Acta Cryst. (2008). E64, o1385 [ doi:10.1107/S1600536808019582 ]
![[alpha]](/logos/entities/alpha_rmgif.gif)
-L-talopyranoseX-ray crystallography showed that the title compound, C6H12O5, crystallizes in the -pyranose form with the six-membered ring in a chair conformation. The crystal structure exists as a three-dimensional hydrogen-bonded network of molecules with each molecule acting as a donor and aceptor for four hydrogen bonds. The absolute configuration was determined by the use of L-fucose as starting material.
The title compound was recrystallized from methanol: m.p. 120–123°C; [α]D20 -18.6 (c, 0.94 in H2O).
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.
Data collection: COLLECT (Nonius, 1997-2001).; 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).
![[Figure 1]](./lh2652fig1thm.gif)
| Fig. 1. Synthetic scheme. |
![[Figure 2]](./lh2652fig2thm.gif)
| 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]](./lh2652fig3thm.gif)
| Fig. 3. Packing diagram of the title compound projected along the a-axis. |
| C6H12O5 | F000 = 352 |
| Mr = 164.16 | Dx = 1.511 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 890 reflections |
| a = 6.4939 (3) Å | θ = 5–27º |
| b = 7.4874 (4) Å | µ = 0.13 mm−1 |
| c = 14.8382 (8) Å | T = 150 K |
| V = 721.47 (6) Å3 | Plate, colourless |
| Z = 4 | 0.25 × 0.25 × 0.02 mm |
| Nonius KappaCCD diffractometer | 863 reflections with I > 2.0σ(I) |
| Monochromator: graphite | Rint = 0.037 |
| T = 150 K | θmax = 27.5º |
| ω scans | θmin = 5.2º |
| Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997) | h = −8→8 |
| Tmin = 0.97, Tmax = 1.00 | k = −9→9 |
| 4390 measured reflections | l = −19→19 |
| 968 independent reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.029 | Method = Modified Sheldrick
w = 1/[σ2(F2) + ( 0.04P)2 + 0.04P]
, where P = (max(Fo2,0) + 2Fc2)/3 |
| wR(F2) = 0.072 | (Δ/σ)max = 0.0002 |
| S = 1.03 | Δρmax = 0.24 e Å−3 |
| 968 reflections | Δρmin = −0.21 e Å−3 |
| 100 parameters | Extinction correction: None |
| Primary atom site location: structure-invariant direct methods |
| C6H12O5 | V = 721.47 (6) Å3 |
| Mr = 164.16 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα |
| a = 6.4939 (3) Å | µ = 0.13 mm−1 |
| b = 7.4874 (4) Å | T = 150 K |
| c = 14.8382 (8) Å | 0.25 × 0.25 × 0.02 mm |
| Nonius KappaCCD diffractometer | 968 independent reflections |
| Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997) | 863 reflections with I > 2.0σ(I) |
| Tmin = 0.97, Tmax = 1.00 | Rint = 0.037 |
| 4390 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | Δρmax = 0.24 e Å−3 |
| wR(F2) = 0.072 | Δρmin = −0.21 e Å−3 |
| S = 1.03 | Absolute structure: ? |
| 968 reflections | Flack parameter: ? |
| 100 parameters | Rogers parameter: ? |
| H-atom parameters constrained |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.95002 (16) | 0.08900 (18) | 0.35376 (7) | 0.0210 | |
| C2 | 0.7416 (2) | 0.1250 (2) | 0.32982 (10) | 0.0175 | |
| C3 | 0.6113 (3) | 0.1509 (3) | 0.41551 (10) | 0.0188 | |
