)* | |
O4' | 0.93920 (15) | 0.5398 (2) | 1.50096 (11) | 0.0202 (3) | |
H4' | 0.890 (3) | 0.578 (4) | 1.552 (3) | 0.027 (7)* | |
O5' | 0.78731 (14) | 0.34767 (19) | 1.20623 (10) | 0.0192 (3) | |
C1' | 0.82595 (18) | 0.4803 (2) | 1.12206 (14) | 0.0144 (4) | |
H1'A | 0.9308 | 0.4621 | 1.1029 | 0.017* | |
C2' | 0.80709 (18) | 0.6659 (3) | 1.17393 (15) | 0.0142 (3) | |
H2'A | 0.6975 | 0.6880 | 1.1758 | 0.017* | |
C3' | 0.88812 (18) | 0.6863 (3) | 1.30373 (15) | 0.0151 (4) | |
H3'A | 0.9990 | 0.6883 | 1.3011 | 0.018* | |
C4' | 0.84947 (19) | 0.5316 (3) | 1.38443 (15) | 0.0162 (4) | |
H4'A | 0.7408 | 0.5380 | 1.3956 | 0.019* | |
C5' | 0.8808 (2) | 0.3556 (3) | 1.32336 (15) | 0.0192 (4) | |
H5'A | 0.9881 | 0.3486 | 1.3115 | 0.023* | |
H5'B | 0.8577 | 0.2537 | 1.3754 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0293 (6) | 0.0175 (7) | 0.0135 (6) | −0.0012 (5) | 0.0009 (5) | −0.0041 (5) |
O2 | 0.0291 (6) | 0.0184 (7) | 0.0149 (6) | 0.0063 (5) | 0.0032 (5) | 0.0011 (5) |
O3 | 0.0289 (7) | 0.0156 (7) | 0.0132 (6) | −0.0028 (5) | 0.0022 (5) | 0.0007 (5) |
O5 | 0.0208 (6) | 0.0143 (7) | 0.0128 (5) | −0.0011 (5) | 0.0040 (4) | −0.0026 (5) |
O6 | 0.0300 (7) | 0.0153 (7) | 0.0140 (5) | 0.0024 (5) | 0.0040 (5) | 0.0014 (5) |
C1 | 0.0177 (8) | 0.0163 (9) | 0.0143 (7) | −0.0008 (6) | 0.0013 (6) | −0.0034 (7) |
C2 | 0.0205 (8) | 0.0151 (9) | 0.0160 (8) | −0.0011 (7) | 0.0031 (6) | −0.0010 (7) |
C3 | 0.0185 (7) | 0.0161 (9) | 0.0119 (7) | −0.0004 (7) | 0.0022 (6) | 0.0001 (6) |
C4 | 0.0172 (7) | 0.0137 (9) | 0.0117 (7) | 0.0011 (6) | 0.0019 (6) | −0.0020 (6) |
C5 | 0.0193 (7) | 0.0143 (9) | 0.0110 (7) | 0.0015 (6) | 0.0016 (6) | −0.0022 (6) |
C6 | 0.0231 (8) | 0.0145 (9) | 0.0121 (7) | −0.0010 (7) | 0.0019 (6) | 0.0004 (6) |
C7 | 0.0338 (10) | 0.0273 (11) | 0.0131 (8) | −0.0024 (8) | 0.0012 (7) | −0.0026 (7) |
O1' | 0.0185 (5) | 0.0147 (6) | 0.0107 (5) | 0.0018 (4) | −0.0006 (4) | −0.0027 (5) |
O2' | 0.0273 (7) | 0.0151 (7) | 0.0138 (6) | −0.0009 (5) | 0.0009 (5) | 0.0033 (5) |
O3' | 0.0271 (6) | 0.0169 (7) | 0.0160 (6) | 0.0036 (5) | −0.0044 (5) | −0.0048 (5) |
O4' | 0.0254 (6) | 0.0247 (8) | 0.0098 (6) | 0.0040 (5) | −0.0005 (5) | −0.0011 (5) |
O5' | 0.0304 (6) | 0.0148 (7) | 0.0112 (5) | −0.0040 (5) | −0.0018 (5) | 0.0010 (5) |
C1' | 0.0173 (7) | 0.0160 (9) | 0.0097 (7) | 0.0004 (6) | 0.0007 (6) | 0.0012 (6) |
