Methyl 3-O-α-l-fucopyranosyl α-d-gal­acto­pyran­oside: a synchrotron study

Eriksson, L.; Widmalm, G.

doi:10.1107/S1600536812002279

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o528

doi:10.1107/S1600536812002279

Open

access

Methyl 3-O-α-L-fucopyranosyl α-D-galactopyranoside: a synchrotron study

Lars Eriksson ^a ^* and Göran Widmalm ^b

^aDepartment of Material and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden, and ^bDepartment of Organic Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden
^*Correspondence e-mail: lars.eriksson@mmk.su.se

(Received 15 December 2011; accepted 18 January 2012; online 31 January 2012)

The title compound, C₁₃H₂₄O₁₀ is the methyl glycoside of a structural element α-L-Fucp-(1→ 3)-α-D-Galp making up two thirds of the repeating unit in the capsular polysaccharide of Klebsiella K63. The conformation of the title compound is described by the glycosidic torsion angles φ_H = 55 (1)° and ψ_H = −24 (1)°. The hydroxymethyl group in the galactose residue is present in the gauche–trans conformation. In the crystal, O—H⋯O hydrogen bonds connect the disaccharide units into chains along the a-axis direction and further hydrogen bonds cross-link the chains.

Related literature

The capsular polysaccharide (CPS) of Klebsiella K63 contains a repeating unit consisting of → 3)-α-D-GalpA–(1 → 3)-α-L-Fucp-(1 → 3)-α-D-Galp-(1 →, see: Joseleau & Marais (1979 ). For an investigation of the CPS S-156 from Klebsiella pneumoniae ATCC 316 46, see: Johansson et al. (1994 ) and of the CPS from Klebsiella pneumoniae I-1507, see: Guetta et al. (2003 ). For a fiber X-ray diffraction study of the Klebsiella K63 CPS, see: Elloway et al. (1980 $[Elloway, H. F., Isaac, D. H. & Atkins, E. T. D. (1980). Fiber Diffraction Methods, ACS Symposium Series, 141, 429-458.]$ ). For the synthesis, see: Baumann et al. (1988 ).

Experimental

Crystal data

C₁₃H₂₄O₁₀
M_r = 340.32
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.78478 (11) Å
b = 15.7859 (5) Å
c = 19.4401 (5) Å
V = 1468.36 (7) Å³
Z = 4
Synchrotron radiation
λ = 0.907 Å
μ = 0.13 mm⁻¹
T = 100 K
0.03 × 0.01 × 0.01 mm

Data collection

Marresearch MARCCD 165 diffractometer
7469 measured reflections
1162 independent reflections
975 reflections with I > 2σ(I)
R_int = 0.117
θ_max = 30.1°

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.177
S = 1.09
1162 reflections
216 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3f—H3f1⋯O6gⁱ	0.84	1.93	2.772 (7)	177
O4f—H4f1⋯O3fⁱⁱ	0.84	2.04	2.880 (7)	175
O2g—H2g1⋯O2gⁱⁱⁱ	0.84	1.92	2.680 (7)	149
O4g—H4g1⋯O5f^iv	0.84	2.08	2.827 (6)	149
O6g—H6g⋯O3f^v	0.84	2.02	2.822 (7)	158
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) x+1, y, z; (v) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

Data collection: MARCCD (Marresearch, 2010 ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812002279/hb6569sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002279/hb6569Isup2.hkl

checkCIF report

Comment top

Analysis of carbohydrate structure forms the basis of further studies related to interaction with other molecules and their function in different environments. Presently, the structural studies are often divided into the determination of the primary structure, i.e., sugar residues and substituents including their absolute configuration, ring form, anomeric configuration and sequential arrangement of the constituent components. Subsequently, in the second part the three-dimensional structure is determined, often by NMR spectroscopy but also with X-ray diffraction (XRD) techniques when crystals of suitable quality and sufficient size are available.

Polysaccharides are often built of repeating units of oligosaccharides having two to seven sugar residues in their repeats. To understand the physicochemical properties and immunological specificity of the polymers it is essential to obtain information on their structures, both the primary and the three-dimensional structures.

