organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

α-Lactose monohydrate: a redetermination at 150 K

aChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England, and b3M Health Care Ltd, Drug Delivery Systems Division, Ashby Road, Loughborough, Leicestershire LE11 3GR, England
*Correspondence e-mail: s.e.dann@lboro.ac.uk

(Received 29 June 2005; accepted 5 July 2005; online 13 July 2005)

The structure of the monohydrate of α-4-(β-D-galactopyran­osido)-D-glucopyran­ose, more commonly known as α-lactose monohydrate, C12H22O11·H2O, has been previously studied by single-crystal diffraction at ca 296 K [Beevers & Hansen (1971[Beevers, C. A. & Hansen, H. N. (1971). Acta Cryst. B27, 1323-1325.]). Acta Cryst. B27, 1323–1325; Fries et al. (1971[Fries, D. C., Rao, S. T. & Sundaralingham, M. (1971). Acta Cryst. B27, 994-1005.]). Acta Cryst. B27, 994–1005; Noordik et al. (1984[Noordik, J. H., Beurskens, P. T., Bennema, P., Visser, R. A. & Gould, R. O. (1984). Z. Kristallogr. 168, 59-65.]). Z. Kristallogr. 168, 59–65]. This redetermination at low temperature [150 (2) K] shows improved precision of geometry. Graph-set analysis of the hydrogen-bonding motifs is presented for the first time.

Comment

α-Lactose monohydrate, (I)[link], is the most common form of lactose and may be used as the parent material for at least four different (pseudo)polymorphs of this disaccharide (Garnier et al., 2002[Garnier, S., Petit, S. & Coquerel, G. (2002). J. Therm. Anal. Calorim. 68, 489-502.]; Figura & Epple, 1995[Figura, L. O. & Epple, M. (1995). J. Therm. Anal. 44, 45-53.]). This reducing sugar is built from a moiety of β-D-galactose and a moiety of α-D-glucose, joined by a 1,4 glycosidic bond between C1′ of the galactose and C4 of the glucose unit (Fig. 1[link]).

[Scheme 1]

A search of the Cambridge Structural Database (Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]; Fletcher et al., 1996[Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746-749.]; Version 5.26, November 2004 update) highlighted previous research on this hydrate with data collections performed at ca 296 K (Beevers & Hansen, 1971[Beevers, C. A. & Hansen, H. N. (1971). Acta Cryst. B27, 1323-1325.]; Fries et al., 1971[Fries, D. C., Rao, S. T. & Sundaralingham, M. (1971). Acta Cryst. B27, 994-1005.]; Noordik et al., 1984[Noordik, J. H., Beurskens, P. T., Bennema, P., Visser, R. A. & Gould, R. O. (1984). Z. Kristallogr. 168, 59-65.]). The redetermin­ation of (I)[link] presented here, obtained from low temperature [150 (2) K] single-crystal diffraction data, has resulted in improved precision compared to the previously determined room-temperature structures. Standard uncertainties on C—O and C—C bond lengths are improved to ca 0.003 compared to ca 0.004 at room temperature, with an improvement to ca 0.0017 compared to ca 0.002 for standard uncertainties on C–O–C angles. The unit cell volume measured at 150 K [768.85 (14) Å3] is ca 0.88% smaller than that determined at room temperature [775.7 (5) Å3; Noordik et al., 1984[Noordik, J. H., Beurskens, P. T., Bennema, P., Visser, R. A. & Gould, R. O. (1984). Z. Kristallogr. 168, 59-65.]], this latter unit-cell volume itself being smaller than that derived from previous measurements.

The unit cell has previously been reported as 7.937 (2) Å, 21.568 (7) Å, 4.815 (1) Å and β = 109.77 (2)° (Noordik et al., 1984[Noordik, J. H., Beurskens, P. T., Bennema, P., Visser, R. A. & Gould, R. O. (1984). Z. Kristallogr. 168, 59-65.]); the unit cell reported here is related to the Noordik unit cell by a simple transformation and is currently regarded as the conventional unit cell, having the shortest possible vectors in the ac plane (Inter­national Tables for X-ray Crystallography, 1969, Vol. 1).

An examination of the final difference Fourier map reveals a peak of 0.27 e Å−3 at a distance of 1.48 Å from C1, close to the equatorial atom H1. Since the α and β anomers establish a 40:60 equilibrium in solution over time, the question arises whether there is a small component of β-lactose present, even though only the α-anomer spontaneously crystallizes below 366.5 K (Walstra & Jenness, 1984[Walstra, P. & Jenness, R. (1984). Dairy Chemistry and Physics, Carbohydrates, ch. 3, pp. 27-41. New York: Wiley.]). In this present determination, the largest ten difference map features lie in the range 0.22–0.32 e Å−3, so this dubious peak is, in fact, indistinguishable from the noise. This means that, if present at all, the percentage of the β-anomer must be in the low single figures and any significant β component can definitely be ruled out.

