Peracetyl­ated α-D-glucopyranosyl fluoride and peracetyl­ated α-maltosyl fluoride

The X-ray analyses of 2,3,4,6-tetra-O-acetyl-α-D-glucopyran­osyl fluoride, C₁₄H₁₉FO₉, (I), and the corresponding maltose derivative 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-D-glucopyran­osyl fluoride, C₂₆H₃₅FO₁₇, (II), are reported. These add to the series of published α-glyco­syl halide structures; those of the peracetyl­ated α-glucosyl chloride [James & Hall (1969). Acta Cryst. A25, S196] and bromide [Takai, Watanabe, Hayashi & Watanabe (1976). Bull. Fac. Eng. Hokkaido Univ. 79, 101–109] have been reported already. In our structures, which have been determined at 140 K, the glycopyranosyl ring appears in a regular ⁴C₁ chair conformation with all the substituents, except for the anomeric fluoride (which adopts an axial orientation), in equatorial positions. The observed bond lengths are consistent with a strong anomeric effect, viz. the C1—O5 (carbohydrate numbering) bond lengths are 1.381 (2) and 1.381 (3) Å in (I) and (II), respectively, both significantly shorter than the C5—O5 bond lengths, viz. 1.448 (2) Å in (I) and 1.444 (3) Å in (II).

S1. Comment

Glycosyl fluorides are widely used in carbohydrate chemistry and biochemistry. The F atom is comparable in size with a hydroxyl group, hence the steric demand upon introduction of this group is quite small (O'Hagan 2008; Howard et al., 1996). The popularity of glycosyl fluorides in chemical synthesis is due to their remarkable stability yet ease of chemospecific activation in performing glycosylation reactions. One notable advantage in using glycosyl fluorides as glycosyl donor is their high thermal stability compared with those of the glycosyl chlorides, bromides or iodides. The utilization of carbohydrate fluorides as glycosyl donors originates from the work by Mukaiyama et al. (1981) on the synthesis of simple glucosides and disaccharides. Progress made in the utilization of glycosyl fluorides as donors in the synthesis of O- and C-glycosides has been reported by Toshima (2000) and updated in the more recent review by Carmona et al. (2008). Interest in glycosyl fluorides has increased since Hayashi et al. (1984) developed a reliable and safe method to prepare these compounds by exposing suitably protected sugars to a 50–70% mixture of hydrogen fluoride in pyridine. The stability of glycosyl fluorides in their deprotected form also makes them important compounds for use as mechanistic probes in the elucidation of enzyme mechanisms and as reagents for enzymatic synthesis (reviewed by Williams & Withers, 2000). Extending our interest in the impact of fluorine substitution on carbohydrate biotransformations (Errey et al., 2009) and the generation of amylose mimetics (Marmuse et al., 2005; Nepogodiev et al., 2007; Clé et al., 2008), we had cause to investigate glucosyl fluorides. In this paper we report the crystal structures of the 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl fluoride, (I), and the corresponding maltose derivative 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl fluoride, (II). The crystal structures obtained integrate with the published series of α-glycosyl halide derivatives; X-ray structures of the peracetylated α-glucosyl chloride (James & Hall, 1969) and bromide (Takai et al., 1976) have been reported previously and the members of this series show most clearly the anomeric effect, where the preference for the axial orientation of the halogen atom renders synthesis of the equatorial counterpart a synthetic challenge. Results from X-ray analyses typically allow direct evaluation of the impact of the anomeric effect on sugar structure.

The glucosyl unit in (I) (Fig. 1) adopts a ⁴C₁ chair conformation. All the bond lengths and angles conform with the values found in acetylated glucose. Values for the bond lengths which are affected by the anomeric effect, with the results from X-ray crystal structures of other acetylated glucosyl halides, are summarized in Table 1. The conformational properties of pyranosyl halides have been explored by a number of theoretical studies using model compounds such as 2-fluorotetrahydropyran or 2-chlorotetrahydropyran. The theoretical approaches to generate three-dimensional structures rely on experimental data to generate the necessary set of parameters. In this context, good agreement was obtained by Tvaroska & Carver (1994) by comparison of their theoretical results with experimental ones obtained for the acetyl and benzoyl D-xylopyranose fluorides. To our knowledge, no crystal structure of anomeric aldohexosyl fluorides has been reported to date. The structural data reported herein are in agreement with the theoretical data obtained by Tvaroska & Carver (1994), supporting the theoretical methodology reported in their study.

Influences on the bond lengths in a series of X-ray crystal structures of glycopyranosides have been examined by Briggs et al. (1984). They concluded that there is no correlation between the electronegativity of the substituent at the anomeric position and the C5–O5 bond length. Comparison of C5—O5 bond lengths in the series of halo-derivatives given in Table 1 shows a similar lack of correlation. The C1—O5 bonds in the fluoro- and chloro-glucosides have similar values [1.381 (2) Å in the fluoride, 1.383 Å in the chloride and 1.381 (3) Å in the maltosyl fluoride]; the same bond is shorter in the glucosyl bromide (1.346 Å). Comparing the sugar-ring bond lengths in these halides with those in pentaacetyl-α-D-glucopyranose (Jones et al., 1982), it seems that the shortening of the C1—O5 bond is accompanied by a proportional lengthening of the C1—C2 and C3—C4 bonds. In contrast, the C2—C3, C4—C5 and C5—O5 bond lengths change little, with no apparent correlation with the C1—O5 bond lengths.

In the maltosyl fluoride structure, (II), both pyranose rings adopt a ⁴C₁ chair conformation (Fig. 2). It is interesting to observe in (II) the orientation of the contiguous pyranose rings, which is described by the torsion angles around the glycosidic bonds, C4—O4 and O4—C41, denoted as conformational angles Ψ and Φ (in (II), Ψ = H4—C4—O4—C41 = -29° and Φ = C4—O4—C41—H41 = -32°), and by the valence angle τ = C4—O4—C41, which is 116.66 (14)° in (II). All these values are in good agreement with those in β-maltose-octaacetate (Brisse et al., 1982) and -octapropanoate (Johnson et al., 2007) and conform closely with those in other maltose derivatives discussed by Johnson et al. (2007) in respect of having short chains containing an α-(1→4) inter-sugar glycosidic linkage, and are therefore useful as models to study starch structure. The twist of the non-reducing sugar ring is defined by the virtual torsion angle O44—C44···C41—O4; this, in compound (II), is -4.8° and, as such, if inserted in an amylose chain of starch (see, for example Takahashi & Nishikawa, 2003), would add to the bias of successive residues, forming a left-handed helix (French & Johnson, 2007).

