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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Comparison of racemic epi-inosose and (−)-epi-inosose

aCentre for Materials Characterization, National Chemical Laboratory, Pune 411 008, India, and bDivision of Organic Chemistry, National Chemical Laboratory, Pune 411 008, India
*Correspondence e-mail: s.krishnaswamy@ncl.res.in

(Received 31 August 2011; accepted 26 September 2011; online 6 October 2011)

The conversion of myo-inositol to epi-inositol can be achieved by the hydride reduction of an inter­mediate epi-inosose derived from myo-inositol. (−)-epi-Inosose, (I), crystallized in the monoclinic space group P21, with two independent mol­ecules in the asymmetric unit [Hosomi et al. (2000[Hosomi, H., Ohba, S., Ogawa, S. & Takahashi, A. (2000). Acta Cryst. C56, e584-e585.]). Acta Cryst. C56, e584–e585]. On the other hand, (2RS,3SR,5SR,6SR)-epi-inosose, C6H10O6, (II), crystallized in the ortho­rhom­bic space group Pca21. Inter­estingly, the conformation of the mol­ecules in the two structures is nearly the same, the only difference being the orientation of the C-3 and C-4 hy­droxy H atoms. As a result, the mol­ecular organization achieved mainly through strong O—H⋯O hydrogen bonding in the racemic and homochiral lattices is similar. The compound also follows Wallach's rule, in that the racemic crystals are denser than the optically active form.

Comment

epi-Inositol is known to affect regulation of the myo-inositol biosynthetic pathway (Shaldubina et al., 2002[Shaldubina, A., Ju, S., Vaden, D. L., Ding, D., Belmaker, R. H. & Greenberg, M. L. (2002). Mol. Psychiatry, 7, 174-180.]) and has been evaluated as a potential anti­depressant drug that could inter­act with the Li+ ion and myo-inositol receptors in the brain (Einat et al., 1998[Einat, H., Elkabaz-Shwortz, Z., Cohen, H., Kofman, O. & Belmaker, R. H. (1998). Int. J. Neuropsychopharmacol. 1, 31-34.]; Belmaker et al., 1998[Belmaker, R. H., Agam, G., Van Calker, D., Richards, M. H. & Kofman, O. (1998). Neuropsychopharmacology, 19, 220-232.]; Williams et al., 2002[Williams, R. S., Cheng, L., Mudge, A. W. & Harwood, A. J. (2002). Nature (London), 417, 292-295.]). We have reported previously the synthesis of epi-inositol by the reduction of racemic epi-inosose (Patil et al., 2011[Patil, M. T., Krishnaswamy, S., Sarmah, M. P. & Shashidhar, M. S. (2011). Tetrahedron Lett. 52, 3756-3758.]).

[Scheme 1]

A Cambridge Structural Database (CSD, Version 5.31; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) search yielded the structure of the optically active (−)-epi-inosose (CSD refcode XEGVUA; Hosomi et al., 2000[Hosomi, H., Ohba, S., Ogawa, S. & Takahashi, A. (2000). Acta Cryst. C56, e584-e585.]) prepared enantio­selectively by a bioconversion from myo-inositol (Hosomi et al., 2000[Hosomi, H., Ohba, S., Ogawa, S. & Takahashi, A. (2000). Acta Cryst. C56, e584-e585.]). We were thus presented with an opportunity for the comparison of the mol­ecular assembly in the crystals of these homochiral, (I), and racemic, (II)[link], inososes. Single-crystal X-ray intensity measurements for crystals of (II)[link] were recorded at ambient temperature (297 K), as reported for (I). Crystals of the racemic ketone are ortho­rhom­bic, belonging to the noncentrosymmetric space group Pca21 (Fig. 1[link]), while the homochiral ketone crystallizes in the noncentrosymmetric space group P21, with two independent mol­ecules (A and B) in the asymmetric unit. The atom numbering for the racemic form is consistent with that reported for the optically active compound to enable easier comparison of the crystal structures.

