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Acta Cryst. (2008). E64, o1705-o1706    [ doi:10.1107/S1600536808024586 ]

1-Deoxy-L-mannitol (6-deoxy-L-mannitol or L-rhamnitol)

S. F. Jenkinson, K. V. Booth, P. Gullapalli, K. Morimoto, K. Izumori, G. W. J. Fleet and D. J. Watkin

Abstract top

The crystalline form of 1-deoxy-L-mannitol, C6H14O5, exists as an extensively hydrogen-bonded structure with each molecule acting as a donor and acceptor for five hydrogen bonds. There are no unusual crystal-packing features; the absolute configuration was determined from the use of 6-deoxy-L-mannose (L-rhamnose) as the starting material.

Comment top

The properties of 1-deoxy ketohexose sugars have been little studied. The crystal structure of 6-deoxy-L-galactitol has recently been published (Jenkinson et al., 2008) and herein we report the crystal structure of a similar deoxy polyol, 1-deoxy-L-mannitol an intermediate in the synthesis of 1-deoxy-L-fructose, 3 (Fig. 1) (Gullapalli et al., 2007).

The demand for the large scale production of rare sugars by biotechnological (Izumori, 2006; Izumori, 2002; Granstrom et al., 2004) and chemical (Beadle et al., 1992) methods is driven by the demand for alternative foodstuffs (Skytte, 2002) and D-tagatose itself is used as a low calorie sweetener (Levin, 2002; Howling & Callagan, 2000; Bertelsen et al. 1999). Rare monosaccharides themselves, however, have been found to demonstrate interesting pharmaceutical properties, for example, D-psicose (Takata et al., 2005; Menavuvu et al., 2006) and D-allose (Sui et al., 2005; Hossain et al., 2006) have significant chemotherapeutic properties and D-tagatose has been found to be an anti-hyperglycemic agent (Donner et al., 1999) and therefore potentially useful in the treatment of diabetes.

1-Deoxy-L-mannitol 2 (Fig. 2) was prepared from the reduction by catalytic hydrogenation of 6-deoxy-L-mannose 1 (L-rhamnose). The X-ray structure shows that the crystal exists as an extensively hydrogen bonded lattice with each molecule acting as a donor and an acceptor for 5 hydrogen bonds (Fig.3).

Related literature top

For related literature see: Jenkinson et al. (2008); Gullapalli et al. (2007); Izumori (2002, 2006); Granstrom et al. (2004); Beadle et al. (1992); Skytte (2002); Sui et al. (2005); Levin (2002); Howling & Callagan (2000); Bertelsen et al. (1999); Takata et al. (2005); Menavuvu et al. (2006); Hossain et al. (2006); Donner et al. (1999).

Experimental top

1-Deoxy-L-mannitol was recrystallized from methanol: m.p. 390K, [α]D20 +1.4 (c, 1.4 in H2O).

Refinement top

In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was determined 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.

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 arbitary radius.
[Figure 3] Fig. 3. Packing diagram for the title compound projected along the b axis. Hydrogen bonds are shown as dotted lines.
1-Deoxy-L-mannitol top
Crystal data top
C6H14O5F000 = 360
Mr = 166.17Dx = 1.427 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1002 reflections
a = 7.3650 (3) Åθ = 5–27º
b = 7.6272 (3) ŵ = 0.12 mm−1
c = 13.7676 (5) ÅT = 150 K
V = 773.39 (5) Å3Plate, colourless
Z = 40.40 × 0.40 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer		974 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 150 Kθmax = 27.5º
ω scansθmin = 5.2º
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)		h = −9→9
Tmin = 0.89, Tmax = 0.99k = −9→9
5170 measured reflectionsl = −17→17
1033 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027  w = 1/[σ2(F2) + (0.04P)2 + 0.19P],
where P = [max(Fo2,0) + 2Fc2]/3
wR(F2) = 0.072(Δ/σ)max = 0.0003
S = 0.97Δρmax = 0.24 e Å−3
1033 reflectionsΔρmin = −0.19 e Å−3
100 parametersExtinction correction: None
Primary atom site location: structure-invariant direct methods
Crystal data top
C6H14O5V = 773.39 (5) Å3
Mr = 166.17Z = 4
Orthorhombic, P212121Mo Kα
a = 7.3650 (3) ŵ = 0.12 mm−1
b = 7.6272 (3) ÅT = 150 K
c = 13.7676 (5) Å0.40 × 0.40 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer		1033 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)		974 reflections with I > 2σ(I)
Tmin = 0.89, Tmax = 0.99Rint = 0.024
5170 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027Δρmax = 0.24 e Å−3
wR(F2) = 0.072Δρmin = −0.19 e Å−3
S = 0.97Absolute structure: ?
1033 reflectionsFlack parameter: ?
100 parametersRogers parameter: ?
H-atom parameters constrained
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.45760 (15)0.66827 (14)0.58528 (7)0.0158
C20.5038 (2)0.53406 (18)0.51734 (10)0.0121
C30.4654 (2)0.35710 (19)0.56608 (11)0.0129
O40.51432 (16)0.21669 (13)0.50177 (8)0.0180
C50.5694 (2)0.3334 (2)0.65961 (11)0.0160
O60.76010 (15)0.34756 (16)0.64310 (8)0.0190
C70.3954 (2)0.55797 (19)0.42326 (11)0.0125
O80.20579 (15)0.57629 (14)0.44513 (8)0.0163
C90.4543 (2)0.7196 (2)0.36498 (10)0.0140
O100.63971 (16)0.69611 (16)0.33563 (8)0.0188
C110.3428 (3)0.7388 (2)0.27300 (11)0.0195
H210.63380.54220.50170.0146*
H310.33660.35070.58360.0149*
H510.52580.42390.70480.0180*
H520.54240.21710.68900.0191*
H710.41470.45690.38160.0137*
H910.44020.82360.40590.0171*
H1110.37910.83900.23430.0290*
H1120.21120.75000.28630.0299*
H1130.35800.63340.23300.0284*
H10.71590.75320.36890.0319*
H20.42490.18980.46270.0307*
H30.17950.47080.45420.0290*
H40.80020.35230.70250.0312*
H50.53100.75600.57710.0285*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0168 (6)0.0130 (5)0.0175 (5)−0.0022 (4)0.0027 (5)−0.0036 (4)
C20.0103 (7)0.0137 (6)0.0122 (6)0.0004 (6)0.0007 (6)−0.0009 (5)
C30.0118 (7)0.0125 (6)0.0145 (7)0.0011 (6)0.0000 (6)0.0014 (5)
O40.0207 (6)0.0137 (5)0.0198 (5)0.0040 (5)−0.0064 (5)−0.0030 (4)
C50.0146 (8)0.0191 (7)0.0144 (7)0.0011 (6)0.0020 (6)0.0022 (6)
O60.0144 (6)0.0283 (6)0.0142 (5)0.0026 (5)−0.0015 (4)−0.0002 (4)
C70.0103 (7)0.0127 (7)0.0146 (7)0.0004 (5)0.0003 (6)−0.0003 (6)
O80.0102 (5)0.0128 (5)0.0259 (6)0.0000 (4)−0.0005 (4)0.0033 (4)
C90.0130 (7)0.0143 (6)0.0148 (7)−0.0010 (6)0.0003 (6)0.0017 (6)
O100.0120 (6)0.0284 (6)0.0160 (5)−0.0049 (5)0.0009 (4)−0.0020 (5)
C110.0173 (8)0.0250 (8)0.0163 (7)0.0002 (7)−0.0017 (6)0.0065 (6)
Geometric parameters (Å, °) top
O1—C21.4277 (17)O6—H40.870
O1—H50.868C7—O81.4354 (18)
C2—C31.5335 (19)C7—C91.533 (2)
C2—C71.5323 (19)C7—H710.971
C2—H210.983O8—H30.837
C3—O41.4354 (18)C9—O101.4352 (19)
C3—C51.509 (2)C9—C111.516 (2)
C3—H310.980C9—H910.979
O4—H20.875O10—H10.845
C5—O61.4269 (18)C11—H1110.969
C5—H510.983C11—H1120.991
C5—H520.995C11—H1130.981
C2—O1—H5108.6C2—C7—O8109.94 (12)
O1—C2—C3107.49 (11)C2—C7—C9112.99 (12)
O1—C2—C7110.15 (12)O8—C7—C9107.87 (12)
C3—C2—C7112.26 (12)C2—C7—H71109.2
O1—C2—H21109.3O8—C7—H71110.1
C3—C2—H21109.3C9—C7—H71106.7
C7—C2—H21108.4C7—O8—H399.4
C2—C3—O4109.91 (11)C7—C9—O10108.44 (13)
C2—C3—C5112.67 (12)C7—C9—C11111.20 (12)
O4—C3—C5108.04 (12)O10—C9—C11106.98 (12)
C2—C3—H31109.3C7—C9—H91108.7
O4—C3—H31111.0O10—C9—H91111.4
C5—C3—H31105.9C11—C9—H91110.2
C3—O4—H2111.5C9—O10—H1114.5
C3—C5—O6110.76 (12)C9—C11—H111112.7
C3—C5—H51106.9C9—C11—H112112.6
O6—C5—H51111.7H111—C11—H112107.7
C3—C5—H52110.6C9—C11—H113109.2
O6—C5—H52109.2H111—C11—H113107.8
H51—C5—H52107.6H112—C11—H113106.6
C5—O6—H4100.8
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O10—H1···O1i0.851.982.782 (2)158
O4—H2···O6ii0.871.922.779 (2)168
O8—H3···O4ii0.841.972.742 (2)152
O6—H4···O10iii0.871.922.772 (2)165
O1—H5···O8i0.871.842.704 (2)173
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+3/2, −y+1, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O10—H1···O1i0.851.982.782 (2)158
O4—H2···O6ii0.871.922.779 (2)168
O8—H3···O4ii0.841.972.742 (2)152
O6—H4···O10iii0.871.922.772 (2)165
O1—H5···O8i0.871.842.704 (2)173
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+3/2, −y+1, z+1/2.
Acknowledgements top

This work was supported in part by the Program for Promotion of Basic Research Activities for Innovative Biosciences (PROBRAIN). We also thank the Oxford University Chemical Crystallography service for use of the instruments.

references
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