Acta Cryst. (2007). E63, o3386 [ doi:10.1107/S1600536807031522 ]
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-L-erythroseThe relative configuration of the title compound, C9H16O5, has been firmly established by X-ray crystallographic analysis. The absolute configuration of this sugar was determined by the use of 2-C-methyl-D-ribono-1,4-lactone as the starting material. The structure exists as a hydrogen-bonded network, with each molecule being a donor and an acceptor for two hydrogen bonds.
Protected 3-C-methyl-L-erythrose (Booth, Best et al., 2007) 2, derived from 2-C-methyl-D-ribono-1,4-lactone 1, was treated with potassium carbonate and an excess of formaldehyde (Fig. 3). This gave a single product 3, a mixture of anomers in solution, which was found to crystallize as the pure β form (Fig. 1). The title compound was recrystallized from methanol; m.p. 337–343 K; [α]D21 +66.2 (c, 1.34 in acetone).
In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned on the basis of 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]](./lh2446fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. |
![[Figure 2]](./lh2446fig2thm.gif)
| Fig. 2. Packing of the title compound projected along the a-axis. Hydrogen bonds are shown as dotted lines. |
![[Figure 3]](./lh2446fig3thm.gif)
| Fig. 3. The reaction scheme. |
| C9H16O5 | F(000) = 440 |
| Mr = 204.22 | Dx = 1.363 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 1304 reflections |
| a = 6.2840 (2) Å | θ = 5–27° |
| b = 11.2043 (3) Å | µ = 0.11 mm−1 |
| c = 14.1345 (5) Å | T = 150 K |
| V = 995.18 (5) Å3 | Plate, colourless |
| Z = 4 | 0.40 × 0.15 × 0.15 mm |
| Nonius KappaCCD area-detector diffractometer | 1174 reflections with I > 2σ(I) |
| graphite | Rint = 0.030 |
| ω scans | θmax = 27.5°, θmin = 5.4° |
| Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −8→8 |
| Tmin = 0.89, Tmax = 0.98 | k = −14→14 |
| 6798 measured reflections | l = −18→18 |
| 1329 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) + (0.04P)2 + 0.26P], where P = [max(Fo2,0) + 2Fc2]/3 |
| S = 0.94 | (Δ/σ)max = 0.0003 |
| 1329 reflections | Δρmax = 0.23 e Å−3 |
| 127 parameters | Δρmin = −0.21 e Å−3 |
| 0 restraints |
| C9H16O5 | V = 995.18 (5) Å3 |
| Mr = 204.22 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 6.2840 (2) Å | µ = 0.11 mm−1 |
| b = 11.2043 (3) Å | T = 150 K |
| c = 14.1345 (5) Å | 0.40 × 0.15 × 0.15 mm |
| Nonius KappaCCD area-detector diffractometer | 1329 independent reflections |
| Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 1174 reflections with I > 2σ(I) |
| Tmin = 0.89, Tmax = 0.98 | Rint = 0.030 |
| 6798 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.074 | Δρmax = 0.23 e Å−3 |
| S = 0.94 | Δρmin = −0.21 e Å−3 |
| 1329 reflections | Absolute structure: ? |
| 127 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.4004 (3) | 0.62732 (15) | 0.82157 (12) | 0.0170 | |
| C2 | 0.4011 (3) | 0.48976 (15) | 0.80312 (11) | 0.0175 | |
| O3 | 0.4963 (2) | 0.47844 (10) | 0.71058 (7) | 0.0207 | |
| C4 | 0.5033 (3) | 0.59116 (14) | 0.66416 (11) | 0.0192 | |
| O5 | 0.4968 (2) | 0.67791 (10) | 0.73859 (8) | 0.0190 | |
| C6 | 0.3161 (4) | 0.60448 (18) | 0.59812 (14) | 0.0310 | |
| C7 | 0.7142 (3) | 0.60183 (18) | 0.61403 (15) | 0.0297 | |
| C8 | 0.5634 (3) | 0.44334 (16) | 0.87399 (12) | 0.0220 | |
| O9 | 0.70020 (19) | 0.54266 (11) | 0.89385 (8) | 0.0226 | |
| C10 | 0.5609 (3) | 0.64203 (16) | 0.90340 (11) | 0.0194 | |
| O11 | 0.4474 (2) | 0.63675 (12) | 0.98858 (8) | 0.0255 | |
| C12 | 0.1885 (3) | 0.42543 (16) | 0.80539 (13) | 0.0238 | |
| C13 | 0.1860 (3) | 0.68450 (15) | 0.83936 (13) | 0.0203 | |
| O14 | 0.2049 (2) | 0.80853 (11) | 0.86261 (9) | 0.0251 | |
| H61 | 0.3262 | 0.6813 | 0.5628 | 0.0499* | |
| H62 | 0.3133 | 0.5390 | 0.5506 | 0.0503* | |
| H63 | 0.1852 | 0.6027 | 0.6356 | 0.0507* | |
| H71 | 0.7202 | 0.6830 | 0.5847 | 0.0470* | |
| H72 | 0.7185 | 0.5393 | 0.5626 | 0.0469* | |
| H73 | 0.8304 | 0.5901 | 0.6610 | 0.0479* | |
| H81 | 0.6440 | 0.3754 | 0.8455 | 0.0286* | |
| H82 | 0.4869 | 0.4191 | 0.9330 | 0.0282* | |
| H101 | 0.6441 | 0.7203 | 0.8990 | 0.0242* | |
| H121 | 0.2147 | 0.3398 | 0.7899 | 0.0380* | |
| H122 | 0.0922 | 0.4610 | 0.7571 | 0.0387* | |
| H123 | 0.1219 | 0.4341 | 0.8684 | 0.0382* | |
| H131 | 0.0965 | 0.6764 | 0.7798 | 0.0269* | |
| H132 | 0.1112 | 0.6441 | 0.8918 | 0.0265* | |
| H15 | 0.5366 | 0.6493 | 1.0330 | 0.0412* | |
| H16 | 0.3095 | 0.8395 | 0.8319 | 0.0416* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0193 (8) | 0.0180 (8) | 0.0137 (8) | −0.0014 (7) | 0.0007 (6) | 0.0000 (6) |
| C2 | 0.0204 (8) | 0.0182 (8) | 0.0137 (7) | −0.0005 (7) | 0.0018 (7) | −0.0017 (7) |
| O3 | 0.0293 (7) | 0.0176 (6) | 0.0152 (5) | 0.0020 (6) | 0.0051 (6) | −0.0006 (4) |
| C4 | 0.0256 (8) | 0.0166 (8) | 0.0154 (7) | 0.0007 (8) | 0.0009 (8) | −0.0020 (6) |
| O5 | 0.0253 (6) | 0.0170 (5) | 0.0148 (5) | −0.0015 (6) | 0.0035 (5) | −0.0010 (4) |
| C6 | 0.0360 (11) | 0.0342 (11) | 0.0226 (9) | −0.0004 (10) | −0.0090 (10) | −0.0014 (9) |
| C7 | 0.0348 (11) | 0.0248 (10) | 0.0294 (10) | −0.0024 (9) | 0.0138 (9) | −0.0023 (8) |
| C8 | 0.0253 (9) | 0.0191 (8) | 0.0216 (9) | −0.0010 (8) | −0.0020 (8) | −0.0004 (7) |
| O9 | 0.0180 (6) | 0.0251 (6) | 0.0247 (6) | 0.0002 (6) | −0.0043 (6) | −0.0013 (5) |
| C10 | 0.0195 (8) | 0.0219 (8) | 0.0168 (8) | −0.0026 (8) | −0.0017 (7) | −0.0028 (7) |
| O11 | 0.0274 (7) | 0.0331 (7) | 0.0161 (6) | −0.0020 (6) | −0.0005 (5) | −0.0037 (5) |
| C12 | 0.0225 (9) | 0.0204 (8) | 0.0285 (9) | −0.0034 (8) | −0.0001 (8) | −0.0015 (8) |
| C13 | 0.0197 (8) | 0.0191 (8) | 0.0220 (8) | 0.0000 (7) | 0.0015 (7) | −0.0022 (7) |
| O14 | 0.0284 (7) | 0.0176 (6) | 0.0294 (7) | 0.0011 (6) | 0.0115 (6) | −0.0030 (5) |
| C1—C2 | 1.563 (2) | C7—H73 | 0.996 |
| C1—O5 | 1.437 (2) | C8—O9 | 1.434 (2) |
| C1—C10 | 1.543 (2) | C8—H81 | 0.999 |
| C1—C13 | 1.513 (2) | C8—H82 | 1.000 |
| C2—O3 | 1.4439 (19) | O9—C10 | 1.423 (2) |
| C2—C8 | 1.522 (2) | C10—O11 | 1.400 (2) |
| C2—C12 | 1.518 (2) | C10—H101 | 1.023 |
| O3—C4 | 1.4240 (19) | O11—H15 | 0.854 |
| C4—O5 | 1.4329 (19) | C12—H121 | 0.998 |
| C4—C6 | 1.509 (3) | C12—H122 | 0.996 |
| C4—C7 | 1.507 (3) | C12—H123 | 0.989 |
| C6—H61 | 0.997 | C13—O14 | 1.433 (2) |
| C6—H62 | 0.996 | C13—H131 | 1.017 |
| C6—H63 | 0.978 | C13—H132 | 0.987 |
| C7—H71 | 1.001 | O14—H16 | 0.861 |
| C7—H72 | 1.010 | ||
| C2—C1—O5 | 104.58 (13) | H71—C7—H73 | 111.6 |
| C2—C1—C10 | 103.22 (14) | H72—C7—H73 | 111.6 |
| O5—C1—C10 | 107.11 (13) | C2—C8—O9 | 105.41 (14) |
| C2—C1—C13 | 116.58 (15) | C2—C8—H81 | 109.6 |
| O5—C1—C13 | 110.13 (14) | O9—C8—H81 | 111.5 |
| C10—C1—C13 | 114.34 (13) | C2—C8—H82 | 108.6 |
| C1—C2—O3 | 103.82 (13) | O9—C8—H82 | 109.6 |
| C1—C2—C8 | 103.23 (14) | H81—C8—H82 | 111.9 |
| O3—C2—C8 | 106.76 (14) | C8—O9—C10 | 104.90 (12) |
| C1—C2—C12 | 117.54 (16) | C1—C10—O9 | 104.32 (13) |
| O3—C2—C12 | 110.00 (14) | C1—C10—O11 | 107.89 (13) |
| C8—C2—C12 | 114.44 (14) | O9—C10—O11 | 111.21 (14) |
| C2—O3—C4 | 110.63 (12) | C1—C10—H101 | 112.3 |
| O3—C4—O5 | 105.21 (12) | O9—C10—H101 | 110.5 |
| O3—C4—C6 | 110.40 (15) | O11—C10—H101 | 110.4 |
| O5—C4—C6 | 111.41 (15) | C10—O11—H15 | 107.0 |
| O3—C4—C7 | 108.31 (15) | C2—C12—H121 | 107.9 |
| O5—C4—C7 | 108.43 (15) | C2—C12—H122 | 109.3 |
| C6—C4—C7 | 112.75 (14) | H121—C12—H122 | 109.6 |
| C1—O5—C4 | 110.11 (12) | C2—C12—H123 | 110.2 |
| C4—C6—H61 | 110.2 | H121—C12—H123 | 111.2 |
| C4—C6—H62 | 111.0 | H122—C12—H123 | 108.7 |
| H61—C6—H62 | 107.5 | C1—C13—O14 | 112.02 (14) |
| C4—C6—H63 | 108.6 | C1—C13—H131 | 108.5 |
| H61—C6—H63 | 110.0 | O14—C13—H131 | 108.8 |
| H62—C6—H63 | 109.6 | C1—C13—H132 | 110.8 |
| C4—C7—H71 | 107.5 | O14—C13—H132 | 108.1 |
| C4—C7—H72 | 107.9 | H131—C13—H132 | 108.5 |
| H71—C7—H72 | 109.3 | C13—O14—H16 | 109.8 |
| C4—C7—H73 | 108.8 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O11—H15···O14i | 0.85 | 1.88 | 2.724 (2) | 172 |
| O14—H16···O3ii | 0.86 | 2.07 | 2.867 (2) | 154 |
| Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) −x+1, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O11—H15···O14i | 0.85 | 1.88 | 2.724 (2) | 172 |
| O14—H16···O3ii | 0.86 | 2.07 | 2.867 (2) | 154 |
| Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) −x+1, y+1/2, −z+3/2. |
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Singly branched sugars have been found in nature and their occurrence has prompted interest in their synthesis and biological evaluation (Chapleur & Chrétien, 1997). For example, 2-C-substituted mannose derivatives have been shown to have therapeutic potential (Mitchell et al., 2007). The Kiliani reaction of ketoses with cyanide (Hotchkiss et al., 2006, Soengas et al., 2005) and calcium oxide treatment of Amadori compounds have proved to be valuable routes towards branched sugars (Hotchkiss et al., 2006, 2007). In addition the Aldol reaction using formaldehyde and potassium carbonate can be used to introduce hydroxymethyl branches to sugars, for example in the synthesis of hamamalose (Ho, 1978) and apiose (Koos & Mosher, 1986).
Sugars containing more than one branch are very rare. Examples of sugars that contain two carbon branches include 2,4-dimethyl-3,4-O-isopropylidene-L-arabinono-1,5-lactone (Booth, Watkin et al., 2007) and various protected forms of 3,5-di-C-methyl-mannono and glucono lactone (Booth et al., 2007a, 2007b, 2007c). 2,3-C-Dimethyl-D-allono-1,4-lactone (Jones et al., 2007) is an example of a sugar with adjacent branching centres.
The crystal structure of the title compound (Fig. 1) exists as a three dimensionally hydrogen bonded lattice with each molecule being both a donor and an acceptor for two hydrogen bonds (Fig. 2).