The superimposition of the mol­ecules in the asymmetric unit of (I) and the corresponding enanti­omer in (II)[link] reveals an excellent fit of the non-H atoms, with r.m.s. deviations of 0.0058 and 0.0094 Å for the overlaid non-H atoms shown in Figs. 2[link]a and 2[link]b, respectively. The most significant differences are in the orientations of the hy­droxy H atoms at C3 and C4. The conformation of the C3 hy­droxy H atom of (II)[link] matches that of mol­ecule B in the asymmetric unit of crystals of (I)[link], whereas the conformation of the C4 hy­droxy group matches that of mol­ecule A.

There is a close correspondence in the unit-cell parameters of the two structures: the a axes lengths are nearly the same and inter­change of the b and c axes of the ortho­rhom­bic racemic form results in edge lengths that are nearly identical to those of the homochiral crystal lattice [a = 11.197 (2), b = 8.932 (2), c = 6.976 (2) Å and β = 90.21 (2)° for (I)]. In accordance with Wallach's rule (Wallach, 1895[Wallach, O. (1895). Liebigs Ann. Chem. 286, 90-143.]; Brock et al., 1991[Brock, C. P., Schweizer, W. B. & Dunitz, J. D. (1991). J. Am. Chem. Soc. 113, 9811-9820.]), the racemic crystal is 1.7% denser than the enantio­merically pure crystal, and its melting point is 492–495 K. The melting point of the crystals of (I) is not available for comparison. The unit cell of racemic epi-inosose consists of four mol­ecules, i.e. two pairs of enanti­omers, whereas that of (−)-epi-inosose contains two pairs of the two symmetry-independent mol­ecules of the asymmetric unit.

The presence of five hy­droxy groups and a carbonyl group results in extensive hydrogen-bonding inter­actions in the crystal. In the crystals of (II)[link], each enanti­omer forms a homochiral hydrogen-bonded chain along the c axis through O6—H6⋯O4v, with adjacent heterochiral mol­ecular chains along the a axis linked by short and linear O3—H3⋯O2ii, O4—H4⋯O6iii, O5—H5⋯O3iv and C3—H8⋯O4vii inter­actions (Fig. 3[link]a, symmetry codes and geometric parameters in Table 1[link]). In the case of (I), each of the two mol­ecules in the asymmetric unit forms a similar O6—H5⋯O4viii hydrogen-bonded chain along the b axis. Inter­estingly, the carbonyl O atom (O7) of only one of the mol­ecules of (I) (mol­ecule B) is involved in O—H⋯O hydrogen bonding [O9—H12⋯O7xi; symmetry codes for (I) as in Fig. 3[link]b], because of the conformational differences in the hy­droxy groups of the two mol­ecules in the asymmetric unit. The adjacent mol­ecular chains along the a axis are linked by a large number of hydrogen-bonding inter­actions (Fig. 3[link]b).

A view of these mol­ecular chains down the c axis in (II)[link] and b axis in (I) shows a corrugated-sheet-like assembly (Fig. 4[link]). Adjacent sheets are linked by bifurcated hydrogen-bonding inter­actions involving carbonyl atom O1 (O2—H2⋯O1i and C2—H7⋯O1vi) and O2—H2⋯O6i and C6—H11⋯O2vi contacts in the racemic crystal (Fig. 4[link]a and Table 1[link]). In the crystals of the optically active form, neighbouring sheets are linked by O2—H1⋯O9xv, O3—H2⋯O10xv, O10—H13⋯O11xvi, O11—H14⋯O6xiv, C2—H6⋯O1xiii and C6—H10⋯O2xiii contacts (Fig. 4[link]b). Thus, the overall mol­ecular organization in the crystals of the racemic and enanti­opure compound is remarkably similar. This is primarily due to the fact that the second mol­ecule in the asymmetric unit of (I) plays the role of the second enanti­omer in the crystal packing. While the thermodynamic stability of the two crystals cannot be experimentally evaluated owing to the absence of adequate thermal data, estimation of lattice energies for (I) and (II)[link] using the Oprop module of the OPiX program suite (Gavezzotti, 2003[Gavezzotti, A. (2003). OPiX. University of Milan, Italy.]) yielded a value of −204.75 kJ mol−1 for (I)[link] and −253.5 kJ mol−1 for (II)[link], consistent with the crystal densities.