| O4 | 0.65011 (17) | 0.31964 (16) | 0.45740 (7) | 0.0183 | |
| C5 | 0.6150 (2) | 0.4717 (2) | 0.39897 (10) | 0.0194 | |
| C6 | 0.6412 (3) | 0.6382 (3) | 0.45454 (12) | 0.0271 | |
| C7 | 0.7657 (2) | 0.4593 (2) | 0.32003 (10) | 0.0187 | |
| C8 | 0.7208 (2) | 0.2889 (3) | 0.26846 (10) | 0.0186 | |
| O9 | 0.85143 (18) | 0.26675 (18) | 0.19178 (7) | 0.0243 | |
| O10 | 0.97297 (17) | 0.45445 (18) | 0.35319 (8) | 0.0232 | |
| O11 | 0.40458 (18) | 0.1333 (2) | 0.39115 (8) | 0.0254 | |
| H21 | 0.6937 | 0.0193 | 0.2985 | 0.0197* | |
| H31 | 0.6474 | 0.0567 | 0.4621 | 0.0197* | |
| H51 | 0.4756 | 0.4675 | 0.3773 | 0.0236* | |
| H61 | 0.6179 | 0.7441 | 0.4188 | 0.0406* | |
| H62 | 0.5480 | 0.6346 | 0.5057 | 0.0398* | |
| H63 | 0.7791 | 0.6452 | 0.4743 | 0.0401* | |
| H71 | 0.7508 | 0.5628 | 0.2786 | 0.0214* | |
| H81 | 0.5761 | 0.2938 | 0.2475 | 0.0221* | |
| H7 | 0.8826 | 0.3664 | 0.1753 | 0.0374* | |
| H8 | 0.9866 | 0.1914 | 0.3632 | 0.0333* | |
| H10 | 1.0243 | 0.5538 | 0.3399 | 0.0350* | |
| H1 | 0.3258 | 0.1436 | 0.4383 | 0.0408* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0198 (5) | 0.0204 (7) | 0.0229 (6) | 0.0030 (5) | −0.0010 (5) | −0.0005 (5) |
| C2 | 0.0184 (7) | 0.0188 (9) | 0.0153 (7) | −0.0001 (8) | −0.0013 (6) | −0.0015 (6) |
| C3 | 0.0209 (8) | 0.0186 (9) | 0.0169 (7) | −0.0037 (7) | 0.0005 (6) | −0.0021 (7) |
| O4 | 0.0223 (5) | 0.0178 (7) | 0.0150 (5) | −0.0008 (5) | −0.0006 (5) | 0.0007 (5) |
| C5 | 0.0220 (8) | 0.0184 (9) | 0.0179 (7) | 0.0019 (8) | −0.0015 (7) | 0.0002 (7) |
| C6 | 0.0378 (10) | 0.0202 (10) | 0.0232 (8) | 0.0022 (9) | 0.0025 (9) | −0.0040 (7) |
| C7 | 0.0183 (7) | 0.0202 (9) | 0.0176 (7) | 0.0031 (7) | 0.0006 (7) | 0.0029 (7) |
| C8 | 0.0197 (7) | 0.0212 (10) | 0.0149 (7) | 0.0011 (7) | 0.0013 (6) | −0.0005 (7) |
| O9 | 0.0335 (6) | 0.0213 (7) | 0.0180 (5) | 0.0043 (6) | 0.0087 (5) | 0.0025 (5) |
| O10 | 0.0195 (5) | 0.0195 (7) | 0.0306 (6) | −0.0026 (5) | −0.0015 (5) | 0.0023 (6) |
| O11 | 0.0199 (5) | 0.0331 (8) | 0.0233 (5) | −0.0074 (6) | 0.0028 (5) | −0.0047 (6) |
| O1—C2 | 1.4250 (19) | C6—H61 | 0.966 |
| O1—H8 | 0.815 | C6—H62 | 0.971 |
| C2—C3 | 1.540 (2) | C6—H63 | 0.944 |
| C2—C8 | 1.534 (2) | C7—C8 | 1.516 (2) |
| C2—H21 | 0.969 | C7—O10 | 1.4334 (19) |
| C3—O4 | 1.430 (2) | C7—H71 | 0.994 |
| C3—O11 | 1.3965 (19) | C8—O9 | 1.4288 (18) |
| C3—H31 | 1.015 | C8—H81 | 0.990 |
| O4—C5 | 1.449 (2) | O9—H7 | 0.811 |
| C5—C6 | 1.504 (2) | O10—H10 | 0.839 |
| C5—C7 | 1.529 (2) | O11—H1 | 0.870 |
| C5—H51 | 0.962 | ||
| C2—O1—H8 | 98.1 | C5—C6—H62 | 109.6 |
| O1—C2—C3 | 109.88 (12) | H61—C6—H62 | 110.8 |
| O1—C2—C8 | 112.50 (13) | C5—C6—H63 | 108.9 |
| C3—C2—C8 | 109.93 (14) | H61—C6—H63 | 105.9 |
| O1—C2—H21 | 105.7 | H62—C6—H63 | 110.5 |
| C3—C2—H21 | 108.8 | C5—C7—C8 | 108.34 (14) |
| C8—C2—H21 | 109.9 | C5—C7—O10 | 109.84 (12) |
| C2—C3—O4 | 111.93 (14) | C8—C7—O10 | 109.43 (14) |
| C2—C3—O11 | 107.62 (12) | C5—C7—H71 | 111.3 |
| O4—C3—O11 | 111.43 (15) | C8—C7—H71 | 109.0 |
| C2—C3—H31 | 110.4 | O10—C7—H71 | 108.9 |
