Methyl 3-O-[beta]-L-fucopyranosyl [alpha]-D-glucopyranoside trihydrate

The water content of the title compound, C₁₃H₂₄O₁₀·3H₂O, creates an extensive hydrogen-bonding pattern, with all the hydroxyl groups of the disaccharide acting as hydrogen-bond donors and acceptors. The water molecules are arranged in columns along the crystallographic b axis and form, together with one of the hydroxyl groups, infinite hydrogen-bonded chains. The conformation of the disaccharide is described by glycosidic torsion angles of -38 and 18°.

S1. Comment

Carbohydrates are one of the most abundant types of molecules found in nature, and many oligo- and polysaccharides play important roles in biological systems (Varki et al., 1999). To understand the role of carbohydrates better, a detailed knowledge of their three-dimensional structure is required. The X-ray diffraction technique is unsurpassed for studying the three- dimensional structure of molecules, as long as suitable crystals can be grown, which has proven difficult for polyhydroxylated carbohydrates. A recent review (Peréz et al., 2000) states that until the year 2000 only 55 unsubstituted disaccharides had been crystallized and solved by X-ray diffraction and only two disaccharides containing fucose had been solved (Eriksson et al., 2000; Watt et al., 1996; Allen, 2002). Furthermore, three trisaccharides containing fucose were found in the Cambridge Strutural Database (Allen, 2002).

The conformation of disaccharide, (I), is described by the two torsion angles around the glycosidic linkage, ϕ_H (defined by H1f—C1f—O3g—C3g) and ψ_H (defined by C1f—O3g—C3g—H3g), where f and g denote the fucosyl and glucosyl residues, respectively (Fig. 1). The value of the ϕ_H torsion angle is mainly governed by the exo-anomeric effect, which predicts that a β-L sugar should have an ϕ_H angle of ~- 60°. The ψ_H torsion angle is set by steric interactions and is generally between −60 and 60°. For (I), ϕ_H is −37.7° and ψ_H is 18.2°. Thus, the glycosidic torsion angles are found in the expected regions. Selected torsion angles are given in Table 1. A grid search using a simplified molecular mechanics potential energy function found the global minimum at ϕ_H = −55° and ψ_H = −5° (Baumann et al., 1991). This conformation differs from the conformation found in the crystalline state by \sim20° at each of the glycosidic torsion angles. The exocyclic torsion angle for the glucose residue has an angle ω_g (defined by O5g—C5g—C6g—O6g) of −66.4 (2)°, which describes a gauche–gauche conformation. The bond angle at the glycosidic linkage τ (defined by C1f–O3g–C3g) is 116.2 (2)°. The calculated Cremer & Pople (1975) puckering parameter shows that both pyranose rings in (I) are in the expected chair conformations, ¹C₄ for the fucosyl ring [Q = 0.583 (2) Å, θ = 172.6 (2)° and ϕ = 145 (2)°] and ⁴C₁ chair for the glucose ring [Q = 0.578 (2) Å, θ = 4.9 (2)° and ϕ = 135 (2)°]. The mean C—C bond length is 1.53 Å, which is in agreement with the average bond length reported for carbohydrates (Peréz et al., 2000). The main packing feature in the structure is the hydrogen-bond network, where the water molecules give rise to a complex hydrogen-bonding scheme (see Table 2). An intra-molecular hydrogen bond, O2g—HO2g···O5f, is observed over the glycosidic linkage.

From an NMR study of disaccharide, (I), in water and aceton (85:15) obtained at 265 K it was concluded that a weak hydrogen bond is present between the two above-mentioned atoms. This conclusion was based on a large negative chemical shift difference, a small value of the J-coupling and a high temperature coefficient for HO2g (Ivarsson et al., 2000).