[Figure 1]
Figure 1
The mol­ecular structure of racemic epi-inosose, (II)[link] [the (2R,3S,5S,6S)-enanti­omer], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
The overlap of the mol­ecules in the crystals of (−)-epi-inosose, (I), and racemic epi-inosose, (II)[link], showing the differences in the orientations of the hy­droxy groups. In (a), one of the two independent mol­ecules in the asymmetric unit of (I) (blue in the electronic version of the paper) and the corresponding enanti­omer in (II)[link] (red) is shown, while in (b) the second independent mol­ecule in the asymmetric unit of (I) (green) and the corresponding enanti­omer in (II)[link] (red) is shown.
[Figure 3]
Figure 3
Chains of mol­ecules linked through hydrogen-bonding inter­actions (dotted lines) in the crystal structures of (a) (II)[link] and (b) (I). The different colours represent the enanti­omers of (II)[link] in (a) (dark blue and light blue in the electronic version of the paper) and the independent mol­ecules in the asymmetric unit of (I) in (b) (purple and light pink). H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (ii) −x + [{1\over 2}], y, z + [{1\over 2}]; (iii) x + [{1\over 2}], −y, z; (iv) x − [{1\over 2}], −y, z; (v) −x, −y, z − [{1\over 2}]; (vii) −x + [{1\over 2}], y, z − [{1\over 2}]; (viii) −x + 2, y − [{1\over 2}], −z; (ix) −x + 2, y + [{1\over 2}], −z; (x) −x + 1, y + [{1\over 2}], −z; (xi) −x + 1, y − [{1\over 2}], −z; (xii) x, y − 1, z.]
[Figure 4]
Figure 4
A view of the mol­ecular packing down (a) the c axis in crystals of (II)[link] and (b) the b axis in crystals of (I). Dotted lines represent hydrogen-bonding inter­actions, some of which (shown in Fig. 3[link]) have been omitted for clarity. [Symmetry codes: (i) x + [{1\over 2}], −y + 1, z; (vi) −x, −y + 1, z + [{1\over 2}]; (xiii) x + 2, y + [{1\over 2}], −z + 1; (xiv) −x + 2, y − [{1\over 2}], −z + 1; (xv) −x + 1, y + [{1\over 2}], −z + 1; (xvi) −x + 1, y − [{1\over 2}], −z + 1.]

Experimental

Racemic epi-inosose, (II)[link], was synthesized as reported previously (Patil et al., 2011[Patil, M. T., Krishnaswamy, S., Sarmah, M. P. & Shashidhar, M. S. (2011). Tetrahedron Lett. 52, 3756-3758.]). Prism-shaped crystals (m.p. 492–495 K) were obtained by slow evaporation from a solution in hot water.

Crystal data
  • C6H10O6

  • Mr = 178.14

  • Orthorhombic, P c a 21

  • a = 11.1825 (18) Å

  • b = 6.9752 (12) Å

  • c = 8.7930 (15) Å

  • V = 685.9 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.16 mm−1

  • T = 297 K

  • 0.29 × 0.29 × 0.17 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2003[Bruker (2003). SADABS (Version 2.05), SMART (Version 5.631) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.956, Tmax = 0.974

  • 3225 measured reflections

  • 653 independent reflections

  • 647 reflections with I > 2σ(I)