Graph-set analysis of the hydrogen-bonding patterns (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]; Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]) within the structure shows the complicated nature of the linking together of the lactose and water mol­ecules. There are 15 different ring motifs involving one mol­ecule of hydrated α-lactose (Figs. 2[link] and 3[link]). The motifs use either two or three mol­ecules of (I)[link], hydrogen bonding with zero, one or two water mol­ecules. Fig. 4[link] shows a stacking formation of the lactose mol­ecules when viewed, as a packing plot, along the crystallographic c axis. The mol­ecules are held rigidly by a chain, C22(4), of hydrogen bonds between O6–H6A⋯O2iii and O2–H2A⋯O6i [symmetry codes: (i) x − 1, y, z − 1; (iii) x, y, 1 + z] propagating along the crystallographic a axis and are also linked through hydrogen bonding to water mol­ecules.

As well as those motifs present along the crystallographic a axis (Fig. 2[link]), higher order motifs R66(21), R44(20), R55(20), R66(23) and R44(18) can be found between layers of (I)[link] and inter­connecting water mol­ecules (Figs. 3[link] and 4[link]).

[Figure 1]
Figure 1
View of (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only hydrox­yl H atoms involved in hydrogen bonding are labelled. Dashed lines indicate hydrogen bonds. One intra­molecular hydrogen bond is present, viz. O9–H9A⋯O5.
[Figure 2]
Figure 2
Packing diagram of (I)[link] showing graph-set notation for hydrogen bonding within the crystal structure when viewed along the crystallographic a axis. It can be observed that each system of (I)[link], results in motifs: (A) S(7); (B) R33(16); (C) R33(14); (D) R33(9); (E) R44(18); (F) R43(16); (G) R33(19); (H) R43(18); (J) R43(15); (K) R54(21) approximately in the bc plane.
[Figure 3]
Figure 3
View of (I)[link] along the crystallographic b axis, showing the remaining hydrogen bonding motifs formed between layers of (I)[link] and water mol­ecules; containing O2—H2A⋯O6i, O3—H3A⋯O12, O6—H6⋯O2iii, O8—H8A⋯O11iii, O9—H9A⋯O5, O11—H11A⋯O9i and O12—H12B⋯O3v hydrogen bonds [symmetry codes: (i) x − 1, y, z − 1; (iii) x, y, 1 + z; (v) 1 + x, y, z].
[Figure 4]
Figure 4
Packing diagram of (I)[link], viewed along the crystallographic c axis, showing the hydrogen bonding linking mol­ecules of (I)[link] and water, above and below a central mol­ecule.

Experimental

Colourless X-ray quality crystals of (I)[link] were produced using powdered D-(+)-α-lactose monohydrate (supplied by Fluka Biochemica, Stenheim). A 10% aqueous solution of (I)[link] was prepared as in methods previously studied by Larhrib et al. (2003[Larhrib, H., Martin, G. P., Prime, P. & Marriott, C. (2003). Eur. J. Pharm. Sci. 19, 211-221.]). This solution was then diluted through addition of acetone, resulting in a 35:65 mixture of 10% lactose solution–acetone. Crystallization occurred upon standing at room temperature over a period of 48 h. A second crystalline sample of (I)[link] was produced by a similar method except that acetone was substituted with a 10% potassium methoxide aqueous solution. Diffraction data from this sample were recorded by the EPSRC National Crystallographic Service, affording very similar unit-cell dimensions.

Crystal data
  • C12H22O11·H2O

  • Mr = 360.31

  • Monoclinic, P 21

  • a = 4.7830 (5) Å

  • b = 21.540 (2) Å

  • c = 7.7599 (8) Å

  • β = 105.911 (2)°

  • V = 768.85 (14) Å3

  • Z = 2

  • Dx = 1.556 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3523 reflections

  • θ = 2.7–28.2°

  • μ = 0.14 mm−1

  • T = 150 (2) K

  • Block, colourless

  • 0.53 × 0.27 × 0.21 mm

Data collection
  • Bruker SMART 1000 CCD diffractometer

  • Narrow-frame ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany.])Tmin = 0.878, Tmax = 0.971

  • 6697 measured reflections

  • 1864 independent reflections

  • 1692 reflections with I > 2σ(I)

