The concomitant crystallization of two polymorphs of 1-de­oxy-α-d-tagatose

Jones, N.A.; Jenkinson, S.F.; Soengas, R.; Izumori, K.; Fleet, G.W.J.; Watkin, D.J.

doi:10.1107/S0108270106048591

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 63| Part 1| January 2007| Pages o7-o10

doi:10.1107/S0108270106048591

The concomitant crystallization of two polymorphs of 1-deoxy-α-D-tagatose

Nigel A. Jones,^a ^* Sarah F. Jenkinson,^a Raquel Soengas,^a Ken Izumori,^b George W. J. Fleet ^a and David J. Watkin ^c

^aDepartment of Organic Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, ^bRare Sugar Research Centre, Kagawa University, 2393 Miki-cho, Kita-gun, Kagawa 761-0795, Japan, and ^cDepartment of Chemical Crystallography, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England
^*Correspondence e-mail: nigel.jones@chem.ox.ac.uk

(Received 24 October 2006; accepted 14 November 2006; online 12 December 2006)

The crystalline form of 1-deoxy-D-tagatose, C₆H₁₂O₅, is shown to be 1-deoxy-α-D-tagatopyranose; the absolute configuration is determined by use of D-lyxono-1,4-lactone as the starting material. The title compound crystallized as concomitant polymorphs from a mixture of ethyl actate and methanol. Although the melting points of the materials differ by 7 K, the molecular conformations are almost identical and, in both polymorphs, each molecule is subject to four O—H⋯O hydrogen bonds.

Comment

The properties of 1-deoxy ketohexose sugars have been little studied. The crystal structure of 1-deoxy-D-sorbose has recently been published (Jones et al., 2006 ) and as part of a project to extend the range of simple monosaccharide derivatives, 1-deoxy-D-tagatose, (2), was synthesized. 1-Deoxy-D-tagatose has previously been synthesized (Wolfrom & Bennett, 1965 ; Dills & Covey, 1981 ; Cubero & Poza, 1985 ), but no crystal structure has been reported.

The demand for the large-scale production of rare sugars by biotechnological (Izumori, 2002 , 2006 ; Granstrom et al., 2004 ) and chemical (Beadle et al., 1992 ) methods is driven by the demand for alternative foodstuffs (Skytte, 2002 ) and D-tagatose itself is used as a low-calorie sweetener (Levin, 2002 ; Howling & Callagan, 2000 ; Bertelsen et al. 1999 ). Rare monosaccharides themselves, however, have been found to demonstrate interesting pharmaceutical properties; for example, D-psicose (Takata et al., 2005 ; Menavuvu et al., 2006 ) and D-allose (Sui et al., 2005 ; Hossain et al., 2006 ) have significant chemotherapeutic properties and D-tagatose has been found to be an antihyperglycemic agent (Zehner et al., 1994 ; Donner et al., 1999 ) and therefore potentially useful in the treatment of diabetes.

1-Deoxy-D-tagatose, (2), was synthesized from protected D-lyxono-1,4-lactone, (1), by methylation using methyl lithium and subsequent deprotection with dowex resin (H+) (Jones et al., 2007 ). The deoxy sugar was readily crystallized and the present paper firmly establishes that, as for 1-deoxy-D-sorbose (Jones et al., 2006), 1-deoxy-D-tagatose exists in the crystalline state as the α-anomer of the pyranose ring form (3), in a chair conformation. Two polymorphic forms were observed to crystallize from the same mother liquor but at different rates. The two forms were needles and hexagonal plates. The hexagonal plates were found to crystallize out after 16 h, whereas the needles were only observed after 72 h. In both polymorphic forms, the title compound was in the α-pyranose form (3). In contrast, in aqueous solution it exists as an equilibrium mixture of the open chain, (2), α-pyranose, (3), α-furanose, (4), β-pyranose, (5), and β-furanose, (6), forms.

Crystals of two distinctly different habits, viz. needles and plates, were observed in approximately equal quantities in the mother liquor. Cell parameters were determined for both forms and found to be different. Full data collections and structure solutions were performed on a sample of each habit. With the exception of the hydroxyl H atoms, the molecules were essentially identical (Figs. 1 and 2), with an r.m.s. displacement between equivalent atoms of 0.05 Å after superimposing one molecule on the other.