  • Rint = 0.016

Refinement
  • R[F2 > 2σ(F2)] = 0.026

  • wR(F2) = 0.068

  • S = 1.15

  • 653 reflections

  • 129 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry in (II) (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O1i 0.85 (4) 2.57 (4) 3.191 (2) 131 (3)
O2—H2⋯O6i 0.85 (4) 2.02 (4) 2.833 (2) 159 (4)
O3—H3⋯O2ii 0.87 (4) 1.93 (4) 2.791 (3) 172 (4)
O4—H4⋯O6iii 0.78 (4) 2.10 (4) 2.844 (2) 161 (3)
O5—H5⋯O3iv 0.91 (3) 1.92 (3) 2.822 (2) 171 (2)
O6—H6⋯O4v 0.79 (3) 2.01 (4) 2.760 (2) 160 (3)
C2—H7⋯O1vi 0.98 2.52 3.374 (3) 145
C3—H8⋯O4vii 0.98 2.52 3.422 (3) 152
C6—H11⋯O2vi 0.98 2.49 3.392 (3) 154
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+1, z]; (ii) [-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]; (iii) [x+{\script{1\over 2}}, -y, z]; (iv) [x-{\script{1\over 2}}, -y, z]; (v) [-x, -y, z-{\script{1\over 2}}]; (vi) [-x, -y+1, z+{\script{1\over 2}}]; (vii) [-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}].

All inositol ring H atoms were placed in geometrically idealized positions, with C—H = 0.98 Å. They were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The O-bound H atoms were located in difference Fourier maps and refined isotropically. The refined O—H distances were in the range 0.79 (3)–0.91 (3) Å. Although (I) is racemic, it crystallizes in a noncentrosymmetric space group. In the absence of strong anomalously scattering elements in the structure, the absolute structure was chosen arbitrarily and the Friedel pairs were merged prior to structure refinement.

Data collection: SMART (Bruker, 2003[Bruker (2003). SADABS (Version 2.05), SMART (Version 5.631) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SADABS (Version 2.05), SMART (Version 5.631) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

epi-Inositol is known to affect regulation of the myo-inositol biosynthetic pathway (Shaldubina et al., 2002) and has been evaluated as a potential antidepressant drug that could interact with the Li+ ion and myo-inositol receptors in the brain (Einat et al., 1998; Belmaker et al., 1998; Williams et al., 2002). We have earlier reported the synthesis of epi-inositol by the reduction of racemic epi-inosose (Patil et al., 2011).

A Cambridge Structural Database (CSD, version 5.31; Allen, 2002) search yielded the structure of the optically active (-)-epi-inosose (CSD refcode: XEGVUA) prepared enantioselectively by a bioconversion from myo-inositol (Hosomi et al., 2000). We were thus presented with an opportunity for the comparison of the molecular assembly in the crystals of these homochiral, (I), and racemic, (II), inososes. Single-crystal X-ray intensity measurements for crystals of (II) were recorded at ambient temperature (297 K) as reported for (I). Crystals of the racemic ketone are orthorhombic, belonging to the space group Pca21 (Fig. 1), while the homochiral ketone crystallizes in the non-centrosymmetric space group P21, with two independent molecules (A and B) in the asymmetric unit. The atom numbering for the racemic form is consistent with that reported for the optically active compound to enable easier comparison of the crystal structures.

