1-De­oxy-d-galactitol (l-fucitol)

Abstract

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,

• a = 4.8486 (3) Å

• b = 4.8827 (3) Å

• c = 16.8354 (13) Å

• β = 92.856 (2)°

• V = 398.07 (5) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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

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.

Supplementary Material

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

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⋯O9iv	0.85	1.85	2.684 (4)	166
O11—H10⋯O11v	0.84	2.01	2.828 (4)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

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.

Experimental

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)].

Refinement

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

The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:1.22 reflect changes in the illuminated volume of the crystal. Changes in illuminated volume were kept to a minimum, and were taken into account (Görbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997).

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 U_iso(H) (in the range 1.2–1.5 times U_eq 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 arbitary radius.

Fig. 3.

The packing diagram for the title compound projected along the b-axis. Hydrogen bonds are shown as dotted lines.

Crystal data

C6H14O5	F000 = 180
Mr = 166.17	Dx = 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 = 5–27º
c = 16.8354 (13) Å	µ = 0.12 mm−1
β = 92.856 (2)º	T = 150 K
V = 398.07 (5) Å3	Block, colourless
Z = 2	0.15 × 0.15 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer	804 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 150 K	θmax = 27.4º
ω scans	θmin = 5.4º
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −6→6
Tmin = 0.81, Tmax = 0.99	k = −5→6
2786 measured reflections	l = −21→21
998 independent reflections

Refinement

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/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 17.0 25.0 12.0 3.16
S = 0.88	(Δ/σ)max = 0.0002
998 reflections	Δρmax = 0.34 e Å−3
100 parameters	Δρmin = −0.31 e Å−3
1 restraint	Extinction correction: none

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···O9iv	0.85	1.85	2.684 (4)	166
O11—H10···O11v	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.