C2' | 0.0163 (7) | 0.0146 (9) | 0.0116 (7) | 0.0005 (6) | 0.0015 (6) | 0.0017 (6) |
C3' | 0.0184 (8) | 0.0149 (9) | 0.0116 (8) | 0.0006 (6) | 0.0002 (6) | −0.0017 (6) |
C4' | 0.0185 (7) | 0.0177 (10) | 0.0117 (7) | 0.0005 (7) | −0.0003 (6) | 0.0006 (7) |
C5' | 0.0273 (9) | 0.0175 (10) | 0.0114 (7) | 0.0013 (7) | −0.0026 (6) | 0.0024 (7) |
O1—C1 | 1.390 (2) | C7—H7A | 0.9800 |
O1—C7 | 1.435 (2) | C7—H7B | 0.9800 |
O2—C2 | 1.424 (2) | C7—H7C | 0.9800 |
O2—H2 | 0.86 (3) | O1'—C1' | 1.3942 (19) |
O3—C3 | 1.430 (2) | O2'—C2' | 1.422 (2) |
O3—H3 | 0.82 (4) | O2'—H2' | 0.82 (3) |
O5—C1 | 1.422 (2) | O3'—C3' | 1.419 (2) |
O5—C5 | 1.428 (2) | O3'—H3' | 0.80 (3) |
O6—C6 | 1.432 (2) | O4'—C4' | 1.425 (2) |
O6—H6 | 0.83 (4) | O4'—H4' | 0.81 (3) |
C1—C2 | 1.523 (2) | O5'—C1' | 1.428 (2) |
C1—H1A | 1.0000 | O5'—C5' | 1.4457 (19) |
C2—C3 | 1.532 (2) | C1'—C2' | 1.515 (2) |
C2—H2A | 1.0000 | C1'—H1'A | 1.0000 |
C3—C4 | 1.526 (2) | C2'—C3' | 1.524 (2) |
C3—H3A | 1.0000 | C2'—H2'A | 1.0000 |
C4—O1' | 1.439 (2) | C3'—C4' | 1.523 (2) |
C4—C5 | 1.535 (2) | C3'—H3'A | 1.0000 |
C4—H4A | 1.0000 | C4'—C5' | 1.517 (3) |
C5—C6 | 1.516 (2) | C4'—H4'A | 1.0000 |
C5—H5A | 1.0000 | C5'—H5'A | 0.9900 |
C6—H6A | 0.9900 | C5'—H5'B | 0.9900 |
C6—H6B | 0.9900 | ||
C1—O1—C7 | 113.58 (15) | O1—C7—H7A | 109.5 |
C2—O2—H2 | 106.5 (18) | O1—C7—H7B | 109.5 |
C3—O3—H3 | 108 (2) | H7A—C7—H7B | 109.5 |
C1—O5—C5 | 112.04 (12) | O1—C7—H7C | 109.5 |
C6—O6—H6 | 108 (2) | H7A—C7—H7C | 109.5 |
O1—C1—O5 | 108.27 (13) | H7B—C7—H7C | 109.5 |
O1—C1—C2 | 108.10 (15) | C1'—O1'—C4 | 117.07 (12) |
O5—C1—C2 | 111.05 (13) | C2'—O2'—H2' | 108 (2) |
O1—C1—H1A | 109.8 | C3'—O3'—H3' | 109 (2) |
O5—C1—H1A | 109.8 | C4'—O4'—H4' | 110.5 (19) |
C2—C1—H1A | 109.8 | C1'—O5'—C5' | 112.83 (13) |
O2—C2—C1 | 107.13 (13) | O1'—C1'—O5' | 106.85 (13) |
O2—C2—C3 | 111.90 (14) | O1'—C1'—C2' | 107.26 (13) |
C1—C2—C3 | 109.53 (15) | O5'—C1'—C2' | 109.89 (13) |
O2—C2—H2A | 109.4 | O1'—C1'—H1'A | 110.9 |
C1—C2—H2A | 109.4 | O5'—C1'—H1'A | 110.9 |
C3—C2—H2A | 109.4 | C2'—C1'—H1'A | 110.9 |
O3—C3—C4 | 112.98 (13) | O2'—C2'—C1' | 108.03 (13) |
O3—C3—C2 | 107.60 (15) | O2'—C2'—C3' | 111.08 (14) |
C4—C3—C2 | 111.48 (13) | C1'—C2'—C3' | 112.39 (14) |
O3—C3—H3A | 108.2 | O2'—C2'—H2'A | 108.4 |
C4—C3—H3A | 108.2 | C1'—C2'—H2'A | 108.4 |
C2—C3—H3A | 108.2 | C3'—C2'—H2'A | 108.4 |