The overlap of molecules in the asymmetric unit of (I) and the corresponding enantiomer in (II) reveals orientational differences in the hydroxy hydrogen atoms at C3 and C4 (Fig. 2). The conformation of the C3 hydroxy hydrogen of (II) (red, Fig. 2b) matches that of molecule B (green, Fig. 2b) in the asymmetric unit of crystals of (II), whereas the conformation of the C4 hydroxy group (red, Fig. 2a) matches that of molecule A (blue, Fig. 2a). There is a close correspondence in the unit-cell parameters of the two structures: the a axes lengths are nearly the same and interchange of the b and c axes of the orthorhombic racemic form results in edge lengths that are nearly identical to those of the homochiral crystal lattice [a = 11.197 (2), b = 8.932 (2), c = 6.976 (2) Å, β = 90.21 (2)° for (I)]. In accordance with Wallach's rule (Wallach, 1895; Brock et al., 1991), the racemic crystal is 1.7% denser than the enantiomer crystal, and its melting point is 492–495 K. The melting point of the crystals of (I) is not available for comparison. The unit cell of racemic epi-inosose consists of four molecules, i.e. two pairs of enantiomers, whereas that of (-)-epi-inosose contains two pairs of the two symmetry-independent molecules of the asymmetric unit. The presence of five hydroxy groups and a ketone carbonyl results in extensive hydrogen-bonding interactions in the crystal.

In the crystals of (II), each enantiomer forms a homochiral O6—H6···O4 hydrogen-bonded chain along the c axis with adjacent heterochiral molecular chains along the a axis linked by short and linear O3—H3···O2, O4—H4···O6, O5—H5···O3 and C3—H8···O4 interactions (Fig. 3a, Table 1). In the case of (I), each of the two molecules in the asymmetric unit forms a similar O6—H5···O4 hydrogen-bonded chain along the b axis. Interestingly, the ketone carbonyl oxygen (O7) of only one of the molecules (molecule B) is involved in O—H···O hydrogen bonding (O9—H12···O7), because of the conformational differences in the hydroxy groups of the two molecules in the asymmetric unit. The adjacent molecular chains along the a axis are linked by a large number of hydrogen-bonding interactions (Fig. 3b).

A view of these molecular chains down the c axis in (II) and b axis in (I) shows a corrugated sheet-like assembly (Fig. 4). Adjacent sheets are linked by bifurcated hydrogen-bonding interactions involving the ketone carbonyl oxygen O1 (O2—H2···O1 and C2—H7···O1) and O2—H2···O6 and C6—H11···O2 contacts in the racemic crystal (Fig. 4a, Table 1). In the crystals of the optically active form, the neighbouring sheets are linked by O2—H1···O9, O3—H2···O10, O10—H13···O11, O11—H14···O6, C2—H6···O1 and C6—H10···O2 contacts (Fig. 4b). Thus, the overall molecular organization in the crystals of the racemic and enantiopure compound is remarkably similar. This is primarily due to the fact that the second molecule in the asymmetric unit of (I) plays the role of the second enantiomer in the crystal packing. While the thermodynamic stability of the two crystals cannot be experimentally evaluated owing to the absence of adequate thermal data, estimation of lattice energies for (I) and (II) using the Oprop module of the OPiX program suite (Gavezzotti, 2003) yielded values of -204.75 (I) and -253.5 (II) kJ mol-1, consistent with the crystal densities.

Related literature top

For related literature, see: Belmaker et al. (1998); Brock et al. (1991); Einat et al. (1998); Gavezzotti (2003); Hosomi et al. (2000); Patil et al. (2011); Shaldubina et al. (2002); Sheldrick (2008); Wallach (1895); Williams et al. (2002).

Experimental top

Racemic epi-inosose, (II), was synthesized as reported previously (Patil et al., 2011). Prism-shaped crystals (m.p. 492–495 K) were obtained by slow evaporation from a solution in hot water.

Refinement top

All inositol ring H atoms were placed in geometrically idealized positions with C—H = 0.98 Å. They were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The O-bound H atoms were located in difference Fourier maps and refined isotropically. The refined O—H distances were in the range 0.79 (2)–0.92 (2) Å. The data were merged using MERG3 in SHELXL97 (Sheldrick, 2008), according to the standard procedure for X-ray Mo Kα measurements of chemical compounds without heavy atoms.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of racemic epi-inosose, (II) [the (2R,3S,5S,6S)-enantiomer], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The overlap of the molecules in the crystals of (-)-epi-inosose, (I), and racemic epi-inosose, (II), showing the difference in orientation of the hydroxy groups. In (a), one of the two independent molecules in the asymmetric unit of (I) (blue in the electronic version of the paper) and the corresponding enantiomer in (II) (red) is shown, while in (b) the second independent molecule in the asymmetric unit of (I) (green) and the corresponding enantiomer in (II) (red) is shown.
[Figure 3] Fig. 3. Molecular chains linked through hydrogen-bonding interactions (dotted lines) in the crystal structures of (a) (II) and (b) (I). The different colours represent the enantiomers of (II) in (a) (green and yellow) and the independent molecules in the asymmetric unit of (I) in (b) (green and blue). Grey molecules are present in the asymmetric unit. H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (i) -x, -y, z-1/2; (ii) x-1/2, -y, z; (iii) -x+1/2, y, z+1/2; (iv) x+1/2, -y, z; (v) -x+1/2, y, z-1/2; (vi) -x+2, y-1/2, -z; (vii) -x+2, y+1/2, -z; (viii) -x+1, y+1/2, -z; (ix) -x+1, y-1/2, -z; (x) x, y-1, z.]
[Figure 4] Fig. 4. A view of the molecular packing down (a) the c axis in crystals of (II) and (b) the b axis in crystals of (I). Dotted lines represent hydrogen-bonding interactions, some of which (shown in Fig. 3) have been omitted for clarity. [Symmetry codes: (xi) -x, -y+1, z+1/2; (xii) x+1/2, -y+1, z; (xiii) x+2, y+1/2, -z+1; (xiv) -x+2, y-1/2, -z+1; (xv) -x+1, y+1/2, -z+1; (xvi) -x+1, y-1/2, -z+1.]
(2RS,3SR,5SR,6SR)-epi-inosose top
Crystal data top
C6H10O6F(000) = 376
Mr = 178.14Dx = 1.725 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 2280 reflections
a = 11.1825 (18) Åθ = 2.9–27.8°
b = 6.9752 (12) ŵ = 0.16 mm1
c = 8.7930 (15) ÅT = 297 K
V = 685.9 (2) Å3Prism, colourless
Z = 40.29 × 0.29 × 0.17 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
653 independent reflections
Radiation source: fine-focus sealed tube647 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ϕ and ω scansθmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 1013
Tmin = 0.956, Tmax = 0.974k = 88
3225 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.0491P)2 + 0.0637P]
where P = (Fo2 + 2Fc2)/3
653 reflections(Δ/σ)max = 0.002
129 parametersΔρmax = 0.25 e Å3
1 restraintΔρmin = 0.13 e Å3
Crystal data top
C6H10O6V = 685.9 (2) Å3
Mr = 178.14Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 11.1825 (18) ŵ = 0.16 mm1
b = 6.9752 (12) ÅT = 297 K
c = 8.7930 (15) Å0.29 × 0.29 × 0.17 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
653 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
647 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.974Rint = 0.016
3225 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0261 restraint
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.15Δρmax = 0.25 e Å3
653 reflectionsΔρmin = 0.13 e Å3
129 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.03349 (15)0.3927 (3)0.0752 (2)0.0405 (5)
O20.19141 (13)0.4974 (2)0.03356 (19)0.0276 (4)