The capsular polysaccharide (CPS) of Klebsiella K63 contains a repeating unit consisting of → 3)-α-D-GalpA– (1 → 3)-α-L-Fucp-(1 → 3)-α-D-Galp-(1 → (Joseleau et al., 1979). More recently the CPS S-156 from Klebsiella pneumoniae ATCC 316 46 (Johansson et al., 1994) and the CPS from Klebsiella pneumoniae I-1507 (Guetta et al., 2003) were investigated. Their backbone structures were identical to that of the CPS from Klebsiella K63, i.e., trisaccharide repeating units, except for stoichiometric O-acetylation at O4 of the galacturonic acid.

The physicochemical effects of O-deacetylation were investigated for 'Fucogel', i.e., the CPS from strain I-1507 and revealed that the presence of the O-acetyl groups decreases the local stiffness of the polymer and lowers the rigidity of the polysaccharide as well as shortens the persistence length. The structural element α-L-Fucp-(1→3)-α-D-Galp makes up two thirds of the repeating unit in these polysaccharides and the title compound is the methyl glycoside thereof.

The torsion angles ϕ_H, ψ_H, and ω describe the major degrees of freedom in an oligosaccharide and for the title compound (I) the two former are present at the glycosidic α-(1 → 3)-linkage. In addition, for the galactose residue the ϕ_H torsion angle is also of interest. The ω torsion angle refers to the conformation of the hydroxymethyl group in the galactose residue. Both of the ϕ_H torsion angles in the structure are described by the exo-anomeric conformation with ϕ_H = 55 (1)° for the fucose residue and ϕ_H = -53 (1)° for the galactose residue (Fig. 1). The ψ_H torsion angle may in solution populate more that one conformational state (see below); for title compound (I) ψ_H = -24 (1)°. The conformation of the hydroxymethyl group is described by one of the three rotamers, gauche-trans, gauche-gauche, or trans-gauche with respect to the conformation of C6–O6 to C5–O5 and to C5–C4, respectively. In the present case the galactose residue has the gt conformation with ω = 70 (1)°, shifted away slightly from an ideal gauche conformation.

The Cremer-Pople parameters for the title compound are Q=0.525 (7) Å, θ=176.4 (8)° and ϕ=142 (10)° for the ring O5f → C5f and Q=0.556 (7) Å, θ=1.8 (7)° and ϕ=288 (14)° for the ring O5g → C5g; thus the conformation of both rings can be described as C-forms.

In the study of Fucogel the conformational space of the constituent disaccharides were investigated by molecular mechanics and Ramachandran maps. Two low energy regions were identified from the adiabatic map of α-L-Fucp-(1→ 3)-α-D-Galp with essentially equal potential energy at their minima being (i) ϕO5 = 279.6° and ψC4 = 140.4° and (ii) ϕO5 = 260.2° and ψC4 = 70.2°, in which the former torsion angle is defined by O5f—C1f—O3g—C3g and the latter by C1g—O3g—C3g—C4g. Interresidue hydrogen bonding was not present for these two conformations although it was identified for a significantly higher-energy conformation.

The conformation of the title compound I and the corresponding glycosidic torsion angles in the polysaccharide are indeed quite similar. The resemblance of the crystal structure and the two low-energy minima of the adiabatic map suggests that torsion angle information from XRD data may be suitable as starting points for molecular modeling of oligo- and polysaccharides.

Interestingly, a fiber X-ray diffraction study of the Klebsiella K63 CPS shows that it forms an extended 2-fold helix (Elloway et al., 1980).

Related literature top

The capsular polysaccharide (CPS) of Klebsiella K63 contains a repeating unit consisting of → 3)-α-D-GalpA–(1 → 3)-α-L-Fucp-(1 → 3)-α-D-Galp-(1 →, see: Joseleau et al. (1979). For an investigation of the CPS S-156 from Klebsiella pneumoniae ATCC 316 46, see: Johansson et al. (1994) and of the CPS from Klebsiella pneumoniae I-1507, see: Guetta et al. (2003). For a fiber X-ray diffraction study of the Klebsiella K63 CPS, see: Elloway et al. (1980). For the synthesis, see: Baumann et al. (1988).