Intermolecular interactions in crystals of both (I) and (II) are principally through weak hydrogen bonds. In (I), there are five contacts (four C—H···O and one C—H···F) in which the H···F/O distance is less than 2.55 Å. In (II), there are six interactions (five C—H···O and one C—H···F). In all these contacts, the angles subtended at the H atoms (in calculated sites) are greater than 137° and most are greater than 150°.

S2. Experimental

2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl fluoride, (I), and 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl fluoride, (II), were both obtained as single α-anomers (as judged by¹H NMR spectroscopy). They were prepared following known procedures (Juennemann et al., 1993), exposing the peracetylated glucose or maltose to a 70% mixture of hydrogen fluoride in pyridine in a Teflon bottle. The resulting products were purified by crystallization from a mixture of ethyl acetate and hexane [Solvent ratio?]. Crystals suitable for X-ray diffraction were obtained as colourless blocks in both cases by slow recrystallization from the same solvent system.

S3. Refinement

Since the anomalous scattering does not allow definitive determination of the absolute configurations in either of these compounds, the intensities of Friedel pairs were merged (using the MERG 3 command in SHELXL97; Sheldrick, 2008). The configurations were established since these compounds were prepared from α-D-glucose and α-D-maltose.

All H atoms were included in idealized positions, with C—H = 0.96–0.98 Å and with U_iso(H) = 1.5U_eq(C) for methyl groups or 1.2U_eq(C) otherwise. The methyl groups were refined as rigid groups rotating about the C—Me bond. In compound (I), three of the methyl groups showed disorder over alternative orientations, all of which were included as idealized methyl groups with two positions rotated by 60° from each other. These were allowed to rotate about the C—Me bond, and the site occupation factors of the two orientations refined to 0.25 (3):0.75 (3), 0.39 (2):0.61 (2) and 0.22 (2):0.78 (2) for the H atoms at C22, C42 and C62, respectively.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); 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: ORTEP (Johnson, 1976; Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the fully acetylated glucosyl fluoride, (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as white rods. The methyl groups of three of the acetyl groups were refined as disordered in two distinct orientations; only one arrangement for each is shown here.
	Fig. 2. The molecular structure of the fully acetylated maltosyl fluoride, (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as white rods.

(I) 2,3,4,6-tetra-O-acetyl-1-fluoro-α-D-glucopyranose

Crystal data

C14H19FO9	Z = 2
Mr = 350.29	F(000) = 368
Monoclinic, P21	Dx = 1.357 Mg m^−3
a = 5.35502 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.96182 (14) Å	µ = 0.12 mm^−1
c = 20.1151 (5) Å	T = 140 K
β = 92.061 (2)°	Plate, colourless
V = 857.06 (3) Å^3	0.55 × 0.31 × 0.11 mm

Data collection

Oxford Xcalibur 3 CCD area-detector diffractometer	2677 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2325 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 16.0050 pixels mm^-1	θmax = 30.0°, θmin = 3.3°
thin–slice ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −11→11
Tmin = 0.970, Tmax = 1.033	l = −28→28
24426 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0461P)^2] where P = (Fo^2 + 2Fc^2)/3
2677 reflections	(Δ/σ)max < 0.001
224 parameters	Δρmax = 0.22 e Å^−3
1 restraint	Δρmin = −0.14 e Å^−3