O30.31840 (13)0.2909 (2)0.1949 (2)0.0285 (4)
O40.19401 (13)0.0091 (2)0.3489 (2)0.0262 (4)
O50.01515 (14)0.0554 (2)0.1209 (2)0.0286 (4)
O60.17930 (12)0.2105 (2)0.1184 (2)0.0260 (4)
C10.00672 (18)0.3622 (3)0.0495 (3)0.0226 (5)
C20.13256 (17)0.4188 (3)0.0947 (2)0.0222 (5)
H70.12870.51590.17520.027*
C30.19932 (18)0.2409 (3)0.1551 (3)0.0222 (5)
H80.20320.14690.07250.027*
C40.13021 (18)0.1496 (3)0.2869 (2)0.0215 (4)
H90.12120.24610.36700.026*
C50.0049 (2)0.0883 (3)0.2355 (2)0.0217 (5)
H100.03850.03530.32270.026*
C60.06406 (18)0.2616 (3)0.1732 (3)0.0227 (4)
H110.07500.35260.25700.027*
H60.166 (3)0.147 (4)0.046 (4)0.040 (9)*
H50.044 (3)0.142 (4)0.139 (3)0.031 (7)*
H20.246 (4)0.573 (4)0.000 (5)0.058 (9)*
H40.215 (3)0.081 (4)0.286 (4)0.040 (9)*
H30.316 (3)0.365 (4)0.275 (5)0.061 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0343 (8)0.0523 (10)0.0348 (10)0.0097 (7)0.0117 (8)0.0174 (10)
O20.0275 (8)0.0312 (8)0.0241 (8)0.0091 (6)0.0006 (6)0.0040 (7)
O30.0182 (7)0.0361 (9)0.0311 (9)0.0002 (6)0.0011 (7)0.0015 (8)
O40.0284 (8)0.0282 (8)0.0221 (8)0.0059 (6)0.0001 (6)0.0037 (8)
O50.0314 (8)0.0255 (8)0.0290 (9)0.0023 (7)0.0005 (8)0.0047 (7)
O60.0187 (8)0.0320 (8)0.0273 (9)0.0007 (6)0.0010 (7)0.0028 (8)
C10.0239 (10)0.0206 (9)0.0234 (11)0.0027 (7)0.0029 (9)0.0023 (9)
C20.0246 (10)0.0227 (10)0.0193 (10)0.0021 (7)0.0003 (8)0.0007 (8)
C30.0188 (8)0.0263 (10)0.0215 (12)0.0004 (8)0.0008 (8)0.0030 (8)
C40.0234 (10)0.0242 (9)0.0169 (10)0.0035 (8)0.0006 (8)0.0001 (9)
C50.0227 (10)0.0248 (10)0.0175 (11)0.0005 (8)0.0024 (8)0.0006 (8)
C60.0196 (9)0.0258 (9)0.0225 (11)0.0016 (8)0.0010 (8)0.0017 (9)
Geometric parameters (Å, º) top
O1—C11.204 (3)C1—C21.515 (3)
O2—C21.416 (3)C1—C61.517 (3)
O2—H20.85 (4)C2—C31.543 (3)
O3—C31.420 (2)C2—H70.9800
O3—H30.87 (4)C3—C41.531 (3)
O4—C41.425 (2)C3—H80.9800
O4—H40.78 (4)C4—C51.533 (3)
O5—C51.426 (3)C4—H90.9800
O5—H50.91 (3)C5—C61.535 (3)
O6—C61.421 (3)C5—H100.9800
O6—H60.79 (3)C6—H110.9800
C2—O2—H2107 (3)C2—C3—H8107.8
C3—O3—H3108 (2)O4—C4—C5110.74 (16)
C4—O4—H4112 (2)O4—C4—C3111.10 (17)
C5—O5—H5106.4 (17)C5—C4—C3110.75 (17)
C6—O6—H6104 (2)O4—C4—H9108.0
O1—C1—C2122.7 (2)C5—C4—H9108.0
O1—C1—C6122.65 (19)C3—C4—H9108.0
C2—C1—C6114.65 (18)O5—C5—C4109.33 (16)
O2—C2—C1108.87 (17)O5—C5—C6109.98 (18)
O2—C2—C3111.13 (16)C4—C5—C6110.20 (16)
C1—C2—C3109.29 (16)O5—C5—H10109.1
O2—C2—H7109.2C4—C5—H10109.1
C1—C2—H7109.2C6—C5—H10109.1
C3—C2—H7109.2O6—C6—C1110.24 (18)
O3—C3—C4112.90 (19)O6—C6—C5112.30 (17)
O3—C3—C2109.93 (18)C1—C6—C5110.97 (16)
C4—C3—C2110.54 (16)O6—C6—H11107.7
O3—C3—H8107.8C1—C6—H11107.7
C4—C3—H8107.8C5—C6—H11107.7
O1—C1—C2—O23.6 (3)O4—C4—C5—O560.6 (2)
C6—C1—C2—O2175.53 (16)C3—C4—C5—O563.1 (2)
O1—C1—C2—C3125.2 (2)O4—C4—C5—C6178.37 (18)
C6—C1—C2—C354.0 (2)C3—C4—C5—C657.9 (2)
O2—C2—C3—O358.6 (2)O1—C1—C6—O60.6 (3)
C1—C2—C3—O3178.73 (18)C2—C1—C6—O6178.56 (16)
O2—C2—C3—C4176.14 (16)O1—C1—C6—C5125.7 (2)
C1—C2—C3—C456.0 (2)C2—C1—C6—C553.5 (2)
O3—C3—C4—O453.4 (2)O5—C5—C6—O657.1 (2)
C2—C3—C4—O4176.96 (16)C4—C5—C6—O6177.66 (18)
O3—C3—C4—C5176.85 (17)O5—C5—C6—C166.8 (2)
C2—C3—C4—C559.5 (2)C4—C5—C6—C153.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.85 (4)2.57 (4)3.191 (2)131 (3)
O2—H2···O6i0.85 (4)2.02 (4)2.833 (2)159 (4)
O3—H3···O2ii0.87 (4)1.93 (4)2.791 (3)172 (4)
O4—H4···O6iii0.78 (4)2.10 (4)2.844 (2)161 (3)
O5—H5···O3iv0.91 (3)1.92 (3)2.822 (2)171 (2)
O6—H6···O4v0.79 (3)2.01 (4)2.760 (2)160 (3)
C2—H7···O1vi0.982.523.374 (3)145
C3—H8···O4vii0.982.523.422 (3)152
C6—H11···O2vi0.982.493.392 (3)154
Symmetry codes: (i) x+1/2, y+1, z; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y, z; (iv) x1/2, y, z; (v) x, y, z1/2; (vi) x, y+1, z+1/2; (vii) x+1/2, y, z1/2.