O1'—C4—C3 | 109.33 (13) | O3'—C3'—C4' | 111.82 (13) |
O1'—C4—C5 | 106.19 (13) | O3'—C3'—C2' | 106.30 (14) |
C3—C4—C5 | 109.24 (13) | C4'—C3'—C2' | 110.71 (14) |
O1'—C4—H4A | 110.7 | O3'—C3'—H3'A | 109.3 |
C3—C4—H4A | 110.7 | C4'—C3'—H3'A | 109.3 |
C5—C4—H4A | 110.7 | C2'—C3'—H3'A | 109.3 |
O5—C5—C6 | 107.07 (13) | O4'—C4'—C5' | 108.68 (14) |
O5—C5—C4 | 109.55 (14) | O4'—C4'—C3' | 110.31 (14) |
C6—C5—C4 | 112.17 (13) | C5'—C4'—C3' | 109.14 (13) |
O5—C5—H5A | 109.3 | O4'—C4'—H4'A | 109.6 |
C6—C5—H5A | 109.3 | C5'—C4'—H4'A | 109.6 |
C4—C5—H5A | 109.3 | C3'—C4'—H4'A | 109.6 |
O6—C6—C5 | 111.02 (14) | O5'—C5'—C4' | 108.11 (14) |
O6—C6—H6A | 109.4 | O5'—C5'—H5'A | 110.1 |
C5—C6—H6A | 109.4 | C4'—C5'—H5'A | 110.1 |
O6—C6—H6B | 109.4 | O5'—C5'—H5'B | 110.1 |
C5—C6—H6B | 109.4 | C4'—C5'—H5'B | 110.1 |
H6A—C6—H6B | 108.0 | H5'A—C5'—H5'B | 108.4 |
C7—O1—C1—O5 | −65.97 (17) | C4—C5—C6—O6 | −163.53 (13) |
C7—O1—C1—C2 | 173.64 (14) | C3—C4—O1'—C1' | 103.39 (15) |
C5—O5—C1—O1 | 178.38 (13) | C5—C4—O1'—C1' | −138.87 (14) |
C5—O5—C1—C2 | −63.08 (18) | C4—O1'—C1'—O5' | −77.62 (16) |
O1—C1—C2—O2 | 52.20 (18) | C4—O1'—C1'—C2' | 164.58 (13) |
O5—C1—C2—O2 | −66.44 (18) | C5'—O5'—C1'—O1' | −176.68 (13) |
O1—C1—C2—C3 | 173.76 (13) | C5'—O5'—C1'—C2' | −60.62 (17) |
O5—C1—C2—C3 | 55.12 (17) | O1'—C1'—C2'—O2' | −69.85 (16) |
O2—C2—C3—O3 | −56.85 (18) | O5'—C1'—C2'—O2' | 174.35 (13) |
C1—C2—C3—O3 | −175.49 (13) | O1'—C1'—C2'—C3' | 167.25 (13) |
O2—C2—C3—C4 | 67.55 (18) | O5'—C1'—C2'—C3' | 51.45 (17) |
C1—C2—C3—C4 | −51.09 (18) | O2'—C2'—C3'—O3' | 67.76 (17) |
O3—C3—C4—O1' | −70.35 (17) | C1'—C2'—C3'—O3' | −171.07 (13) |
C2—C3—C4—O1' | 168.33 (13) | O2'—C2'—C3'—C4' | −170.60 (14) |
O3—C3—C4—C5 | 173.83 (14) | C1'—C2'—C3'—C4' | −49.44 (18) |
C2—C3—C4—C5 | 52.51 (18) | O3'—C3'—C4'—O4' | −68.69 (18) |
C1—O5—C5—C6 | −174.22 (13) | C2'—C3'—C4'—O4' | 172.98 (13) |
C1—O5—C5—C4 | 63.91 (16) | O3'—C3'—C4'—C5' | 171.97 (14) |
O1'—C4—C5—O5 | −175.39 (12) | C2'—C3'—C4'—C5' | 53.64 (17) |
C3—C4—C5—O5 | −57.58 (16) | C1'—O5'—C5'—C4' | 65.87 (17) |
O1'—C4—C5—C6 | 65.86 (16) | O4'—C4'—C5'—O5' | 179.06 (13) |
C3—C4—C5—C6 | −176.34 (14) | C3'—C4'—C5'—O5' | −60.60 (17) |
O5—C5—C6—O6 | 76.26 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2′i | 0.86 (3) | 2.01 (3) | 2.8368 (19) | 162 (3) |