| O4—C3—H31 | 106.1 | C2—C8—C7 | 110.89 (12) |
| O11—C3—H31 | 109.4 | C2—C8—O9 | 109.12 (13) |
| C3—O4—C5 | 113.97 (11) | C7—C8—O9 | 112.67 (13) |
| O4—C5—C6 | 107.79 (12) | C2—C8—H81 | 107.4 |
| O4—C5—C7 | 108.05 (13) | C7—C8—H81 | 108.0 |
| C6—C5—C7 | 113.45 (14) | O9—C8—H81 | 108.5 |
| O4—C5—H51 | 108.8 | C8—O9—H7 | 106.4 |
| C6—C5—H51 | 108.5 | C7—O10—H10 | 105.7 |
| C7—C5—H51 | 110.1 | C3—O11—H1 | 110.4 |
| C5—C6—H61 | 111.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O9—H7···O1i | 0.81 | 2.04 | 2.818 (2) | 162 |
| O1—H8···C7 | 0.82 | 2.55 | 3.061 (2) | 122 |
| O1—H8···O10 | 0.82 | 1.98 | 2.740 (2) | 156 |
| O10—H10···O9i | 0.84 | 1.85 | 2.686 (2) | 177 |
| O11—H1···O4ii | 0.87 | 1.94 | 2.812 (2) | 177 |
| Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O9—H7···O1i | 0.81 | 2.04 | 2.818 (2) | 162 |
| O1—H8···O10 | 0.82 | 1.98 | 2.740 (2) | 156 |
| O10—H10···O9i | 0.84 | 1.85 | 2.686 (2) | 177 |
| O11—H1···O4ii | 0.87 | 1.94 | 2.812 (2) | 177 |
| Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1. |
We gratefully acknowledge the Oxford University Chemical Crystallography service for use of the instruments. This work was supported in part by the Program for Promotion of Basic Research Activities for Innovative Biosciences (PROBRAIN).
Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435–435.
Beadle, J. R., Saunders, J. P. & Wajda, T. J. (1992). US Patent 5 078 796.
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487–?.
Granstrom, T. B., Takata, G., Tokuda, M. & Izumori, K. (2004). J. Biosci. Bioeng. 97, 89–94.
Izumori, K. (2002). Naturwissenschaften, 89, 120–124.
Izumori, K. (2006). J. Biotech. 124, 717–722.
Nonius (1997–2001). COLLECT. Nonius BV, Delft, The Netherlands.
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.
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.
Yoshihara, A., Haraguchi, S., Gullapalli, P., Rao, D., Morimoto, K., Takata, G., Jones, N., Jenkinson, S. F., Wormald, M. R., Dwek, R. A., Fleet, G. W. J. & Izumori, K. (2008). Tetrahedron Asymmetry, 19, 739–745.
The range of rare sugars that are now readily available has increased in recent years due to both chemical (Beadle et al., 1992) and biotechnological (Izumori, 2006; Izumori, 2002; Granstrom et al., 2004) advances. The methodology developed by Izumori et al. 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) in large amounts in water.
The Izumoring method is demonstrated here with the synthesis of 6-deoxy-L-talose 3 from L-fucose 1(Fig. 1) by a series of isomerizations. Firstly, using D-arabinose isomerase, L-fucose was isomerized to 6-deoxy-L-tagatose 2 and then using L-rhamnose isomerase this was further isomerized to give 6-deoxy-L-talose 3.
6-Deoxy-L-talose crystallizes solely in the α-pyranose form (Fig. 2). The absolute configuration was determined from the starting material. The crystal exists as an hydrogen bonded network with each molecule acting as a donor and acceptor for 4 hydrogen bonds. Non-conventional hydrogen bonds have been ignored.