Special details

Experimental. CrysAlisPro RED (Oxford Diffraction Ltd., Version 1.171.32.24). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
C1	0.6033 (3)	0.0924 (2)	0.77495 (8)	0.0328 (4)
H1	0.6134	−0.0175	0.7969	0.039*
F1	0.35222 (18)	0.12992 (12)	0.76037 (5)	0.0404 (3)
C2	0.7110 (3)	0.2240 (2)	0.82211 (8)	0.0328 (4)
H2	0.8718	0.1842	0.8409	0.039*
O2	0.5423 (2)	0.2501 (2)	0.87516 (6)	0.0439 (3)
C21	0.5919 (3)	0.1744 (2)	0.93372 (8)	0.0318 (4)
O21	0.7746 (2)	0.0915 (2)	0.94472 (6)	0.0452 (3)
C22	0.3888 (4)	0.2075 (3)	0.98137 (10)	0.0472 (5)
H22A	0.2421	0.2465	0.9573	0.071*	0.25 (3)
H22B	0.4436	0.2914	1.0129	0.071*	0.25 (3)
H22C	0.3507	0.1057	1.0045	0.071*	0.25 (3)
H22D	0.4488	0.1825	1.0258	0.071*	0.75 (3)
H22E	0.2473	0.1376	0.9702	0.071*	0.75 (3)
H22F	0.3403	0.3234	0.9786	0.071*	0.75 (3)
C3	0.7486 (3)	0.3919 (2)	0.78877 (8)	0.0284 (3)
H3	0.5886	0.4499	0.7813	0.034*
O3	0.9140 (2)	0.48888 (16)	0.83218 (6)	0.0364 (3)
C31	0.8463 (3)	0.6464 (2)	0.84832 (8)	0.0306 (3)
O31	0.6465 (2)	0.70525 (15)	0.83370 (7)	0.0394 (3)
C32	1.0518 (3)	0.7312 (3)	0.88735 (10)	0.0458 (5)
H32A	0.9960	0.8395	0.9017	0.069*
H32B	1.1937	0.7446	0.8600	0.069*
H32C	1.0980	0.6642	0.9255	0.069*
C4	0.8793 (3)	0.36885 (18)	0.72381 (8)	0.0246 (3)
H4	1.0515	0.3313	0.7327	0.029*
O4	0.8793 (2)	0.53069 (13)	0.69203 (6)	0.0287 (2)
C41	1.1004 (3)	0.5908 (2)	0.67263 (8)	0.0292 (3)
O41	1.2878 (2)	0.51069 (18)	0.67489 (8)	0.0493 (4)
C42	1.0749 (4)	0.7672 (2)	0.64776 (10)	0.0412 (4)
H42A	0.9049	0.7874	0.6332	0.062*	0.39 (2)
H42B	1.1827	0.7836	0.6112	0.062*	0.39 (2)
H42C	1.1209	0.8440	0.6829	0.062*	0.39 (2)
H42D	1.2341	0.8226	0.6517	0.062*	0.61 (2)
H42E	0.9563	0.8264	0.6737	0.062*	0.61 (2)
H42F	1.0181	0.7660	0.6020	0.062*	0.61 (2)
C5	0.7405 (3)	0.24153 (19)	0.68033 (8)	0.0250 (3)
H5	0.5703	0.2814	0.6701	0.030*
O5	0.7315 (2)	0.08485 (13)	0.71669 (6)	0.0297 (2)
C6	0.8690 (3)	0.20300 (19)	0.61687 (7)	0.0265 (3)
H6A	0.8979	0.3053	0.5921	0.032*
H6B	1.0283	0.1485	0.6263	0.032*
O6	0.7027 (2)	0.09256 (14)	0.57958 (5)	0.0288 (2)
C61	0.7852 (3)	0.0334 (2)	0.52204 (8)	0.0276 (3)
O61	0.9860 (2)	0.06861 (17)	0.50114 (7)	0.0382 (3)
C62	0.5989 (3)	−0.0825 (2)	0.48918 (10)	0.0385 (4)
H62A	0.4429	−0.0743	0.5110	0.058*	0.78 (2)
H62B	0.6596	−0.1958	0.4922	0.058*	0.78 (2)
H62C	0.5747	−0.0519	0.4432	0.058*	0.78 (2)
H62D	0.6752	−0.1404	0.4533	0.058*	0.22 (2)
H62E	0.4585	−0.0188	0.4721	0.058*	0.22 (2)
H62F	0.5434	−0.1628	0.5211	0.058*	0.22 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0315 (8)	0.0285 (7)	0.0386 (9)	0.0109 (7)	0.0070 (7)	0.0106 (7)
F1	0.0291 (5)	0.0380 (6)	0.0544 (6)	0.0062 (4)	0.0055 (4)	0.0086 (5)
C2	0.0296 (8)	0.0422 (9)	0.0269 (8)	0.0180 (7)	0.0070 (6)	0.0088 (7)
O2	0.0376 (7)	0.0600 (8)	0.0348 (6)	0.0242 (7)	0.0123 (5)	0.0101 (6)
C21	0.0328 (8)	0.0379 (9)	0.0248 (8)	−0.0023 (7)	0.0019 (6)	−0.0062 (7)
O21	0.0443 (7)	0.0622 (9)	0.0293 (6)	0.0149 (7)	0.0041 (5)	0.0091 (6)
C22	0.0421 (10)	0.0666 (14)	0.0337 (9)	0.0012 (10)	0.0106 (8)	−0.0074 (9)
C3	0.0265 (8)	0.0309 (8)	0.0276 (8)	0.0115 (6)	−0.0032 (6)	−0.0016 (6)
O3	0.0327 (6)	0.0418 (7)	0.0341 (7)	0.0161 (5)	−0.0090 (5)	−0.0094 (5)
C31	0.0312 (8)	0.0341 (8)	0.0271 (7)	0.0057 (7)	0.0091 (6)	−0.0011 (6)
O31	0.0320 (7)	0.0313 (6)	0.0548 (8)	0.0084 (5)	0.0026 (6)	−0.0022 (6)
C32	0.0370 (10)	0.0552 (12)	0.0453 (11)	0.0017 (9)	0.0042 (8)	−0.0140 (10)
C4	0.0229 (7)	0.0229 (7)	0.0277 (8)	0.0089 (6)	−0.0009 (6)	0.0031 (6)
O4	0.0280 (6)	0.0220 (5)	0.0360 (6)	0.0089 (4)	0.0012 (5)	0.0046 (5)
C41	0.0321 (8)	0.0234 (7)	0.0319 (8)	0.0033 (7)	−0.0012 (6)	−0.0018 (6)
O41	0.0285 (7)	0.0420 (8)	0.0778 (10)	0.0092 (6)	0.0066 (6)	0.0190 (7)
C42	0.0498 (11)	0.0242 (8)	0.0502 (11)	0.0055 (8)	0.0086 (8)	0.0030 (7)
C5	0.0259 (7)	0.0209 (6)	0.0280 (7)	0.0061 (6)	−0.0002 (6)	0.0047 (6)
O5	0.0340 (6)	0.0216 (5)	0.0340 (6)	0.0078 (5)	0.0069 (4)	0.0058 (5)
C6	0.0266 (7)	0.0236 (7)	0.0293 (8)	0.0014 (6)	−0.0001 (6)	−0.0008 (6)
O6	0.0259 (5)	0.0302 (5)	0.0302 (6)	0.0003 (5)	0.0016 (4)	−0.0039 (5)
C61	0.0277 (8)	0.0251 (7)	0.0300 (8)	0.0052 (6)	−0.0008 (6)	−0.0004 (6)
O61	0.0314 (6)	0.0462 (7)	0.0375 (6)	−0.0051 (5)	0.0073 (5)	−0.0074 (5)
C62	0.0311 (9)	0.0428 (10)	0.0416 (10)	−0.0030 (8)	0.0021 (7)	−0.0122 (8)

Geometric parameters (Å, º)