The formation of two different polymorphs of a material simultaneously in the same environment is termed `concomitant polymorphism' (Bernstein et al., 1995 ). There seems to be some uncertainly about the frequency of occurrence of this phenomenon. Bernstein et al. (1995) remark that it is rarely reported in the recent literature, but that it had been widely observed (von Groth et al., 1906 ) before the advent of X-ray crystallography. Perhaps this is because the thrust of many structure determinations has been focused on the molecular structure rather than the crystal structure, so that the work was performed on the first good quality crystal obtained rather than on a survey of a whole batch of material. Bowes et al. (2003 ) support this: `our identification, essentially by chance, of four such examples within a rather short space of time suggests to us that the phenomenon of concomitant polymorphism may, in fact, be a rather common one, certainly far more common than the current literature tends to suggest, but one which goes largely unnoticed.' In recent years, the current authors have analysed almost 100 saccharide derivatives and this is the first one where polymorphism was clearly evident.

The different polymorphs arise from differences in the hydrogen-bonding network (Figs. 3 and 4, and Tables 1 and 2). The most densely packed molecules occur in the plate-like crystals. As is usual in P2₁2₁2₁, the molecules are linked into hydrogen-bonded helices around the twofold screw axes. The relationship between the two polymorphs is most easily visualized by concentrating on the helices containing atoms O7 and O10. In the more dense polymorph, this is a helix involving four molecules. One turn consists of the sequence O7—H7⋯O10—H10⋯O7—H7⋯O10—H10⋯O7. In projection along the a axis, the four O atoms form an approximate square (Fig. 4). In the less dense polymorph, the helix is expanded to contain contributions from six molecules. Atom O10 still donates to atom O7, but atom O7 is now linked via atoms O8 and O9 back to an equivalent molecule that uses atom O10. One turn of this extended sequence contains O10—H10⋯O7—H7⋯O8⋯H9—O9 and the same pattern repeated by symmetry (Fig. 3). In the plate-like crystal, molecules 1 and 2 lie more or less side by side. In the needle-shaped crystals they are displaced with respect to each other so that the cross-section of the helix becomes oval. Other O—H⋯O hydrogen bonds crosslink these helices. There are no unusually short intermolecular contacts.

In summary, 1-deoxy-D-tagatose, (2), exists in the crystalline state as 1-deoxy-α-D-tagatopyranose, (3); the absolute configuration is determined by the use of D-lyxono-1,4-lactone as the starting material. The X-ray crystal structure determined the stereochemistry at the anomeric position as being α, with the hydroxyl group in the axial position. As well as the potential biological properties of 1-deoxy ketoses, they are likely to provide a new set of building blocks for the synthesis of a wide variety of complex biomolecules.

The crystallographic interest in these materials arises from the concomitant polymorphism, few cases of which are reported in the literature, but which may eventually be of use for the fine-tuning of structure prediction programs.

Figure 1
The title compound from the needle crystals, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii.

Figure 2
The title compound from the hexagonal plate crystals, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii.

Figure 3
Part of the three-dimensional hydrogen-bonding network in the needle crystals, viewed approximately parallel to a and showing one turn of the helix (starting from the molecule with symmetry code ii). Molecules labelled 1 and 2 are described in the Comment. [Symmetry codes: (i) x, y − 1, z; (ii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (iii) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (iv) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (v) −x + 2, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vi) −x + $[{3\over 2}]$ , −y + 1, z + $[{1\over 2}]$ .]

Figure 4
The equivalent part of the three-dimensional hydrogen-bonding network in the plate crystals, viewed approximately parallel to a and showing one turn of the helix (starting from the molecule with symmetry code i). In strict a-axis projection, the sides of the helix form an almost square lozenge. Molecules labelled 1 and 2 are described in the Comment. [Symmetry codes: (i) x − 1, y, z; (ii) x, y + 1, z; (iii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1; (iv) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1.]

Experimental

The title compound was recrystallized from a mixture of ethyl acetate and methanol to give colourless crystals; [α]_D²² −13 (c 2.0, H₂O). The melting points of the two crystalline forms were found to be different, viz. 409–411 K for the needles and 416–418 K for the hexagonal plates.