  • Rint = 0.022

  • θmax = 28.9°

  • h = −6 → 6

  • k = −27 → 27

  • l = −9 → 9

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.079

  • S = 1.10

  • 1864 reflections

  • 231 parameters

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

  • w = 1/[σ2(Fo2) + (0.0394P)2 + 0.1957P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Selected geometric parameters (Å, °)[link]

O1—C1′ 1.398 (3)
O1—C4 1.437 (3)
C1—O7 1.399 (3)
C1′—O1—C4 116.88 (17)

Table 2
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2A⋯O6i 0.84 1.85 2.665 (2) 163
O3—H3A⋯O12 0.84 1.89 2.722 (3) 168
O4—H4A⋯O8ii 0.84 1.97 2.806 (3) 173
O6—H6⋯O2iii 0.84 1.90 2.707 (2) 161
O7—H7A⋯O12iv 0.84 1.97 2.772 (2) 161
O8—H8A⋯O11iii 0.84 1.91 2.700 (3) 157
O9—H9A⋯O5 0.84 2.02 2.819 (2) 159
O11—H11A⋯O9i 0.84 1.92 2.755 (2) 174
O12—H12B⋯O3v 0.85 (1) 1.89 (2) 2.740 (3) 174 (4)
O12—H12A⋯O8vi 0.84 (1) 2.23 (2) 2.920 (2) 140 (3)
Symmetry codes: (i) x-1, y, z-1; (ii) [-x, y+{\script{1\over 2}}, -z+2]; (iii) x, y, z+1; (iv) [-x, y-{\script{1\over 2}}, -z+1]; (v) x+1, y, z; (vi) [-x+1, y+{\script{1\over 2}}, -z+2].

Non-water H atoms were placed in geometric positions using a riding model [C—H = 0.99 (methyl­ene H) and 1.00 Å (methine H); O—H = 0.84 Å], and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). The data set was truncated at 2θ = 52°, as only statistically insignificant data were present above this limit. Water H atoms were located in a difference Fourier map and refined using restraints on the O—H bond length [target value 0.840 (15) Å] and the 1,3-distance [target value 1.43 (2) Å] and Uiso(H) = 1.5Ueq(O). In the absence of significant anomalous dispersion effects, 1526 Friedel pairs were merged during the refinement of (I)[link].

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000[Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Comment top

α-Lactose monohydrate, (I), is the most common form of lactose and may be used as the parent material for at least four different (pseudo)polymorphs of this disaccharide (Garnier et al., 2002; Figura & Epple, 1995). This reducing sugar is built from a moiety of β-D-galactose and a moiety of α-D-glucose, joined by a 1,4 glycosidic bond between C1' of the galactose and C4 of the glucose unit (Fig. 1).

A search of the Cambridge Structural Database (Allen, 2002; Fletcher et al., 1996; Version 5.26, November 2004 update) highlighted previous research on this polymorph with data collections performed at ca 296 K (Beevers & Hansen, 1971; Fries et al., 1971; Noordik et al., 1984). The redetermination of (I) presented here, obtained from low temperature [150 (2) K] single-crystal diffraction data, has resulted in improved precision compared to the previously determined room-temperature structures. Standard uncertainties on C—O and C—C bond lengths are improved to ca 0.003 compared to ca 0.004 at room temperature, with an improvement to ca 0.0017 compared to ca 0.002 for standard uncertainties on C–O–C angles. The unit cell volume measured at 150 K [768.85 (14) Å3] is ca 0.88% smaller than that determined at room temperature [775.7 (5) Å3; Noordik et al., 1984], this latter unit-cell volume itself being smaller than that derived from previous measurements.

The unit cell has previously been reported as 7.937 (2) Å, 21.568 (7) Å, 4.815 (1) Å and β = 109.77 (2) ° (Noordik et al., 1984), the unit cell reported here is related to the Noordik unit cell by a simple transformation and is currently regarded as the conventional unit cell, having the shortest possible vectors in the ac plane (International Tables for X-ray Crystallography, 1969, Vol. 1).

An examination of the final difference Fourier map reveals a peak of 0.27 e Å-3 at a distance of 1.48 Å from C1, close to the equatorial atom H1. Since the α and β anomers establish a 40:60 equilibrium in solution over time, the question arises whether there is a small component of β-lactose present, even though only the α-anomer spontaneously crystallizes below 366.5 K (Walstra & Jenness, 1984). In this present determination, the largest ten difference map features lie in the range 0.22–0.32 e Å-3, so this dubious peak is, in fact, indistinguishable from the noise. This means that, if present at all, the percentage of the β-anomer must be in the low single figures and any significant β component can definitely be ruled out.

