Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031510/lh2448sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031510/lh2448Isup2.hkl |
CCDC reference: 657674
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 the 2,6-anhydro derivative 3 (Curran et al. 2007) and the lactone 4 (Fig. 3). X-Ray crystallographic analysis of the title lactone 3 removed any ambiguity as to the stereochemistry at the new C-2 chiral centre. The title compound was recrystallized from a mixture of cyclohexane and ethyl acetate; m.p. 420 K; [α]D22 +106.1 (c, 0.64 in chlororform).
In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned from the starting material.
The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:1.19) 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 Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.
Branched sugars are a relatively unstudied class of compounds but recent biological results have indicated they could have a potential use as therapeutics (Mitchell et al. 2007). The Kiliani ascension on ketoses and deoxy ketoses has proved a valuable route towards branched sugars (Hotchkiss et al., 2004,2006; Soengas et al., 2005; Jones, Watkin et al. 2007). Currently, there are very limited examples of di-branched carbohydrates reported. Examples of sugars that contain two carbon branches in the literature include 2,4-C-dimethyl-3,4-O-isopropylidene-L-arabinono-1,5-lactone (Booth, Watkin et al. 2007) and various protected forms of 3,5-C-dimethyl-mannono and glucono lactone (Booth, Jenkinson, Fleet & Watkin, 2007a, 2007b, 2007c). 2-C-Hydroxymethyl-2,3-O-isopropylidene-3-C-methyl-β-L– erythrose (Booth, Jenkinson, Watkin & Fleet, 2007d) is a rare example of a sugar with adjacent branched centres.
The crystal structure of the title compound (Fig. 1) exists as a three dimensionally hydrogen bonded network (Fig. 2) with each molecule acting as an acceptor and a donor for two hydrogen bonds.
For related literature see: Jones, Curran et al. (2007); Jones, Watkin et al. (2007); Mitchell et al. (2007); Hotchkiss et al. (2004, 2006); Soengas et al. (2005); Booth, Watkin et al. (2007); Booth et al. (2007a, 2007b, 2007c, 2007d); Curran et al. (2007); Görbitz (1999).
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.
C11H18O6 | F(000) = 528 |
Mr = 246.26 | Dx = 1.361 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1357 reflections |
a = 6.9089 (2) Å | θ = 5–27° |
b = 12.2072 (5) Å | µ = 0.11 mm−1 |
c = 14.2507 (5) Å | T = 150 K |
V = 1201.88 (7) Å3 | Plate, colourless |
Z = 4 | 0.20 × 0.20 × 0.05 mm |
Nonius KappaCCD diffractometer | 1303 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 27.5°, θmin = 5.2° |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −8→8 |
Tmin = 0.83, Tmax = 0.99 | k = −15→15 |
5554 measured reflections | l = −18→18 |
1561 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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.073 | w = 1/[σ2(F2) + (0.03P)2 + 0.22P], where P = [max(Fo2,0) + 2Fc2]/3 |
S = 0.92 | (Δ/σ)max = 0.000203 |
1561 reflections | Δρmax = 0.26 e Å−3 |
154 parameters | Δρmin = −0.24 e Å−3 |
0 restraints |
C11H18O6 | V = 1201.88 (7) Å3 |
Mr = 246.26 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.9089 (2) Å | µ = 0.11 mm−1 |
b = 12.2072 (5) Å | T = 150 K |
c = 14.2507 (5) Å | 0.20 × 0.20 × 0.05 mm |
Nonius KappaCCD diffractometer | 1561 independent reflections |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 1303 reflections with I > 2.0σ(I) |
Tmin = 0.83, Tmax = 0.99 | Rint = 0.031 |
5554 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.26 e Å−3 |
1561 reflections | Δρmin = −0.24 e Å−3 |
154 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6355 (3) | 0.35060 (15) | 0.21409 (12) | 0.0168 | |
C2 | 0.7020 (3) | 0.45680 (13) | 0.26378 (12) | 0.0185 | |
C3 | 0.7261 (3) | 0.42656 (14) | 0.36718 (13) | 0.0225 | |
O4 | 0.5794 (2) | 0.37424 (10) | 0.40921 (8) | 0.0233 | |
C5 | 0.4030 (3) | 0.34688 (15) | 0.35788 (12) | 0.0191 | |
C6 | 0.4458 (3) | 0.30862 (13) | 0.25760 (12) | 0.0173 | |
O7 | 0.29790 (19) | 0.34924 (10) | 0.19778 (8) | 0.0190 | |
C8 | 0.3790 (3) | 0.35046 (16) | 0.10563 (12) | 0.0194 | |
O9 | 0.57947 (19) | 0.38010 (10) | 0.12033 (8) | 0.0198 | |
C10 | 0.2817 (3) | 0.43932 (15) | 0.04956 (13) | 0.0249 | |
C11 | 0.3659 (3) | 0.23797 (15) | 0.06080 (13) | 0.0262 | |
C12 | 0.3044 (3) | 0.25957 (14) | 0.41507 (13) | 0.0234 | |
O13 | 0.4187 (2) | 0.16239 (10) | 0.41357 (8) | 0.0249 | |
O14 | 0.8717 (2) | 0.44346 (11) | 0.41227 (9) | 0.0336 | |
O15 | 0.54750 (19) | 0.53432 (9) | 0.26178 (9) | 0.0216 | |
C16 | 0.8859 (3) | 0.50609 (16) | 0.22511 (14) | 0.0263 | |
C17 | 0.7921 (3) | 0.26278 (15) | 0.21373 (13) | 0.0238 | |
H51 | 0.3215 | 0.4124 | 0.3552 | 0.0251* | |
H61 | 0.4470 | 0.2263 | 0.2567 | 0.0225* | |
H101 | 0.3438 | 0.4423 | −0.0118 | 0.0346* | |
H102 | 0.2985 | 0.5093 | 0.0839 | 0.0349* | |
H103 | 0.1455 | 0.4193 | 0.0424 | 0.0349* | |
H111 | 0.4183 | 0.2437 | −0.0033 | 0.0397* | |
H112 | 0.4415 | 0.1852 | 0.0988 | 0.0394* | |
H113 | 0.2318 | 0.2141 | 0.0579 | 0.0391* | |
H121 | 0.2880 | 0.2871 | 0.4802 | 0.0300* | |
H122 | 0.1741 | 0.2432 | 0.3886 | 0.0301* | |
H161 | 0.9086 | 0.5757 | 0.2581 | 0.0405* | |
H162 | 0.9937 | 0.4554 | 0.2353 | 0.0400* | |
H163 | 0.8697 | 0.5198 | 0.1581 | 0.0397* | |
H171 | 0.7428 | 0.1979 | 0.1804 | 0.0363* | |
H172 | 0.9047 | 0.2937 | 0.1824 | 0.0372* | |
H173 | 0.8235 | 0.2434 | 0.2792 | 0.0366* | |
H5 | 0.5431 | 0.5604 | 0.2065 | 0.0319* | |
H19 | 0.3990 | 0.1194 | 0.4586 | 0.0389* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0184 (9) | 0.0180 (9) | 0.0140 (8) | 0.0009 (8) | −0.0006 (8) | 0.0008 (7) |
C2 | 0.0215 (10) | 0.0159 (7) | 0.0181 (8) | 0.0009 (8) | −0.0027 (8) | 0.0033 (8) |
C3 | 0.0301 (12) | 0.0158 (8) | 0.0216 (9) | −0.0012 (9) | −0.0041 (9) | −0.0001 (8) |
O4 | 0.0286 (8) | 0.0239 (7) | 0.0173 (6) | −0.0042 (7) | −0.0033 (6) | 0.0011 (6) |
C5 | 0.0204 (10) | 0.0199 (9) | 0.0169 (8) | 0.0024 (9) | 0.0000 (8) | 0.0005 (8) |
C6 | 0.0181 (9) | 0.0165 (8) | 0.0172 (8) | 0.0006 (8) | 0.0003 (9) | 0.0003 (8) |
O7 | 0.0157 (7) | 0.0246 (7) | 0.0166 (6) | 0.0007 (6) | −0.0010 (6) | 0.0013 (6) |
C8 | 0.0157 (10) | 0.0267 (10) | 0.0158 (8) | −0.0028 (9) | 0.0016 (8) | 0.0012 (8) |
O9 | 0.0172 (7) | 0.0270 (7) | 0.0153 (6) | −0.0030 (6) | −0.0005 (6) | 0.0012 (5) |
C10 | 0.0229 (11) | 0.0283 (10) | 0.0234 (9) | −0.0010 (10) | −0.0045 (9) | 0.0060 (9) |
C11 | 0.0289 (11) | 0.0287 (10) | 0.0210 (9) | −0.0025 (10) | −0.0037 (9) | −0.0021 (9) |
C12 | 0.0267 (11) | 0.0234 (9) | 0.0202 (9) | 0.0010 (10) | 0.0057 (9) | 0.0011 (8) |
O13 | 0.0355 (8) | 0.0184 (6) | 0.0208 (6) | 0.0030 (7) | 0.0048 (6) | 0.0049 (5) |
O14 | 0.0384 (9) | 0.0354 (8) | 0.0272 (7) | −0.0107 (8) | −0.0143 (7) | 0.0073 (7) |
O15 | 0.0279 (8) | 0.0153 (5) | 0.0217 (6) | 0.0026 (6) | −0.0007 (7) | 0.0029 (6) |
C16 | 0.0242 (11) | 0.0258 (10) | 0.0288 (10) | −0.0055 (9) | −0.0040 (10) | 0.0066 (9) |
C17 | 0.0223 (10) | 0.0223 (9) | 0.0268 (10) | 0.0049 (9) | −0.0008 (9) | −0.0014 (8) |
C1—C2 | 1.547 (2) | C8—C11 | 1.517 (3) |
C1—C6 | 1.538 (2) | C10—H101 | 0.975 |
C1—O9 | 1.437 (2) | C10—H102 | 0.991 |
C1—C17 | 1.524 (2) | C10—H103 | 0.977 |
C2—C3 | 1.528 (2) | C11—H111 | 0.985 |
C2—O15 | 1.427 (2) | C11—H112 | 0.990 |
C2—C16 | 1.510 (3) | C11—H113 | 0.972 |
C3—O4 | 1.339 (2) | C12—O13 | 1.425 (2) |
C3—O14 | 1.212 (2) | C12—H121 | 0.994 |
O4—C5 | 1.460 (2) | C12—H122 | 0.996 |
C5—C6 | 1.532 (2) | O13—H19 | 0.840 |
C5—C12 | 1.505 (3) | O15—H5 | 0.850 |
C5—H51 | 0.979 | C16—H161 | 0.983 |
C6—O7 | 1.420 (2) | C16—H162 | 0.979 |
C6—H61 | 1.005 | C16—H163 | 0.976 |
O7—C8 | 1.428 (2) | C17—H171 | 0.984 |
C8—O9 | 1.447 (2) | C17—H172 | 0.972 |
C8—C10 | 1.506 (3) | C17—H173 | 0.987 |
C2—C1—C6 | 110.36 (15) | C10—C8—C11 | 113.71 (15) |
C2—C1—O9 | 107.19 (13) | C8—O9—C1 | 109.25 (14) |
C6—C1—O9 | 103.24 (13) | C8—C10—H101 | 107.8 |
C2—C1—C17 | 112.35 (15) | C8—C10—H102 | 107.8 |
C6—C1—C17 | 111.86 (14) | H101—C10—H102 | 111.0 |
O9—C1—C17 | 111.37 (14) | C8—C10—H103 | 107.8 |
C1—C2—C3 | 105.74 (13) | H101—C10—H103 | 109.8 |
C1—C2—O15 | 108.93 (14) | H102—C10—H103 | 112.3 |
C3—C2—O15 | 105.12 (15) | C8—C11—H111 | 107.8 |
C1—C2—C16 | 114.64 (16) | C8—C11—H112 | 109.1 |
C3—C2—C16 | 110.89 (16) | H111—C11—H112 | 111.1 |
O15—C2—C16 | 110.97 (13) | C8—C11—H113 | 110.2 |
C2—C3—O4 | 117.66 (17) | H111—C11—H113 | 109.3 |
C2—C3—O14 | 124.09 (18) | H112—C11—H113 | 109.3 |
O4—C3—O14 | 118.19 (16) | C5—C12—O13 | 109.30 (15) |
C3—O4—C5 | 121.10 (13) | C5—C12—H121 | 108.6 |
O4—C5—C6 | 112.08 (15) | O13—C12—H121 | 111.0 |
O4—C5—C12 | 105.58 (14) | C5—C12—H122 | 110.2 |
C6—C5—C12 | 112.12 (15) | O13—C12—H122 | 109.2 |
O4—C5—H51 | 108.2 | H121—C12—H122 | 108.6 |
C6—C5—H51 | 108.9 | C12—O13—H19 | 114.7 |
C12—C5—H51 | 109.9 | C2—O15—H5 | 107.0 |
C1—C6—C5 | 116.03 (15) | C2—C16—H161 | 107.7 |
C1—C6—O7 | 104.76 (12) | C2—C16—H162 | 109.5 |
C5—C6—O7 | 108.34 (14) | H161—C16—H162 | 110.7 |
C1—C6—H61 | 108.7 | C2—C16—H163 | 109.2 |
C5—C6—H61 | 108.5 | H161—C16—H163 | 109.8 |
O7—C6—H61 | 110.4 | H162—C16—H163 | 109.9 |
C6—O7—C8 | 105.87 (13) | C1—C17—H171 | 108.8 |
O7—C8—O9 | 104.19 (13) | C1—C17—H172 | 107.3 |
O7—C8—C10 | 108.69 (15) | H171—C17—H172 | 111.6 |
O9—C8—C10 | 108.91 (15) | C1—C17—H173 | 108.7 |
O7—C8—C11 | 110.77 (15) | H171—C17—H173 | 109.9 |
O9—C8—C11 | 110.13 (16) | H172—C17—H173 | 110.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O15—H5···O13i | 0.85 | 2.13 | 2.957 (2) | 163 |
O13—H19···O14ii | 0.84 | 2.00 | 2.817 (2) | 163 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H18O6 |
Mr | 246.26 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 6.9089 (2), 12.2072 (5), 14.2507 (5) |
V (Å3) | 1201.88 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.20 × 0.20 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.83, 0.99 |
No. of measured, independent and observed [I > 2.0σ(I)] reflections | 5554, 1561, 1303 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.073, 0.92 |
No. of reflections | 1561 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.24 |
Computer programs: COLLECT (Nonius, 2001)., DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.
D—H···A | D—H | H···A | D···A | D—H···A |
O15—H5···O13i | 0.85 | 2.13 | 2.957 (2) | 163 |
O13—H19···O14ii | 0.84 | 2.00 | 2.817 (2) | 163 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1. |
Branched sugars are a relatively unstudied class of compounds but recent biological results have indicated they could have a potential use as therapeutics (Mitchell et al. 2007). The Kiliani ascension on ketoses and deoxy ketoses has proved a valuable route towards branched sugars (Hotchkiss et al., 2004,2006; Soengas et al., 2005; Jones, Watkin et al. 2007). Currently, there are very limited examples of di-branched carbohydrates reported. Examples of sugars that contain two carbon branches in the literature include 2,4-C-dimethyl-3,4-O-isopropylidene-L-arabinono-1,5-lactone (Booth, Watkin et al. 2007) and various protected forms of 3,5-C-dimethyl-mannono and glucono lactone (Booth, Jenkinson, Fleet & Watkin, 2007a, 2007b, 2007c). 2-C-Hydroxymethyl-2,3-O-isopropylidene-3-C-methyl-β-L– erythrose (Booth, Jenkinson, Watkin & Fleet, 2007d) is a rare example of a sugar with adjacent branched centres.
The crystal structure of the title compound (Fig. 1) exists as a three dimensionally hydrogen bonded network (Fig. 2) with each molecule acting as an acceptor and a donor for two hydrogen bonds.