In total there are 11 inter-molecular hydrogen bonds in the range 2.68–3.07 Å. All hydroxyl groups act as hydrogen-bond donors, both to other hydroxyl groups and to water molecules. The water molecules are grouped together in a channel through the structure along the crystallographic b axis and form an infinite hydrogen-bonded chain, as depicted in Fig. 2, where the sequence donor → acceptor is O6g → OW1 → OW2 → OW3 → O6gⁱ. Several more hydrogen-bond clusters and chains are also present.

S2. Experimental

The synthesis of methyl 3-O-β-L-fucopyranosyl α-D-glucopyranoside was described previously (Baumann et al., 1991). Crystals suitable for single-crystal X-ray diffraction were grown at 295 K with the sitting-drop technique, in which the solvent was allowed to evaporate. Compound (I) was dissolved in water to a concentration of 375 mg ml^-1 and mixed with an equal amount of 30% PEG-400 in water at ambient temperature. After approximately one week, the crystals were harvested and mounted in capillaries to avoid the loss of crystal water. Data were collected at ambient temperature on beamline I711 at the Swedish synchrotron radiation facility MAXLAB, Lund.

S3. Refinement

The initial electron-density map contained all non-H atoms including the three water O atoms. The water H atoms were located from difference electron-density maps, while the H atoms on the carbohydrate molecule were positioned geometrically. Restraints were applied to bond lengths and to the distance between the H atoms on the water molecules, to stabilize the structure during refinement. The O—H distance was set to 0.82 Å while the C—H distances were set to 0.98, 0.97 and 0.96 Å in the CH, CH₂ and CH₃ groups, respectively. All non-H atoms were refined with anistropic displacement parameters employing a rigid-bond restraint to U^ij of the two bonded atoms (Rollett, 1970). The H atoms were allowed to ride on the coordinates of their parent atoms during the least-squares refinement. The U_iso(H) values were 1.5U_eq(C, O) for methyl and hydroxyl groups with U_iso(H) of 1.2U_eq(C) for all other atoms. H atoms in the hydroxyl groups were allowed to rotate around the X—C—O—H torsion angle during the refinment using the AFIX 147 instruction available in SHELXL97.

The absolute configuration of (I) is set by the components in the synthesis. As the value of the Flack parameter initially calculated was meaningless, the Friedel equivalents (1497) were included in the merging process (MERG 3 in SHELXL97).

Computing details

Data collection: MARCCD control software (MAR, 2002); cell refinement: Twinsolve (Svensson, 2002); data reduction: Twinsolve; program(s) used to solve structure: SHELXD (Sheldrick & Schneider, 2001); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: PLATON (Spek, 2002).

Figures

	Fig. 1. The molecular structure of the disaccharide (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. H atoms are drawn as small spheres of arbitrary radii. An internal hydrogen bond, O2g—HO2g···O5f, is also shown (dashed). The water molecules are omitted.
	Fig. 2. A view of the hydrogen-bond scheme for the three water molecules. Hydrogen bonding is indicated by dashed lines. Some H atoms are removed for clarity. [Symmetry codes: (i) 0.5 − x, 1 − y, −0.5 + z; (ii) 1.5 − x, 1 − y, −0.5 + z; (iii) 0.5 + x, 1.5 − y, 1 − z; (iv) 2 − x, 0.5 + y, 0.5 − z.]

Methyl 3-O-β-L-fucopyranosyl α-D-glucopyranoside trihydrate

Crystal data

C13H24O10·3(H2O)	F(000) = 848
Mr = 394.37	Dx = 1.414 Mg m^−3
Orthorhombic, P212121	Synchrotron radiation, λ = 0.8720 Å
Hall symbol: P 2ac 2ab	Cell parameters from 882 reflections
a = 6.8638 (16) Å	θ = 2.0–32.0°
b = 15.861 (4) Å	µ = 0.21 mm^−1
c = 17.014 (7) Å	T = 293 K
V = 1852.2 (10) Å^3	Needle, colourless
Z = 4	0.35 × 0.1 × 0.1 mm