Graph-set analysis of the hydrogen-bonding patterns (Bernstein et al., 1995; Etter et al., 1990) within the structure shows the complicated nature of the linking together of the lactose and water molecules. There are 15 different ring motifs emanating from one molecule of hydrated α-lactose (Figs. 2 and 3). The motifs use either two or three molecules of (I), hydrogen bonding with zero, one or two water molecules. Fig. 4 shows a stacking formation of the lactose molecules when viewed, as a packing plot, along the crystallographic c axis. The molecules are held rigidly by a chain, C22(4), of hydrogen bonds between O6–H6A···O2iii and O2–H2A···O6i [symmetry codes: (i) x - 1, y, z - 1; (iii) x, y, 1 + z] propagating along the crystallographic a axis and are also linked through hydrogen bonding to water molecules.

As well as those motifs present along the crystallographic a axis (Fig. 2), higher order motifs R66(21), R44(20), R55(20), R66(23) and R44(18) can be found between layers of (I) and interconnecting water molecules (Figs. 3 and 4).

Experimental top

Colourless X-ray quality crystals of (I) were produced using powdered D-(+)-α-lactose monohydrate (supplied by Fluka Biochemica, Stenheim). A 10% aqueous solution of (I) was prepared as in methods previously studied by Larhrib et al. (2003). This solution was then diluted through addition of acetone, resulting in a 35:65 mixture of 10% lactose solution–acetone. Crystallization occurred upon standing at room temperature over a period 48 h. A second crystalline sample of (I) was produced by a similar method except that acetone was substituted with a 10% potassium methoxide aqueous solution. Diffraction data from this sample were recorded by the EPSRC National Crystallographic Service, affording very similar unit-cell dimensions.

Refinement top

H atoms were placed in geometric positions using a riding model [C—H = 0.99 (methylene H) and 1.00 Å (methine H); O—H = 0.84 Å], and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). The data set was truncated at 2θ = 52°, as only statistically insignificant data were present above this limit. Water H atoms were located in the difference Fourier map and refined using restraints on the O—H bond length [target value 0.840 (15) Å] and the 1,3-distance [target value 1.43 (2) Å] and Uiso(H) values = 1.5Ueq(O). In the absence of significant anomalous dispersion effects, 1526 Friedel pairs were merged during the refinement of (I).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. View of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only hydroxyl H atoms involved in hydrogen bonding are labelled. One intramolecular hydrogen bond is present, viz. O9–H9A···O5.
[Figure 2] Fig. 2. Packing diagram of (I) showing graph-set notation for hydrogen bonding within the crystal lattice when viewed along the crystallographic a axis. It can be observed that each system of (I), results in motifs: (A) S(7); (B) R33(16); (C) R33(14); (D) R33(9); (E) R44(18); (F) R43(16); (G) R33(19); (H) R43(18); (J) R43(15); (K) R54(21) approximately in the bc plane.
[Figure 3] Fig. 3. View of (I) along the crystallographic b axis, showing the remaining hydrogen bonding motifs formed between layers of (I) and water molecules; containing O2—H2A···O6i, O3—H3A···O12, O6—H6···O2iii, O8—H8A···O11iii, O9—H9A···O5, O11—H11A···O9i and O12—H12B···O3v hydrogen bonds [symmetry codes: (i) x - 1, y, z - 1; (iii) x, y, 1 + z; (v) 1 + x, y, z].
[Figure 4] Fig. 4. Packing diagram of (I), viewed along the crystallographic c axis, showing the hydrogen bonding linking molecules of (I) and water, above and below a central molecule.
α-4-O-(β-D-galactopyranosido)-D-glucopyranose top
Crystal data top
C12H22O11·H2OF(000) = 384
Mr = 360.31Dx = 1.556 Mg m3
Monoclinic, P21Melting point: 220 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 4.7830 (5) ÅCell parameters from 3523 reflections
b = 21.540 (2) Åθ = 2.7–28.2°
c = 7.7599 (8) ŵ = 0.14 mm1
β = 105.911 (2)°T = 150 K
V = 768.85 (14) Å3Block, colourless
Z = 20.53 × 0.27 × 0.21 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
1864 independent reflections
Radiation source: sealed tube1692 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω rotation with narrow frames scansθmax = 28.9°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 66
Tmin = 0.878, Tmax = 0.971k = 2727
6697 measured reflectionsl = 99
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)] = 0.033Hydrogen site location: Geom except H12A&B coords freely refined
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0394P)2 + 0.1957P]
where P = (Fo2 + 2Fc2)/3
1864 reflections(Δ/σ)max < 0.001
231 parametersΔρmax = 0.32 e Å3
4 restraintsΔρmin = 0.17 e Å3
Crystal data top
C12H22O11·H2OV = 768.85 (14) Å3
Mr = 360.31Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.7830 (5) ŵ = 0.14 mm1
b = 21.540 (2) ÅT = 150 K
c = 7.7599 (8) Å0.53 × 0.27 × 0.21 mm
β = 105.911 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
1864 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1692 reflections with I > 2σ(I)
Tmin = 0.878, Tmax = 0.971Rint = 0.022
6697 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0334 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.32 e Å3
1864 reflectionsΔρmin = 0.17 e Å3
231 parameters
Special details top