Polymorph (I)

Crystal data

C₆H₁₂O₅
M_r = 164.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0243 (2) Å
b = 7.5022 (3) Å
c = 15.9717 (8) Å
V = 721.85 (5) Å³
Z = 4
D_x = 1.510 Mg m⁻³
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 190 K
Needle, colourless
0.40 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.829, T_max = 0.987
5125 measured reflections
975 independent reflections
879 reflections with I > 2σ(I)
R_int = 0.057
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.069
S = 1.00
975 reflections
100 parameters
H-atom parameters constrained
w = 1/[σ²(F²) + (0.03P)² + 0.18P], where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max < 0.001
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °) for polymorph (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O8^vii	0.87	1.93	2.788 (2)	170
O8—H8⋯O6^viii	0.85	1.88	2.698 (2)	164
O10—H10⋯O7ⁱⁱⁱ	0.83	2.05	2.865 (2)	165
O9—H9⋯O8^v	0.84	2.10	2.913 (2)	162
Symmetry codes: (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (v) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) -x+2, $[y+{\script{1\over 2}}]$ , $[-z+{\script{1\over 2}}]$ ; (viii) x+1, y, z.

Polymorph (II)

Crystal data

C₆H₁₂O₅
M_r = 164.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0177 (2) Å
b = 6.4672 (2) Å
c = 18.0218 (7) Å
V = 701.37 (4) Å³
Z = 4
D_x = 1.555 Mg m⁻³
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 190 K
Hexagonal plate, colourless
0.20 × 0.20 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) T_min = 0.865, T_max = 0.986
3322 measured reflections
949 independent reflections
883 reflections with I > 2σ(I)
R_int = 0.023
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 1.03
949 reflections
100 parameters
H-atom parameters constrained
w = 1/[σ²(F²) + (0.02P)² + 0.2P], where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max < 0.001
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 2
Hydrogen-bond geometry (Å, °) for polymorph (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10⋯O7ⁱⁱⁱ	0.99	1.80	2.778 (2)	170
O7—H7⋯O10ⁱⁱ	0.90	1.90	2.791 (2)	172
O9—H9⋯O8^v	0.91	1.88	2.786 (2)	174
O8—H8⋯O6^vi	0.95	1.87	2.803 (2)	165
Symmetry codes: (ii) x, y+1, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) x+1, y, z.

In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration assigned from the starting materials. The relatively large ratio of minimum to maximum corrections applied in the multi-scan process (1:1.19 and 1:1.14) include factors in addition to absorption, which were taken into account (Görbitz, 1999 ) by the multi-scan inter-frame scaling (DENZO/SCALEPACK; Otwinowski & Minor, 1997). H atoms were all located in a difference map, but those attached to C atoms were repositioned geometrically. H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å and O—H = 0.82 Å) and U_iso(H) values (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints.

For both compounds, 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.

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270106048591/sk3070sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106048591/sk3070Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270106048591/sk3070IIsup3.hkl

Comment top

The properties of 1-deoxy ketohexose sugars have been little studied. The crystal structure of 1-deoxy-D-sorbose has recently been published (Jones et al., 2006) and as part of extending the range of simple monosaccharide derivatives, 1-deoxy-D-tagatose, (2), was synthesized. 1-Deoxy-D-tagatose has previously been synthesized (Wolfrom & Bennett, 1965; Dills & Covey, 1981; Cubero & Poza, 1985), but no crystal structure has been reported.

The demand for the large-scale production of rare sugars by biotechnological (Izumori, 2002, 2006; Granstrom et al., 2004) and chemical (Beadle et al., 1992) methods is driven by the demand for alternative foodstuffs (Skytte, 2002) and D-tagatose itself is used as a low-calorie sweetener (Levin, 2002; Howling & Callagan, 2000; Bertelsen et al. 1999) Rare monosaccharides themselves, however, have been found to demonstrate interesting pharmaceutical properties; for example, D-psicose (Takata et al., 2005; Menavuvu et al., 2006) and D-allose (Sui et al., 2005; Hossain et al., 2006) have significant chemotherapeutic properties and D-tagatose has been found to be an anti-hyperglycemic agent (Zehner et al., 1994; Donner et al., 1999) and therefore potentially useful in the treatment of diabetes.

1-Deoxy-D-tagatose, (2), was synthesized from protected D-lyxono-1,4-lactone, (1), by methylation using methyl lithium and subsequent deprotection with dowex resin (H+) (Jones et al., 2007). The deoxy sugar was readily crystallized and the present paper firmly establishes that, as for 1-deoxy-D-sorbose (Jones et al., 2006), 1-deoxy-D-tagatose exists in the crystalline state as the α-anomer of the pyranose ring form (3), in a chair conformation. Two polymorphic forms were observed to crystallize from the same mother liquor but at different rates. The two forms were needles and hexagonal plates. The hexagonal plates were found to crystallize out after 16 h, whereas the needles were only observed after 72 h. In both polymorphic forms, the title compound was in the α-pyranose form (3). In contrast, in aqueous solution it exists as an equilibrium mixture of the open chain, (2), α-pyranose, (3), α-furanose, (4), β-pyranose, (5) and β-furanose, (6), forms.