Experimental top

The synthesis of (I) was described by Baumann et al. (1988) in which the fucose and galactose residues have the L and D absolute configurations, respectively. The compound was crystallized by slow evaporation of a mixture of water and ethanol (1:1) at ambient temperature.

Computing details top

Data collection: MARCCD (Marresearch, 2010); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of I showing 50% probability displacement ellipsoids. The atom-label suffixes refer to the fucose(f) and galactose (g) residues. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. Reconstructed view of the H0L plane of reciprocal space

Methyl 3-O-α-L-fucopyranosyl α-D-galactopyranoside top

Crystal data top

C₁₃H₂₄O₁₀	Z = 4
M_r = 340.32	F(000) = 728
Orthorhombic, P2₁2₁2₁	D_x = 1.539 Mg m⁻³
Hall symbol: P 2ac 2ab	Synchrotron radiation, λ = 0.907 Å
a = 4.78478 (11) Å	µ = 0.13 mm⁻¹
b = 15.7859 (5) Å	T = 100 K
c = 19.4401 (5) Å	Prism, colorless
V = 1468.36 (7) Å³	0.03 × 0.01 × 0.01 mm

Data collection top

Marresearch MARCCD 165 diffractometer	975 reflections with I > 2σ(I)
Radiation source: I911, Maxlab	R_int = 0.117
Si(111) monochromator	θ_max = 30.1°, θ_min = 3.1°
Detector resolution: 0.0806 pixels mm^-1	h = −5→5
ϕ scans	k = −17→17
7469 measured reflections	l = −20→20
1162 independent reflections

Refinement top

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.177	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.1211P)² + 0.7072P] where P = (F_o² + 2F_c²)/3
1162 reflections	(Δ/σ)_max < 0.001
216 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₃H₂₄O₁₀	V = 1468.36 (7) Å³
M_r = 340.32	Z = 4
Orthorhombic, P2₁2₁2₁	Synchrotron radiation, λ = 0.907 Å
a = 4.78478 (11) Å	µ = 0.13 mm⁻¹
b = 15.7859 (5) Å	T = 100 K
c = 19.4401 (5) Å	0.03 × 0.01 × 0.01 mm

Data collection top

Marresearch MARCCD 165 diffractometer	975 reflections with I > 2σ(I)
7469 measured reflections	R_int = 0.117
1162 independent reflections	θ_max = 30.1°

