Acta Cryst. (2007). E63, o3388 [ doi:10.1107/S1600536807031546 ]
![[beta]](/logos/entities/beta_rmgif.gif)
-D-ribo-hex-2-ulofuranoseThe relative configuration of the title compound, C10H16O4, was firmly established by X-ray crystallographic analysis. The absolute configuration was determined by the use of 2-C-methyl-D-ribono-1,4-lactone as the starting material.
Treatment of 1-deoxy-3-C-methyl-D-psicose 2 (Jones et al. in preparation) derived from 2-C-methyl-D-ribono-1,4-lactone 1 (Hotchkiss et al., 2006), with sodium cyanide, gave a mixture of 2,6-anhydro derivative 3 and lactone 4 (Curran et al. 2007) (Fig. 3). X-ray analysis firmly established the structure of the title compound as the 2,6-anhydro furanose 3. m.p. 321–326 K; [α]D22 -47.0 (c, 1.0 in acetone).
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, 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.
![[Figure 1]](./lh2449fig1thm.gif)
| Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. |
![[Figure 2]](./lh2449fig2thm.gif)
| Fig. 2. Packing of the title compound projected along the b-axis. |
![[Figure 3]](./lh2449fig3thm.gif)
| Fig. 3. The reaction scheme. |
| C10H16O4 | F(000) = 432 |
| Mr = 200.23 | Dx = 1.277 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 1321 reflections |
| a = 6.6307 (2) Å | θ = 5–27° |
| b = 11.1029 (4) Å | µ = 0.10 mm−1 |
| c = 14.1409 (5) Å | T = 150 K |
| V = 1041.05 (6) Å3 | Plate, colourless |
| Z = 4 | 0.60 × 0.50 × 0.10 mm |
| Nonius KappaCCD diffractometer | 1160 reflections with I > 2σ(I) |
| graphite | Rint = 0.045 |
| ω scans | θmax = 27.5°, θmin = 5.3° |
| Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997) | h = −8→8 |
| Tmin = 0.95, Tmax = 1.00 | k = −14→14 |
| 6557 measured reflections | l = −18→18 |
| 1370 independent reflections |
| 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)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.074 | w = 1/[σ2(F2) + (0.03P)2 + 0.18P], where P = [max(Fo2,0) + 2Fc2]/3 |
| S = 0.93 | (Δ/σ)max = 0.0002 |
| 1370 reflections | Δρmax = 0.24 e Å−3 |
| 127 parameters | Δρmin = −0.19 e Å−3 |
| 0 restraints |
| C10H16O4 | V = 1041.05 (6) Å3 |
| Mr = 200.23 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 6.6307 (2) Å | µ = 0.10 mm−1 |
| b = 11.1029 (4) Å | T = 150 K |
| c = 14.1409 (5) Å | 0.60 × 0.50 × 0.10 mm |
| Nonius KappaCCD diffractometer | 1370 independent reflections |
| Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997) | 1160 reflections with I > 2σ(I) |
| Tmin = 0.95, Tmax = 1.00 | Rint = 0.045 |
| 6557 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.074 | Δρmax = 0.24 e Å−3 |
| S = 0.93 | Δρmin = −0.19 e Å−3 |
| 1370 reflections | Absolute structure: ? |
| 127 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.3568 (2) | 0.21011 (14) | 0.20100 (10) | 0.0212 | |
| C2 | 0.4422 (2) | 0.31928 (14) | 0.14619 (10) | 0.0217 | |