Crystals of two distinctly different habits, needles and plates, were observed in approximately equal quantities in the mother liquor. Cell parameters were determined for both forms and found to be different. Full data collections and structure solutions were performed on a sample of each habit. With the exception of the hydroxyl H atoms, the molecules were essentially identical (Figs. 1 and 2), with an r.m.s displacement between equivalent atoms of 0.05 Å after superposing one molecule on the other.

The formation of two different polymorphs of a material simultaneously in the same environment is termed `concomitant polymorphism' (Bernstein et al., 1995). There seems to be some uncertainly about the frequency of occurrence of this phenomenon. Bernstein et al. (1995) remark that it is rarely reported in the recent literature, but that it had been widely observed (von Groth et al., 1906) before the advent of X-ray crystallography. Perhaps this is because the thrust of many structure determinations has been focused on the molecular structure rather than the crystal structure, so that the work was performed on the first good quality crystal obtained rather than on a survey of a whole batch of material. Bowes et al. (2003) support this; 'Our identification, essentially by chance, of four such examples within a rather short space of time suggests to us that the phenomenon of concomitant polymorphism may, in fact, be a rather common one, certainly far more common than the current literature tends to suggest, but one which goes largely unnoticed.' In recent years the current authors have analysed almost 100 saccharide derivatives and this is the first one where polymorphism was clearly evident.

The different polymorphs arise from differences in the hydrogen-bonding network (Fig. 3 and 4). The most densely packed molecules occur in the plate-like crystals. As is usual in P2₁2₁2₁, the molecules are linked into hydrogen-bonded helices around the twofold screw axes. The relationship between the two polymorphs is most easily visualized by concentrating on the helices containing O7 and O10. In the more dense polymorph, this is a helix involving four molecules. One turn consists of the sequence O7—H7···O10—H10···O7—H7···O10—H10···O7. In projection along the a axis, the four O atoms form an approximate square (Fig. 4). In the less dense polymorph, the helix is expanded to contain contributions from six molecules. Atom O10 still donates to O7, but atom O7 is now linked via atoms O8 and O9 back to an equivalent molecule that uses atom O10. One turn of this extended sequence contains O10—H10···O7—H7···O8···H9—O9 and the same pattern repeated by symmetry (Fig. 3). In the plate-like crystal, molecules 1 and 2 lie more or less side by side. In the needle-shaped crystals they are displaced with respect to each other so that the cross section of the helix becomes oval. Other O—H···O hydrogen bonds cross-link these helices. There are no unusually short inter-molecular contacts.

In summary 1-deoxy-D-tagatose, (2), exists in the crystalline state as 1-deoxy-α-D-tagatopyranose, (3); the absolute configuration is determined by the use of D-lyxono-1,4-lactone as the starting material. The X-ray crystal structure determined the stereochemistry at the anomeric position as being α, with the hydroxyl group in the axial position. As well as the potential biological properties of 1-deoxy ketoses, they are likely to provide a new set of building blocks for the synthesis of a wide variety of complex biomolecules.

Experimental top

The title compound was recrystallized from a mixture of ethyl acetate and methanol to give colourless crystals. [α]_D²² −13 (c 2.0, H₂O). The melting points of the two crystalline forms were found to be different (needles 409–411 K; hexagonal plate 416–418 K).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1997-2001).; 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.

Figures top

Fig. 1.

The title compound from the needle crystals, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radii.

Fig. 2.

The title compound from the hexagonal plate crystals, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radii.

Fig. 3.

Part of the three-dimensional hydrogen-bonding network in the needle crystals, viewed approximately parallel to a and showing one turn of the helix (starting from the molecule with symmetry code ii). Molecules labelled 1 and 2 are described in the text. [Symmetry codes: (i) x, y − 1, z; (ii) x − 1/2, 1/2 − y, 1 − z; (iii) x − 1/2, 3/2 − y, 1 − z; (iv) x + 1/2, 1/2 − y, 1 − z; (v) 2 − x, y − 1/2, 1/2 − z; (vi) 3/2 − x, 1 − y, z + 1/2.]

