1-Deoxy-1-(4-fluoro­phenyl)-β-D-ribo­furan­ose, its hemihydrate, and 1-­deoxy-1-(2,4-di­fluoro­phenyl)-β-D-ribo­furan­ose: structural evidence for intermolecular C—H...F—C interactions

The structures of 1-deoxy-1-(4-fluoro­phenyl)-β-D-ribo­furan­ose in two crystal forms, (Ia) and (Ib) (C₁₁H₁₃FO₄), 1-deoxy-1-(4-fluoro­phenyl)-β-D-ribo­furan­ose hemihydrate, (Ic) (C₁₁H₁₃­FO₄·0.5H₂O) and 1-deoxy-1-(2,4-di­fluoro­phenyl)-β-D-ribo­furan­ose, (II) (C₁₁H₁₂F₂O₄), show two-dimensional networks of intermolecular hydrogen bonds between the hydroxyl groups. Weak intermolecular C—H...F—C and C—H...π_arene interactions complete the packing in the third dimension. The ribo­furan­ose ring has a conformation intermediate between a C1′-exo,C2′-endo twist and a C2′-endo envelope for (Ia) and (Ic), a conformation intermediate between a C2′-endo,C3′-exo twist and a C2′-endo envelope for (Ib) and an unsymmetrical C2′-exo,C3′-endo twist conformation for (II).

S1. Comment

This paper presents the crystal structures of four ribofuranose-based compounds, namely, 1-deoxy-1-(4-fluorophenyl)-β-D-ribofuranose in two crystal forms, (Ia) and (Ib), 1-deoxy-1-(4-fluorophenyl)-β-D-ribofuranose hemihydrate, (Ic), and 1-deoxy-1-(2,4-difluorophenyl)-β-D-ribofuranose, (II).

The five-membered ribofuranose rings in (Ia) and (Ic) (Fig. 1) have rather similar conformations. The ring puckering parameters defined by Cremer & Pople (1975) are q = 0.375 Å and ϕ = 60.2° for (Ia), and q = 0.421 Å and ϕ = 63.4° for (Ic). This corresponds to a conformation intermediate between a C1'-exo, C2'-endo twist and a C2'-endo envelope. The hydroxyl group on O2 and the phenyl group attached to C1 are both in pseudo-equatorial positions, while the hydroxyl group on O3 is in a pseudo-axial position and the methanol group attached to C4 is in a bisecting position with respect to the five-membered ring. No short intramolecular contacts are observed for this conformation.

The five-membered ribofuranose ring in (Ib) (Fig. 1) is considerably different. It has a conformation intermediate between a C2'-endo,C3'-exo twist and a C2'-endo envelope. The ring puckering parameters are q = 0.368 Å and ϕ = 81.6°. The hydroxyl group on O2 and the phenyl group attached to C1 are in pseudo-equatorial positions, while the hydroxyl group on O3 and the methanol group attached to C4 are both in pseudo-axial positions with respect to the five-membered ring.

The five-membered ribofuranose ring in (II) (Fig. 1) is different again. It has approximately an unsymmetrical C2'-exo,C3'-endo twist conformation. The ring puckering parameters are q = 0.390 Å and ϕ = 274.8°. The hydroxyl group on O2 is in an axial position, the hydroxyl group on O3 is in an equatorial position, the methanol group attached to C4 is in a pseudo-equatorial position and the phenyl group attached to C1 is in a pseudo-axial position with respect to the five-membered ring.

Molecules (Ib) and (II) show a short intramolecular contact distance of 2.42 (2) for (Ib) and 2.44 (2) Å for (II) between O4 and H7. This distance is equal to the van der Waals contact distance of 2.4 Å between O and H. Each molecule of (Ia) and (Ib) is connected by intermolecular hydrogen bonding (Table 1, Table 2, Fig. 2, Fig. 3) to six neighbouring molecules, leading to a two-dimensional network in the ab direction.

For (Ic), a rather similar two-dimensional network is found in the bc direction. In this case, the water molecule is included in the network. Each molecule of (Ic) is connected by hydrogen bonding (Table 3, Fig. 4) to three neighbouring molecules of (Ic) and to two different water molecules.

Each molecule of (II) is connected by intermolecular hydrogen bonding (Table 4, Fig. 5) to four different neighbouring molecules, leading to a two-dimensional network in the ab direction. Two-dimensional networks of hydrogen bonds have also been observed in the crystal structures of 1-deoxy-1-phenyl-β-D-ribofuranose (Matulic Adamic, 1996), 1-deoxy-1-(2-fluorophenyl)-β-D-ribofuranose (Bats et al., 1999a) and 1-deoxy-1-(3-fluorophenyl)-β-D-ribofuranose (Bats et al., 1999b).

The packing in the direction of the long dimension of the unit cell consists entirely of intermolecular interactions between the fluorophenyl groups. Rather short intermolecular C—H···F—C contacts are observed in (Ia), (Ib) and (Ic). The intermolecular H10···F distance is 2.30 (2) in (Ia), 2.42 (2) in (Ib) and 2.38 (2) Å in (Ic). These distances are comparable to the van der Waals contact distance between F and H [2.35 Å according to Pauling (1960) or 2.47 Å according to Bondi (1964)]. Each 4-fluorophenyl group is involved in two of these contacts, resulting in zigzag chains of molecules (Fig. 6). In addition to these C—H···F—C interactions, the crystal packing of (Ia), (Ib) and (Ic) also shows intermolecular C—H···π_arene interactions. The H8···C_g distance is 2.82 in (Ia), 2.84 in (Ib) and 2.82 Å in (Ic) (C_g is the centroid of the phenyl ring). Intermolecular C—H···π_arene interactions play a significant role in crystal structures (Brady et al., 1998; Gallagher et al., 1998). Koch & Egert (1995) have shown these interactions to be of an electrostatic nature.