C1—O5	1.381 (2)	C4—C5	1.516 (2)
C1—F1	1.3981 (19)	C4—H4	0.9800
C1—C2	1.514 (3)	O4—C41	1.348 (2)
C1—H1	0.9800	C41—O41	1.188 (2)
C2—O2	1.4378 (19)	C41—C42	1.496 (2)
C2—C3	1.512 (2)	C42—H42A	0.9600
C2—H2	0.9800	C42—H42B	0.9600
O2—C21	1.341 (2)	C42—H42C	0.9600
C21—O21	1.194 (2)	C42—H42D	0.9600
C21—C22	1.499 (2)	C42—H42E	0.9600
C22—H22A	0.9600	C42—H42F	0.9600
C22—H22B	0.9600	C5—O5	1.4477 (18)
C22—H22C	0.9600	C5—C6	1.503 (2)
C22—H22D	0.9600	C5—H5	0.9800
C22—H22E	0.9600	C6—O6	1.4424 (18)
C22—H22F	0.9600	C6—H6A	0.9700
C3—O3	1.445 (2)	C6—H6B	0.9700
C3—C4	1.515 (2)	O6—C61	1.339 (2)
C3—H3	0.9800	C61—O61	1.202 (2)
O3—C31	1.348 (2)	C61—C62	1.495 (2)
C31—O31	1.195 (2)	C62—H62A	0.9600
C31—C32	1.490 (3)	C62—H62B	0.9600
C32—H32A	0.9600	C62—H62C	0.9600
C32—H32B	0.9600	C62—H62D	0.9600
C32—H32C	0.9600	C62—H62E	0.9600
C4—O4	1.4384 (18)	C62—H62F	0.9600
O5—C1—F1	109.58 (13)	O41—C41—C42	125.72 (17)
O5—C1—C2	111.84 (14)	O4—C41—C42	111.08 (14)
F1—C1—C2	108.98 (13)	C41—C42—H42A	109.5
O5—C1—H1	108.8	C41—C42—H42B	109.5
F1—C1—H1	108.8	H42A—C42—H42B	109.5
C2—C1—H1	108.8	C41—C42—H42C	109.5
O2—C2—C3	107.38 (14)	H42A—C42—H42C	109.5
O2—C2—C1	109.25 (15)	H42B—C42—H42C	109.5
C3—C2—C1	112.83 (13)	C41—C42—H42D	109.5
O2—C2—H2	109.1	H42A—C42—H42D	141.1
C3—C2—H2	109.1	H42B—C42—H42D	56.3
C1—C2—H2	109.1	H42C—C42—H42D	56.3
C21—O2—C2	118.48 (13)	C41—C42—H42E	109.5
O21—C21—O2	123.11 (15)	H42A—C42—H42E	56.3
O21—C21—C22	125.95 (17)	H42B—C42—H42E	141.1
O2—C21—C22	110.93 (16)	H42C—C42—H42E	56.3
C21—C22—H22A	109.5	H42D—C42—H42E	109.5
C21—C22—H22B	109.5	C41—C42—H42F	109.5
H22A—C22—H22B	109.5	H42A—C42—H42F	56.3
C21—C22—H22C	109.5	H42B—C42—H42F	56.3
H22A—C22—H22C	109.5	H42C—C42—H42F	141.1
H22B—C22—H22C	109.5	H42D—C42—H42F	109.5
C21—C22—H22D	109.5	H42E—C42—H42F	109.5
H22A—C22—H22D	141.1	O5—C5—C6	106.12 (12)
H22B—C22—H22D	56.3	O5—C5—C4	108.02 (11)
H22C—C22—H22D	56.3	C6—C5—C4	113.36 (13)
C21—C22—H22E	109.5	O5—C5—H5	109.7
H22A—C22—H22E	56.3	C6—C5—H5	109.7
H22B—C22—H22E	141.1	C4—C5—H5	109.7
H22C—C22—H22E	56.3	C1—O5—C5	114.70 (12)
H22D—C22—H22E	109.5	O6—C6—C5	105.85 (12)
C21—C22—H22F	109.5	O6—C6—H6A	110.6
H22A—C22—H22F	56.3	C5—C6—H6A	110.6
H22B—C22—H22F	56.3	O6—C6—H6B	110.6
H22C—C22—H22F	141.1	C5—C6—H6B	110.6
H22D—C22—H22F	109.5	H6A—C6—H6B	108.7
H22E—C22—H22F	109.5	C61—O6—C6	116.57 (12)
O3—C3—C2	107.03 (13)	O61—C61—O6	123.18 (15)
O3—C3—C4	107.09 (13)	O61—C61—C62	125.47 (16)
C2—C3—C4	110.39 (13)	O6—C61—C62	111.33 (14)
O3—C3—H3	110.7	C61—C62—H62A	109.5
C2—C3—H3	110.7	C61—C62—H62B	109.5
C4—C3—H3	110.7	H62A—C62—H62B	109.5
C31—O3—C3	118.57 (13)	C61—C62—H62C	109.5
O31—C31—O3	123.49 (16)	H62A—C62—H62C	109.5
O31—C31—C32	126.11 (17)	H62B—C62—H62C	109.5
O3—C31—C32	110.39 (15)	C61—C62—H62D	109.5
C31—C32—H32A	109.5	H62A—C62—H62D	141.1
C31—C32—H32B	109.5	H62B—C62—H62D	56.3
H32A—C32—H32B	109.5	H62C—C62—H62D	56.3
C31—C32—H32C	109.5	C61—C62—H62E	109.5
H32A—C32—H32C	109.5	H62A—C62—H62E	56.3
H32B—C32—H32C	109.5	H62B—C62—H62E	141.1
O4—C4—C3	106.38 (12)	H62C—C62—H62E	56.3
O4—C4—C5	110.52 (11)	H62D—C62—H62E	109.5
C3—C4—C5	110.27 (13)	C61—C62—H62F	109.5
O4—C4—H4	109.9	H62A—C62—H62F	56.3
C3—C4—H4	109.9	H62B—C62—H62F	56.3
C5—C4—H4	109.9	H62C—C62—H62F	141.1
C41—O4—C4	117.43 (12)	H62D—C62—H62F	109.5
O41—C41—O4	123.20 (15)	H62E—C62—H62F	109.5
O5—C1—C2—O2	168.42 (12)	C2—C3—C4—C5	53.23 (16)
F1—C1—C2—O2	47.11 (17)	C3—C4—O4—C41	127.16 (14)
O5—C1—C2—C3	49.06 (17)	C5—C4—O4—C41	−113.13 (14)
F1—C1—C2—C3	−72.25 (16)	C4—O4—C41—O41	7.2 (2)
C3—C2—O2—C21	−137.54 (16)	C4—O4—C41—C42	−173.47 (14)
C1—C2—O2—C21	99.78 (17)	O4—C4—C5—O5	−176.06 (12)
C2—O2—C21—O21	3.0 (3)	C3—C4—C5—O5	−58.72 (15)
C2—O2—C21—C22	−176.58 (17)	O4—C4—C5—C6	66.65 (15)
O2—C2—C3—O3	75.69 (16)	C3—C4—C5—C6	−176.01 (13)
C1—C2—C3—O3	−163.87 (13)	F1—C1—O5—C5	63.56 (18)
O2—C2—C3—C4	−168.09 (13)	C2—C1—O5—C5	−57.40 (16)
C1—C2—C3—C4	−47.66 (18)	C6—C5—O5—C1	−175.67 (13)
C2—C3—O3—C31	−129.48 (15)	C4—C5—O5—C1	62.46 (16)
C4—C3—O3—C31	112.13 (15)	O5—C5—C6—O6	66.43 (14)
C3—O3—C31—O31	7.1 (2)	C4—C5—C6—O6	−175.17 (11)
C3—O3—C31—C32	−174.11 (15)	C5—C6—O6—C61	−176.41 (12)
O3—C3—C4—O4	−70.72 (14)	C6—O6—C61—O61	−0.2 (2)
C2—C3—C4—O4	173.10 (13)	C6—O6—C61—C62	178.56 (13)
O3—C3—C4—C5	169.42 (11)