Fig. 4.

The equivalent part of the three-dimensional hydrogen-bonding network in the plate crystals, viewed approximately parallel to a and showing one turn of the helix (starting from the molecule with symmetry code i). In strict a axis projection, the sides of the helix form an almost square lozenge. Molecules labelled 1 and 2 are described in the text. [Symmetry codes: (i) x − 1, y, z; (ii) x, y + 1, z; (iii) x − 1/2, 1/2 − y, 1 − z; (iv) x − 1/2, 3/2 − y, 1 − z.]

(I) 1-deoxy-α-D-tagatopyranose top

Crystal data top

C₆H₁₂O₅	D_x = 1.510 Mg m⁻³
M_r = 164.16	Melting point: 410 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 950 reflections
a = 6.0243 (2) Å	θ = 5–27°
b = 7.5022 (3) Å	µ = 0.13 mm⁻¹
c = 15.9717 (8) Å	T = 190 K
V = 721.85 (5) Å³	Needle, colourless
Z = 4	0.40 × 0.10 × 0.10 mm
F(000) = 352

Data collection top

Nonius KappaCCD diffractometer	879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ω scans	θ_max = 27.5°, θ_min = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −7→7
T_min = 0.829, T_max = 0.987	k = −9→9
5125 measured reflections	l = −20→20
975 independent reflections

Refinement top

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)] = 0.029	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F²) + (0.03P)² + 0.18P], where P = [max(F_o²,0) + 2F_c²]/3
S = 1.01	(Δ/σ)_max = 0.000221
975 reflections	Δρ_max = 0.21 e Å⁻³
100 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints

Crystal data top

C₆H₁₂O₅	V = 721.85 (5) Å³
M_r = 164.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0243 (2) Å	µ = 0.13 mm⁻¹
b = 7.5022 (3) Å	T = 190 K
c = 15.9717 (8) Å	0.40 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	975 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	879 reflections with I > 2σ(I)
T_min = 0.829, T_max = 0.987	R_int = 0.057
5125 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.01	Δρ_max = 0.21 e Å⁻³
975 reflections	Δρ_min = −0.19 e Å⁻³
100 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5929 (3)	0.4965 (2)	0.42010 (11)	0.0191
C2	0.7853 (3)	0.4814 (2)	0.35731 (10)	0.0195
C3	0.9254 (3)	0.6509 (2)	0.35894 (10)	0.0178
C4	0.7820 (3)	0.8125 (2)	0.34139 (10)	0.0178
C5	0.5824 (3)	0.8149 (2)	0.39944 (11)	0.0203
O6	0.46117 (19)	0.64971 (16)	0.39797 (7)	0.0196
O7	0.9050 (2)	0.97311 (16)	0.35788 (7)	0.0241
O8	1.10068 (18)	0.64141 (17)	0.29777 (7)	0.0225
O9	0.6941 (2)	0.45542 (16)	0.27647 (7)	0.0257
O10	0.6906 (2)	0.52030 (17)	0.49875 (7)	0.0226
C11	0.4368 (3)	0.3392 (2)	0.41843 (12)	0.0265
H21	0.8770	0.3759	0.3741	0.0245*
H31	0.9907	0.6635	0.4166	0.0193*
H41	0.7354	0.8096	0.2822	0.0211*
H51	0.6332	0.8376	0.4573	0.0244*
H52	0.4808	0.9086	0.3793	0.0259*
H111	0.3208	0.3588	0.4597	0.0410*
H112	0.5205	0.2337	0.4325	0.0410*
H113	0.3771	0.3262	0.3613	0.0410*
H7	0.9157	1.0161	0.3077	0.0373*
H8	1.2230	0.6278	0.3229	0.0338*
H10	0.5959	0.5059	0.5362	0.0370*
H9	0.7710	0.3822	0.2491	0.0404*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0156 (8)	0.0213 (9)	0.0206 (8)	0.0002 (7)	−0.0020 (7)	0.0016 (7)
C2	0.0175 (8)	0.0221 (9)	0.0190 (8)	0.0027 (8)	−0.0034 (7)	−0.0019 (7)
C3	0.0149 (8)	0.0245 (9)	0.0141 (7)	0.0003 (8)	0.0008 (7)	−0.0019 (8)
C4	0.0171 (8)	0.0200 (9)	0.0162 (7)	−0.0018 (7)	0.0003 (7)	0.0005 (6)
C5	0.0194 (8)	0.0185 (9)	0.0230 (8)	0.0013 (8)	0.0021 (7)	0.0011 (7)
O6	0.0137 (5)	0.0204 (6)	0.0247 (6)	0.0001 (5)	−0.0007 (5)	0.0015 (5)
O7	0.0274 (7)	0.0241 (7)	0.0209 (6)	−0.0067 (6)	−0.0014 (6)	0.0027 (5)
O8	0.0135 (6)	0.0350 (7)	0.0190 (6)	0.0028 (6)	0.0016 (5)	−0.0009 (6)
O9	0.0241 (6)	0.0324 (7)	0.0206 (6)	0.0006 (7)	−0.0025 (5)	−0.0104 (5)
O10	0.0202 (6)	0.0305 (7)	0.0172 (6)	−0.0018 (6)	−0.0014 (5)	0.0025 (5)
C11	0.0245 (9)	0.0240 (10)	0.0310 (9)	−0.0036 (9)	−0.0016 (8)	0.0023 (8)