Data collection

MAR-CCD area detector diffractometer	2062 independent reflections
Radiation source: Beamline I-711, MaxLab, Lund, Sweden	1811 reflections with I > 2σ(I)
Si monochromator	Rint = 0.048
Detector resolution: 12.4 pixels mm^-1	θmax = 32.4°, θmin = 2.2°
Area detector, ϕ–scan	h = −8→8
Absorption correction: numerical X-RED (Stoe & Cie, 1997)	k = −19→19
Tmin = 0.93, Tmax = 0.98	l = −20→20
25554 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.56	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
2062 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.16 e Å^−3
9 restraints	Δρmin = −0.15 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles 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 (Ų)

	x	y	z	Uiso*/Ueq
O3G	0.9331 (2)	0.44658 (9)	0.02578 (9)	0.0289 (4)
O4G	1.3310 (3)	0.41662 (9)	−0.02105 (10)	0.0351 (4)
HO4G	1.2685	0.3810	−0.0452	0.053*
O5G	1.3118 (3)	0.64758 (9)	−0.01916 (9)	0.0350 (4)
O2F	0.9148 (3)	0.26488 (10)	0.04291 (10)	0.0393 (4)
HO2F	0.9454	0.2754	−0.0026	0.059*
O1G	1.2541 (3)	0.64770 (10)	0.11662 (9)	0.0387 (4)
O4F	0.3564 (3)	0.36405 (11)	0.13598 (11)	0.0408 (4)
HO4F	0.3868	0.3810	0.0921	0.061*
O5F	0.7235 (2)	0.46018 (9)	0.12954 (9)	0.0328 (4)
O3F	0.5650 (3)	0.20878 (10)	0.10776 (11)	0.0400 (4)
HO3F	0.4640	0.2014	0.1325	0.060*
C2G	1.0048 (4)	0.59850 (13)	0.03282 (15)	0.0324 (5)
H2G	0.9458	0.6066	−0.0191	0.039*
C3G	1.0846 (3)	0.50807 (13)	0.03752 (13)	0.0262 (5)
H3G	1.1458	0.4991	0.0889	0.031*
C4G	1.2360 (4)	0.49657 (13)	−0.02739 (13)	0.0276 (5)
H4G	1.1722	0.5009	−0.0788	0.033*
O6G	1.4397 (3)	0.57012 (11)	−0.16448 (11)	0.0474 (5)
HO6G	1.4038	0.6190	−0.1708	0.071*
C2F	0.7699 (4)	0.32358 (12)	0.06852 (13)	0.0277 (5)
H2F	0.6777	0.3343	0.0257	0.033*
O2G	0.8630 (3)	0.61826 (11)	0.09103 (13)	0.0515 (5)
HO2G	0.8119	0.5747	0.1067	0.077*
C3F	0.6633 (4)	0.28256 (13)	0.13722 (13)	0.0300 (5)
H3F	0.7615	0.2638	0.1752	0.036*
C5G	1.3957 (3)	0.56388 (13)	−0.02115 (14)	0.0297 (5)
H5G	1.4699	0.5546	0.0273	0.036*
C5F	0.6453 (4)	0.42388 (14)	0.20100 (13)	0.0340 (5)
H5F	0.7534	0.4075	0.2354	0.041*
C6G	1.5349 (4)	0.56251 (16)	−0.09051 (16)	0.0401 (6)
H6G1	1.6273	0.6084	−0.0849	0.048*
H6G2	1.6077	0.5101	−0.0896	0.048*
C1G	1.1747 (4)	0.65996 (13)	0.04117 (14)	0.0342 (5)
H1G	1.1244	0.7177	0.0376	0.041*
C1F	0.8651 (3)	0.40594 (13)	0.09338 (13)	0.0265 (5)
H1F	0.9730	0.3950	0.1297	0.032*
C4F	0.5276 (3)	0.34505 (15)	0.17948 (14)	0.0311 (5)
H4F	0.4863	0.3185	0.2288	0.037*
CM	1.3942 (5)	0.71000 (19)	0.13900 (19)	0.0569 (8)
H1M	1.4428	0.6974	0.1906	0.085*
H2M	1.3337	0.7646	0.1393	0.085*
H3M	1.5001	0.7098	0.1022	0.085*
C6F	0.5265 (5)	0.49154 (19)	0.24140 (19)	0.0540 (8)
H6F1	0.6087	0.5389	0.2532	0.081*
H6F2	0.4728	0.4694	0.2892	0.081*
H6F3	0.4228	0.5093	0.2074	0.081*
OW1	1.3589 (5)	0.73298 (12)	−0.19392 (13)	0.0711 (8)
H1W1	1.346 (8)	0.756 (2)	−0.2458 (9)	0.107*
H2W1	1.380 (8)	0.7801 (16)	−0.1598 (16)	0.107*
OW2	1.3176 (3)	0.81074 (13)	−0.34403 (13)	0.0537 (5)
H1W2	1.401 (4)	0.8551 (16)	−0.3269 (19)	0.081*
H2W2	1.386 (4)	0.7814 (19)	−0.3847 (17)	0.081*
OW3	1.5566 (6)	0.91571 (16)	−0.26618 (16)	0.0927 (11)
H1W3	1.559 (9)	0.9740 (10)	−0.280 (2)	0.139*
H2W3	1.574 (9)	0.913 (3)	−0.2108 (8)	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3G	0.0305 (8)	0.0270 (7)	0.0290 (8)	−0.0070 (7)	0.0009 (7)	−0.0010 (6)
O4G	0.0358 (9)	0.0251 (7)	0.0443 (10)	0.0008 (7)	0.0034 (8)	−0.0040 (7)
O5G	0.0449 (10)	0.0231 (7)	0.0371 (9)	−0.0040 (8)	0.0048 (8)	0.0027 (6)
O2F	0.0481 (11)	0.0269 (8)	0.0429 (10)	0.0054 (8)	0.0140 (9)	−0.0013 (7)
O1G	0.0467 (11)	0.0340 (8)	0.0353 (9)	−0.0072 (8)	−0.0027 (8)	−0.0056 (7)
O4F	0.0262 (9)	0.0491 (10)	0.0471 (11)	−0.0020 (8)	−0.0017 (8)	0.0101 (8)
O5F	0.0332 (9)	0.0268 (7)	0.0383 (8)	−0.0022 (7)	0.0078 (7)	−0.0039 (6)
O3F	0.0434 (11)	0.0286 (8)	0.0479 (11)	−0.0117 (8)	0.0046 (9)	−0.0013 (7)
C2G	0.0319 (13)	0.0254 (10)	0.0399 (13)	0.0025 (10)	−0.0008 (11)	−0.0027 (9)
C3G	0.0284 (12)	0.0218 (9)	0.0284 (11)	−0.0044 (9)	−0.0017 (9)	−0.0018 (8)
C4G	0.0294 (12)	0.0246 (9)	0.0286 (11)	−0.0003 (9)	0.0012 (10)	0.0015 (8)
O6G	0.0692 (14)	0.0379 (9)	0.0351 (10)	0.0016 (10)	0.0098 (10)	0.0017 (7)
C2F	0.0286 (12)	0.0248 (10)	0.0298 (11)	−0.0002 (10)	0.0011 (9)	−0.0019 (9)
O2G	0.0449 (11)	0.0295 (8)	0.0799 (15)	−0.0004 (8)	0.0242 (11)	−0.0107 (9)
C3F	0.0298 (12)	0.0249 (10)	0.0355 (12)	−0.0021 (10)	−0.0030 (10)	0.0015 (9)
C5G	0.0317 (13)	0.0253 (10)	0.0320 (12)	−0.0027 (9)	−0.0030 (10)	0.0008 (9)
C5F	0.0347 (13)	0.0381 (12)	0.0293 (12)	−0.0011 (11)	0.0025 (10)	−0.0052 (9)
C6G	0.0358 (14)	0.0357 (12)	0.0486 (15)	−0.0058 (11)	0.0081 (12)	0.0029 (11)
C1G	0.0410 (15)	0.0233 (10)	0.0384 (13)	0.0006 (10)	0.0031 (11)	−0.0005 (9)
C1F	0.0264 (11)	0.0266 (10)	0.0265 (11)	0.0004 (9)	0.0037 (9)	−0.0019 (8)
C4F	0.0277 (12)	0.0352 (11)	0.0306 (12)	−0.0023 (10)	0.0001 (9)	0.0075 (9)
CM	0.066 (2)	0.0476 (15)	0.0576 (19)	−0.0182 (15)	−0.0123 (16)	−0.0127 (13)
C6F	0.0563 (19)	0.0499 (15)	0.0558 (18)	0.0019 (15)	0.0195 (15)	−0.0152 (13)
OW2	0.0504 (13)	0.0527 (11)	0.0582 (12)	−0.0093 (10)	0.0077 (10)	0.0061 (9)
OW1	0.120 (2)	0.0406 (10)	0.0530 (13)	0.0049 (13)	0.0149 (15)	0.0009 (9)
OW3	0.132 (3)	0.0711 (15)	0.0748 (18)	−0.0500 (18)	0.0501 (19)	−0.0269 (13)

Geometric parameters (Å, º)

O3G—C1F	1.399 (3)	C2F—C3F	1.525 (3)
O3G—C3G	1.440 (3)	C2F—H2F	0.9800
O4G—C4G	1.430 (3)	O2G—HO2G	0.8200
O4G—HO4G	0.8200	C3F—C4F	1.538 (3)
O5G—C1G	1.406 (3)	C3F—H3F	0.9800
O5G—C5G	1.447 (3)	C5G—C6G	1.519 (4)
O2F—C2F	1.431 (3)	C5G—H5G	0.9800
O2F—HO2F	0.8200	C5F—C6F	1.513 (3)
O1G—C1G	1.408 (3)	C5F—C4F	1.533 (3)
O1G—CM	1.430 (3)	C5F—H5F	0.9800
O4F—C4F	1.421 (3)	C6G—H6G1	0.9700
O4F—HO4F	0.8200	C6G—H6G2	0.9700
O5F—C1F	1.436 (3)	C1G—H1G	0.9800
O5F—C5F	1.449 (3)	C1F—H1F	0.9800
O3F—C3F	1.441 (3)	C4F—H4F	0.9800
O3F—HO3F	0.8200	CM—H1M	0.9600
C2G—O2G	1.423 (3)	CM—H2M	0.9600
C2G—C1G	1.527 (3)	CM—H3M	0.9600
C2G—C3G	1.537 (3)	C6F—H6F1	0.9600
C2G—H2G	0.9800	C6F—H6F2	0.9600
C3G—C4G	1.528 (3)	C6F—H6F3	0.9600
C3G—H3G	0.9800	OW2—H1W2	0.96 (2)
C4G—C5G	1.534 (3)	OW2—H2W2	0.96 (3)
C4G—H4G	0.9800	OW1—H1W1	0.95 (3)
O6G—C6G	1.423 (4)	OW1—H2W1	0.96 (3)
O6G—HO6G	0.8200	OW3—H1W3	0.95 (2)
C2F—C1F	1.521 (3)	OW3—H2W3	0.95 (12)
C1F—O3G—C3G	116.05 (16)	O5F—C5F—C6F	107.4 (2)
C4G—O4G—HO4G	109.5	O5F—C5F—C4F	108.61 (17)
C1G—O5G—C5G	114.29 (16)	C6F—C5F—C4F	113.8 (2)
C2F—O2F—HO2F	109.5	O5F—C5F—H5F	109.0
C1G—O1G—CM	114.1 (2)	C6F—C5F—H5F	109.0
C4F—O4F—HO4F	109.5	C4F—C5F—H5F	109.0
C1F—O5F—C5F	111.86 (16)	O6G—C6G—C5G	113.4 (2)
C3F—O3F—HO3F	109.5	O6G—C6G—H6G1	108.9
O2G—C2G—C1G	108.48 (18)	C5G—C6G—H6G1	108.9
O2G—C2G—C3G	114.37 (19)	O6G—C6G—H6G2	108.9
C1G—C2G—C3G	108.59 (19)	C5G—C6G—H6G2	108.9
O2G—C2G—H2G	108.4	H6G1—C6G—H6G2	107.7
C1G—C2G—H2G	108.4	O5G—C1G—O1G	112.8 (2)
C3G—C2G—H2G	108.4	O5G—C1G—C2G	110.74 (18)
O3G—C3G—C4G	108.08 (16)	O1G—C1G—C2G	107.00 (18)
O3G—C3G—C2G	111.57 (18)	O5G—C1G—H1G	108.7
C4G—C3G—C2G	108.42 (18)	O1G—C1G—H1G	108.7