Experimental details

Crystal data
Chemical formulaC6H10O6
Mr178.14
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)297
a, b, c (Å)11.1825 (18), 6.9752 (12), 8.7930 (15)
V3)685.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.29 × 0.29 × 0.17
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.956, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
3225, 653, 647
Rint0.016
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.068, 1.15
No. of reflections653
No. of parameters129
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.13

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.85 (4)2.57 (4)3.191 (2)131 (3)
O2—H2···O6i0.85 (4)2.02 (4)2.833 (2)159 (4)
O3—H3···O2ii0.87 (4)1.93 (4)2.791 (3)172 (4)
O4—H4···O6iii0.78 (4)2.10 (4)2.844 (2)161 (3)
O5—H5···O3iv0.91 (3)1.92 (3)2.822 (2)171 (2)
O6—H6···O4v0.79 (3)2.01 (4)2.760 (2)160 (3)
C2—H7···O1vi0.982.523.374 (3)145.3
C3—H8···O4vii0.982.523.422 (3)152.4
C6—H11···O2vi0.982.493.392 (3)153.5
Symmetry codes: (i) x+1/2, y+1, z; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y, z; (iv) x1/2, y, z; (v) x, y, z1/2; (vi) x, y+1, z+1/2; (vii) x+1/2, y, z1/2.
 

Acknowledgements

SK and MTP are recipients of Senior Research Fellowships from CSIR, New Delhi, India. This work was supported by the Department of Science and Technology, New Delhi, India.

References

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