Geometric parameters (Å, º) top

C1—C2	1.537 (2)	C4—H41	0.986
C1—O6	1.441 (2)	C5—O6	1.439 (2)
C1—O10	1.399 (2)	C5—H51	0.988
C1—C11	1.509 (2)	C5—H52	0.986
C2—C3	1.527 (2)	O7—H7	0.867
C2—O9	1.417 (2)	O8—H8	0.845
C2—H21	1.002	O9—H9	0.841
C3—C4	1.515 (2)	O10—H10	0.834
C3—O8	1.4402 (18)	C11—H111	0.972
C3—H31	1.006	C11—H112	0.965
C4—C5	1.519 (2)	C11—H113	0.986
C4—O7	1.438 (2)

C2—C1—O6	108.31 (13)	C3—C4—H41	108.8
C2—C1—O10	106.15 (13)	C5—C4—H41	111.1
O6—C1—O10	110.50 (14)	O7—C4—H41	109.9
C2—C1—C11	113.62 (14)	C4—C5—O6	112.44 (13)
O6—C1—C11	106.04 (13)	C4—C5—H51	109.1
O10—C1—C11	112.20 (13)	O6—C5—H51	108.7
C1—C2—C3	110.14 (13)	C4—C5—H52	107.5
C1—C2—O9	108.20 (14)	O6—C5—H52	107.1
C3—C2—O9	110.15 (13)	H51—C5—H52	112.0
C1—C2—H21	107.5	C1—O6—C5	113.81 (11)
C3—C2—H21	110.4	C4—O7—H7	100.4
O9—C2—H21	110.4	C3—O8—H8	108.9
C2—C3—C4	110.39 (13)	C2—O9—H9	110.5
C2—C3—O8	110.63 (13)	C1—O10—H10	109.9
C4—C3—O8	109.40 (13)	C1—C11—H111	108.5
C2—C3—H31	108.0	C1—C11—H112	108.2
C4—C3—H31	108.5	H111—C11—H112	109.9
O8—C3—H31	109.9	C1—C11—H113	108.7
C3—C4—C5	110.37 (13)	H111—C11—H113	112.4
C3—C4—O7	110.05 (12)	H112—C11—H113	109.0
C5—C4—O7	106.62 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O8ⁱ	0.87	1.93	2.788 (2)	170
O8—H8···O6ⁱⁱ	0.85	1.88	2.698 (2)	164
O10—H10···O7ⁱⁱⁱ	0.83	2.05	2.865 (2)	165
O9—H9···O8^iv	0.84	2.10	2.913 (2)	162

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+2, y−1/2, −z+1/2.

(II) 1-deoxy-α-D-tagatopyranose top

Crystal data top

C₆H₁₂O₅	D_x = 1.555 Mg m⁻³
M_r = 164.16	Melting point: 417 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 826 reflections
a = 6.0177 (2) Å	θ = 5–27°
b = 6.4672 (2) Å	µ = 0.14 mm⁻¹
c = 18.0218 (7) Å	T = 190 K
V = 701.37 (4) Å³	Hexagonal plate, colourless
Z = 4	0.20 × 0.20 × 0.10 mm
F(000) = 352

Data collection top

Nonius KappaCCD diffractometer	883 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.5°, θ_min = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −7→7
T_min = 0.865, T_max = 0.986	k = −8→8
3322 measured reflections	l = −22→23
949 independent reflections

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F²) + (0.02P)² + 0.2P], where P = [max(F_o²,0) + 2F_c²]/3
S = 1.03	(Δ/σ)_max = 0.000232
949 reflections	Δρ_max = 0.22 e Å⁻³
100 parameters	Δρ_min = −0.19 e Å⁻³
19 restraints

Crystal data top

C₆H₁₂O₅	V = 701.37 (4) Å³
M_r = 164.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0177 (2) Å	µ = 0.14 mm⁻¹
b = 6.4672 (2) Å	T = 190 K
c = 18.0218 (7) Å	0.20 × 0.20 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	949 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	883 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.986	R_int = 0.023
3322 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	19 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.03	Δρ_max = 0.22 e Å⁻³
949 reflections	Δρ_min = −0.19 e Å⁻³
100 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7170 (3)	0.0840 (2)	0.38341 (8)	0.0164
C2	0.9081 (3)	0.1432 (2)	0.33058 (8)	0.0159
C3	1.0591 (3)	0.3034 (2)	0.36665 (8)	0.0148
C4	0.9243 (3)	0.4903 (2)	0.39003 (8)	0.0151
C5	0.7330 (3)	0.4220 (3)	0.43951 (9)	0.0185
O6	0.59682 (19)	0.26528 (17)	0.40555 (6)	0.0173
O7	1.06403 (19)	0.62698 (18)	0.43249 (6)	0.0200
O8	1.23071 (18)	0.36448 (18)	0.31620 (6)	0.0195
O9	0.8191 (2)	0.22943 (18)	0.26426 (6)	0.0214
O10	0.81963 (19)	−0.00833 (17)	0.44640 (6)	0.0179
C11	0.5454 (3)	−0.0585 (3)	0.34920 (9)	0.0212
H21	0.9970	0.0170	0.3184	0.0180*
H31	1.1283	0.2409	0.4118	0.0171*
H41	0.8653	0.5635	0.3453	0.0179*
H51	0.6384	0.5449	0.4510	0.0218*
H52	0.7961	0.3650	0.4866	0.0218*
H111	0.4276	−0.0898	0.3867	0.0249*
H112	0.4766	0.0101	0.3051	0.0249*
H113	0.6187	−0.1900	0.3334	0.0249*
H10	0.7135	−0.0465	0.4858	0.0500*
H7	0.9976	0.7506	0.4359	0.0500*
H9	0.7961	0.1161	0.2358	0.0500*
H8	1.3699	0.3453	0.3405	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0162 (8)	0.0155 (7)	0.0176 (7)	0.0038 (7)	−0.0010 (6)	0.0004 (7)
C2	0.0173 (8)	0.0156 (7)	0.0146 (7)	0.0040 (7)	−0.0002 (6)	0.0005 (6)
C3	0.0129 (8)	0.0172 (7)	0.0143 (6)	0.0023 (7)	0.0005 (6)	0.0029 (6)
C4	0.0152 (7)	0.0144 (7)	0.0159 (7)	0.0005 (7)	−0.0024 (6)	−0.0002 (6)
C5	0.0188 (8)	0.0168 (7)	0.0198 (7)	0.0009 (7)	0.0031 (7)	−0.0032 (7)
O6	0.0139 (6)	0.0156 (5)	0.0224 (5)	0.0012 (5)	0.0001 (5)	−0.0028 (5)
O7	0.0212 (6)	0.0151 (5)	0.0237 (5)	−0.0004 (6)	−0.0043 (5)	−0.0013 (5)
O8	0.0149 (6)	0.0231 (6)	0.0207 (5)	0.0016 (5)	0.0032 (5)	0.0050 (5)
O9	0.0286 (7)	0.0209 (5)	0.0147 (5)	−0.0007 (6)	−0.0058 (5)	0.0009 (5)
O10	0.0175 (6)	0.0193 (5)	0.0170 (5)	0.0008 (5)	−0.0008 (5)	0.0042 (5)
C11	0.0184 (8)	0.0187 (8)	0.0266 (8)	−0.0007 (7)	−0.0020 (7)	−0.0029 (7)

Geometric parameters (Å, º) top

C1—C2	1.542 (2)	C4—H41	1.000
C1—O6	1.4339 (18)	C5—O6	1.4399 (19)
C1—O10	1.4239 (18)	C5—H51	1.000
C1—C11	1.515 (2)	C5—H52	1.000
C2—C3	1.523 (2)	O7—H7	0.896
C2—O9	1.4235 (17)	O8—H8	0.953
C2—H21	1.000	O9—H9	0.906
C3—C4	1.515 (2)	O10—H10	0.986
C3—O8	1.4316 (18)	C11—H111	1.000
C3—H31	1.000	C11—H112	1.000
C4—C5	1.522 (2)	C11—H113	1.000
C4—O7	1.4400 (18)

C2—C1—O6	110.20 (12)	C3—C4—H41	110.1
C2—C1—O10	105.83 (12)	C5—C4—H41	109.9
O6—C1—O10	109.87 (11)	O7—C4—H41	110.2
C2—C1—C11	114.10 (13)	C4—C5—O6	112.70 (12)
O6—C1—C11	105.48 (12)	C4—C5—H51	108.8
O10—C1—C11	111.39 (13)	O6—C5—H51	108.9
C1—C2—C3	110.50 (12)	C4—C5—H52	108.5
C1—C2—O9	109.56 (12)	O6—C5—H52	108.5
C3—C2—O9	108.45 (12)	H51—C5—H52	109.5
C1—C2—H21	109.4	C5—O6—C1	113.98 (12)
C3—C2—H21	109.3	C4—O7—H7	108.9
O9—C2—H21	109.7	C3—O8—H8	107.9
C2—C3—C4	110.00 (13)	C2—O9—H9	102.5
C2—C3—O8	110.30 (12)	C1—O10—H10	113.5
C4—C3—O8	110.01 (12)	C1—C11—H111	109.3
C2—C3—H31	108.7	C1—C11—H112	109.6
C4—C3—H31	108.6	H111—C11—H112	109.5
O8—C3—H31	109.1	C1—C11—H113	109.4
C3—C4—C5	109.63 (12)	H111—C11—H113	109.5
C3—C4—O7	108.98 (12)	H112—C11—H113	109.5
C5—C4—O7	107.97 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···O7ⁱ	0.99	1.80	2.778 (2)	170
O7—H7···O10ⁱⁱ	0.90	1.90	2.791 (2)	172
O9—H9···O8ⁱⁱⁱ	0.91	1.88	2.786 (2)	174
O8—H8···O6^iv	0.95	1.87	2.803 (2)	165

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x, y+1, z; (iii) −x+2, y−1/2, −z+1/2; (iv) x+1, y, z.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₆H₁₂O₅	C₆H₁₂O₅
M_r	164.16	164.16
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Orthorhombic, P2₁2₁2₁
Temperature (K)	190	190
a, b, c (Å)	6.0243 (2), 7.5022 (3), 15.9717 (8)	6.0177 (2), 6.4672 (2), 18.0218 (7)
V (Å³)	721.85 (5)	701.37 (4)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.13	0.14
Crystal size (mm)	0.40 × 0.10 × 0.10	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.829, 0.987	0.865, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	5125, 975, 879	3322, 949, 883
R_int	0.057	0.023
(sin θ/λ)_max (Å⁻¹)	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.069, 1.01	0.027, 0.066, 1.03
No. of reflections	975	949
No. of parameters	100	100
No. of restraints	0	19
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19	0.22, −0.19

Computer programs: COLLECT (Nonius, 1997-2001)., DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O8ⁱ	0.87	1.93	2.788 (2)	170
O8—H8···O6ⁱⁱ	0.85	1.88	2.698 (2)	164
O10—H10···O7ⁱⁱⁱ	0.83	2.05	2.865 (2)	165
O9—H9···O8^iv	0.84	2.10	2.913 (2)	162

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···O7ⁱ	0.99	1.80	2.778 (2)	170
O7—H7···O10ⁱⁱ	0.90	1.90	2.791 (2)	172
O9—H9···O8ⁱⁱⁱ	0.91	1.88	2.786 (2)	174
O8—H8···O6^iv	0.95	1.87	2.803 (2)	165

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x, y+1, z; (iii) −x+2, y−1/2, −z+1/2; (iv) x+1, y, z.

Acknowledgements

Financial support (to RS), provided through the European Community's Human Potential Programme under contract HPRN-CT-2002-00173, is gratefully acknowledged.

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ISSN: 2053-2296

Volume 63| Part 1| January 2007| Pages o7-o10

doi:10.1107/S0108270106048591