O3—H3···O5′ | 0.82 (4) | 1.91 (4) | 2.690 (2) | 158 (3) |
O6—H6···O1ii | 0.83 (4) | 2.26 (4) | 2.972 (2) | 144 (3) |
O6—H6···O2ii | 0.83 (4) | 2.25 (3) | 2.952 (2) | 143 (3) |
O2′—H2′···O3ii | 0.82 (3) | 2.02 (3) | 2.755 (2) | 149 (3) |
O3′—H3′···O4′iii | 0.80 (3) | 2.00 (3) | 2.7776 (18) | 162 (3) |
O4′—H4′···O6iv | 0.81 (3) | 1.87 (3) | 2.6806 (19) | 174 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+2, y+1/2, −z+3; (iv) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H22O10 |
Mr | 326.29 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 8.9763 (9), 7.4575 (7), 11.0026 (11) |
β (°) | 97.406 (2) |
V (Å3) | 730.38 (12) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.32 × 0.14 × 0.11 |
Data collection | |
Diffractometer | Bruker APEXII diffractometer |
Absorption correction | Numerical (SADABS; Sheldrick, 2008) |
Tmin, Tmax | 0.909, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10641, 2571, 2567 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.615 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.069, 1.06 |
No. of reflections | 2571 |
No. of parameters | 224 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 |
Absolute structure | Flack x determined using 1029 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61). |
Absolute structure parameter | 0.03 (5) |
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXT (Sheldrick, 2012a), SHELXL2012 (Sheldrick, 2012b), POV-RAY (Cason, 2003) and DIAMOND (Brandenburg, 2009), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).
Parameter | Man–Xyl (IA) | Man–Xyl (IB) | Xyl–Man (II) | Me-βXylp (IX) |
Bond lengths and | ||||
internuclear | ||||
distances (Å) | ||||
C1—C2 | 1.524 (2) | 1.523 (2) | 1.523 (2) | 1.528 |
C2—C3 | 1.526 (2) | 1.526 (2) | 1.532 (2) | 1.520 |
C3—C4 | 1.523 (2) | 1.530 (2) | 1.526 (2) | 1.521 |
C4—C5 | 1.520 (2) | 1.528 (2) | 1.535 (2) | 1.519 |
C5—C6 | 1.516 (2) | |||
C1'—C2' | 1.520 (2) | 1.518 (2) | 1.515 (2) | |
C2'—C3' | 1.528 (2) | 1.529 (2) | 1.523 (2) | |
C3'—C4' | 1.521 (2) | 1.527 (2) | 1.522 (2) | |
C4'—C5' | 1.533 (2) | 1.523 (2) | 1.517 (3) | |
C5'—C6' | 1.508 (2) | 1.509 (2) | ||
C1—O1 | 1.386 (2) | 1.371 (2) | 1.390 (2) | 1.381 |
C1—O5 | 1.429 (2) | 1.446 (2) | 1.422 (2) | 1.427 |
C2—O2 | 1.424 (2) | 1.419 (2) | 1.424 (2) | 1.416 |
C3—O3 | 1.424 (2) | 1.4224 (19) | 1.430 (2) | 1.421 |