The crystal structure of (II) shows pairs of molecules related by a twofold axis, with intermolecular distances of 2.57 (2) Å between F1 and H10(-x, y, −z) (Fig. 7). These distances are longer than the van der Waals contact distance. No other intermolecular interactions between the phenyl groups are found in this case, which can explain the crystal packing in the c direction. Intermolecular F···H contacts have also been reported for other crystal structures (Karipides et al., 1988; Bruno et al., 1997; Antolić et al., 1996; Vij et al., 1996; Shimoni et al., 1994; Weiss et al., 1997). A search of the Spring 1999 release of the Cambridge Structural Data Base (Allen & Kennard, 1993?) for structures containing fluorophenyl groups, with H-atom coordinates included and no disorder reported, revealed 1144 crystal structures. Among those structures, 1596 different C—H···F—C contacts were found with H···F distances shorter than 2.6 Å (652 shorter than 2.5, 182 shorter than 2.4 and 37 shorter than 2.3 Å). About one third of these interactions were C_phenyl—H···F—C_phenyl contacts. The number of dimeric structures as found for (II) is rather small. Only 35 dimers were found with both C—H···F—C contacts shorter than 2.6 Å. Larsen & Marthi (1994) and Kubota & Ohba (1992) have shown the F atom in fluorophenyl groups to bear a small negative charge of about −0.1 e Å⁻³. Thus, the C—F bond is a likely candidate for electrostatic interactions with electropositive C—H bonds.

Howard et al. (1996) calculated the C—H···F—C interaction energy of a complex between CH₃F and H₄C to be approximately −0.2 kcalmol⁻¹, which is an order of magnitude smaller than the corresponding value for a complex between CH₃F and H₂O. They termed the C—H···F—C interaction as a van der Waals interaction rather than a hydrogen bond. Thalladi et al. (1998) showed the packing in fluorobenzenes containing no elements other than C, H and F to be dominated by C—H···F—C interactions. They also showed the C—H···F interactions to have similar characteristics to those of weak C—H···O and C—H···N hydrogen bonds. These interactions are rather weak and thus are easily overridden by stronger intermolecular interactions. In the crystal structures reported here, however, stronger interactions are missing in one direction. Thus, weaker C—H···F—C and C—H···π interactions dominate the crystal packing in this direction.

S2. Experimental

The title compounds were prepared according to Krohn et al. (1992). Thus, 1-bromo-4-fluorobenzene [for (I)] or 1-bromo-2,4-difluorobenzene [for (II)] was lithiated and added to 2',3',5'-tri-O-benzyl-D-ribono-1,4-lactone (Barker & Fletcher, 1961; Timpe et al., 1975). The resulting intermediate lactol was directly dehydroxylated to yield a sterically uniform β-C-riboside. Debenzylation of the hydroxyl groups resulted in the unprotected C-nucleoside. Compound (I) was recrystallized from methanol, resuling in two different crystalline modifications, (Ia) and (Ib), while recrystallization from water yielded the hemihydrate (Ic). Compound (II) was also recrystallized from water.

Computing details

For all compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL; software used to prepare material for publication: CIF in SHELXL97.

Figures

	Fig. 1. The molecules of (Ia), (Ib), (Ic) and (II) with 50% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radii.
	Fig. 2. The crystal packing of (Ia) shown down the a axis.
	Fig. 3. The crystal packing of (Ib) shown down the a axis.
	Fig. 4. The crystal packing of (Ic) shown down the b axis.
	Fig. 5. The crystal packing of (II) shown down the b axis.
	Fig. 6. Zigzag chains of molecules connected by C—H···F interactions in (Ia). Similar chains occur in (Ib) and (Ic).
	Fig. 7. Dimers of molecules of (II) connected by C—H···F interactions.

(Ia) 1'-deoxy-1'-(4-fluorophenyl)-β-D-ribofuranose

Crystal data

C11H13FO4	Dx = 1.416 Mg m^−3
Mr = 228.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 279 reflections
a = 5.4741 (9) Å	θ = 3–23°
b = 7.3018 (7) Å	µ = 0.12 mm^−1
c = 26.791 (3) Å	T = 134 K
V = 1070.9 (2) Å^3	Plate, colourless
Z = 4	1.30 × 0.64 × 0.15 mm
F(000) = 480

Data collection

Siemens SMART diffractometer	3273 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.084
Graphite monochromator	θmax = 31.3°, θmin = 2.9°
ω scans	h = −7→8
18913 measured reflections	k = −10→10
3431 independent reflections	l = −38→35

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)] = 0.037	Hydrogen site location: difference Fourier map
wR(F^2) = 0.111	All H-atom parameters refined
S = 1.39	w = 1/[σ^2(Fo^2) + (0.06P)^2] where P = (Fo^2 + 2Fc^2)/3
3431 reflections	(Δ/σ)max = 0.002
197 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.20 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
O2	0.76882 (16)	0.33447 (10)	0.78927 (3)	0.01865 (17)
F	0.5477 (2)	0.63072 (12)	1.01688 (3)	0.0391 (2)
O3	0.63932 (16)	−0.00392 (11)	0.74918 (3)	0.02119 (17)
O4	0.58996 (18)	−0.03869 (11)	0.86967 (3)	0.02431 (19)
O5	1.02384 (16)	−0.37191 (11)	0.81932 (3)	0.02209 (18)
C2	0.78380 (19)	0.17676 (13)	0.81964 (4)	0.01504 (18)
C3	0.79950 (19)	−0.00591 (13)	0.79128 (4)	0.01600 (19)
C1	0.5644 (2)	0.14795 (14)	0.85402 (4)	0.01712 (19)
C10	0.3775 (3)	0.53286 (17)	0.94093 (5)	0.0290 (3)
C7	0.7353 (2)	0.26211 (18)	0.93564 (4)	0.0237 (2)
C6	0.5575 (2)	0.27333 (14)	0.89837 (4)	0.01727 (19)
C9	0.5541 (2)	0.51538 (16)	0.97721 (5)	0.0257 (2)
C8	0.7339 (2)	0.38401 (19)	0.97552 (4)	0.0271 (2)
C5	0.9144 (2)	−0.25106 (14)	0.85456 (4)	0.0212 (2)
C4	0.7080 (2)	−0.14229 (14)	0.83058 (4)	0.0185 (2)
C11	0.3813 (2)	0.40980 (16)	0.90120 (4)	0.0234 (2)
H7	0.859 (4)	0.161 (3)	0.9349 (6)	0.030 (4)*
H2	0.925 (3)	0.191 (2)	0.8403 (6)	0.020 (4)*
H1	0.421 (3)	0.171 (2)	0.8320 (5)	0.010 (3)*
H5B	1.045 (4)	−0.164 (2)	0.8646 (6)	0.024 (4)*
H8	0.849 (4)	0.380 (3)	1.0015 (7)	0.031 (4)*
H3	0.957 (3)	−0.0349 (19)	0.7808 (5)	0.014 (3)*
HO5	0.937 (5)	−0.454 (3)	0.8111 (7)	0.040 (5)*
H4	0.583 (3)	−0.224 (2)	0.8160 (5)	0.017 (3)*
H11	0.267 (4)	0.415 (2)	0.8775 (7)	0.036 (5)*
H5A	0.840 (4)	−0.319 (3)	0.8835 (7)	0.039 (5)*
H10	0.262 (5)	0.639 (3)	0.9446 (7)	0.054 (6)*
HO3	0.733 (4)	0.050 (3)	0.7269 (7)	0.045 (5)*
HO2	0.634 (5)	0.346 (3)	0.7739 (7)	0.040 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0208 (4)	0.0152 (3)	0.0199 (3)	−0.0011 (3)	0.0000 (3)	0.0016 (3)
F	0.0458 (5)	0.0397 (4)	0.0318 (4)	−0.0062 (4)	0.0017 (4)	−0.0213 (3)
O3	0.0246 (4)	0.0230 (4)	0.0160 (3)	−0.0038 (3)	−0.0047 (3)	−0.0008 (3)
O4	0.0354 (5)	0.0159 (3)	0.0215 (4)	0.0003 (3)	0.0104 (3)	0.0006 (3)
O5	0.0245 (4)	0.0171 (4)	0.0247 (4)	0.0006 (3)	−0.0008 (3)	−0.0031 (3)
C2	0.0155 (4)	0.0147 (4)	0.0150 (4)	−0.0002 (3)	−0.0005 (4)	−0.0012 (3)
C3	0.0177 (4)	0.0159 (4)	0.0143 (4)	0.0006 (3)	−0.0009 (3)	−0.0019 (3)
C1	0.0169 (4)	0.0169 (4)	0.0176 (4)	−0.0001 (4)	0.0010 (4)	−0.0023 (3)
C10	0.0313 (6)	0.0237 (5)	0.0319 (6)	0.0075 (5)	−0.0005 (5)	−0.0084 (4)
C7	0.0217 (5)	0.0305 (5)	0.0188 (5)	0.0064 (5)	−0.0020 (4)	−0.0031 (4)
C6	0.0177 (4)	0.0181 (4)	0.0160 (4)	0.0008 (4)	0.0011 (4)	−0.0010 (3)
C9	0.0301 (6)	0.0251 (5)	0.0219 (5)	−0.0058 (5)	0.0027 (4)	−0.0088 (4)
C8	0.0244 (5)	0.0382 (6)	0.0188 (5)	0.0002 (5)	−0.0030 (4)	−0.0067 (4)
C5	0.0294 (5)	0.0176 (4)	0.0165 (4)	0.0012 (4)	−0.0028 (4)	−0.0005 (4)
C4	0.0231 (5)	0.0153 (4)	0.0173 (4)	0.0000 (4)	0.0004 (4)	−0.0012 (3)
C11	0.0229 (5)	0.0241 (5)	0.0232 (5)	0.0062 (4)	−0.0036 (4)	−0.0052 (4)

Geometric parameters (Å, º)

O2—C2	1.4124 (12)	C1—C6	1.5004 (13)
F—C9	1.3565 (12)	C10—C9	1.3770 (18)
O3—C3	1.4286 (12)	C10—C11	1.3933 (15)
O4—C1	1.4327 (13)	C7—C8	1.3907 (15)
O4—C4	1.4445 (13)	C7—C6	1.3969 (15)
O5—C5	1.4245 (13)	C6—C11	1.3888 (16)
C2—C1	1.5282 (14)	C9—C8	1.3751 (19)
C2—C3	1.5374 (13)	C5—C4	1.5235 (16)
C3—C4	1.5333 (14)
C1—O4—C4	109.25 (8)	C11—C6—C7	119.14 (10)
O2—C2—C1	114.44 (8)	C11—C6—C1	119.90 (10)
O2—C2—C3	115.21 (8)	C7—C6—C1	120.85 (10)
C1—C2—C3	102.85 (8)	F—C9—C8	118.52 (11)
O3—C3—C4	110.37 (9)	F—C9—C10	118.50 (11)
O3—C3—C2	110.30 (8)	C8—C9—C10	122.96 (10)
C4—C3—C2	101.88 (7)	C9—C8—C7	118.40 (11)
O4—C1—C6	110.56 (8)	O5—C5—C4	110.81 (8)
O4—C1—C2	103.33 (8)	O4—C4—C5	107.39 (8)
C6—C1—C2	114.40 (9)	O4—C4—C3	107.69 (8)
C9—C10—C11	117.97 (11)	C5—C4—C3	112.69 (9)
C8—C7—C6	120.52 (11)	C6—C11—C10	120.99 (11)
O2—C2—C3—O3	−40.37 (11)	C11—C10—C9—F	−177.96 (12)
C1—C2—C3—O3	84.83 (9)	C11—C10—C9—C8	0.7 (2)
O2—C2—C3—C4	−157.57 (9)	F—C9—C8—C7	177.92 (11)
C1—C2—C3—C4	−32.36 (10)	C10—C9—C8—C7	−0.8 (2)
C4—O4—C1—C6	−153.22 (9)	C6—C7—C8—C9	−0.13 (19)
C4—O4—C1—C2	−30.39 (11)	C1—O4—C4—C5	131.18 (9)
O2—C2—C1—O4	164.70 (8)	C1—O4—C4—C3	9.57 (12)
C3—C2—C1—O4	38.99 (10)	O5—C5—C4—O4	173.87 (8)
O2—C2—C1—C6	−75.05 (11)	O5—C5—C4—C3	−67.70 (11)
C3—C2—C1—C6	159.24 (8)	O3—C3—C4—O4	−102.07 (10)
C8—C7—C6—C11	1.04 (18)	C2—C3—C4—O4	15.08 (11)
C8—C7—C6—C1	177.17 (11)	O3—C3—C4—C5	139.67 (9)
O4—C1—C6—C11	−133.56 (11)	C2—C3—C4—C5	−103.18 (9)
C2—C1—C6—C11	110.31 (12)	C7—C6—C11—C10	−1.08 (18)
O4—C1—C6—C7	50.33 (13)	C1—C6—C11—C10	−177.25 (11)
C2—C1—C6—C7	−65.80 (13)	C9—C10—C11—C6	0.21 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—HO2···O3^i	0.85 (2)	1.96 (2)	2.729 (1)	151 (2)
O3—HO3···O5^ii	0.88 (2)	1.91 (2)	2.774 (1)	169 (2)
O5—HO5···O2^iii	0.80 (2)	1.89 (2)	2.682 (1)	172 (2)

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

(Ib) 1'-deoxy-1'-(4-fluorophenyl)-β-D-ribofuranose

Crystal data

C11H13FO4	Dx = 1.461 Mg m^−3
Mr = 228.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 161 reflections
a = 6.7109 (14) Å	θ = 3–23°
b = 6.7653 (7) Å	µ = 0.12 mm^−1
c = 22.846 (3) Å	T = 135 K
V = 1037.2 (3) Å^3	Rod, colourless
Z = 4	0.66 × 0.45 × 0.28 mm
F(000) = 480

Data collection

Siemens SMART diffractometer	3512 independent reflections
Radiation source: fine-focus sealed tube	2944 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 31.9°, θmin = 1.8°
Absorption correction: numerical (SHELXTL; sheldrick, 1996) ?	h = −9→9
Tmin = 0.932, Tmax = 0.968	k = −10→10
19895 measured reflections	l = −34→31

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	All H-atom parameters refined
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
3512 reflections	Δρmax = 0.30 e Å^−3
198 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (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
O3	0.13084 (14)	0.41021 (13)	0.76631 (4)	0.02036 (19)
O5	0.73253 (12)	0.22777 (12)	0.66755 (4)	0.02106 (19)
F	0.33765 (16)	1.11352 (13)	0.46221 (4)	0.0454 (3)
O4	0.46441 (12)	0.56444 (12)	0.68270 (4)	0.02004 (19)
O2	−0.06632 (12)	0.57415 (13)	0.67107 (4)	0.01943 (18)
C7	0.4733 (2)	0.77456 (18)	0.57821 (6)	0.0244 (3)
C4	0.42437 (16)	0.36681 (17)	0.70464 (5)	0.0159 (2)
C11	0.14812 (19)	0.91003 (18)	0.59712 (5)	0.0215 (3)
C1	0.28136 (16)	0.66180 (15)	0.66811 (5)	0.0154 (2)
C6	0.30337 (19)	0.78431 (16)	0.61310 (5)	0.0178 (2)
C5	0.52017 (17)	0.21584 (17)	0.66459 (6)	0.0189 (2)
C2	0.12640 (16)	0.49594 (16)	0.66321 (5)	0.0153 (2)
C3	0.19792 (17)	0.34891 (17)	0.70967 (5)	0.0159 (2)
C10	0.1592 (2)	1.0222 (2)	0.54614 (6)	0.0281 (3)
C9	0.3288 (2)	1.00628 (19)	0.51258 (5)	0.0303 (3)
C8	0.4866 (2)	0.8878 (2)	0.52740 (6)	0.0311 (3)
H2	0.142 (2)	0.437 (2)	0.6228 (6)	0.022 (4)*
H4	0.485 (2)	0.3559 (18)	0.7426 (5)	0.007 (3)*
H1	0.239 (2)	0.751 (2)	0.7013 (6)	0.016 (3)*
H3	0.148 (2)	0.217 (2)	0.7025 (5)	0.014 (3)*
H11	0.022 (2)	0.9189 (19)	0.6210 (6)	0.012 (3)*
HO5	0.775 (3)	0.133 (3)	0.6905 (7)	0.028 (4)*
H5B	0.483 (2)	0.242 (2)	0.6230 (7)	0.030 (4)*
H5A	0.472 (2)	0.084 (2)	0.6770 (6)	0.020 (4)*
H7	0.582 (2)	0.693 (3)	0.5899 (6)	0.028 (4)*
HO3	0.122 (3)	0.317 (4)	0.7873 (9)	0.057 (6)*
H8	0.599 (2)	0.885 (2)	0.5036 (7)	0.029 (4)*
H10	0.054 (3)	1.100 (3)	0.5344 (8)	0.038 (5)*
HO2	−0.152 (2)	0.485 (3)	0.6690 (7)	0.036 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0240 (5)	0.0182 (4)	0.0189 (4)	−0.0025 (4)	0.0051 (3)	0.0011 (3)
O5	0.0134 (4)	0.0181 (4)	0.0316 (5)	0.0007 (3)	0.0001 (3)	0.0017 (4)
F	0.0740 (7)	0.0364 (5)	0.0260 (4)	−0.0143 (5)	0.0018 (5)	0.0117 (3)
O4	0.0134 (4)	0.0128 (4)	0.0340 (5)	−0.0007 (3)	−0.0020 (3)	0.0033 (3)
O2	0.0121 (4)	0.0173 (4)	0.0289 (5)	−0.0002 (3)	−0.0001 (3)	−0.0014 (4)
C7	0.0259 (7)	0.0180 (5)	0.0292 (6)	−0.0007 (5)	0.0079 (5)	−0.0025 (5)
C4	0.0147 (5)	0.0147 (5)	0.0182 (5)	−0.0008 (4)	−0.0010 (4)	0.0005 (4)
C11	0.0237 (6)	0.0187 (5)	0.0221 (6)	−0.0009 (5)	−0.0018 (5)	0.0010 (4)
C1	0.0139 (5)	0.0138 (4)	0.0185 (5)	−0.0012 (4)	−0.0001 (4)	−0.0017 (4)
C6	0.0212 (6)	0.0132 (5)	0.0188 (5)	−0.0034 (4)	0.0011 (4)	−0.0023 (4)
C5	0.0144 (5)	0.0166 (5)	0.0258 (6)	−0.0003 (4)	0.0002 (5)	−0.0039 (5)
C2	0.0131 (5)	0.0147 (5)	0.0182 (5)	−0.0006 (4)	−0.0004 (4)	−0.0018 (4)
C3	0.0150 (5)	0.0144 (5)	0.0183 (5)	−0.0017 (4)	0.0021 (4)	−0.0010 (4)
C10	0.0357 (8)	0.0203 (6)	0.0284 (7)	−0.0022 (5)	−0.0070 (6)	0.0048 (5)
C9	0.0515 (10)	0.0206 (6)	0.0186 (5)	−0.0115 (6)	0.0005 (6)	0.0027 (5)
C8	0.0402 (9)	0.0255 (7)	0.0275 (7)	−0.0058 (6)	0.0149 (6)	−0.0015 (5)

Geometric parameters (Å, º)

O3—C3	1.4314 (14)	C4—C3	1.5288 (16)
O5—C5	1.4290 (14)	C11—C10	1.3920 (17)
F—C9	1.3616 (14)	C11—C6	1.3937 (17)
O4—C1	1.4332 (14)	C1—C6	1.5126 (15)
O4—C4	1.4530 (14)	C1—C2	1.5340 (15)
O2—C2	1.4089 (13)	C2—C3	1.5318 (16)
C7—C6	1.3932 (17)	C10—C9	1.3762 (19)
C7—C8	1.3938 (19)	C9—C8	1.371 (2)
C4—C5	1.5146 (16)
C1—O4—C4	110.16 (8)	O5—C5—C4	110.89 (10)
C6—C7—C8	120.18 (13)	O2—C2—C3	116.31 (9)
O4—C4—C5	109.48 (9)	O2—C2—C1	109.77 (9)
O4—C4—C3	106.42 (9)	C3—C2—C1	102.24 (9)
C5—C4—C3	114.45 (10)	O3—C3—C4	110.95 (9)
C10—C11—C6	120.78 (12)	O3—C3—C2	109.86 (9)
O4—C1—C6	111.18 (9)	C4—C3—C2	102.00 (9)
O4—C1—C2	105.18 (9)	C9—C10—C11	117.89 (13)
C6—C1—C2	113.98 (9)	F—C9—C8	119.12 (13)
C7—C6—C11	119.41 (11)	F—C9—C10	117.73 (13)
C7—C6—C1	121.96 (11)	C8—C9—C10	123.15 (12)
C11—C6—C1	118.62 (11)	C9—C8—C7	118.55 (13)
C1—O4—C4—C5	118.21 (10)	O4—C1—C2—C3	33.81 (11)
C1—O4—C4—C3	−5.98 (12)	C6—C1—C2—C3	155.85 (9)
C4—O4—C1—C6	−141.43 (9)	O4—C4—C3—O3	−90.15 (11)
C4—O4—C1—C2	−17.61 (11)	C5—C4—C3—O3	148.78 (10)
C8—C7—C6—C11	−0.79 (18)	O4—C4—C3—C2	26.81 (11)
C8—C7—C6—C1	179.09 (11)	C5—C4—C3—C2	−94.26 (11)
C10—C11—C6—C7	1.45 (17)	O2—C2—C3—O3	−38.12 (13)
C10—C11—C6—C1	−178.44 (11)	C1—C2—C3—O3	81.44 (10)
O4—C1—C6—C7	8.79 (14)	O2—C2—C3—C4	−155.86 (9)
C2—C1—C6—C7	−109.87 (12)	C1—C2—C3—C4	−36.30 (10)
O4—C1—C6—C11	−171.33 (10)	C6—C11—C10—C9	−0.66 (18)
C2—C1—C6—C11	70.01 (13)	C11—C10—C9—F	178.85 (11)
O4—C4—C5—O5	67.36 (13)	C11—C10—C9—C8	−0.8 (2)
C3—C4—C5—O5	−173.29 (10)	F—C9—C8—C7	−178.21 (12)
O4—C1—C2—O2	157.86 (9)	C10—C9—C8—C7	1.5 (2)
C6—C1—C2—O2	−80.11 (11)	C6—C7—C8—C9	−0.63 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—HO2···O5^i	0.83 (2)	1.91 (2)	2.706 (1)	160 (1)
O3—HO3···O2^ii	0.79 (2)	1.94 (2)	2.721 (1)	170 (1)
O5—HO5···O3^iii	0.88 (2)	1.91 (2)	2.782 (1)	174 (1)

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

(Ic) 1'-deoxy-1'-(4-fluorophenyl)-β-D-ribofuranose hemihydrate

Crystal data

C11H13FO4·0.5H2O	F(000) = 500
Mr = 237.22	Dx = 1.378 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 29.356 (6) Å	Cell parameters from 185 reflections
b = 5.3068 (7) Å	θ = 3–23°
c = 7.3530 (11) Å	µ = 0.12 mm^−1
β = 93.215 (10)°	T = 154 K
V = 1143.7 (3) Å^3	Block, colourless
Z = 4	0.45 × 0.44 × 0.40 mm

Data collection

Siemens SMART diffractometer	2746 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 29.0°, θmin = 1.4°
ω scans	h = −40→37
5566 measured reflections	k = −7→6
2827 independent reflections	l = −9→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	All H-atom parameters refined
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.49	(Δ/σ)max = 0.001
2827 reflections	Δρmax = 0.35 e Å^−3
207 parameters	Δρmin = −0.17 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.006 (2)

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
O1	1/2	0.4642 (3)	0	0.0229 (3)
O5	0.42037 (3)	−0.29036 (19)	−0.12047 (12)	0.0253 (2)
O2	0.44746 (3)	−0.0340 (2)	0.59397 (11)	0.0276 (2)
O3	0.47406 (3)	0.1638 (2)	0.27211 (12)	0.0238 (2)
F	0.23974 (4)	0.0784 (2)	0.88272 (15)	0.0476 (3)
O4	0.36669 (3)	0.0947 (2)	0.22057 (12)	0.0268 (2)
C11	0.34127 (5)	0.2884 (3)	0.67354 (19)	0.0263 (3)
C1	0.38200 (4)	0.1323 (2)	0.40715 (15)	0.0191 (2)
C5	0.38855 (5)	−0.2240 (3)	0.01174 (16)	0.0231 (3)
C6	0.34325 (4)	0.1166 (2)	0.53157 (15)	0.0198 (2)
C2	0.41858 (4)	−0.0702 (2)	0.43697 (15)	0.0177 (2)
C4	0.40457 (4)	0.0065 (2)	0.12087 (16)	0.0202 (2)
C3	0.44395 (4)	−0.0474 (2)	0.26191 (15)	0.0192 (2)
C7	0.31067 (5)	−0.0741 (3)	0.5132 (2)	0.0275 (3)
C10	0.30653 (6)	0.2742 (3)	0.79519 (19)	0.0323 (3)
C9	0.27470 (5)	0.0877 (3)	0.77005 (19)	0.0299 (3)
C8	0.27581 (5)	−0.0892 (3)	0.6332 (2)	0.0318 (3)
H2	0.4041 (6)	−0.231 (4)	0.438 (2)	0.018 (4)*
H11	0.3635 (5)	0.418 (4)	0.685 (2)	0.017 (4)*
H1	0.3972 (5)	0.299 (3)	0.423 (2)	0.012 (3)*
HO5	0.4459 (6)	−0.375 (4)	−0.069 (2)	0.029 (4)*
HO3	0.5008 (7)	0.113 (4)	0.331 (2)	0.035 (5)*
H5B	0.3595 (6)	−0.192 (4)	−0.050 (2)	0.025 (4)*
H3	0.4588 (6)	−0.204 (4)	0.239 (2)	0.023 (4)*
H5A	0.3850 (6)	−0.374 (4)	0.099 (2)	0.026 (4)*
H4	0.4130 (5)	0.140 (4)	0.040 (2)	0.023 (4)*
H8	0.2534 (7)	−0.214 (5)	0.621 (2)	0.039 (5)*
HO2	0.4345 (7)	−0.106 (4)	0.686 (3)	0.035 (5)*
H7	0.3135 (7)	−0.202 (4)	0.423 (2)	0.033 (5)*
H10	0.3038 (8)	0.398 (6)	0.887 (3)	0.063 (7)*
HO1	0.5068 (7)	0.369 (5)	−0.085 (3)	0.044 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0309 (6)	0.0205 (6)	0.0179 (6)	0	0.0077 (5)	0
O5	0.0309 (5)	0.0299 (5)	0.0154 (4)	0.0038 (4)	0.0033 (3)	−0.0003 (4)
O2	0.0207 (4)	0.0466 (6)	0.0154 (4)	−0.0057 (4)	0.0004 (3)	0.0052 (4)
O3	0.0187 (4)	0.0318 (5)	0.0210 (4)	−0.0028 (4)	0.0025 (3)	0.0064 (3)
F	0.0421 (6)	0.0542 (7)	0.0497 (6)	−0.0022 (5)	0.0306 (5)	0.0068 (5)
O4	0.0237 (4)	0.0405 (6)	0.0161 (4)	0.0128 (4)	0.0015 (3)	0.0003 (4)
C11	0.0292 (6)	0.0256 (6)	0.0250 (6)	−0.0041 (5)	0.0087 (5)	−0.0055 (5)
C1	0.0216 (5)	0.0207 (6)	0.0155 (5)	0.0015 (4)	0.0035 (4)	0.0002 (4)
C5	0.0242 (6)	0.0276 (6)	0.0177 (5)	−0.0019 (5)	0.0027 (4)	−0.0003 (5)
C6	0.0205 (5)	0.0206 (6)	0.0185 (5)	0.0015 (4)	0.0038 (4)	−0.0003 (4)
C2	0.0172 (5)	0.0215 (6)	0.0145 (5)	0.0001 (4)	0.0017 (4)	0.0034 (4)
C4	0.0210 (5)	0.0239 (6)	0.0160 (5)	0.0026 (4)	0.0034 (4)	0.0012 (4)
C3	0.0198 (5)	0.0224 (6)	0.0155 (5)	0.0024 (4)	0.0027 (4)	0.0014 (4)
C7	0.0251 (6)	0.0260 (7)	0.0318 (7)	−0.0022 (5)	0.0038 (5)	−0.0053 (6)
C10	0.0368 (8)	0.0360 (8)	0.0252 (6)	0.0002 (6)	0.0123 (5)	−0.0060 (6)
C9	0.0271 (6)	0.0349 (7)	0.0292 (7)	0.0033 (6)	0.0143 (5)	0.0078 (6)
C8	0.0252 (6)	0.0288 (7)	0.0419 (8)	−0.0050 (5)	0.0076 (5)	0.0005 (6)

Geometric parameters (Å, º)

O5—C5	1.4296 (14)	C1—C2	1.5261 (16)
O2—C2	1.4066 (14)	C5—C4	1.5228 (18)
O3—C3	1.4270 (16)	C6—C7	1.3936 (18)
F—C9	1.3553 (13)	C2—C3	1.5277 (15)
O4—C1	1.4335 (14)	C4—C3	1.5359 (17)
O4—C4	1.4439 (14)	C7—C8	1.3905 (18)
C11—C6	1.3897 (17)	C10—C9	1.367 (2)
C11—C10	1.3959 (17)	C9—C8	1.378 (2)
C1—C6	1.5016 (15)
C1—O4—C4	108.77 (9)	O4—C4—C5	107.70 (10)
C6—C11—C10	120.58 (13)	O4—C4—C3	106.83 (10)
O4—C1—C6	111.57 (9)	C5—C4—C3	113.88 (11)
O4—C1—C2	102.71 (9)	O3—C3—C2	110.35 (9)
C6—C1—C2	115.12 (10)	O3—C3—C4	109.25 (10)
O5—C5—C4	111.21 (10)	C2—C3—C4	101.51 (9)
C11—C6—C7	119.45 (11)	C8—C7—C6	120.41 (12)
C11—C6—C1	119.10 (11)	C9—C10—C11	118.10 (13)
C7—C6—C1	121.37 (11)	F—C9—C10	118.61 (13)
O2—C2—C1	114.11 (10)	F—C9—C8	118.13 (13)
O2—C2—C3	112.39 (9)	C10—C9—C8	123.25 (12)
C1—C2—C3	101.28 (9)	C9—C8—C7	118.18 (13)
C4—O4—C1—C6	−156.02 (10)	O2—C2—C3—O3	−43.78 (13)
C4—O4—C1—C2	−32.17 (13)	C1—C2—C3—O3	78.40 (11)
C10—C11—C6—C7	−1.2 (2)	O2—C2—C3—C4	−159.53 (11)
C10—C11—C6—C1	−177.95 (13)	C1—C2—C3—C4	−37.35 (11)
O4—C1—C6—C11	−138.36 (13)	O4—C4—C3—O3	−97.35 (11)
C2—C1—C6—C11	105.12 (14)	C5—C4—C3—O3	143.88 (10)
O4—C1—C6—C7	44.98 (16)	O4—C4—C3—C2	19.20 (13)
C2—C1—C6—C7	−71.54 (15)	C5—C4—C3—C2	−99.56 (11)
O4—C1—C2—O2	164.23 (10)	C11—C6—C7—C8	1.5 (2)
C6—C1—C2—O2	−74.31 (13)	C1—C6—C7—C8	178.14 (13)
O4—C1—C2—C3	43.25 (11)	C6—C11—C10—C9	−0.2 (2)
C6—C1—C2—C3	164.71 (10)	C11—C10—C9—F	−177.30 (13)
C1—O4—C4—C5	130.79 (11)	C11—C10—C9—C8	1.4 (2)
C1—O4—C4—C3	8.08 (14)	F—C9—C8—C7	177.57 (13)
O5—C5—C4—O4	167.32 (10)	C10—C9—C8—C7	−1.1 (2)
O5—C5—C4—C3	−74.41 (13)	C6—C7—C8—C9	−0.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···O3^i	0.84 (2)	1.86 (2)	2.701 (1)	176 (2)
O2—HO2···O5^ii	0.88 (2)	1.79 (2)	2.661 (1)	167 (2)
O3—HO3···O2^iii	0.92 (2)	1.77 (2)	2.669 (1)	168 (2)
O5—HO5···O1^iv	0.93 (2)	1.85 (2)	2.777 (1)	172 (2)

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

(II) 1'-deoxy-1'-(2,4-difluorophenyl)-β-D-ribofuranose

Crystal data

C11H12F2O4	F(000) = 512
Mr = 246.21	Dx = 1.536 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 14.684 (2) Å	Cell parameters from 217 reflections
b = 4.6609 (6) Å	θ = 3–23°
c = 15.772 (2) Å	µ = 0.14 mm^−1
β = 99.476 (11)°	T = 134 K
V = 1064.7 (2) Å^3	Thick plate, colourless
Z = 4	0.75 × 0.70 × 0.20 mm

Data collection

Siemens SMART diffractometer	2794 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.068
Graphite monochromator	θmax = 30.6°, θmin = 2.6°
ω scans	h = −20→21
9578 measured reflections	k = −6→6
3048 independent reflections	l = −22→21

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)] = 0.046	Hydrogen site location: difference Fourier map
wR(F^2) = 0.122	All H-atom parameters refined
S = 1.40	w = 1/[σ^2(Fo^2) + (0.06P)^2] where P = (Fo^2 + 2Fc^2)/3
3048 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.37 e Å^−3
1 restraint	Δρmin = −0.25 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
F2	0.02678 (6)	0.7268 (3)	0.21085 (7)	0.0271 (3)
F1	−0.10379 (8)	1.4124 (3)	0.00868 (7)	0.0318 (3)
O5	−0.37647 (7)	0.8548 (3)	0.42169 (8)	0.0196 (2)
O4	−0.23391 (7)	0.5471 (3)	0.27468 (7)	0.0190 (3)
O3	−0.15553 (8)	0.8680 (3)	0.48253 (8)	0.0196 (3)
O2	−0.06523 (8)	0.4483 (3)	0.40898 (8)	0.0197 (3)
C6	−0.13283 (10)	0.8192 (4)	0.19743 (10)	0.0172 (3)
C7	−0.20907 (11)	0.9690 (4)	0.15442 (11)	0.0204 (3)
C2	−0.09098 (10)	0.6931 (4)	0.35722 (10)	0.0160 (3)
C9	−0.11363 (13)	1.2161 (4)	0.07061 (11)	0.0225 (3)
C4	−0.25176 (10)	0.6421 (4)	0.35703 (11)	0.0161 (3)
C3	−0.17079 (10)	0.8380 (4)	0.39217 (10)	0.0168 (3)
C10	−0.03547 (11)	1.0737 (4)	0.10997 (11)	0.0232 (4)
C5	−0.34654 (11)	0.7837 (4)	0.34261 (11)	0.0203 (3)
C1	−0.13874 (10)	0.6002 (4)	0.26730 (10)	0.0164 (3)
C11	−0.04810 (10)	0.8765 (4)	0.17248 (10)	0.0195 (3)
C8	−0.20042 (12)	1.1682 (4)	0.09082 (12)	0.0225 (4)
H2	−0.0395 (13)	0.810 (5)	0.3560 (11)	0.013 (5)*
H8	−0.2511 (17)	1.264 (7)	0.0595 (15)	0.036 (7)*
H7	−0.2698 (19)	0.939 (7)	0.1719 (16)	0.041 (7)*
H5B	−0.3434 (14)	0.948 (6)	0.3124 (12)	0.016 (5)*
H5A	−0.3889 (13)	0.643 (5)	0.3089 (12)	0.013 (5)*
HO5	−0.3637 (15)	0.722 (6)	0.4545 (14)	0.024 (6)*
H1	−0.1144 (15)	0.417 (5)	0.2492 (13)	0.024 (6)*
H10	0.025 (2)	1.115 (8)	0.0964 (16)	0.047 (8)*
H4	−0.2477 (13)	0.489 (6)	0.3949 (12)	0.016 (5)*
H3	−0.1834 (15)	1.020 (6)	0.3674 (13)	0.021 (5)*
HO2	−0.0089 (18)	0.436 (7)	0.4163 (15)	0.038 (7)*
HO3	−0.1447 (18)	0.726 (7)	0.5058 (16)	0.033 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F2	0.0161 (4)	0.0324 (6)	0.0341 (6)	0.0064 (4)	0.0074 (4)	0.0093 (5)
F1	0.0377 (6)	0.0293 (7)	0.0303 (6)	0.0020 (5)	0.0110 (5)	0.0115 (5)
O5	0.0170 (5)	0.0194 (6)	0.0239 (6)	0.0058 (5)	0.0074 (4)	0.0023 (5)
O4	0.0141 (5)	0.0216 (6)	0.0224 (6)	−0.0045 (4)	0.0068 (4)	−0.0051 (5)
O3	0.0230 (5)	0.0159 (6)	0.0201 (6)	0.0005 (5)	0.0037 (4)	−0.0020 (5)
O2	0.0129 (5)	0.0194 (6)	0.0271 (6)	0.0025 (4)	0.0043 (4)	0.0061 (5)
C6	0.0165 (6)	0.0161 (8)	0.0191 (7)	0.0003 (6)	0.0039 (5)	−0.0024 (6)
C7	0.0171 (6)	0.0217 (8)	0.0226 (8)	0.0011 (6)	0.0036 (6)	−0.0015 (6)
C2	0.0137 (6)	0.0155 (8)	0.0191 (7)	−0.0006 (6)	0.0039 (5)	0.0004 (6)
C9	0.0285 (8)	0.0198 (9)	0.0201 (8)	−0.0008 (7)	0.0061 (6)	0.0012 (6)
C4	0.0137 (6)	0.0140 (7)	0.0212 (8)	0.0006 (5)	0.0050 (5)	−0.0007 (6)
C3	0.0154 (6)	0.0136 (7)	0.0217 (8)	0.0006 (6)	0.0039 (5)	−0.0014 (6)
C10	0.0223 (7)	0.0243 (9)	0.0249 (8)	−0.0014 (7)	0.0096 (6)	0.0029 (7)
C5	0.0150 (6)	0.0247 (9)	0.0216 (8)	0.0045 (6)	0.0044 (6)	0.0007 (6)
C1	0.0135 (6)	0.0163 (8)	0.0204 (7)	−0.0018 (6)	0.0059 (5)	−0.0015 (6)
C11	0.0167 (6)	0.0196 (9)	0.0226 (8)	0.0029 (6)	0.0047 (6)	0.0010 (6)
C8	0.0222 (8)	0.0222 (9)	0.0226 (8)	0.0035 (6)	0.0017 (6)	−0.0001 (6)

Geometric parameters (Å, º)

F2—C11	1.3575 (18)	C6—C1	1.515 (2)
F1—C9	1.363 (2)	C7—C8	1.388 (3)
O5—C5	1.428 (2)	C2—C3	1.532 (2)
O4—C4	1.4365 (19)	C2—C1	1.537 (2)
O4—C1	1.4428 (17)	C9—C10	1.382 (3)
O3—C3	1.4127 (19)	C9—C8	1.382 (2)
O2—C2	1.418 (2)	C4—C5	1.523 (2)
C6—C11	1.391 (2)	C4—C3	1.529 (2)
C6—C7	1.397 (2)	C10—C11	1.383 (2)
C4—O4—C1	110.09 (11)	C5—C4—C3	115.62 (14)
C11—C6—C7	116.71 (15)	O3—C3—C4	114.17 (13)
C11—C6—C1	119.73 (14)	O3—C3—C2	113.77 (13)
C7—C6—C1	123.55 (14)	C4—C3—C2	101.64 (13)
C8—C7—C6	121.59 (15)	C9—C10—C11	116.16 (15)
O2—C2—C3	107.15 (13)	O5—C5—C4	112.04 (13)
O2—C2—C1	110.02 (14)	O4—C1—C6	110.28 (13)
C3—C2—C1	101.32 (12)	O4—C1—C2	105.94 (12)
F1—C9—C10	117.78 (15)	C6—C1—C2	114.16 (13)
F1—C9—C8	118.98 (16)	F2—C11—C10	117.75 (13)
C10—C9—C8	123.24 (17)	F2—C11—C6	118.15 (15)
O4—C4—C5	107.27 (12)	C10—C11—C6	124.08 (15)
O4—C4—C3	105.36 (12)	C9—C8—C7	118.20 (16)
C11—C6—C7—C8	−0.9 (3)	C11—C6—C1—O4	−172.31 (15)
C1—C6—C7—C8	179.92 (16)	C7—C6—C1—O4	6.8 (2)
C1—O4—C4—C5	139.81 (14)	C11—C6—C1—C2	68.57 (19)
C1—O4—C4—C3	16.10 (17)	C7—C6—C1—C2	−112.30 (17)
O4—C4—C3—O3	−157.35 (13)	O2—C2—C1—O4	83.09 (15)
C5—C4—C3—O3	84.42 (18)	C3—C2—C1—O4	−30.05 (16)
O4—C4—C3—C2	−34.42 (16)	O2—C2—C1—C6	−155.36 (12)
C5—C4—C3—C2	−152.66 (13)	C3—C2—C1—C6	91.49 (15)
O2—C2—C3—O3	46.40 (18)	C9—C10—C11—F2	178.22 (16)
C1—C2—C3—O3	161.69 (14)	C9—C10—C11—C6	−0.8 (3)
O2—C2—C3—C4	−76.80 (15)	C7—C6—C11—F2	−177.64 (15)
C1—C2—C3—C4	38.49 (15)	C1—C6—C11—F2	1.6 (2)
F1—C9—C10—C11	179.95 (16)	C7—C6—C11—C10	1.4 (3)
C8—C9—C10—C11	−0.3 (3)	C1—C6—C11—C10	−179.46 (17)
O4—C4—C5—O5	172.73 (14)	F1—C9—C8—C7	−179.58 (16)
C3—C4—C5—O5	−70.09 (19)	C10—C9—C8—C7	0.7 (3)
C4—O4—C1—C6	−114.97 (14)	C6—C7—C8—C9	0.0 (3)
C4—O4—C1—C2	9.04 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—HO2···O5^i	0.82 (2)	1.97 (2)	2.780 (1)	171 (2)
O3—HO3···O5^ii	0.76 (2)	2.07 (2)	2.827 (1)	174 (2)
O5—HO5···O3^ii	0.81 (2)	1.92 (2)	2.724 (1)	171 (2)

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