Experimental. 1526 Friedel pairs. Equivalent reflections and Friedel pairs merged (MERG 4 in SHELXL) since Mo radiation & no element heavier than O.

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
O10.0485 (4)0.06111 (7)0.7307 (2)0.0172 (3)
C1'0.1611 (5)0.01414 (11)0.7705 (3)0.0168 (5)
H1'0.35300.03040.76250.020*
C2'0.0574 (5)0.03808 (11)0.6356 (3)0.0182 (5)
H2'0.14670.04940.63220.022*
O20.0640 (4)0.01591 (9)0.4648 (2)0.0222 (4)
H2A0.10650.00930.40190.033*
C3'0.2515 (5)0.09504 (11)0.6874 (3)0.0189 (5)
H3'0.44890.08550.67380.023*
O30.1249 (4)0.14411 (8)0.5683 (2)0.0242 (4)
H3A0.25720.16600.54740.036*
C4'0.2784 (5)0.11279 (11)0.8832 (3)0.0189 (5)
H4'0.42010.14770.92000.023*
O40.0032 (4)0.13101 (8)0.9035 (3)0.0228 (4)
H4A0.02080.16920.88330.034*
C5'0.3853 (5)0.05660 (12)1.0023 (3)0.0179 (5)
H5'0.57960.04350.99010.022*
C6'0.4085 (6)0.06982 (12)1.1971 (3)0.0223 (5)
H6'A0.55260.10321.24140.027*
H6'B0.21810.08411.20940.027*
O60.4960 (4)0.01480 (9)1.3010 (2)0.0237 (4)
H60.38590.00891.36720.036*
O50.1815 (4)0.00615 (8)0.9485 (2)0.0180 (3)
C10.0864 (5)0.25161 (12)0.8074 (3)0.0207 (5)
H10.02210.29600.81910.025*
O70.3771 (4)0.24879 (10)0.8105 (2)0.0277 (4)
H7A0.48410.26260.71360.042*
C20.0961 (5)0.21524 (11)0.9691 (3)0.0178 (5)
H20.30480.22110.97210.021*
O80.0602 (4)0.23976 (8)1.1327 (2)0.0209 (4)
H8A0.08560.22341.15460.031*
C30.0325 (5)0.14595 (11)0.9477 (3)0.0175 (5)
H30.16830.13790.95770.021*
O90.2382 (4)0.11500 (8)1.0912 (2)0.0235 (4)
H9A0.22280.07641.07550.035*
C40.0540 (5)0.12383 (11)0.7645 (3)0.0168 (5)
H40.26090.12620.76050.020*
C50.1351 (5)0.16374 (11)0.6149 (3)0.0174 (5)
H50.34320.15990.61550.021*
C60.1058 (6)0.14661 (12)0.4311 (3)0.0225 (5)
H6A0.14940.10190.40840.027*
H6B0.09650.15400.42690.027*
O110.3010 (4)0.18277 (9)0.2957 (2)0.0262 (4)
H11A0.44000.16040.23950.039*
O100.0445 (4)0.22706 (8)0.6468 (2)0.0186 (4)
O120.6064 (4)0.20401 (9)0.5314 (2)0.0234 (4)
H12A0.619 (7)0.2294 (13)0.616 (3)0.035*
H12B0.764 (5)0.1835 (14)0.548 (4)0.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0176 (8)0.0132 (8)0.0192 (8)0.0004 (6)0.0023 (7)0.0010 (7)
C1'0.0166 (10)0.0174 (11)0.0170 (11)0.0003 (9)0.0056 (9)0.0010 (9)
C2'0.0184 (11)0.0182 (11)0.0183 (12)0.0015 (9)0.0054 (9)0.0003 (9)
O20.0227 (9)0.0293 (10)0.0142 (8)0.0004 (8)0.0041 (7)0.0012 (7)
C3'0.0172 (11)0.0193 (12)0.0207 (12)0.0015 (9)0.0063 (9)0.0051 (10)
O30.0229 (9)0.0221 (9)0.0277 (10)0.0003 (7)0.0069 (8)0.0117 (8)
C4'0.0193 (12)0.0163 (12)0.0211 (12)0.0003 (9)0.0056 (9)0.0007 (9)