O3G—C3G—H3G	109.6	C2G—C1G—H1G	108.7
C4G—C3G—H3G	109.6	O3G—C1F—O5F	107.58 (16)
C2G—C3G—H3G	109.6	O3G—C1F—C2F	108.10 (17)
O4G—C4G—C3G	111.20 (16)	O5F—C1F—C2F	110.06 (18)
O4G—C4G—C5G	106.61 (18)	O3G—C1F—H1F	110.3
C3G—C4G—C5G	110.68 (17)	O5F—C1F—H1F	110.3
O4G—C4G—H4G	109.4	C2F—C1F—H1F	110.3
C3G—C4G—H4G	109.4	O4F—C4F—C5F	112.78 (19)
C5G—C4G—H4G	109.4	O4F—C4F—C3F	113.2 (2)
C6G—O6G—HO6G	109.5	C5F—C4F—C3F	108.54 (19)
O2F—C2F—C1F	110.17 (19)	O4F—C4F—H4F	107.3
O2F—C2F—C3F	106.82 (17)	C5F—C4F—H4F	107.3
C1F—C2F—C3F	111.08 (17)	C3F—C4F—H4F	107.3
O2F—C2F—H2F	109.6	O1G—CM—H1M	109.5
C1F—C2F—H2F	109.6	O1G—CM—H2M	109.5
C3F—C2F—H2F	109.6	H1M—CM—H2M	109.5
C2G—O2G—HO2G	109.5	O1G—CM—H3M	109.5
O3F—C3F—C2F	107.73 (18)	H1M—CM—H3M	109.5
O3F—C3F—C4F	113.7 (2)	H2M—CM—H3M	109.5
C2F—C3F—C4F	111.95 (17)	C5F—C6F—H6F1	109.5
O3F—C3F—H3F	107.7	C5F—C6F—H6F2	109.5
C2F—C3F—H3F	107.7	H6F1—C6F—H6F2	109.5
C4F—C3F—H3F	107.7	C5F—C6F—H6F3	109.5
O5G—C5G—C6G	106.36 (18)	H6F1—C6F—H6F3	109.5
O5G—C5G—C4G	110.83 (18)	H6F2—C6F—H6F3	109.5
C6G—C5G—C4G	112.70 (19)	H1W2—OW2—H2W2	106 (2)
O5G—C5G—H5G	109.0	H1W1—OW1—H2W1	107 (2)
C6G—C5G—H5G	109.0	H1W3—OW3—H2W3	107 (15)
C4G—C5G—H5G	109.0
H1F—C1F—O3G—C3G	−37.76	O4G—C4G—C5G—C6G	66.6 (2)
C1F—O3G—C3G—C4G	137.58 (18)	C3G—C4G—C5G—C6G	−172.35 (19)
C3G—O3G—C1F—O5F	82.7 (2)	C1F—O5F—C5F—C6F	170.2 (2)
CM—O1G—C1G—H1G	−52.79	C1F—O5F—C5F—C4F	−66.3 (2)
C3G—O3G—C1F—C2F	−158.51 (17)	C4G—C5G—C6G—O6G	55.2 (3)
O5G—C1G—O1G—CM	67.9 (3)	C5G—O5G—C1G—O1G	60.1 (2)
C1F—O3G—C3G—H3G	18.22	C5G—O5G—C1G—C2G	−59.7 (2)
C2G—C1G—O1G—CM	−170.1 (2)	O2G—C2G—C1G—O5G	−175.17 (19)
C1F—O3G—C3G—C2G	−103.3 (2)	C3G—C2G—C1G—O5G	60.0 (2)
O5G—C5G—C6G—O6G	−66.5 (2)	O2G—C2G—C1G—O1G	61.6 (2)
O2G—C2G—C3G—O3G	61.8 (3)	C3G—C2G—C1G—O1G	−63.3 (2)
C1G—C2G—C3G—O3G	−176.86 (18)	C5F—O5F—C1F—O3G	−179.39 (17)
O2G—C2G—C3G—C4G	−179.3 (2)	C5F—O5F—C1F—C2F	63.0 (2)
C1G—C2G—C3G—C4G	−58.0 (2)	O2F—C2F—C1F—O3G	71.0 (2)
O3G—C3G—C4G—O4G	−65.1 (2)	C3F—C2F—C1F—O3G	−170.79 (18)
C2G—C3G—C4G—O4G	173.81 (18)	O2F—C2F—C1F—O5F	−171.72 (17)
O3G—C3G—C4G—C5G	176.58 (17)	C3F—C2F—C1F—O5F	−53.5 (2)
C2G—C3G—C4G—C5G	55.5 (2)	O5F—C5F—C4F—O4F	−67.2 (3)
O2F—C2F—C3F—O3F	−64.2 (2)	C6F—C5F—C4F—O4F	52.4 (3)
C1F—C2F—C3F—O3F	175.65 (18)	O5F—C5F—C4F—C3F	59.0 (2)
O2F—C2F—C3F—C4F	170.05 (18)	C6F—C5F—C4F—C3F	178.6 (2)
C1F—C2F—C3F—C4F	49.9 (3)	O3F—C3F—C4F—O4F	−48.8 (3)
C1G—O5G—C5G—C6G	178.77 (19)	C2F—C3F—C4F—O4F	73.6 (2)
C1G—O5G—C5G—C4G	56.0 (2)	O3F—C3F—C4F—C5F	−174.79 (18)
O4G—C4G—C5G—O5G	−174.36 (17)	C2F—C3F—C4F—C5F	−52.4 (2)
C3G—C4G—C5G—O5G	−53.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2G—HO2G···O5F	0.82	1.95	2.763 (2)	169
O6G—HO6G···OW1	0.82	1.88	2.689 (3)	171
O4G—HO4G···O3F^i	0.82	2.26	3.077 (3)	173
O2F—HO2F···O3F^i	0.82	1.99	2.794 (3)	169
O3F—HO3F···OW2^ii	0.82	1.98	2.769 (3)	160
O4F—HO4F···O4G^iii	0.82	2.04	2.804 (3)	154
OW1—H1W1···OW2	0.96 (2)	1.89 (2)	2.850 (3)	175 (3)
OW1—H2W1···O2G^iv	0.96 (3)	2.00 (3)	2.938 (3)	168 (5)
OW2—H1W2···OW3	0.95 (3)	1.77 (3)	2.687 (4)	160 (3)
OW2—H2W2···O2F^v	0.96 (3)	1.98 (3)	2.918 (3)	166 (3)
OW3—H1W3···O6G^vi	0.95 (2)	1.79 (2)	2.719 (3)	162 (3)
OW3—H2W3···O1G^iv	0.95 (2)	2.24 (4)	3.054 (4)	143 (4)

Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+3/2, −y+1, z+1/2; (iii) x−1, y, z; (iv) x+1/2, −y+3/2, −z; (v) −x+5/2, −y+1, z−1/2; (vi) −x+3, y+1/2, −z−1/2.