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.09	Δρ_max = 0.30 e Å⁻³
1162 reflections	Δρ_min = −0.27 e Å⁻³
216 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1F	0.2242 (15)	0.5346 (4)	0.5260 (3)	0.0359 (16)
H1F	0.0917	0.5802	0.5114	0.054*
C2F	0.3048 (14)	0.4827 (5)	0.4636 (3)	0.0409 (17)
H2F	0.1270	0.4633	0.4416	0.061*
C3F	0.4713 (14)	0.4025 (4)	0.4827 (3)	0.0394 (17)
H3F	0.6577	0.4217	0.4999	0.059*
C4F	0.3298 (15)	0.3548 (5)	0.5419 (3)	0.0382 (17)
H4F	0.4571	0.3089	0.5585	0.057*
C5F	0.2588 (15)	0.4126 (4)	0.6012 (3)	0.0403 (17)
H5F	0.4368	0.4347	0.6214	0.060*
O5F	0.0941 (9)	0.4845 (3)	0.5765 (2)	0.0393 (12)
C6F	0.0937 (17)	0.3710 (5)	0.6571 (3)	0.0465 (19)
H6F1	0.0533	0.4124	0.6933	0.070*
H6F2	0.2017	0.3240	0.6764	0.070*
H6F3	−0.0822	0.3494	0.6381	0.070*
O2F	0.4489 (10)	0.5325 (3)	0.4138 (2)	0.0430 (13)
H2F1	0.5624	0.5648	0.4338	0.065*
O3F	0.5214 (11)	0.3485 (3)	0.4262 (2)	0.0458 (13)
H3F1	0.3725	0.3417	0.4040	0.069*
O4F	0.0806 (9)	0.3171 (3)	0.5133 (3)	0.0430 (13)
H4F1	0.0532	0.2697	0.5316	0.065*
C1G	0.6262 (16)	0.7690 (5)	0.6550 (3)	0.0400 (17)
H1G	0.7796	0.8113	0.6487	0.060*
C2G	0.6339 (14)	0.7069 (4)	0.5935 (3)	0.0371 (17)
H2G	0.8264	0.6823	0.5909	0.056*
C3G	0.4279 (14)	0.6336 (4)	0.6047 (3)	0.0362 (16)
H3G	0.2321	0.6554	0.6017	0.054*
C4G	0.4759 (15)	0.5952 (5)	0.6746 (4)	0.0406 (18)
H4G	0.3289	0.5514	0.6831	0.061*
C5G	0.4618 (15)	0.6608 (4)	0.7312 (4)	0.0420 (18)
H5G	0.2701	0.6860	0.7328	0.063*
C6G	0.5295 (18)	0.6222 (5)	0.7996 (3)	0.0463 (19)
H6G1	0.4176	0.5700	0.8059	0.069*
H6G2	0.7295	0.6062	0.8006	0.069*
O1G	0.3648 (10)	0.8128 (3)	0.6509 (2)	0.0434 (13)
O2G	0.5808 (10)	0.7497 (3)	0.5311 (2)	0.0436 (13)
H2G1	0.7044	0.7370	0.5022	0.065*
O3G	0.4759 (10)	0.5731 (3)	0.5507 (2)	0.0412 (12)
O4G	0.7492 (10)	0.5552 (3)	0.6797 (2)	0.0444 (13)
H4G1	0.7904	0.5329	0.6418	0.067*
O5G	0.6680 (10)	0.7279 (3)	0.7175 (2)	0.0418 (13)
O6G	0.4725 (10)	0.6796 (3)	0.8553 (2)	0.0446 (13)
H6G	0.5970	0.6748	0.8855	0.067*
C7	0.3647 (18)	0.8825 (5)	0.6975 (3)	0.049 (2)
H7A	0.3842	0.8615	0.7447	0.073*
H7B	0.1885	0.9137	0.6931	0.073*
H7C	0.5213	0.9202	0.6867	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1F	0.026 (3)	0.053 (4)	0.029 (3)	0.002 (3)	−0.004 (3)	−0.006 (3)
C2F	0.021 (3)	0.061 (4)	0.041 (4)	−0.004 (3)	−0.012 (3)	0.005 (4)
C3F	0.025 (3)	0.058 (4)	0.035 (4)	−0.001 (4)	−0.003 (3)	−0.007 (3)
C4F	0.028 (4)	0.051 (4)	0.035 (4)	−0.004 (3)	−0.007 (3)	−0.005 (3)
C5F	0.024 (3)	0.054 (4)	0.044 (4)	0.005 (4)	−0.003 (3)	0.006 (3)
O5F	0.023 (2)	0.057 (3)	0.038 (3)	0.000 (2)	0.002 (2)	0.002 (2)
C6F	0.038 (4)	0.062 (5)	0.040 (4)	0.007 (4)	0.001 (3)	0.000 (4)
O2F	0.030 (3)	0.061 (3)	0.038 (2)	−0.004 (2)	0.004 (2)	0.000 (2)
O3F	0.026 (3)	0.067 (3)	0.044 (3)	0.000 (3)	−0.002 (2)	−0.001 (2)
O4F	0.023 (3)	0.058 (3)	0.048 (3)	−0.005 (2)	0.000 (2)	−0.001 (2)
C1G	0.036 (4)	0.051 (4)	0.032 (4)	0.005 (4)	0.001 (3)	0.007 (3)
C2G	0.020 (3)	0.059 (4)	0.032 (3)	0.006 (3)	0.001 (3)	0.000 (3)
C3G	0.020 (3)	0.049 (4)	0.040 (4)	0.001 (3)	−0.012 (3)	−0.003 (3)
C4G	0.021 (3)	0.051 (4)	0.050 (4)	0.005 (3)	−0.007 (3)	0.000 (4)
C5G	0.025 (4)	0.059 (5)	0.043 (4)	0.002 (4)	−0.002 (3)	0.002 (3)
C6G	0.047 (5)	0.055 (4)	0.037 (4)	0.006 (4)	−0.002 (4)	−0.004 (4)
O1G	0.029 (3)	0.059 (3)	0.042 (3)	0.006 (3)	−0.006 (2)	0.006 (2)
O2G	0.023 (3)	0.071 (3)	0.038 (2)	0.008 (3)	0.002 (2)	0.008 (3)
O3G	0.025 (3)	0.058 (3)	0.041 (3)	0.000 (2)	−0.009 (2)	−0.002 (2)
O4G	0.031 (3)	0.063 (3)	0.040 (3)	0.010 (3)	0.003 (2)	−0.006 (2)
O5G	0.028 (3)	0.061 (3)	0.037 (3)	−0.005 (2)	−0.002 (2)	0.000 (2)
O6G	0.029 (3)	0.069 (3)	0.036 (3)	−0.003 (3)	−0.002 (2)	−0.004 (3)
C7	0.042 (4)	0.068 (5)	0.036 (4)	0.010 (4)	−0.008 (3)	−0.004 (4)

