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

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

doi:10.1107/S1600536808024586

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages o1705-o1706

doi:10.1107/S1600536808024586

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

Sarah F. Jenkinson,^a K. Victoria Booth,^a ^* Pushpakiran Gullapalli,^b Kenji Morimoto,^b Ken Izumori,^b George W. J. Fleet ^a and David J. Watkin ^c

^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, and ^cDepartment of Chemical Crystallography, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England
^*Correspondence e-mail: victoria.booth@chem.ox.ac.uk

(Received 25 July 2008; accepted 31 July 2008; online 6 August 2008)

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.

Related literature

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

Crystal data

C₆H₁₄O₅
M_r = 166.17
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.3650 (3) Å
b = 7.6272 (3) Å
c = 13.7676 (5) Å
V = 773.39 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 150 K
0.40 × 0.40 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.89, T_max = 0.99
5170 measured reflections
1033 independent reflections
974 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.072
S = 0.97
1033 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H1⋯O1ⁱ	0.85	1.98	2.782 (2)	158
O4—H2⋯O6ⁱⁱ	0.87	1.92	2.779 (2)	168
O8—H3⋯O4ⁱⁱ	0.84	1.97	2.742 (2)	152
O6—H4⋯O10ⁱⁱⁱ	0.87	1.92	2.772 (2)	165
O1—H5⋯O8ⁱ	0.87	1.84	2.704 (2)	173
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 2001 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024586/lh2670sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024586/lh2670Isup2.hkl

checkCIF report

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).

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

	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 arbitary radius.
	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

C₆H₁₄O₅	F(000) = 360
M_r = 166.17	D_x = 1.427 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1002 reflections
a = 7.3650 (3) Å	θ = 5–27°
b = 7.6272 (3) Å	µ = 0.12 mm⁻¹
c = 13.7676 (5) Å	T = 150 K
V = 773.39 (5) Å³	Plate, colourless
Z = 4	0.40 × 0.40 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 27.5°, θ_min = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −9→9
T_min = 0.89, T_max = 0.99	k = −9→9
5170 measured reflections	l = −17→17
1033 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F²) + (0.04P)² + 0.19P], where P = [max(F_o²,0) + 2F_c²]/3
S = 0.97	(Δ/σ)_max = 0.000327
1033 reflections	Δρ_max = 0.24 e Å⁻³
100 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints

Crystal data top

C₆H₁₄O₅	V = 773.39 (5) Å³
M_r = 166.17	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.3650 (3) Å	µ = 0.12 mm⁻¹
b = 7.6272 (3) Å	T = 150 K
c = 13.7676 (5) Å	0.40 × 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)
T_min = 0.89, T_max = 0.99	R_int = 0.024
5170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 0.97	Δρ_max = 0.24 e Å⁻³
1033 reflections	Δρ_min = −0.19 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.45760 (15)	0.66827 (14)	0.58528 (7)	0.0158
C2	0.5038 (2)	0.53406 (18)	0.51734 (10)	0.0121
C3	0.4654 (2)	0.35710 (19)	0.56608 (11)	0.0129
O4	0.51432 (16)	0.21669 (13)	0.50177 (8)	0.0180
C5	0.5694 (2)	0.3334 (2)	0.65961 (11)	0.0160
O6	0.76010 (15)	0.34756 (16)	0.64310 (8)	0.0190
C7	0.3954 (2)	0.55797 (19)	0.42326 (11)	0.0125
O8	0.20579 (15)	0.57629 (14)	0.44513 (8)	0.0163
C9	0.4543 (2)	0.7196 (2)	0.36498 (10)	0.0140
O10	0.63971 (16)	0.69611 (16)	0.33563 (8)	0.0188
C11	0.3428 (3)	0.7388 (2)	0.27300 (11)	0.0195
H21	0.6338	0.5422	0.5017	0.0146*
H31	0.3366	0.3507	0.5836	0.0149*
H51	0.5258	0.4239	0.7048	0.0180*
H52	0.5424	0.2171	0.6890	0.0191*
H71	0.4147	0.4569	0.3816	0.0137*
H91	0.4402	0.8236	0.4059	0.0171*
H111	0.3791	0.8390	0.2343	0.0290*
H112	0.2112	0.7500	0.2863	0.0299*
H113	0.3580	0.6334	0.2330	0.0284*
H1	0.7159	0.7532	0.3689	0.0319*
H2	0.4249	0.1898	0.4627	0.0307*
H3	0.1795	0.4708	0.4542	0.0290*
H4	0.8002	0.3523	0.7025	0.0312*
H5	0.5310	0.7560	0.5771	0.0285*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0168 (6)	0.0130 (5)	0.0175 (5)	−0.0022 (4)	0.0027 (5)	−0.0036 (4)
C2	0.0103 (7)	0.0137 (6)	0.0122 (6)	0.0004 (6)	0.0007 (6)	−0.0009 (5)
C3	0.0118 (7)	0.0125 (6)	0.0145 (7)	0.0011 (6)	0.0000 (6)	0.0014 (5)
O4	0.0207 (6)	0.0137 (5)	0.0198 (5)	0.0040 (5)	−0.0064 (5)	−0.0030 (4)
C5	0.0146 (8)	0.0191 (7)	0.0144 (7)	0.0011 (6)	0.0020 (6)	0.0022 (6)
O6	0.0144 (6)	0.0283 (6)	0.0142 (5)	0.0026 (5)	−0.0015 (4)	−0.0002 (4)
C7	0.0103 (7)	0.0127 (7)	0.0146 (7)	0.0004 (5)	0.0003 (6)	−0.0003 (6)
O8	0.0102 (5)	0.0128 (5)	0.0259 (6)	0.0000 (4)	−0.0005 (4)	0.0033 (4)
C9	0.0130 (7)	0.0143 (6)	0.0148 (7)	−0.0010 (6)	0.0003 (6)	0.0017 (6)
O10	0.0120 (6)	0.0284 (6)	0.0160 (5)	−0.0049 (5)	0.0009 (4)	−0.0020 (5)
C11	0.0173 (8)	0.0250 (8)	0.0163 (7)	0.0002 (7)	−0.0017 (6)	0.0065 (6)

Geometric parameters (Å, º) top

O1—C2	1.4277 (17)	O6—H4	0.870
O1—H5	0.868	C7—O8	1.4354 (18)
C2—C3	1.5335 (19)	C7—C9	1.533 (2)
C2—C7	1.5323 (19)	C7—H71	0.971
C2—H21	0.983	O8—H3	0.837
C3—O4	1.4354 (18)	C9—O10	1.4352 (19)
C3—C5	1.509 (2)	C9—C11	1.516 (2)
C3—H31	0.980	C9—H91	0.979
O4—H2	0.875	O10—H1	0.845
C5—O6	1.4269 (18)	C11—H111	0.969
C5—H51	0.983	C11—H112	0.991
C5—H52	0.995	C11—H113	0.981

C2—O1—H5	108.6	C2—C7—O8	109.94 (12)
O1—C2—C3	107.49 (11)	C2—C7—C9	112.99 (12)
O1—C2—C7	110.15 (12)	O8—C7—C9	107.87 (12)
C3—C2—C7	112.26 (12)	C2—C7—H71	109.2
O1—C2—H21	109.3	O8—C7—H71	110.1
C3—C2—H21	109.3	C9—C7—H71	106.7
C7—C2—H21	108.4	C7—O8—H3	99.4
C2—C3—O4	109.91 (11)	C7—C9—O10	108.44 (13)
C2—C3—C5	112.67 (12)	C7—C9—C11	111.20 (12)
O4—C3—C5	108.04 (12)	O10—C9—C11	106.98 (12)
C2—C3—H31	109.3	C7—C9—H91	108.7
O4—C3—H31	111.0	O10—C9—H91	111.4
C5—C3—H31	105.9	C11—C9—H91	110.2
C3—O4—H2	111.5	C9—O10—H1	114.5
C3—C5—O6	110.76 (12)	C9—C11—H111	112.7
C3—C5—H51	106.9	C9—C11—H112	112.6
O6—C5—H51	111.7	H111—C11—H112	107.7
C3—C5—H52	110.6	C9—C11—H113	109.2
O6—C5—H52	109.2	H111—C11—H113	107.8
H51—C5—H52	107.6	H112—C11—H113	106.6
C5—O6—H4	100.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H1···O1ⁱ	0.85	1.98	2.782 (2)	158
O4—H2···O6ⁱⁱ	0.87	1.92	2.779 (2)	168
O8—H3···O4ⁱⁱ	0.84	1.97	2.742 (2)	152
O6—H4···O10ⁱⁱⁱ	0.87	1.92	2.772 (2)	165
O1—H5···O8ⁱ	0.87	1.84	2.704 (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.

Experimental details

Crystal data
Chemical formula	C₆H₁₄O₅
M_r	166.17
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	7.3650 (3), 7.6272 (3), 13.7676 (5)
V (Å³)	773.39 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.40 × 0.40 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.89, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	5170, 1033, 974
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.072, 0.97
No. of reflections	1033
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

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···A	D—H	H···A	D···A	D—H···A
O10—H1···O1ⁱ	0.85	1.98	2.782 (2)	158
O4—H2···O6ⁱⁱ	0.87	1.92	2.779 (2)	168
O8—H3···O4ⁱⁱ	0.84	1.97	2.742 (2)	152
O6—H4···O10ⁱⁱⁱ	0.87	1.92	2.772 (2)	165
O1—H5···O8ⁱ	0.87	1.84	2.704 (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

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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