(II) 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→ 4)-2,3,6-tri-O-acetyl-1-fluoro-α-D-glucopyranose

Crystal data

C26H35FO17	Z = 2
Mr = 638.54	F(000) = 672
Monoclinic, P21	Dx = 1.392 Mg m^−3
a = 5.63832 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 18.2908 (3) Å	µ = 0.12 mm^−1
c = 14.8144 (2) Å	T = 140 K
β = 94.4966 (15)°	Prism, colourless
V = 1523.09 (4) Å^3	0.42 × 0.37 × 0.14 mm

Data collection

Oxford Xcalibur 3 CCD area-detector diffractometer	4545 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3785 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 16.0050 pixels mm^-1	θmax = 30.0°, θmin = 3.6°
thin slice ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −25→25
Tmin = 0.923, Tmax = 1.070	l = −20→20
40401 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0679P)^2 + 0.1222P] where P = (Fo^2 + 2Fc^2)/3
4545 reflections	(Δ/σ)max < 0.001
404 parameters	Δρmax = 0.70 e Å^−3
1 restraint	Δρmin = −0.46 e Å^−3

Special details

Experimental. CrysAlisPro RED (Oxford Diffraction Ltd., Version 1.171.32.24). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.8543 (5)	0.75932 (16)	0.47776 (19)	0.0281 (6)
H1	0.8815	0.8013	0.5184	0.034*
F1	1.0726 (3)	0.72718 (10)	0.46416 (12)	0.0326 (4)
C2	0.7013 (5)	0.70408 (16)	0.52227 (17)	0.0258 (5)
H2	0.5584	0.7282	0.5414	0.031*
O2	0.8410 (4)	0.67711 (14)	0.60025 (12)	0.0344 (5)
C21	0.7528 (6)	0.6813 (2)	0.68088 (19)	0.0359 (7)
O21	0.5548 (6)	0.6998 (3)	0.69031 (19)	0.0815 (12)
C22	0.9284 (6)	0.6531 (2)	0.7536 (2)	0.0443 (8)
H22A	0.9142	0.6009	0.7577	0.066*
H22B	0.8970	0.6748	0.8105	0.066*
H22C	1.0865	0.6656	0.7394	0.066*
C3	0.6293 (4)	0.64091 (14)	0.45845 (16)	0.0202 (5)
H3	0.7656	0.6088	0.4509	0.024*
O3	0.4392 (3)	0.60079 (11)	0.49598 (12)	0.0253 (4)
C31	0.4958 (5)	0.54205 (19)	0.5482 (2)	0.0341 (7)
O31	0.6948 (4)	0.51879 (16)	0.5608 (2)	0.0550 (8)
C32	0.2820 (6)	0.5108 (2)	0.5865 (3)	0.0489 (9)
H32A	0.2053	0.5479	0.6196	0.073*
H32B	0.3289	0.4711	0.6264	0.073*
H32C	0.1736	0.4931	0.5381	0.073*
C4	0.5274 (4)	0.67022 (14)	0.36663 (16)	0.0202 (5)
H4	0.3700	0.6917	0.3722	0.024*
O4	0.5111 (3)	0.61181 (10)	0.30199 (11)	0.0204 (3)
C5	0.6943 (5)	0.72693 (14)	0.32998 (17)	0.0238 (5)
H5	0.8418	0.7028	0.3154	0.029*
O5	0.7499 (4)	0.78380 (10)	0.39587 (13)	0.0292 (4)
C6	0.5868 (5)	0.76593 (16)	0.24753 (19)	0.0296 (6)
H6A	0.7000	0.8004	0.2259	0.035*
H6B	0.5443	0.7311	0.1996	0.035*
O6	0.3775 (4)	0.80396 (12)	0.27250 (15)	0.0355 (5)
C61	0.3229 (6)	0.86492 (18)	0.2293 (3)	0.0429 (8)
O61	0.4214 (7)	0.8825 (2)	0.1631 (3)	0.1068 (17)
C62	0.1211 (6)	0.90479 (18)	0.2675 (2)	0.0392 (7)
H62A	0.0221	0.9265	0.2190	0.059*
H62B	0.1832	0.9424	0.3080	0.059*
H62C	0.0287	0.8710	0.2999	0.059*
C41	0.2934 (4)	0.57372 (15)	0.29205 (17)	0.0218 (5)
H41	0.2211	0.5732	0.3501	0.026*
C42	0.3466 (4)	0.49612 (14)	0.26440 (17)	0.0217 (5)
H42	0.2009	0.4667	0.2615	0.026*
O42	0.5249 (3)	0.46378 (11)	0.32721 (13)	0.0287 (4)
C421	0.4574 (5)	0.41221 (18)	0.3840 (2)	0.0372 (7)
O421	0.2547 (5)	0.3998 (2)	0.3934 (3)	0.0928 (15)
C422	0.6667 (6)	0.3744 (2)	0.4311 (3)	0.0450 (9)
H42A	0.7975	0.4080	0.4392	0.067*
H42B	0.7115	0.3337	0.3951	0.067*
H42C	0.6258	0.3571	0.4890	0.067*
C43	0.4525 (4)	0.49523 (13)	0.17340 (18)	0.0210 (5)
H43	0.6088	0.5190	0.1786	0.025*
O43	0.4777 (3)	0.41974 (10)	0.14757 (14)	0.0264 (4)
C431	0.7009 (5)	0.39281 (16)	0.1475 (2)	0.0267 (6)
O431	0.8748 (3)	0.42949 (12)	0.15643 (17)	0.0374 (5)
C432	0.6975 (6)	0.31181 (19)	0.1342 (4)	0.0558 (11)
H43A	0.6128	0.2893	0.1806	0.084*
H43B	0.8577	0.2937	0.1376	0.084*
H43C	0.6198	0.3004	0.0759	0.084*
C44	0.2902 (4)	0.53365 (14)	0.10220 (17)	0.0210 (5)
H44	0.1508	0.5036	0.0840	0.025*
O44	0.4317 (3)	0.54654 (11)	0.02680 (12)	0.0259 (4)
C441	0.3355 (5)	0.53338 (15)	−0.05887 (18)	0.0265 (5)
O441	0.1375 (4)	0.51048 (12)	−0.07524 (14)	0.0335 (5)
C442	0.5070 (6)	0.55528 (18)	−0.1255 (2)	0.0359 (7)
H44A	0.6585	0.5329	−0.1095	0.054*
H44B	0.5246	0.6075	−0.1249	0.054*
H44C	0.4485	0.5396	−0.1849	0.054*