C4—O4 | 1.417 | |||
C5—O5 | 1.429 (2) | 1.425 (2) | 1.428 (2) | 1.421 |
C6—O6 | 1.432 (2) | |||
C1'—O1' | 1.399 (2) | 1.405 (2) | 1.3942 (19) | |
C1'—O5' | 1.430 (2) | 1.436 (2) | 1.428 (2) | |
C2'—O2' | 1.422 (2) | 1.418 (2) | 1.422 (2) | |
C3'—O3' | 1.4191 (19) | 1.423 (2) | 1.419 (2) | |
C4'—O4' | 1.419 (2) | 1.420 (2) | 1.425 (2) | |
C5'—O5' | 1.4470 (19) | 1.4482 (19) | 1.4457 (18) | |
C6'—O6' | 1.429 (2) | 1.417 (2) | ||
C4—O1' | 1.439 (2) | 1.429 (2) | 1.439 (2) | |
O3···O5' | 2.7268 (16) | 2.6920 (17) | 2.690 (2) | |
O3···O6' | 4.4522 (18) | 3.0694 (17) | ||
Bond angles (°) | ||||
C1—O1—CH3 | 113.53 (17) | 114.79 (17) | 113.58 (15) | 113.0 |
C1'—O1'—C4 | 115.85 (14) | 115.95 (13) | 117.07 (12) | |
Torsion angles (°) | ||||
C2—C1—O1—CH3(ϕ) | 165.60 (17) | 156.37 (16) | 173.64 (14) | 169.7 |
O5—C1—O1—CH3(ϕ) | -76.2 (2) | -86.34 (19) | -65.97 (17) | -72.1 |
C2'—C1'—O1'—C4(ϕ') | 151.23 (15) | 150.97 (14) | 164.58 (13) | |
O5'—C1'—O1'—C4(ϕ') | -88.38 (17) | -89.82 (17) | -77.62 (16) | |
C1'—O1'—C4—C3(ψ') | 90.97 (18) | 80.98 (19) | 103.39 (15) | |
C1'—O1'—C4—C5(ψ') | -149.22 (15) | -159.98 (14) | -138.87 (14) | |
H1'—C1'—O1'—C4(ϕ') | 30.79 | -30.63 | 43.32 | |
C1'—O1'—C4—H4(ψ') | 29.69 | -42.10 | -18.76 | |
O5'—C5'—C6'—O6'(ω') | -64.08 (18)(gg) | 71.34 (19)(gt) | ||
O5—C5—C6—O6(ω) | 76.26 (17)(gt) |
Compound | θ (°) | ϕ (°) | Q (Å) | q2 (Å) | q3 (Å) |
(IA), βManp | 3.76 | 305.2255 | 0.6085 | 0.0399 | 0.6072 |
(IA), βXylp | 8.13 | 338.1776 | 0.5763 | 0.0814 | 0.5705 |
(IB), βManp | 3.92 | 3.7915 | 0.5848 | 0.0400 | 0.5834 |
(IB), βXylp | 4.34 | 268.2893 | 0.5847 | 0.0442 | 0.5831 |
(II), βManp | 4.42 | 336 | 0.5753 | 0.0465 | 0.5736 |
(II), βXylp | 8.15 | 307.4 | 0.5757 | 0.0813 | 0.5699 |
(IX), βXylp | 8.17 | 36.411 | 0.5795 | 0.0824 | 0.5737 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2'i | 0.86 (3) | 2.01 (3) | 2.8368 (19) | 162 (3) |
O3—H3···O5' | 0.82 (4) | 1.91 (4) | 2.690 (2) | 158 (3) |
O6—H6···O1ii | 0.83 (4) | 2.26 (4) | 2.972 (2) | 144 (3) |
O6—H6···O2ii | 0.83 (4) | 2.25 (3) | 2.952 (2) | 143 (3) |
O2'—H2'···O3ii | 0.82 (3) | 2.02 (3) | 2.755 (2) | 149 (3) |
O3'—H3'···O4'iii | 0.80 (3) | 2.00 (3) | 2.7776 (18) | 162 (3) |
O4'—H4'···O6iv | 0.81 (3) | 1.87 (3) | 2.6806 (19) | 174 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+2, y+1/2, −z+3; (iv) x, y, z+1. |