O40.0245 (9)0.0171 (9)0.0289 (9)0.0046 (7)0.0107 (8)0.0028 (7)
C5'0.0161 (11)0.0179 (11)0.0184 (11)0.0015 (9)0.0023 (9)0.0008 (9)
C6'0.0260 (12)0.0208 (12)0.0189 (12)0.0012 (10)0.0040 (10)0.0006 (10)
O60.0228 (9)0.0310 (10)0.0167 (8)0.0002 (8)0.0044 (7)0.0035 (8)
O50.0220 (8)0.0166 (8)0.0144 (8)0.0029 (7)0.0032 (6)0.0001 (7)
C10.0247 (12)0.0176 (11)0.0210 (12)0.0016 (10)0.0081 (10)0.0024 (10)
O70.0239 (9)0.0367 (11)0.0227 (9)0.0081 (8)0.0065 (7)0.0055 (9)
C20.0208 (11)0.0144 (11)0.0174 (11)0.0002 (9)0.0039 (9)0.0004 (9)
O80.0260 (9)0.0173 (9)0.0200 (9)0.0021 (7)0.0070 (7)0.0022 (7)
C30.0201 (11)0.0157 (11)0.0145 (11)0.0006 (8)0.0012 (9)0.0019 (9)
O90.0338 (10)0.0141 (8)0.0161 (8)0.0016 (7)0.0041 (7)0.0013 (7)
C40.0175 (11)0.0156 (11)0.0159 (11)0.0016 (9)0.0022 (9)0.0009 (9)
C50.0174 (11)0.0181 (11)0.0155 (11)0.0012 (9)0.0025 (9)0.0022 (9)
C60.0290 (13)0.0220 (13)0.0151 (12)0.0029 (10)0.0037 (10)0.0021 (10)
O110.0297 (10)0.0268 (10)0.0176 (9)0.0045 (8)0.0013 (7)0.0038 (8)
O100.0217 (8)0.0167 (8)0.0176 (8)0.0004 (6)0.0055 (7)0.0032 (6)
O120.0228 (9)0.0235 (9)0.0225 (9)0.0004 (7)0.0039 (8)0.0044 (7)
Geometric parameters (Å, º) top
O1—C1'1.398 (3)C1—O71.399 (3)
O1—C41.437 (3)C1—O101.418 (3)
C1'—O51.427 (3)C1—C21.533 (3)
C1'—C2'1.524 (3)C1—H11.0000
C1'—H1'1.0000O7—H7A0.8400
C2'—O21.417 (3)C2—O81.428 (3)
C2'—C3'1.524 (3)C2—C31.523 (3)
C2'—H2'1.0000C2—H21.0000
O2—H2A0.8400O8—H8A0.8400
C3'—O31.425 (3)C3—O91.432 (3)
C3'—C4'1.538 (3)C3—C41.529 (3)
C3'—H3'1.0000C3—H31.0000
O3—H3A0.8400O9—H9A0.8400
C4'—O41.423 (3)C4—C51.526 (3)
C4'—C5'1.524 (3)C4—H41.0000
C4'—H4'1.0000C5—O101.432 (3)
O4—H4A0.8400C5—C61.516 (3)
C5'—O51.443 (3)C5—H51.0000
C5'—C6'1.512 (3)C6—O111.430 (3)
C5'—H5'1.0000C6—H6A0.9900
C6'—O61.430 (3)C6—H6B0.9900
C6'—H6'A0.9900O11—H11A0.8400
C6'—H6'B0.9900O12—H12A0.842 (14)
O6—H60.8400O12—H12B0.851 (14)
C1'—O1—C4116.88 (17)O7—C1—O10112.3 (2)
O1—C1'—O5106.85 (17)O7—C1—C2108.01 (19)
O1—C1'—C2'107.69 (18)O10—C1—C2110.05 (19)
O5—C1'—C2'111.22 (19)O7—C1—H1108.8
O1—C1'—H1'110.3O10—C1—H1108.8
O5—C1'—H1'110.3C2—C1—H1108.8
C2'—C1'—H1'110.3C1—O7—H7A109.5
O2—C2'—C1'107.89 (19)O8—C2—C3113.0 (2)
O2—C2'—C3'110.5 (2)O8—C2—C1111.00 (19)
C1'—C2'—C3'110.67 (19)C3—C2—C1111.1 (2)
O2—C2'—H2'109.3O8—C2—H2107.1
C1'—C2'—H2'109.3C3—C2—H2107.1
C3'—C2'—H2'109.3C1—C2—H2107.1
C2'—O2—H2A109.5C2—O8—H8A109.5
O3—C3'—C2'107.83 (19)O9—C3—C2107.30 (19)
O3—C3'—C4'111.2 (2)O9—C3—C4111.76 (19)
C2'—C3'—C4'109.9 (2)C2—C3—C4110.1 (2)