| O3 | 0.56240 (17) | 0.37828 (10) | 0.21534 (8) | 0.0263 | |
| C4 | 0.6883 (2) | 0.27622 (15) | 0.23612 (11) | 0.0272 | |
| C5 | 0.5351 (2) | 0.18346 (15) | 0.26887 (10) | 0.0245 | |
| O6 | 0.46475 (18) | 0.21350 (13) | 0.36068 (7) | 0.0352 | |
| C7 | 0.2509 (3) | 0.22921 (16) | 0.35888 (11) | 0.0270 | |
| O8 | 0.19903 (16) | 0.25108 (11) | 0.26189 (7) | 0.0283 | |
| C9 | 0.1985 (3) | 0.34073 (17) | 0.41531 (13) | 0.0403 | |
| C10 | 0.1483 (3) | 0.11679 (18) | 0.39421 (13) | 0.0396 | |
| C11 | 0.7600 (3) | 0.24199 (19) | 0.13709 (12) | 0.0353 | |
| O12 | 0.58629 (17) | 0.27261 (11) | 0.07985 (8) | 0.0317 | |
| C13 | 0.2974 (3) | 0.40276 (16) | 0.09881 (12) | 0.0305 | |
| C14 | 0.2857 (3) | 0.10662 (15) | 0.13904 (12) | 0.0308 | |
| H41 | 0.8009 | 0.2937 | 0.2816 | 0.0355* | |
| H51 | 0.5810 | 0.0978 | 0.2636 | 0.0310* | |
| H91 | 0.0522 | 0.3542 | 0.4084 | 0.0621* | |
| H92 | 0.2310 | 0.3255 | 0.4825 | 0.0614* | |
| H93 | 0.2804 | 0.4099 | 0.3910 | 0.0617* | |
| H101 | 0.0017 | 0.1299 | 0.3883 | 0.0594* | |
| H102 | 0.1804 | 0.1039 | 0.4613 | 0.0595* | |
| H103 | 0.1903 | 0.0467 | 0.3550 | 0.0594* | |
| H111 | 0.7881 | 0.1541 | 0.1327 | 0.0480* | |
| H112 | 0.8841 | 0.2875 | 0.1191 | 0.0473* | |
| H131 | 0.3743 | 0.4706 | 0.0698 | 0.0479* | |
| H132 | 0.1972 | 0.4328 | 0.1459 | 0.0487* | |
| H133 | 0.2281 | 0.3599 | 0.0465 | 0.0489* | |
| H141 | 0.2242 | 0.0438 | 0.1796 | 0.0485* | |
| H142 | 0.4037 | 0.0743 | 0.1055 | 0.0487* | |
| H143 | 0.1825 | 0.1383 | 0.0923 | 0.0481* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0180 (7) | 0.0224 (8) | 0.0231 (7) | 0.0020 (7) | −0.0018 (6) | −0.0006 (7) |
| C2 | 0.0217 (7) | 0.0228 (8) | 0.0207 (7) | 0.0003 (7) | −0.0004 (7) | −0.0020 (6) |
| O3 | 0.0255 (6) | 0.0219 (5) | 0.0316 (6) | −0.0021 (5) | −0.0053 (5) | −0.0018 (5) |
| C4 | 0.0185 (7) | 0.0304 (9) | 0.0326 (8) | 0.0012 (8) | −0.0031 (7) | 0.0014 (8) |
| C5 | 0.0219 (8) | 0.0267 (8) | 0.0248 (7) | 0.0014 (8) | −0.0033 (7) | 0.0028 (7) |
| O6 | 0.0274 (6) | 0.0560 (8) | 0.0221 (5) | 0.0010 (7) | −0.0034 (5) | 0.0044 (6) |
| C7 | 0.0257 (8) | 0.0348 (10) | 0.0204 (7) | −0.0004 (8) | −0.0008 (6) | 0.0021 (7) |
| O8 | 0.0205 (5) | 0.0431 (7) | 0.0214 (5) | 0.0029 (6) | 0.0011 (5) | 0.0025 (5) |
| C9 | 0.0467 (12) | 0.0394 (10) | 0.0347 (9) | 0.0016 (10) | −0.0041 (9) | −0.0070 (8) |
| C10 | 0.0441 (11) | 0.0375 (10) | 0.0372 (9) | −0.0035 (10) | 0.0063 (9) | 0.0071 (9) |
| C11 | 0.0221 (8) | 0.0443 (11) | 0.0394 (10) | 0.0043 (9) | 0.0037 (8) | 0.0026 (9) |
| O12 | 0.0273 (6) | 0.0415 (7) | 0.0262 (5) | 0.0031 (6) | 0.0057 (5) | 0.0001 (6) |
| C13 | 0.0350 (10) | 0.0261 (8) | 0.0304 (8) | 0.0022 (9) | −0.0060 (8) | 0.0045 (7) |
| C14 | 0.0323 (9) | 0.0254 (8) | 0.0348 (9) | −0.0029 (8) | −0.0085 (8) | −0.0010 (8) |
| C1—C2 | 1.546 (2) | C7—C10 | 1.507 (3) |
| C1—C5 | 1.551 (2) | C9—H91 | 0.986 |
| C1—O8 | 1.4293 (18) | C9—H92 | 0.988 |
| C1—C14 | 1.520 (2) | C9—H93 | 1.001 |
| C2—O3 | 1.4214 (18) | C10—H101 | 0.986 |
| C2—O12 | 1.4357 (18) | C10—H102 | 0.983 |
| C2—C13 | 1.493 (2) | C10—H103 | 0.995 |
| O3—C4 | 1.438 (2) | C11—O12 | 1.448 (2) |
| C4—C5 | 1.519 (2) | C11—H111 | 0.995 |
| C4—C11 | 1.527 (2) | C11—H112 | 0.998 |
| C4—H41 | 1.004 | C13—H131 | 0.998 |
| C5—O6 | 1.4193 (19) | C13—H132 | 0.999 |
| C5—H51 | 1.001 | C13—H133 | 0.993 |
| O6—C7 | 1.429 (2) | C14—H141 | 0.991 |
| C7—O8 | 1.4348 (18) | C14—H142 | 0.983 |
| C7—C9 | 1.514 (2) | C14—H143 | 1.014 |
| C2—C1—C5 | 100.40 (12) | C7—O8—C1 | 110.27 (12) |
| C2—C1—O8 | 108.70 (12) | C7—C9—H91 | 107.3 |
| C5—C1—O8 | 104.24 (11) | C7—C9—H92 | 108.4 |
| C2—C1—C14 | 114.66 (13) | H91—C9—H92 | 109.6 |
| C5—C1—C14 | 116.67 (13) | C7—C9—H93 | 108.8 |
| O8—C1—C14 | 111.16 (13) | H91—C9—H93 | 112.5 |
| C1—C2—O3 | 102.81 (11) | H92—C9—H93 | 110.0 |
| C1—C2—O12 | 106.76 (12) | C7—C10—H101 | 107.1 |
| O3—C2—O12 | 104.05 (12) | C7—C10—H102 | 110.0 |
| C1—C2—C13 | 118.43 (14) | H101—C10—H102 | 108.4 |
| O3—C2—C13 | 112.53 (13) | C7—C10—H103 | 109.6 |
| O12—C2—C13 | 111.02 (13) | H101—C10—H103 | 110.2 |
| C2—O3—C4 | 95.90 (11) | H102—C10—H103 | 111.4 |
| O3—C4—C5 | 102.05 (13) | C4—C11—O12 | 101.92 (12) |
| O3—C4—C11 | 100.93 (13) | C4—C11—H111 | 111.1 |
| C5—C4—C11 | 108.61 (15) | O12—C11—H111 | 110.1 |
| O3—C4—H41 | 114.2 | C4—C11—H112 | 111.4 |
| C5—C4—H41 | 115.7 | O12—C11—H112 | 113.2 |
| C11—C4—H41 | 113.8 | H111—C11—H112 | 109.0 |
| C1—C5—C4 | 101.05 (12) | C11—O12—C2 | 104.40 (11) |
| C1—C5—O6 | 105.70 (12) | C2—C13—H131 | 108.9 |
| C4—C5—O6 | 109.83 (14) | C2—C13—H132 | 109.6 |
| C1—C5—H51 | 111.5 | H131—C13—H132 | 111.3 |
| C4—C5—H51 | 114.7 | C2—C13—H133 | 109.5 |
| O6—C5—H51 | 113.0 | H131—C13—H133 | 107.0 |
| C5—O6—C7 | 109.79 (12) | H132—C13—H133 | 110.5 |
| O6—C7—O8 | 106.00 (12) | C1—C14—H141 | 109.1 |
| O6—C7—C9 | 108.58 (16) | C1—C14—H142 | 107.9 |
| O8—C7—C9 | 108.08 (14) | H141—C14—H142 | 110.5 |
| O6—C7—C10 | 109.95 (16) | C1—C14—H143 | 108.8 |
| O8—C7—C10 | 110.41 (14) | H141—C14—H143 | 110.0 |
| C9—C7—C10 | 113.52 (15) | H142—C14—H143 | 110.5 |
Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435–?.
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487–?.
Curran, L. A., Jenkinson, S. F., Jones, N. A., Watkin, D. J. & Fleet, G. W. J. (2007). Acta Cryst. E (LH2448).
Hotchkiss, D. J., Jenkinson, S. F., Storer, R., Heinz, T. & Fleet, G. W. J. (2006). Tetrahedron Lett. 47, 315–318.
Jones, N. A., Curran, L. A., Wormald, M. R., Dwek, R. A. & Fleet, G. W. J. (2007). preparation.
Nonius (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, University of Oxford, England.
For background information see the previous paper (Curran et al., 2007). The crystal structure of the title compound (Fig. 1) exists as alternating layers of molecules running parallel to the ab-face (Fig.2). There is no hydrogen bonding.