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1-De­­oxy-1-fluoro-L-galactitol

aDepartment of Organic Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, bRare Sugar Research Centre, Kagawa University, 2393 Miki-cho, Kita-gun, Kagawa 761-0795, Japan, cSummit PLC, 91 Milton Park, Abingdon, Oxon, OX14 4RY, England, dDextra Laboratories Ltd, Science and Technology Centre, Whiteknights Road, Reading RG6 6BZ, England, and eDepartment of Chemical Crystallography, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England
*Correspondence e-mail: sarah.jenkinson@chem.ox.ac.uk

(Received 23 April 2010; accepted 6 May 2010; online 12 May 2010)

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[Kent, P. W. & Wright, J. R. (1972). Carbohydr. Res. 22, 193-200.]); Jenkinson et al. (2010[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.]).

[Scheme 1]

Experimental

Crystal data
  • C6H13FO5

  • Mr = 184.16

  • Monoclinic, P 21

  • 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[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.]) Tmin = 0.88, Tmax = 0.99

  • 3069 measured reflections

  • 947 independent reflections

  • 788 reflections with I > 2σ(I)

  • Rint = 0.039

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O4—H41⋯O8i 0.82 1.94 2.738 (4) 165
O10—H101⋯O12ii 0.82 1.95 2.730 (4) 160
O8—H81⋯O10iii 0.82 1.87 2.691 (4) 172
O6—H61⋯O4iv 0.82 1.89 2.703 (4) 170
O12—H121⋯F1v 0.84 2.08 2.895 (3) 163
Symmetry codes: (i) [-x+2, y-{\script{1\over 2}}, -z+1]; (ii) [-x+1, y+{\script{1\over 2}}, -z]; (iii) x+1, y, z; (iv) x-1, y, z; (v) x-1, y, z-1.

Data collection: COLLECT (Nonius, 2001[Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997[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.]); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.]); software used to prepare material for publication: CRYSTALS.

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Structure description top

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.

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. Synthetic Scheme.
[Figure 2] Fig. 2. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
[Figure 3] Fig. 3. Packing diagram for the title compound projected along the c-axis. Hydrogen bonds are indicated by dotted lines.
[Figure 4] Fig. 4. Packing diagram for the title compound projected along the b-axis. Hydrogen bonds are indicated by dotted lines.
1-Deoxy-1-fluoro-L-galactitol top
Crystal data top
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 top
Area
diffractometer
788 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
ω scansθmax = 27.5°, θmin = 5.2°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 66
Tmin = 0.88, Tmax = 0.99k = 1011
3069 measured reflectionsl = 1212
947 independent reflections
Refinement top
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 = 0.000109
947 reflectionsΔρmax = 0.35 e Å3
109 parametersΔρmin = 0.36 e Å3
1 restraint
Crystal data top
C6H13FO5V = 394.12 (4) Å3
Mr = 184.16Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.7968 (3) ŵ = 0.15 mm1
b = 8.5957 (5) ÅT = 150 K
c = 9.8194 (7) Å0.40 × 0.10 × 0.05 mm
β = 103.233 (3)°
Data collection top
Area
diffractometer
947 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
788 reflections with I > 2σ(I)
Tmin = 0.88, Tmax = 0.99Rint = 0.039
3069 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0401 restraint
wR(F2) = 0.095H-atom parameters constrained
S = 0.99Δρmax = 0.35 e Å3
947 reflectionsΔρmin = 0.36 e Å3
109 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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*
H1210.36960.68660.08510.0400*
Atomic displacement parameters (Å2) top
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, º) top
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, º) top
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, y1/2, z+1; (iii) x+1, y+1/2, z; (iv) x+1, y, z; (v) x1, y, z; (vi) x1, y, z1.

Experimental details

Crystal data
Chemical formulaC6H13FO5
Mr184.16
Crystal system, space groupMonoclinic, P21
Temperature (K)150
a, b, c (Å)4.7968 (3), 8.5957 (5), 9.8194 (7)
β (°) 103.233 (3)
V3)394.12 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.40 × 0.10 × 0.05
Data collection
DiffractometerArea
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.88, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
3069, 947, 788
Rint0.039
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.095, 0.99
No. of reflections947
No. of parameters109
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.36

Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H41···O8i0.821.942.738 (4)165
O10—H101···O12ii0.821.952.730 (4)160
O8—H81···O10iii0.821.872.691 (4)172
O6—H61···O4iv0.821.892.703 (4)170
O12—H121···F1v0.842.082.895 (3)163
Symmetry codes: (i) x+2, y1/2, z+1; (ii) x+1, y+1/2, z; (iii) x+1, y, z; (iv) x1, y, z; (v) x1, y, z1.
 

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals Google Scholar
First citationBetteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.  Web of Science CrossRef IUCr Journals Google Scholar
First citationJenkinson, 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.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKent, P. W. & Wright, J. R. (1972). Carbohydr. Res. 22, 193–200.  CrossRef CAS PubMed Web of Science Google Scholar
First citationNonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, 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.  Google Scholar
First citationWatkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.  Google Scholar

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