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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1330.
Published online 2010 May 12. doi:  10.1107/S1600536810016624
PMCID: PMC2979521

1-De­oxy-1-fluoro-l-galactitol

Abstract

The crystal structure unequivocally confirms the relative stereochemistry of the title compound, C6H13FO5 [6-de­oxy-6-fluoro-d-galactitol or (2S,3R,4R,5S)-6-fluoro­hexane-1,2,3,4,5-penta­ol]. The absolute stereochemistry was determined from the use of d-galactose as the starting material. In the crystal, the molecules are linked by O—H(...)O and O—H(...)F hydrogen bonds, forming a three-dimensional network with each mol­ecule acting as a donor and acceptor for five hydrogen bonds.

Related literature

For literature regarding fluoro­galactitol and fluoro­galactose, see: Kent & Wright (1972 [triangle]); Jenkinson et al. (2010 [triangle]).

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Object name is e-66-o1330-scheme1.jpg

Experimental

Crystal data

  • C6H13FO5
  • M r = 184.16
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1330-efi1.jpg
  • a = 4.7968 (3) Å
  • b = 8.5957 (5) Å
  • c = 9.8194 (7) Å
  • β = 103.233 (3)°
  • V = 394.12 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.15 mm−1
  • T = 150 K
  • 0.40 × 0.10 × 0.05 mm

Data collection

  • Area diffractometer
  • Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 [triangle]) T min = 0.88, T max = 0.99
  • 3069 measured reflections
  • 947 independent reflections
  • 788 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.095
  • S = 0.99
  • 947 reflections
  • 109 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: COLLECT (Nonius, 2001 [triangle]); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 [triangle]); molecular graphics: CAMERON (Watkin et al., 1996 [triangle]); software used to prepare material for publication: CRYSTALS.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016624/lh5036sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016624/lh5036Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

1-Deoxy-1-fluoro-L-galactitol [6-deoxy-6-fluoro-D-galactitol, (2S,3R,4R,5S)-6-fluorohexane-1,2,3,4,5-pentaol] 3 was prepared in 88% yield by reduction of 6-deoxy-6-fluoro-D-galactose 2, itself readily available from D-galactose (Jenkinson et al., 2010) with sodium borohydride in water (see fig. 1).

1-Deoxy-1-fluoro-L-galactitol 3 (Fig. 2) exists as an extensively hydrogen bonded lattice with each molecule acting as a donor and acceptor for 5 hydrogen bonds (Fig. 3 and Fig. 4). Only classical hydrogen bonding is considered.

Experimental

The title compound was recrystallised by vapour diffusion from a mixture of methanol and water: m.p. 445-447 K, [α]D25 +4.1 (c 1.06, H2O) {Lit. (Kent & Wright, 1972) m.p. 446-447 K, [α]D21 +4.2 (c 0.5, H2O)}.

Refinement

In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned from the starting material.

The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, O—H = 0.82 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.

Figures

Fig. 1.
Synthetic Scheme.
Fig. 2.
The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
Fig. 3.
Packing diagram for the title compound projected along the c-axis. Hydrogen bonds are indicated by dotted lines.
Fig. 4.
Packing diagram for the title compound projected along the b-axis. Hydrogen bonds are indicated by dotted lines.

Crystal data

C6H13FO5F(000) = 196
Mr = 184.16Dx = 1.552 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 828 reflections
a = 4.7968 (3) Åθ = 5–27°
b = 8.5957 (5) ŵ = 0.15 mm1
c = 9.8194 (7) ÅT = 150 K
β = 103.233 (3)°Needle, colourless
V = 394.12 (4) Å30.40 × 0.10 × 0.05 mm
Z = 2

Data collection

Area diffractometer788 reflections with I > 2σ(I)
graphiteRint = 0.039
ω scansθmax = 27.5°, θmin = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)h = −6→6
Tmin = 0.88, Tmax = 0.99k = −10→11
3069 measured reflectionsl = −12→12
947 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.095 Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.04P)2 + 0.16P], where P = [max(Fo2,0) + 2Fc2]/3
S = 0.99(Δ/σ)max = 0.0001
947 reflectionsΔρmax = 0.35 e Å3
109 parametersΔρmin = −0.36 e Å3
1 restraint

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

xyzUiso*/Ueq
F11.0608 (4)0.8416 (3)0.81046 (18)0.0300
C20.8382 (7)0.7956 (4)0.6953 (3)0.0222
C30.9617 (6)0.7729 (3)0.5690 (3)0.0165
O41.1674 (4)0.6479 (3)0.5922 (2)0.0198
C50.7225 (6)0.7433 (3)0.4383 (3)0.0161
O60.5806 (5)0.6003 (2)0.4502 (2)0.0195
C70.8349 (6)0.7338 (3)0.3047 (3)0.0157
O80.9746 (4)0.8784 (3)0.2914 (2)0.0195
C90.5959 (7)0.7026 (4)0.1752 (3)0.0192
O100.3879 (4)0.8258 (3)0.1522 (2)0.0207
C110.7088 (7)0.6776 (4)0.0451 (3)0.0215
O120.4930 (5)0.6156 (3)−0.0668 (2)0.0275
H210.69500.87810.67740.0260*
H220.74910.69990.71730.0258*
H311.06310.86910.55400.0186*
H510.58260.82970.42970.0192*
H710.97440.64730.31260.0169*
H910.49650.60830.19180.0218*
H1110.78180.77570.01800.0236*
H1120.86500.60170.06590.0245*
H411.09760.56920.61690.0297*
H1010.45790.90110.12210.0326*
H811.09430.86920.24360.0307*
H610.44340.62050.48470.0315*
H1210.36960.6866−0.08510.0400*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0335 (11)0.0350 (11)0.0187 (9)0.0018 (10)0.0002 (8)−0.0045 (8)
C20.0217 (15)0.0270 (17)0.0166 (14)0.0023 (12)0.0019 (12)−0.0039 (12)
C30.0168 (14)0.0140 (13)0.0181 (13)0.0019 (11)0.0029 (11)−0.0004 (11)
O40.0176 (11)0.0202 (11)0.0222 (10)0.0029 (8)0.0054 (8)0.0048 (8)
C50.0162 (14)0.0136 (14)0.0194 (14)0.0000 (11)0.0058 (11)0.0011 (11)
O60.0229 (12)0.0169 (10)0.0215 (10)−0.0052 (9)0.0109 (9)−0.0024 (8)
C70.0172 (14)0.0148 (15)0.0149 (13)−0.0012 (12)0.0029 (11)−0.0027 (11)
O80.0208 (12)0.0165 (11)0.0233 (10)−0.0033 (9)0.0094 (9)−0.0024 (9)
C90.0200 (14)0.0201 (15)0.0173 (14)−0.0015 (12)0.0037 (12)0.0006 (12)
O100.0190 (11)0.0217 (11)0.0223 (11)0.0015 (9)0.0064 (8)0.0042 (9)
C110.0227 (16)0.0257 (17)0.0145 (14)0.0006 (13)0.0011 (12)−0.0018 (13)
O120.0312 (14)0.0274 (12)0.0201 (11)0.0025 (10)−0.0017 (10)−0.0078 (10)

Geometric parameters (Å, °)

F1—C21.422 (3)C7—O81.432 (4)
C2—C31.504 (4)C7—C91.528 (4)
C2—H210.975C7—H710.992
C2—H220.974O8—H810.824
C3—O41.441 (4)C9—O101.437 (4)
C3—C51.534 (4)C9—C111.513 (4)
C3—H310.987C9—H910.973
O4—H410.816O10—H1010.815
C5—O61.422 (4)C11—O121.429 (3)
C5—C71.530 (3)C11—H1110.973
C5—H510.992C11—H1120.979
O6—H610.825O12—H1210.840
F1—C2—C3109.0 (3)C5—C7—C9112.2 (2)
F1—C2—H21108.1O8—C7—C9110.7 (2)
C3—C2—H21109.9C5—C7—H71109.7
F1—C2—H22110.2O8—C7—H71109.6
C3—C2—H22110.4C9—C7—H71107.3
H21—C2—H22109.1C7—O8—H81111.8
C2—C3—O4110.5 (2)C7—C9—O10111.3 (2)
C2—C3—C5110.6 (2)C7—C9—C11112.5 (2)
O4—C3—C5111.3 (2)O10—C9—C11110.0 (2)
C2—C3—H31108.3C7—C9—H91108.0
O4—C3—H31107.7O10—C9—H91107.0
C5—C3—H31108.3C11—C9—H91107.8
C3—O4—H41110.6C9—O10—H101108.3
C3—C5—O6110.8 (2)C9—C11—O12111.5 (3)
C3—C5—C7112.5 (2)C9—C11—H111109.2
O6—C5—C7107.1 (2)O12—C11—H111110.9
C3—C5—H51108.0C9—C11—H112108.9
O6—C5—H51109.1O12—C11—H112107.3
C7—C5—H51109.3H111—C11—H112109.2
C5—O6—H61107.1C11—O12—H121104.2
C5—C7—O8107.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H21···O6i0.972.493.409 (4)157
O4—H41···O8ii0.821.942.738 (4)165
O10—H101···O12iii0.821.952.730 (4)160
O8—H81···O10iv0.821.872.691 (4)172
O6—H61···O4v0.821.892.703 (4)170
O12—H121···F1vi0.842.082.895 (3)163

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5036).

References

  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.27, 435.
  • Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst.36, 1487.
  • Jenkinson, S. F., Best, D., Izumori, K., Wilson, F. X., Weymouth-Wilson, A. C., Fleet, G. W. J. & Thompson, A. L. (2010). Acta Cryst. E66, o1315. [PMC free article] [PubMed]
  • Kent, P. W. & Wright, J. R. (1972). Carbohydr. Res.22, 193–200. [PubMed]
  • Nonius (2001). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON Chemical Crystallography Laboratory, Oxford, England.

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