Geometric parameters (Å, º) top

C1F—O5F	1.406 (8)	C1G—C2G	1.546 (9)
C1F—O3G	1.432 (8)	C1G—H1G	1.0000
C1F—C2F	1.515 (9)	C2G—O2G	1.414 (8)
C1F—H1F	1.0000	C2G—C3G	1.535 (9)
C2F—O2F	1.425 (8)	C2G—H2G	1.0000
C2F—C3F	1.541 (10)	C3G—O3G	1.438 (8)
C2F—H2F	1.0000	C3G—C4G	1.505 (9)
C3F—O3F	1.411 (8)	C3G—H3G	1.0000
C3F—C4F	1.532 (10)	C4G—O4G	1.456 (9)
C3F—H3F	1.0000	C4G—C5G	1.513 (10)
C4F—O4F	1.444 (8)	C4G—H4G	1.0000
C4F—C5F	1.509 (9)	C5G—O5G	1.471 (8)
C4F—H4F	1.0000	C5G—C6G	1.498 (10)
C5F—O5F	1.462 (8)	C5G—H5G	1.0000
C5F—C6F	1.495 (10)	C6G—O6G	1.437 (8)
C5F—H5F	1.0000	C6G—H6G1	0.9900
C6F—H6F1	0.9800	C6G—H6G2	0.9900
C6F—H6F2	0.9800	O1G—C7	1.424 (8)
C6F—H6F3	0.9800	O2G—H2G1	0.8400
O2F—H2F1	0.8400	O4G—H4G1	0.8400
O3F—H3F1	0.8400	O6G—H6G	0.8400
O4F—H4F1	0.8400	C7—H7A	0.9800
C1G—O5G	1.392 (8)	C7—H7B	0.9800
C1G—O1G	1.431 (9)	C7—H7C	0.9800

O5F—C1F—O3G	112.2 (5)	O1G—C1G—H1G	108.2
O5F—C1F—C2F	111.6 (5)	C2G—C1G—H1G	108.2
O3G—C1F—C2F	106.5 (5)	O2G—C2G—C3G	111.5 (5)
O5F—C1F—H1F	108.8	O2G—C2G—C1G	110.9 (5)
O3G—C1F—H1F	108.8	C3G—C2G—C1G	110.7 (5)
C2F—C1F—H1F	108.8	O2G—C2G—H2G	107.9
O2F—C2F—C1F	111.7 (6)	C3G—C2G—H2G	107.9
O2F—C2F—C3F	111.5 (5)	C1G—C2G—H2G	107.9
C1F—C2F—C3F	112.5 (5)	O3G—C3G—C4G	111.5 (5)
O2F—C2F—H2F	106.9	O3G—C3G—C2G	107.1 (5)
C1F—C2F—H2F	106.9	C4G—C3G—C2G	109.5 (5)
C3F—C2F—H2F	106.9	O3G—C3G—H3G	109.6
O3F—C3F—C4F	111.3 (6)	C4G—C3G—H3G	109.6
O3F—C3F—C2F	113.4 (5)	C2G—C3G—H3G	109.6
C4F—C3F—C2F	110.9 (6)	O4G—C4G—C3G	111.9 (6)
O3F—C3F—H3F	107.0	O4G—C4G—C5G	106.7 (6)
C4F—C3F—H3F	107.0	C3G—C4G—C5G	112.0 (6)
C2F—C3F—H3F	107.0	O4G—C4G—H4G	108.7
O4F—C4F—C5F	110.9 (6)	C3G—C4G—H4G	108.7
O4F—C4F—C3F	106.1 (5)	C5G—C4G—H4G	108.7
C5F—C4F—C3F	112.1 (6)	O5G—C5G—C6G	108.0 (6)
O4F—C4F—H4F	109.2	O5G—C5G—C4G	109.2 (6)
C5F—C4F—H4F	109.2	C6G—C5G—C4G	111.0 (6)
C3F—C4F—H4F	109.2	O5G—C5G—H5G	109.5
O5F—C5F—C6F	107.1 (6)	C6G—C5G—H5G	109.5
O5F—C5F—C4F	109.8 (5)	C4G—C5G—H5G	109.5
C6F—C5F—C4F	114.1 (6)	O6G—C6G—C5G	111.7 (6)
O5F—C5F—H5F	108.5	O6G—C6G—H6G1	109.3
C6F—C5F—H5F	108.5	C5G—C6G—H6G1	109.3
C4F—C5F—H5F	108.5	O6G—C6G—H6G2	109.3
C1F—O5F—C5F	115.3 (5)	C5G—C6G—H6G2	109.3
C5F—C6F—H6F1	109.5	H6G1—C6G—H6G2	107.9
C5F—C6F—H6F2	109.5	C7—O1G—C1G	109.8 (5)
H6F1—C6F—H6F2	109.5	C2G—O2G—H2G1	109.5
C5F—C6F—H6F3	109.5	C1F—O3G—C3G	113.1 (5)
H6F1—C6F—H6F3	109.5	C4G—O4G—H4G1	109.5
H6F2—C6F—H6F3	109.5	C1G—O5G—C5G	113.4 (5)
C2F—O2F—H2F1	109.5	C6G—O6G—H6G	109.5
C3F—O3F—H3F1	109.5	O1G—C7—H7A	109.5
C4F—O4F—H4F1	109.5	O1G—C7—H7B	109.5
O5G—C1G—O1G	113.5 (5)	H7A—C7—H7B	109.5
O5G—C1G—C2G	112.0 (5)	O1G—C7—H7C	109.5
O1G—C1G—C2G	106.6 (5)	H7A—C7—H7C	109.5
O5G—C1G—H1G	108.2	H7B—C7—H7C	109.5

O5F—C1F—C2F—O2F	−177.1 (5)	O2G—C2G—C3G—O3G	64.1 (6)
O3G—C1F—C2F—O2F	−54.4 (7)	C1G—C2G—C3G—O3G	−172.1 (5)
O5F—C1F—C2F—C3F	−50.8 (7)	O2G—C2G—C3G—C4G	−174.9 (5)
O3G—C1F—C2F—C3F	71.9 (7)	C1G—C2G—C3G—C4G	−51.0 (7)
O2F—C2F—C3F—O3F	−60.3 (8)	O3G—C3G—C4G—O4G	53.0 (7)
C1F—C2F—C3F—O3F	173.3 (6)	C2G—C3G—C4G—O4G	−65.3 (7)
O2F—C2F—C3F—C4F	173.7 (5)	O3G—C3G—C4G—C5G	172.8 (6)
C1F—C2F—C3F—C4F	47.3 (7)	C2G—C3G—C4G—C5G	54.4 (7)
O3F—C3F—C4F—O4F	−55.3 (7)	O4G—C4G—C5G—O5G	65.6 (6)
C2F—C3F—C4F—O4F	71.8 (6)	C3G—C4G—C5G—O5G	−57.1 (7)
O3F—C3F—C4F—C5F	−176.6 (6)	O4G—C4G—C5G—C6G	−53.3 (8)
C2F—C3F—C4F—C5F	−49.5 (7)	C3G—C4G—C5G—C6G	−176.1 (6)
O4F—C4F—C5F—O5F	−64.9 (7)	O5G—C5G—C6G—O6G	69.9 (7)
C3F—C4F—C5F—O5F	53.6 (7)	C4G—C5G—C6G—O6G	−170.4 (6)
O4F—C4F—C5F—C6F	55.4 (8)	O5G—C1G—O1G—C7	67.5 (7)
C3F—C4F—C5F—C6F	173.9 (6)	C2G—C1G—O1G—C7	−168.6 (5)
O3G—C1F—O5F—C5F	−61.8 (6)	O5F—C1F—O3G—C3G	−65.4 (7)
C2F—C1F—O5F—C5F	57.6 (7)	C2F—C1F—O3G—C3G	172.3 (5)
C6F—C5F—O5F—C1F	176.5 (5)	C4G—C3G—O3G—C1F	97.7 (6)
C4F—C5F—O5F—C1F	−59.0 (7)	C2G—C3G—O3G—C1F	−142.5 (5)
O5G—C1G—C2G—O2G	177.9 (5)	O1G—C1G—O5G—C5G	62.6 (7)
O1G—C1G—C2G—O2G	53.1 (7)	C2G—C1G—O5G—C5G	−58.2 (7)
O5G—C1G—C2G—C3G	53.6 (7)	C6G—C5G—O5G—C1G	−179.8 (5)
O1G—C1G—C2G—C3G	−71.1 (6)	C4G—C5G—O5G—C1G	59.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3f—H3f1···O6gⁱ	0.84	1.93	2.772 (7)	177
O4f—H4f1···O3fⁱⁱ	0.84	2.04	2.880 (7)	175
O2g—H2g1···O2gⁱⁱⁱ	0.84	1.92	2.680 (7)	149
O4g—H4g1···O5f^iv	0.84	2.08	2.827 (6)	149
O6g—H6g···O3f^v	0.84	2.02	2.822 (7)	158

Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1, y, z; (v) −x+3/2, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₄O₁₀
M_r	340.32
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	4.78478 (11), 15.7859 (5), 19.4401 (5)
V (Å³)	1468.36 (7)
Z	4
Radiation type	Synchrotron, λ = 0.907 Å
µ (mm⁻¹)	0.13
Crystal size (mm)	0.03 × 0.01 × 0.01

Data collection
Diffractometer	Marresearch MARCCD 165 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7469, 1162, 975
R_int	0.117
θ_max (°)	30.1
(sin θ/λ)_max (Å⁻¹)	0.553

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.177, 1.09
No. of reflections	1162
No. of parameters	216
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.27

Computer programs: MARCCD (Marresearch, 2010), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3f—H3f1···O6gⁱ	0.84	1.93	2.772 (7)	177
O4f—H4f1···O3fⁱⁱ	0.84	2.04	2.880 (7)	175
O2g—H2g1···O2gⁱⁱⁱ	0.84	1.92	2.680 (7)	149
O4g—H4g1···O5f^iv	0.84	2.08	2.827 (6)	149
O6g—H6g···O3f^v	0.84	2.02	2.822 (7)	158

Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1, y, z; (v) −x+3/2, −y+1, z+1/2.

Acknowledgements

This work was supported by a grant from the Swedish Research Council and by the Faculty of Natural Sciences at Stockholm University

References

Baumann, H., Jansson, P.-E. & Kenne, L. (1988). J. Chem. Soc. Perkin Trans. 1, pp. 209–217. CrossRef Web of Science Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Elloway, H. F., Isaac, D. H. & Atkins, E. T. D. (1980). Fiber Diffraction Methods, ACS Symposium Series, 141, 429–458. Google Scholar
Guetta, O., Mazeau, K., Auzely, R., Milas, M. & Rinaudo, M. (2003). Biomacromolecules, 4, 1362–1371. CrossRef PubMed CAS Google Scholar
Johansson, A., Jansson, P.-E. & Widmalm, G. (1994). Carbohydr. Res. 253, 317–322. CrossRef CAS PubMed Google Scholar
Joseleau, J.-P. & Marais, M.-R. (1979). Carbohydr. Res. 77, 183–190. CrossRef CAS PubMed Google Scholar
Marresearch (2010). MARCCD. Marresearch GmbH, Norderstedt, Germany. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar