1-De­oxy-d-galactitol (l-fucitol)

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

doi:10.1107/S1600536808020345

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1429

doi:10.1107/S1600536808020345

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1-Deoxy-D-galactitol (L-fucitol)

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

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

(Received 25 June 2008; accepted 2 July 2008; online 9 July 2008)

1-Deoxy-D-galactitol, C₆H₁₄O₅, exists in the crystalline form as hydrogen-bonded layers of molecules running parallel to the ac plane, with each molecule acting as a donor and acceptor of five hydrogen bonds.

Related literature

For related literature, see: Yoshihara et al. (2008 ); Jones et al. (2007 ); Görbitz (1999 ); Izumori (2002 , 2006 ); Prince (1982 ); Watkin (1994 ).

Experimental

Crystal data

C₆H₁₄O₅
M_r = 166.17
Monoclinic, P 2₁
a = 4.8486 (3) Å
b = 4.8827 (3) Å
c = 16.8354 (13) Å
β = 92.856 (2)°
V = 398.07 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 150 K
0.15 × 0.15 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.81, T_max = 0.99
2786 measured reflections
998 independent reflections
804 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.111
S = 0.88
998 reflections
100 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1⋯O6ⁱ	0.83	1.91	2.691 (4)	155
O9—H3⋯O4ⁱⁱ	0.83	1.97	2.753 (4)	156
O6—H4⋯O1ⁱⁱⁱ	0.81	2.10	2.758 (4)	138
O1—H9⋯O9^iv	0.85	1.85	2.684 (4)	166
O11—H10⋯O11^v	0.84	2.01	2.828 (4)	163
Symmetry codes: (i) x+1, y, z; (ii) x, y-1, z; (iii) x, y+1, z; (iv) x-1, y, z; (v) $[-x+2, y+{\script{1\over 2}}, -z+2]$ .

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/S1600536808020345/lh2653sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020345/lh2653Isup2.hkl

checkCIF report

Comment top

The methodology developed by Izumori (2002, 2006) for the interconversion of tetroses, pentoses and hexoses by enzymatic oxidation, inversion at C3 with a single epimerase, and reduction to the aldose has been seen to be generally applicable for the 1-deoxy ketohexoses (Yoshihara et al., 2008). This methodology could allow access to rare monosaccharides in water in large amounts. An example of this is the subsequent formation of 1-deoxy-D-galactitol 2 by hydrogenation of L-fucose 1 (Fig. 1) which subsequently could be oxidized enzymatically to 1-deoxy-D-tagatose (Jones et al., 2007) 3.

If the terminal hydroxyl group and H atoms are ignored there is a pseudo centre of symmetry between C2 and C3 (Fig. 2). The crystal structure exists of hydrogen-bonded layers of molecules running parallel to the c-axis (Fig. 3). Each molecule acts as a donor and acceptor of 5 hydrogen bonds, all intra-molecular hydrogen bonds have been omitted.

Related literature top

For related literature, see: Yoshihara et al. (2008); Jones et al. (2007); Görbitz (1999); Izumori (2002, 2006); Prince (1982); Watkin (1994).

Experimental top

The title compound was recrystallized from methanol: m.p. 420-422K; [α]_D²¹ +1.6 (c, 1.13 in H₂O) [Lit. (Yoshihara et al., 2008) for enantiomer [α]_D²⁰ -1.9 (c, 1.0 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. The packing diagram for the title compound projected along the b-axis. Hydrogen bonds are shown as dotted lines.

1-Deoxy-D-galactitol top

Crystal data top

C₆H₁₄O₅	F(000) = 180
M_r = 166.17	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 4.8486 (3) Å	Cell parameters from 844 reflections
b = 4.8827 (3) Å	θ = 5–27°
c = 16.8354 (13) Å	µ = 0.12 mm⁻¹
β = 92.856 (2)°	T = 150 K
V = 398.07 (5) Å³	Block, colourless
Z = 2	0.15 × 0.15 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	804 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 27.4°, θ_min = 5.4°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −6→6
T_min = 0.81, T_max = 0.99	k = −5→6
2786 measured reflections	l = −21→21
998 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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.111	Method, part 1, Chebychev polynomial, (Watkin, 1994; Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 17.0 25.0 12.0 3.16
S = 0.88	(Δ/σ)_max = 0.000240
998 reflections	Δρ_max = 0.34 e Å⁻³
100 parameters	Δρ_min = −0.31 e Å⁻³
1 restraint

Crystal data top

C₆H₁₄O₅	V = 398.07 (5) Å³
M_r = 166.17	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.8486 (3) Å	µ = 0.12 mm⁻¹
b = 4.8827 (3) Å	T = 150 K
c = 16.8354 (13) Å	0.15 × 0.15 × 0.05 mm
β = 92.856 (2)°

Data collection top

Nonius KappaCCD diffractometer	998 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	804 reflections with I > 2σ(I)
T_min = 0.81, T_max = 0.99	R_int = 0.038
2786 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.111	H-atom parameters constrained
S = 0.88	Δρ_max = 0.34 e Å⁻³
998 reflections	Δρ_min = −0.31 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	0.4779 (4)	0.0226 (5)	0.76245 (11)	0.0217
C2	0.6328 (6)	0.2631 (7)	0.78168 (17)	0.0186
C3	0.7866 (6)	0.3389 (7)	0.70769 (17)	0.0189
O4	0.9430 (4)	0.5805 (5)	0.72728 (12)	0.0227
C5	0.5946 (6)	0.3936 (7)	0.63490 (17)	0.0207
O6	0.4117 (4)	0.6179 (5)	0.64879 (12)	0.0238
C7	0.7550 (7)	0.4471 (9)	0.56067 (18)	0.0330
C8	0.8283 (6)	0.2108 (7)	0.85426 (17)	0.0190
O9	1.0094 (4)	−0.0141 (5)	0.84026 (12)	0.0222
C10	0.6698 (6)	0.1572 (7)	0.92859 (17)	0.0236
O11	0.8526 (4)	0.1176 (5)	0.99759 (12)	0.0260
H21	0.5071	0.4100	0.7945	0.0249*
H31	0.9082	0.1875	0.6971	0.0263*
H51	0.4763	0.2307	0.6253	0.0282*
H71	0.6272	0.4510	0.5138	0.0515*
H72	0.8900	0.3047	0.5550	0.0518*
H73	0.8493	0.6223	0.5674	0.0506*
H81	0.9485	0.3709	0.8670	0.0243*
H101	0.5642	−0.0123	0.9193	0.0325*
H102	0.5415	0.3107	0.9363	0.0333*
H1	1.0737	0.5438	0.6989	0.0372*
H3	0.9415	−0.1296	0.8087	0.0364*
H4	0.5121	0.7060	0.6789	0.0402*
H9	0.3277	0.0397	0.7859	0.0353*
H10	0.9076	0.2813	0.9992	0.0410*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0179 (9)	0.0228 (13)	0.0249 (10)	−0.0051 (9)	0.0048 (8)	−0.0061 (10)
C2	0.0180 (13)	0.0189 (15)	0.0189 (13)	−0.0011 (11)	0.0010 (10)	0.0011 (12)
C3	0.0196 (13)	0.0173 (15)	0.0202 (13)	−0.0016 (12)	0.0031 (11)	−0.0029 (12)
O4	0.0212 (10)	0.0235 (13)	0.0237 (9)	−0.0059 (10)	0.0057 (8)	−0.0040 (10)
C5	0.0210 (14)	0.0218 (17)	0.0196 (13)	0.0007 (13)	0.0029 (11)	−0.0017 (12)
O6	0.0188 (9)	0.0271 (13)	0.0254 (10)	0.0014 (10)	0.0003 (8)	−0.0008 (11)
C7	0.0320 (17)	0.048 (2)	0.0192 (14)	0.0027 (17)	0.0047 (12)	0.0033 (16)
C8	0.0166 (13)	0.0198 (15)	0.0204 (13)	0.0021 (12)	0.0006 (10)	−0.0004 (12)
O9	0.0206 (10)	0.0227 (12)	0.0233 (10)	0.0015 (10)	0.0011 (8)	−0.0047 (10)
C10	0.0223 (14)	0.031 (2)	0.0179 (13)	0.0020 (13)	0.0023 (11)	−0.0001 (13)
O11	0.0323 (11)	0.0248 (11)	0.0206 (9)	−0.0028 (11)	−0.0024 (8)	0.0022 (10)

Geometric parameters (Å, º) top

O1—C2	1.423 (4)	O6—H4	0.809
O1—H9	0.849	C7—H71	0.979
C2—C3	1.529 (4)	C7—H72	0.963
C2—C8	1.530 (4)	C7—H73	0.974
C2—H21	0.972	C8—O9	1.433 (4)
C3—O4	1.432 (4)	C8—C10	1.523 (4)
C3—C5	1.525 (4)	C8—H81	0.992
C3—H31	0.968	O9—H3	0.832
O4—H1	0.832	C10—O11	1.439 (4)
C5—O6	1.436 (4)	C10—H101	0.982
C5—C7	1.527 (4)	C10—H102	0.987
C5—H51	0.989	O11—H10	0.843

C2—O1—H9	105.6	C5—C7—H71	109.6
O1—C2—C3	106.7 (2)	C5—C7—H72	109.6
O1—C2—C8	110.0 (3)	H71—C7—H72	109.9
C3—C2—C8	112.6 (2)	C5—C7—H73	108.1
O1—C2—H21	109.2	H71—C7—H73	110.5
C3—C2—H21	109.8	H72—C7—H73	109.1
C8—C2—H21	108.5	C2—C8—O9	110.9 (2)
C2—C3—O4	106.6 (2)	C2—C8—C10	111.5 (2)
C2—C3—C5	113.2 (2)	O9—C8—C10	110.0 (3)
O4—C3—C5	109.6 (3)	C2—C8—H81	112.0
C2—C3—H31	106.9	O9—C8—H81	106.3
O4—C3—H31	110.6	C10—C8—H81	105.8
C5—C3—H31	109.8	C8—O9—H3	113.5
C3—O4—H1	95.8	C8—C10—O11	111.8 (2)
C3—C5—O6	111.1 (2)	C8—C10—H101	107.1
C3—C5—C7	111.9 (2)	O11—C10—H101	108.1
O6—C5—C7	110.3 (3)	C8—C10—H102	108.9
C3—C5—H51	108.5	O11—C10—H102	111.3
O6—C5—H51	106.4	H101—C10—H102	109.5
C7—C5—H51	108.6	C10—O11—H10	94.6
C5—O6—H4	98.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O6ⁱ	0.83	1.91	2.691 (4)	155
O9—H3···O4ⁱⁱ	0.83	1.97	2.753 (4)	156
O6—H4···O1ⁱⁱⁱ	0.81	2.10	2.758 (4)	138
O6—H4···O4	0.81	2.29	2.842 (4)	126
O1—H9···O9^iv	0.85	1.85	2.684 (4)	166
O11—H10···O11^v	0.84	2.01	2.828 (4)	163

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

Experimental details

Crystal data
Chemical formula	C₆H₁₄O₅
M_r	166.17
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	150
a, b, c (Å)	4.8486 (3), 4.8827 (3), 16.8354 (13)
β (°)	92.856 (2)
V (Å³)	398.07 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.15 × 0.15 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.81, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	2786, 998, 804
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 0.88
No. of reflections	998
No. of parameters	100
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31

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
O4—H1···O6ⁱ	0.83	1.91	2.691 (4)	155
O9—H3···O4ⁱⁱ	0.83	1.97	2.753 (4)	156
O6—H4···O1ⁱⁱⁱ	0.81	2.10	2.758 (4)	138
O1—H9···O9^iv	0.85	1.85	2.684 (4)	166
O11—H10···O11^v	0.84	2.01	2.828 (4)	163

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

Acknowledgements

This work was supported in part by the Programme for Promotion of Basic Research Activities for Innovative Biosciences (PROBRAIN).

References

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