C45	0.2157 (5)	0.60876 (15)	0.13594 (17)	0.0220 (5)
H45	0.3523	0.6419	0.1368	0.026*
O45	0.1328 (3)	0.60589 (11)	0.22489 (12)	0.0243 (4)
C46	0.0165 (5)	0.63951 (14)	0.07376 (19)	0.0277 (6)
H46A	0.0434	0.6285	0.0113	0.033*
H46B	−0.1335	0.6177	0.0872	0.033*
O46	0.0076 (4)	0.71792 (10)	0.08672 (13)	0.0304 (4)
C461	−0.1296 (6)	0.75321 (17)	0.02403 (19)	0.0357 (7)
O461	−0.2391 (7)	0.72173 (15)	−0.0365 (2)	0.0771 (11)
C462	−0.1235 (8)	0.83421 (17)	0.0351 (2)	0.0427 (8)
H46C	−0.2457	0.8490	0.0728	0.064*
H46D	−0.1498	0.8571	−0.0232	0.064*
H46E	0.0290	0.8487	0.0627	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0276 (14)	0.0277 (14)	0.0291 (13)	0.0017 (11)	0.0043 (11)	−0.0114 (11)
F1	0.0252 (8)	0.0353 (9)	0.0379 (9)	0.0000 (7)	0.0064 (7)	−0.0088 (8)
C2	0.0250 (13)	0.0333 (14)	0.0194 (11)	0.0047 (11)	0.0045 (10)	−0.0066 (10)
O2	0.0320 (10)	0.0530 (13)	0.0183 (8)	0.0091 (10)	0.0020 (7)	−0.0066 (9)
C21	0.0380 (16)	0.0502 (19)	0.0206 (12)	−0.0040 (14)	0.0102 (11)	−0.0032 (13)
O21	0.0615 (18)	0.151 (4)	0.0347 (13)	0.028 (2)	0.0206 (13)	0.0108 (18)
C22	0.0487 (19)	0.060 (2)	0.0231 (14)	−0.0130 (17)	−0.0022 (13)	0.0018 (14)
C3	0.0187 (11)	0.0259 (12)	0.0164 (10)	0.0011 (9)	0.0031 (9)	0.0005 (9)
O3	0.0186 (8)	0.0363 (11)	0.0214 (8)	−0.0003 (8)	0.0035 (7)	0.0042 (8)
C31	0.0278 (14)	0.0475 (18)	0.0266 (13)	−0.0048 (13)	−0.0005 (11)	0.0146 (13)
O31	0.0283 (12)	0.0648 (18)	0.0713 (17)	0.0044 (11)	−0.0002 (11)	0.0437 (15)
C32	0.0353 (17)	0.068 (3)	0.0439 (18)	−0.0107 (17)	0.0060 (14)	0.0234 (18)
C4	0.0194 (11)	0.0235 (12)	0.0182 (11)	0.0035 (9)	0.0041 (9)	−0.0016 (9)
O4	0.0196 (8)	0.0236 (9)	0.0182 (8)	−0.0037 (7)	0.0033 (6)	−0.0019 (7)
C5	0.0282 (13)	0.0206 (12)	0.0236 (12)	−0.0003 (10)	0.0085 (10)	−0.0035 (10)
O5	0.0385 (11)	0.0223 (9)	0.0269 (9)	−0.0004 (8)	0.0046 (8)	−0.0065 (8)
C6	0.0413 (16)	0.0239 (13)	0.0246 (13)	−0.0029 (11)	0.0090 (12)	0.0005 (11)
O6	0.0418 (12)	0.0288 (11)	0.0368 (11)	0.0029 (9)	0.0086 (9)	0.0100 (9)
C61	0.0418 (18)	0.0295 (16)	0.058 (2)	−0.0048 (13)	0.0052 (16)	0.0131 (15)
O61	0.100 (3)	0.085 (3)	0.146 (4)	0.042 (2)	0.072 (3)	0.080 (3)
C62	0.0417 (17)	0.0272 (15)	0.0471 (18)	−0.0009 (13)	−0.0063 (14)	−0.0010 (14)
C41	0.0169 (11)	0.0285 (13)	0.0198 (11)	−0.0044 (9)	0.0007 (9)	0.0073 (10)
C42	0.0172 (11)	0.0217 (12)	0.0251 (12)	−0.0037 (9)	−0.0049 (9)	0.0088 (10)
O42	0.0242 (9)	0.0289 (10)	0.0314 (10)	−0.0056 (8)	−0.0074 (8)	0.0153 (8)
C421	0.0281 (15)	0.0391 (17)	0.0438 (17)	−0.0019 (12)	−0.0002 (12)	0.0253 (14)
O421	0.0295 (13)	0.139 (3)	0.109 (3)	−0.0079 (16)	0.0017 (15)	0.102 (3)
C422	0.0337 (16)	0.0413 (18)	0.058 (2)	0.0005 (14)	−0.0107 (15)	0.0300 (16)
C43	0.0167 (11)	0.0160 (11)	0.0299 (13)	−0.0022 (9)	−0.0010 (9)	0.0042 (9)
O43	0.0186 (8)	0.0199 (9)	0.0399 (11)	−0.0027 (7)	−0.0028 (8)	−0.0003 (8)
C431	0.0226 (13)	0.0241 (13)	0.0335 (14)	−0.0009 (10)	0.0022 (11)	0.0024 (11)
O431	0.0202 (10)	0.0368 (12)	0.0553 (14)	−0.0052 (9)	0.0050 (9)	−0.0040 (10)
C432	0.0328 (17)	0.0274 (16)	0.109 (4)	0.0034 (13)	0.017 (2)	0.000 (2)
C44	0.0202 (11)	0.0210 (11)	0.0214 (11)	−0.0040 (9)	−0.0017 (9)	0.0053 (10)
O44	0.0254 (9)	0.0299 (10)	0.0223 (9)	−0.0083 (8)	0.0011 (7)	0.0016 (8)
C441	0.0331 (14)	0.0218 (13)	0.0239 (12)	0.0012 (11)	−0.0012 (11)	0.0026 (10)
O441	0.0347 (11)	0.0353 (11)	0.0291 (10)	−0.0050 (9)	−0.0057 (8)	−0.0027 (9)
C442	0.0465 (18)	0.0359 (17)	0.0258 (14)	−0.0043 (14)	0.0057 (12)	0.0027 (12)
C45	0.0239 (11)	0.0199 (11)	0.0214 (11)	−0.0034 (10)	−0.0036 (9)	0.0051 (9)
O45	0.0183 (8)	0.0274 (10)	0.0268 (9)	0.0007 (7)	−0.0004 (7)	0.0041 (8)
C46	0.0323 (14)	0.0178 (12)	0.0309 (14)	0.0007 (10)	−0.0113 (11)	0.0016 (10)
O46	0.0460 (12)	0.0184 (9)	0.0253 (9)	0.0029 (8)	−0.0080 (8)	0.0014 (7)
C461	0.059 (2)	0.0237 (14)	0.0227 (13)	0.0088 (13)	−0.0065 (13)	0.0033 (11)
O461	0.122 (3)	0.0328 (14)	0.0649 (18)	0.0213 (16)	−0.0638 (19)	−0.0080 (13)
C462	0.079 (3)	0.0221 (14)	0.0269 (14)	0.0086 (15)	0.0037 (15)	0.0032 (12)

Geometric parameters (Å, º)

C1—O5	1.381 (3)	C41—H41	0.9800
C1—F1	1.393 (3)	C42—O42	1.442 (3)
C1—C2	1.513 (4)	C42—C43	1.517 (4)
C1—H1	0.9800	C42—H42	0.9800
C2—O2	1.434 (3)	O42—C421	1.339 (3)
C2—C3	1.527 (4)	C421—O421	1.184 (4)
C2—H2	0.9800	C421—C422	1.493 (4)
O2—C21	1.332 (3)	C422—H42A	0.9600
C21—O21	1.185 (4)	C422—H42B	0.9600
C21—C22	1.496 (5)	C422—H42C	0.9600
C22—H22A	0.9600	C43—O43	1.443 (3)
C22—H22B	0.9600	C43—C44	1.514 (3)
C22—H22C	0.9600	C43—H43	0.9800
C3—O3	1.446 (3)	O43—C431	1.352 (3)
C3—C4	1.532 (3)	C431—O431	1.187 (3)
C3—H3	0.9800	C431—C432	1.495 (4)
O3—C31	1.348 (4)	C432—H43A	0.9600
C31—O31	1.201 (4)	C432—H43B	0.9600
C31—C32	1.486 (4)	C432—H43C	0.9600
C32—H32A	0.9600	C44—O44	1.442 (3)
C32—H32B	0.9600	C44—C45	1.532 (4)
C32—H32C	0.9600	C44—H44	0.9800
C4—O4	1.433 (3)	O44—C441	1.362 (3)
C4—C5	1.529 (4)	C441—O441	1.200 (3)
C4—H4	0.9800	C441—C442	1.489 (4)
O4—C41	1.409 (3)	C442—H44A	0.9600
C5—O5	1.444 (3)	C442—H44B	0.9600
C5—C6	1.501 (4)	C442—H44C	0.9600
C5—H5	0.9800	C45—O45	1.433 (3)
C6—O6	1.443 (4)	C45—C46	1.505 (4)
C6—H6A	0.9700	C45—H45	0.9800
C6—H6B	0.9700	C46—O46	1.448 (3)
O6—C61	1.310 (4)	C46—H46A	0.9700
C61—O61	1.209 (5)	C46—H46B	0.9700
C61—C62	1.499 (5)	O46—C461	1.329 (3)
C62—H62A	0.9600	C461—O461	1.196 (4)
C62—H62B	0.9600	C461—C462	1.491 (4)
C62—H62C	0.9600	C462—H46C	0.9600
C41—O45	1.420 (3)	C462—H46D	0.9600
C41—C42	1.514 (4)	C462—H46E	0.9600
O5—C1—F1	109.3 (2)	C42—C41—H41	109.4
O5—C1—C2	112.4 (2)	O42—C42—C41	110.7 (2)
F1—C1—C2	108.8 (2)	O42—C42—C43	105.4 (2)
O5—C1—H1	108.8	C41—C42—C43	110.5 (2)
F1—C1—H1	108.8	O42—C42—H42	110.0
C2—C1—H1	108.8	C41—C42—H42	110.0
O2—C2—C1	106.6 (2)	C43—C42—H42	110.0
O2—C2—C3	109.9 (2)	C421—O42—C42	118.5 (2)
C1—C2—C3	111.6 (2)	O421—C421—O42	122.2 (3)
O2—C2—H2	109.6	O421—C421—C422	126.2 (3)
C1—C2—H2	109.6	O42—C421—C422	111.5 (3)
C3—C2—H2	109.6	C421—C422—H42A	109.5
C21—O2—C2	118.9 (2)	C421—C422—H42B	109.5
O21—C21—O2	122.9 (3)	H42A—C422—H42B	109.5
O21—C21—C22	126.1 (3)	C421—C422—H42C	109.5
O2—C21—C22	110.7 (3)	H42A—C422—H42C	109.5
C21—C22—H22A	109.5	H42B—C422—H42C	109.5
C21—C22—H22B	109.5	O43—C43—C44	109.0 (2)
H22A—C22—H22B	109.5	O43—C43—C42	107.4 (2)
C21—C22—H22C	109.5	C44—C43—C42	110.8 (2)
H22A—C22—H22C	109.5	O43—C43—H43	109.8
H22B—C22—H22C	109.5	C44—C43—H43	109.8
O3—C3—C2	108.4 (2)	C42—C43—H43	109.8
O3—C3—C4	106.32 (19)	C431—O43—C43	117.4 (2)
C2—C3—C4	110.4 (2)	O431—C431—O43	123.7 (3)
O3—C3—H3	110.6	O431—C431—C432	125.2 (3)
C2—C3—H3	110.6	O43—C431—C432	111.0 (2)
C4—C3—H3	110.6	C431—C432—H43A	109.5
C31—O3—C3	118.4 (2)	C431—C432—H43B	109.5
O31—C31—O3	123.2 (3)	H43A—C432—H43B	109.5
O31—C31—C32	125.5 (3)	C431—C432—H43C	109.5
O3—C31—C32	111.3 (3)	H43A—C432—H43C	109.5
C31—C32—H32A	109.5	H43B—C432—H43C	109.5
C31—C32—H32B	109.5	O44—C44—C43	105.93 (19)
H32A—C32—H32B	109.5	O44—C44—C45	106.77 (19)
C31—C32—H32C	109.5	C43—C44—C45	110.8 (2)
H32A—C32—H32C	109.5	O44—C44—H44	111.1
H32B—C32—H32C	109.5	C43—C44—H44	111.1
O4—C4—C5	106.10 (18)	C45—C44—H44	111.1
O4—C4—C3	109.4 (2)	C441—O44—C44	119.3 (2)
C5—C4—C3	110.7 (2)	O441—C441—O44	123.1 (3)
O4—C4—H4	110.2	O441—C441—C442	127.0 (3)
C5—C4—H4	110.2	O44—C441—C442	109.8 (2)
C3—C4—H4	110.2	C441—C442—H44A	109.5
C41—O4—C4	116.61 (19)	C441—C442—H44B	109.5
O5—C5—C6	105.1 (2)	H44A—C442—H44B	109.5
O5—C5—C4	110.84 (19)	C441—C442—H44C	109.5
C6—C5—C4	113.0 (2)	H44A—C442—H44C	109.5
O5—C5—H5	109.3	H44B—C442—H44C	109.5
C6—C5—H5	109.3	O45—C45—C46	107.1 (2)
C4—C5—H5	109.3	O45—C45—C44	112.6 (2)
C1—O5—C5	114.5 (2)	C46—C45—C44	110.2 (2)
O6—C6—C5	107.9 (2)	O45—C45—H45	108.9
O6—C6—H6A	110.1	C46—C45—H45	108.9
C5—C6—H6A	110.1	C44—C45—H45	108.9
O6—C6—H6B	110.1	C41—O45—C45	115.04 (19)
C5—C6—H6B	110.1	O46—C46—C45	108.7 (2)
H6A—C6—H6B	108.4	O46—C46—H46A	109.9
C61—O6—C6	116.8 (2)	C45—C46—H46A	109.9
O61—C61—O6	121.1 (3)	O46—C46—H46B	109.9
O61—C61—C62	126.0 (3)	C45—C46—H46B	109.9
O6—C61—C62	112.7 (3)	H46A—C46—H46B	108.3
C61—C62—H62A	109.5	C461—O46—C46	114.4 (2)
C61—C62—H62B	109.5	O461—C461—O46	121.9 (3)
H62A—C62—H62B	109.5	O461—C461—C462	124.6 (3)
C61—C62—H62C	109.5	O46—C461—C462	113.5 (3)
H62A—C62—H62C	109.5	C461—C462—H46C	109.5
H62B—C62—H62C	109.5	C461—C462—H46D	109.5
O4—C41—O45	111.8 (2)	H46C—C462—H46D	109.5
O4—C41—C42	107.6 (2)	C461—C462—H46E	109.5
O45—C41—C42	109.1 (2)	H46C—C462—H46E	109.5
O4—C41—H41	109.4	H46D—C462—H46E	109.5
O45—C41—H41	109.4
O5—C1—C2—O2	173.4 (2)	O4—C41—C42—O42	53.6 (3)
F1—C1—C2—O2	52.2 (3)	O45—C41—C42—O42	175.12 (19)
O5—C1—C2—C3	53.4 (3)	O4—C41—C42—C43	−62.8 (2)
F1—C1—C2—C3	−67.8 (3)	O45—C41—C42—C43	58.7 (2)
C1—C2—O2—C21	125.0 (3)	C41—C42—O42—C421	107.7 (3)
C3—C2—O2—C21	−113.9 (3)	C43—C42—O42—C421	−132.8 (3)
C2—O2—C21—O21	7.5 (5)	C42—O42—C421—O421	−11.0 (6)
C2—O2—C21—C22	−177.8 (3)	C42—O42—C421—C422	168.8 (3)
O2—C2—C3—O3	76.1 (2)	O42—C42—C43—O43	65.7 (2)
C1—C2—C3—O3	−165.9 (2)	C41—C42—C43—O43	−174.72 (18)
O2—C2—C3—C4	−167.9 (2)	O42—C42—C43—C44	−175.3 (2)
C1—C2—C3—C4	−49.9 (3)	C41—C42—C43—C44	−55.7 (3)
C2—C3—O3—C31	−94.0 (3)	C44—C43—O43—C431	129.2 (2)
C4—C3—O3—C31	147.4 (2)	C42—C43—O43—C431	−110.6 (2)
C3—O3—C31—O31	−4.5 (5)	C43—O43—C431—O431	−9.6 (4)
C3—O3—C31—C32	175.8 (3)	C43—O43—C431—C432	170.8 (3)
O3—C3—C4—O4	−75.6 (2)	O43—C43—C44—O44	−76.6 (2)
C2—C3—C4—O4	167.10 (19)	C42—C43—C44—O44	165.32 (19)
O3—C3—C4—C5	167.8 (2)	O43—C43—C44—C45	167.94 (19)
C2—C3—C4—C5	50.5 (3)	C42—C43—C44—C45	49.9 (3)
C5—C4—O4—C41	−148.2 (2)	C43—C44—O44—C441	136.4 (2)
C3—C4—O4—C41	92.3 (2)	C45—C44—O44—C441	−105.4 (2)
O4—C4—C5—O5	−172.08 (19)	C44—O44—C441—O441	−0.9 (4)
C3—C4—C5—O5	−53.4 (3)	C44—O44—C441—C442	176.1 (2)
O4—C4—C5—C6	70.3 (3)	O44—C44—C45—O45	−163.48 (18)
C3—C4—C5—C6	−171.1 (2)	C43—C44—C45—O45	−48.6 (3)
F1—C1—O5—C5	62.8 (3)	O44—C44—C45—C46	76.9 (3)
C2—C1—O5—C5	−58.0 (3)	C43—C44—C45—C46	−168.2 (2)
C6—C5—O5—C1	−179.4 (2)	O4—C41—O45—C45	59.8 (3)
C4—C5—O5—C1	58.2 (3)	C42—C41—O45—C45	−59.1 (3)
O5—C5—C6—O6	−59.8 (3)	C46—C45—O45—C41	176.2 (2)
C4—C5—C6—O6	61.2 (3)	C44—C45—O45—C41	54.8 (3)
C5—C6—O6—C61	149.0 (3)	O45—C45—C46—O46	77.4 (3)
C6—O6—C61—O61	10.7 (6)	C44—C45—C46—O46	−159.7 (2)
C6—O6—C61—C62	−173.1 (3)	C45—C46—O46—C461	167.7 (3)
C4—O4—C41—O45	89.8 (2)	C46—O46—C461—O461	1.4 (5)
C4—O4—C41—C42	−150.4 (2)	C46—O46—C461—C462	−176.1 (3)