O3—C3'—H3'109.3O9—C3—H3109.2
C2'—C3'—H3'109.3C2—C3—H3109.2
C4'—C3'—H3'109.3C4—C3—H3109.2
C3'—O3—H3A109.5C3—O9—H9A109.5
O4—C4'—C5'108.6 (2)O1—C4—C5106.83 (18)
O4—C4'—C3'110.4 (2)O1—C4—C3110.87 (19)
C5'—C4'—C3'108.96 (19)C5—C4—C3110.79 (19)
O4—C4'—H4'109.6O1—C4—H4109.4
C5'—C4'—H4'109.6C5—C4—H4109.4
C3'—C4'—H4'109.6C3—C4—H4109.4
C4'—O4—H4A109.5O10—C5—C6107.02 (19)
O5—C5'—C6'106.82 (19)O10—C5—C4108.48 (18)
O5—C5'—C4'109.58 (18)C6—C5—C4113.0 (2)
C6'—C5'—C4'112.2 (2)O10—C5—H5109.4
O5—C5'—H5'109.4C6—C5—H5109.4
C6'—C5'—H5'109.4C4—C5—H5109.4
C4'—C5'—H5'109.4O11—C6—C5110.4 (2)
O6—C6'—C5'109.7 (2)O11—C6—H6A109.6
O6—C6'—H6'A109.7C5—C6—H6A109.6
C5'—C6'—H6'A109.7O11—C6—H6B109.6
O6—C6'—H6'B109.7C5—C6—H6B109.6
C5'—C6'—H6'B109.7H6A—C6—H6B108.1
H6'A—C6'—H6'B108.2C6—O11—H11A109.5
C6'—O6—H6109.5C1—O10—C5113.47 (18)
C1'—O5—C5'111.85 (17)H12A—O12—H12B110 (2)
C4—O1—C1'—O593.4 (2)O7—C1—C2—O857.8 (3)
C4—O1—C1'—C2'147.00 (19)O10—C1—C2—O8179.21 (18)
O1—C1'—C2'—O267.6 (2)O7—C1—C2—C368.7 (3)
O5—C1'—C2'—O2175.61 (17)O10—C1—C2—C354.2 (3)
O1—C1'—C2'—C3'171.40 (18)O8—C2—C3—O962.2 (3)
O5—C1'—C2'—C3'54.6 (3)C1—C2—C3—O9172.33 (19)
O2—C2'—C3'—O367.0 (2)O8—C2—C3—C4175.98 (19)
C1'—C2'—C3'—O3173.61 (19)C1—C2—C3—C450.5 (2)
O2—C2'—C3'—C4'171.67 (19)C1'—O1—C4—C5143.26 (19)
C1'—C2'—C3'—C4'52.2 (3)C1'—O1—C4—C395.9 (2)
O3—C3'—C4'—O455.1 (3)O9—C3—C4—O169.7 (2)
C2'—C3'—C4'—O464.3 (2)C2—C3—C4—O1171.10 (19)
O3—C3'—C4'—C5'174.24 (19)O9—C3—C4—C5171.83 (19)
C2'—C3'—C4'—C5'54.9 (2)C2—C3—C4—C552.7 (2)
O4—C4'—C5'—O560.5 (2)O1—C4—C5—O10178.42 (18)
C3'—C4'—C5'—O559.8 (2)C3—C4—C5—O1057.6 (2)
O4—C4'—C5'—C6'57.9 (3)O1—C4—C5—C663.1 (2)
C3'—C4'—C5'—C6'178.2 (2)C3—C4—C5—C6176.0 (2)
O5—C5'—C6'—O657.2 (2)O10—C5—C6—O1164.3 (2)
C4'—C5'—C6'—O6177.2 (2)C4—C5—C6—O11176.3 (2)
O1—C1'—O5—C5'177.84 (17)O7—C1—O10—C558.4 (3)
C2'—C1'—O5—C5'60.6 (2)C2—C1—O10—C562.0 (2)
C6'—C5'—O5—C1'174.86 (18)C6—C5—O10—C1174.31 (18)
C4'—C5'—O5—C1'63.4 (2)C4—C5—O10—C163.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O6i0.841.852.665 (2)163
O3—H3A···O120.841.892.722 (3)168
O4—H4A···O8ii0.841.972.806 (3)173
O6—H6···O2iii0.841.902.707 (2)161
O7—H7A···O12iv0.841.972.772 (2)161
O8—H8A···O11iii0.841.912.700 (3)157
O9—H9A···O50.842.022.819 (2)159
O11—H11A···O9i0.841.922.755 (2)174
O12—H12B···O3v0.85 (1)1.89 (2)2.740 (3)174 (4)
O12—H12A···O8vi0.84 (1)2.23 (2)2.920 (2)140 (3)
Symmetry codes: (i) x1, y, z1; (ii) x, y+1/2, z+2; (iii) x, y, z+1; (iv) x, y1/2, z+1; (v) x+1, y, z; (vi) x+1, y+1/2, z+2.

Experimental details

Crystal data
Chemical formulaC12H22O11·H2O
Mr360.31
Crystal system, space groupMonoclinic, P21
Temperature (K)150
a, b, c (Å)4.7830 (5), 21.540 (2), 7.7599 (8)
β (°) 105.911 (2)
V3)768.85 (14)
Z2
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.53 × 0.27 × 0.21
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.878, 0.971
No. of measured, independent and
observed [I > 2σ(I)] reflections
6697, 1864, 1692
Rint0.022
(sin θ/λ)max1)0.680
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.079, 1.10
No. of reflections1864
No. of parameters231
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.17

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL and local programs.

Selected geometric parameters (Å, º) top
O1—C1'1.398 (3)C1—O71.399 (3)
O1—C41.437 (3)
C1'—O1—C4116.88 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O6i0.841.852.665 (2)163
O3—H3A···O120.841.892.722 (3)168
O4—H4A···O8ii0.841.972.806 (3)173
O6—H6···O2iii0.841.902.707 (2)161
O7—H7A···O12iv0.841.972.772 (2)161
O8—H8A···O11iii0.841.912.700 (3)157
O9—H9A···O50.842.022.819 (2)159
O11—H11A···O9i0.841.922.755 (2)174
O12—H12B···O3v0.851 (14)1.893 (15)2.740 (3)174 (4)
O12—H12A···O8vi0.842 (14)2.23 (2)2.920 (2)140 (3)
Symmetry codes: (i) x1, y, z1; (ii) x, y+1/2, z+2; (iii) x, y, z+1; (iv) x, y1/2, z+1; (v) x+1, y, z; (vi) x+1, y+1/2, z+2.
 

Footnotes

Current address: School of Natural Sciences (Chemistry), University of Newcastle Upon Tyne, Newcastle Upon Tyne NE1 7RU, England

Acknowledgements

The authors acknowledge the use of the EPSRC's Chemical Database Service at Daresbury (Fletcher et al., 1996[Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746-749.]) and the EPSRC National Crystallographic Service in Southampton. We also thank 3M Health Care, Loughborough, England, for funding.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals
First citationBeevers, C. A. & Hansen, H. N. (1971). Acta Cryst. B27, 1323–1325. CSD CrossRef IUCr Journals Web of Science
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science
First citationBruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.
First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals
First citationFigura, L. O. & Epple, M. (1995). J. Therm. Anal. 44, 45–53. CrossRef CAS
First citationFletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746–749. CrossRef CAS Web of Science
First citationFries, D. C., Rao, S. T. & Sundaralingham, M. (1971). Acta Cryst. B27, 994–1005. CSD CrossRef IUCr Journals Web of Science
First citationGarnier, S., Petit, S. & Coquerel, G. (2002). J. Therm. Anal. Calorim. 68, 489–502. Web of Science CSD CrossRef CAS
First citationLarhrib, H., Martin, G. P., Prime, P. & Marriott, C. (2003). Eur. J. Pharm. Sci. 19, 211–221. Web of Science CrossRef PubMed CAS
First citationNoordik, J. H., Beurskens, P. T., Bennema, P., Visser, R. A. & Gould, R. O. (1984). Z. Kristallogr. 168, 59–65. CrossRef CAS Web of Science
First citationSheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationSheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany.
First citationWalstra, P. & Jenness, R. (1984). Dairy Chemistry and Physics, Carbohydrates, ch. 3, pp. 27–41. New York: Wiley.

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds