Crystal structure of potassium (1S)-d-lyxit-1-yl­sulfonate monohydrate

Haines, A.H.; Hughes, D.L.

doi:10.1107/S2056989015014139

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 8| August 2015| Pages 993-996

https://doi.org/10.1107/S2056989015014139

Open

access

Crystal structure of potassium (1S)-D-lyxit-1-ylsulfonate monohydrate

Alan H. Haines ^a ^* and David L. Hughes ^a ^*

^aSchool of Chemistry, University of East Anglia, Norwich NR4 7TJ, United Kingdom
^*Correspondence e-mail: a.haines@uea.ac.uk, d.l.hughes@uea.ac.uk

Edited by A. J. Lough, University of Toronto, Canada (Received 30 June 2015; accepted 27 July 2015; online 31 July 2015)

The title compound, K⁺·C₅H₁₁O₈S⁻·H₂O [systematic name: potassium (1S,2S,3S,4R)-1,2,3,4,5-pentahydroxypentane-1-sulfonate monohydrate], formed by reaction of D-lyxose with potassium hydrogen sulfite in water, crystallizes as colourless square prisms. The anion has an open-chain structure in which the S atom, the C atoms of the sugar chain and the oxygen atom of the hydroxymethyl group form an essentially all-trans chain with the corresponding torsion angles lying between 178.61 (12) and 157.75 (10)°. A three-dimensional bonding network exists in the crystal structure involving coordination of two crystallographically independent potassium ions by O atoms (one cation being hexa- and the other octa-coordinate, with each lying on a twofold rotation axis), and extensive intermolecular O—H⋯O hydrogen bonding.

Keywords: crystal structure; D-lyxose bisulfite adduct; potassium hydrogen sulfite; potassium metabisulfite; hydrogen bonding.

CCDC reference: 1415264

1. Chemical context

In aqueous solution, the bisulfite anion HSO₃⁻ exists in a complex, pH-dependent equilibrium with sulfurous acid H₂SO₃ and the sulfite anion SO₃²⁻. These sulfur compounds are widely used in the preservation of foodstuffs because of their anti-oxidant and antimicrobial properties. Dissolution of sodium or potassium metabisulfite (Na₂S₂O₅ or K₂S₂O₅, respectively) in water affords a mixture of such compounds, along with sulfur dioxide, and they are widely used (e.g. as food additive E223) for their anti-oxidant, bactericidal and preservative properties. The reaction of the bisulfite ion with carbonyl compounds to give hydroxysulfonic acids has long been known as a method of aldehyde purification; less well recognized generally is that reaction of an aldehydo-sugar, which exists predominantly in a cyclic, hemi-acetal form, with a bisulfite anion affords the open-chain form of the carbohydrate in which the carbonyl group has undergone addition of the sulfur nucleophile. A possible role in the stabilization of food stuffs led to early studies (Gehman & Osman, 1954 ) and evidence for the acyclic nature of such compounds was first provided by Ingles (1959 ), who reported on such adducts from D-glucose, D-galactose, D-mannose, L-arabinose and L-rhamnose. However, conclusive proof of the acyclic nature of these bisulfite adducts was first given through the X-ray studies of Cole et al. (2001 ) who reported the crystal structures of D-glucose- and D-mannose-derived potassium sulfonates. Later studies by X-ray crystallography on the sodium sulfonate derived from D-glucose (Haines & Hughes, 2012 ) and the potassium sulfonates from D-galactose (Haines & Hughes, 2010 ) and D-ribose (Haines & Hughes, 2014 ) proved their acyclic nature and allowed, in each case, the configuration at the newly formed chiral centre to be determined.

The crystallization of the bisulfite adducts of aldoses requires reactions to be conducted in concentrated solution, and success can be dependent on the particular aldose and the choice of the alkali metal ion. Thus, we have prepared the potassium adduct from L-arabinose as described by Ingles (1959), having properties in agreement with those reported, but despite prolonged efforts have not succeeded in obtaining suitable crystals for X-ray determination. Our attempts to make a crystalline potassium sulfonate from D-xylose have not been successful. In contrast, D-ribose readily afforded suitable crystals (Haines & Hughes, 2014) and we were therefore prompted to investigate the reaction of the remaining pentose, D-lyxose, with the bisulfite ion, from which we isolated the nicely crystalline title product (see Scheme). We report here its crystal structure.

2. Structural commentary

The systematic name for the salt is potassium (1S,2S,3S,4R)-1,2,3,4,5-pentahydroxypentane-1-sulfonate monohydrate. The anion has an open-chain structure in which the S atom, the C atoms of the sugar chain and the O atom of the hydroxymethyl group form an essentially all-trans chain with the corresponding torsion angles lying between absolute values of 178.61 (12) (for C2—C3—C4—C5) and 157.75 (10)° (for S1—C1—C2—C3). The newly formed chiral centre at C1 has the S configuration (Fig. 1). For each lyxose residue, all hydroxy groups act as hydrogen-bond donors (Table 1). Atom H2O is involved in a bifurcated hydrogen bond to O11 in the same molecule and to O1 in a neighbouring molecule (at x, y, z − 1). Atom H1O is involved in hydrogen bonding to atom O9 of a water molecule, the H atoms of which are hydrogen-bonded to O5 and O12 of adjoining molecules. Two crystallographically independent potassium ions are present, each one lying on a twofold rotation axis, with one cation possessing a coordination sphere of six O atoms (assuming a cut-off distance of 3 Å), four coming from two different sulfonate residues and two from O atoms of hydroxymethyl groups. The other cation is octacoordinate with oxygen atoms arising from two water molecules, two O atoms at new chiral centres at C1, and from two pairs of O atoms from different sulfonate residues. The range of cation–oxygen bond lengths in the coordination spheres lie in the range 2.7787 (12) to 2.9855 (12) Å, but it should be noted that the designated hexacoordinate potassium ion does have two further neighbouring O atoms at 3.1131 (12) and 3.3824 (13) Å. Variability in the coordination spheres of potassium ions in related coordination environments was observed in the D-galactose bisulfite (Haines & Hughes, 2010), D-glucose bisulfite (Cole et al. 2001; Haines & Hughes, 2012) and dehydro-L-ascorbic acid bisulfite (Haines & Hughes, 2013 ) adducts, where the potassium ion is, respectively, six-, seven- and eight-coordinate.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O9ⁱ	0.80 (3)	1.90 (3)	2.6716 (19)	160 (2)
O2—H2O⋯O1ⁱ	0.77 (3)	2.35 (3)	2.9810 (17)	141 (2)
O2—H2O⋯O11	0.77 (3)	2.41 (2)	2.9935 (16)	134 (2)
O3—H3O⋯O4ⁱⁱ	0.85 (3)	1.91 (3)	2.7609 (17)	173 (3)
O4—H4O⋯O2ⁱⁱⁱ	0.76 (3)	2.17 (3)	2.8586 (17)	151 (3)
O5—H5O⋯O13^iv	0.78 (3)	2.03 (3)	2.7152 (17)	146 (2)
O9—H9A⋯O5^v	0.81 (3)	1.95 (3)	2.7426 (18)	167 (3)
O9—H9B⋯O12^vi	0.84 (3)	1.90 (3)	2.7289 (17)	170 (3)
Symmetry codes: (i) x, y, z-1; (ii) x, y, z+1; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+1]$ ; (vi) -x+1, -y+1, z+1.

Figure 1
View of a molecule of a D-lyxose-KHSO₃ adduct and water molecule, indicating the atom-numbering scheme. The coordination spheres of the two potassium ions (both lying on twofold rotation axes), and the hydrogen bonds (dashed lines) on the lyxose unit, are shown. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (1) −x + 1, −y + 2, z; (2) x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (3) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + 1; (4) −x + 1, −y + 2, z + 1; (5) x, y, z + 1; (6) −x + 1, −y + 1, z; (7) −x + 1, −y + 1, z + 1; (8) x, y − 1, z; (9) x, y, z − 1; (10) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + 1; (11) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z; (12) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z.]

A view along the c axis (Fig. 2) indicates the approximately parallel but alternating alignment of the D-lyxose chains between sheets of potassium ions and water molecules, with hydrogen bonds shown as dashed bonds except for the bifurcated hydrogen bonds which are denoted by fine line bonds. Cation coordination with D-lyxose sulfite anions and water molecules is depicted in Fig. 3 and a view along the a axis (Fig. 4) shows the approximately parallel alignment of the D-lyxose chains.

Figure 2
Packing diagram, viewed along the c axis, showing the approximately parallel alignment of the D-lyxose chains between sheets of potassium ions and water molecules. Hydrogen bonds are shown as dashed lines; the fine line bonds are of bifurcated hydrogen bonds. Please note that the atoms labelled O2, O4 and O11 are eclipsing the real atoms of those names.

Figure 3
View (slightly offset from along the c axis) of the sheets of potassium ions which are linked through coordinating D-lyxose-sulfite anions and water molecules. Symmetry codes are as in Fig. 1

Figure 4
View along the a axis, showing the approximately parallel alignment of the D-lyxose chains.

3. Supramolecular features

A three-dimensional network exists in the crystal structure through coordination of (i) a hexacoordinate potassium ion with O atoms from four different D-lyxose bisulfite residues, (ii) an octacoordinate potassium ion with O atoms from four different D-lyxose bisulfite residues and two different water molecules, (iii) intermolecular hydrogen bonding between hydroxy groups of the D-lyxose moieties, and (iv) hydrogen bonding between a water molecule and two different lyxose residues. Despite spectroscopic evidence for a diastereoisomeric adduct in solution, only the 1S stereoisomer crystallized from the reaction mixture.

4. Spectroscopic findings

High-resolution mass spectrometry in negative-ion mode showed no significant peak for ([C₅H₁₁O₈S₁]⁻) at the calculated m/z of 231.0180, but a significant peak was observed at 213.0073 ([C₅H₁₁O₈S – H₂O] ⁻). A similar loss of water from the parent anion was observed in the case of the D-ribose adduct (Haines & Hughes, 2014). A peak at 149.0457 ([C₅H₉O₅]⁻) arose from the parent sugar and the base peak was at 299.0979 ([C₁₀H₁₉O₁₀]⁻). The latter corresponds to the ion of the product formed by reaction between the bisulfite adduct and D-lyxose with displacement of potassium bisulfite.

The ¹H NMR spectrum of the adduct in D₂O showed the presence the α- and β-pyranose forms of D-lyxose and the major and minor forms of the acyclic sulfonate in the % ratios of 35.48 : 11.29 : 48.39 : 4.84. The adduct undergoes partial hydrolysis in aqueous media; notably, it is present in a larger proportion in the more concentrated solution used for ¹³C NMR spectroscopy (see below). A large J_2,3 coupling of 9.4 Hz suggests the conformation about the C2—C3 bond is similar in solution and the crystalline state.

In the ¹³C NMR spectrum, signals for C1 nuclei allow identification of the α- and β-pyranose forms of D-lyxose and the major (δ_C 82.20) and minor (δ_C 84.26) adducts in the ratios of 17.05 : 5.43 : 71.32 : 6.20, respectively.

5. Synthesis and crystallization

Water (0.5 ml) was added to potassium metabisulfite (0.37 g) which did not completely dissolve even on warming but which appeared to change its crystalline form as it underwent hydrolysis to yield potassium hydrogen sulfite. To this suspension was added a solution of D-lyxose (0.5 g) in water (0.35 ml), leading to immediate and complete solution of the reaction mixture. Seed crystals were obtained by evaporation of a small proportion of the solution, and these were added to the bulk of the solution which was then stored at 277 K, leading to the formation of large, well separated crystals. The mother liquor was removed with a Pasteur pipette, and the crystals were dried by pressing between filter papers to give, as a monohydrate, potassium (1S)-D-lyxit-1-ylsulfonate (0.396 g, 41%), m.p. 392–400 K (with decomposition); [α]_D 7.1 (30 min.) (c, 0.75 in 9:1 H₂O:HOAc). ¹H NMR (D₂O, 400 MHz, reference Me₃COH at δ_H 1.24): δ_H 4.93 (d, J_1,2 = 4.5 Hz, H-1 of α-pyranose), 4.86 (d, J_1,2 = 1.5 Hz, H-1 of β-pyranose); signals for the major acyclic sulfonate: δ_H 4.70 (d, J_1,2 = 1 Hz, H-1), 4.19 (dd, J_2,3 = 9.4 Hz, H-2), 3.99 (td, J_3,4 = 6.5, J_4,5b = 6.5, J_4,5a = 1.5 Hz, H-4), 3.62 (dd, J_5a,5b = −9.4, H-5a); for the minor acyclic sulfonate: δ_H 4.62 (d, J_1,2 = 5.5 Hz, H-1); ratio of major to minor sulfonate = 10:1. ¹³C NMR (D₂O, 100 MHz, reference Me₃COH at δ_C 30.29): δ_C 94.86 (C1, β-pyranose), 94.70 (C1, α-pyranose); signals for the major acyclic sulfonate: δ_C 82.20 (C1), 70.45, 69.88, 69.35 (C2, C3, C4), 63.80 (C5); the minor acyclic sulfonate showed a peak at δ_C 84.26 (C1).

Integration of the various signals for H-1 in the ¹H NMR spectrum, five minutes after sample dissolution, indicated the species α-pyranose, β-pyranose, major acyclic sulfonate and minor acyclic sulfonate were present in the % ratios of 35.48: 11.29: 48.39: 4.84. In the more concentrated solution prepared for ¹³C NMR the corresponding ratios were 17.05:5.43:71.32:6.20.

HRESMS (negative ion mode, measured in H₂O/MeOH, solution) gave a peak at m/z 149.0457 ([C₅H₉O₅]⁻), a significant peak at 213.0073 ([C₅H₁₁O₈S – H₂O] ⁻), and the base peak at 299.0979 ([C₁₀H₁₉O₁₀]⁻). The latter corresponds to the ion of the product formed by reaction between the bisulfite adduct and D-lyxose with displacement of potassium bisulfite. No significant peak was observed for ([C₅H₁₁O₈S₁]⁻) at the calculated m/z of 231.0180.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All the hydrogen atoms were located in difference maps and were refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	K⁺·C₅H₁₁O₈S⁻·H₂O
M_r	288.31
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	140
a, b, c (Å)	23.3536 (5), 9.0434 (2), 4.9939 (1)
V (Å³)	1054.69 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.74
Crystal size (mm)	0.28 × 0.26 × 0.11

Data collection
Diffractometer	Oxford Diffraction Xcalibur 3/Sapphire3 CCD
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.914, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20712, 3062, 3008
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.048, 1.12
No. of reflections	3062
No. of parameters	198
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.34
Absolute structure	Flack x determined using 1229 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.023 (11)
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) ORTEP (Johnson, 1976 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1415264

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014139/lh5775sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014139/lh5775Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015014139/lh5775Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and WinGX (Farrugia, 2012).

Potassium (1S,2S,3S,4R)-1,2,3,4,5-pentahydroxypentane-1-sulfonate monohydrate top

Crystal data top

K⁺·C₅H₁₁O₈S⁻·H₂O	D_x = 1.816 Mg m⁻³
M_r = 288.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2	Cell parameters from 10753 reflections
a = 23.3536 (5) Å	θ = 3.5–32.6°
b = 9.0434 (2) Å	µ = 0.74 mm⁻¹
c = 4.9939 (1) Å	T = 140 K
V = 1054.69 (4) Å³	Square prism, colourless
Z = 4	0.28 × 0.26 × 0.11 mm
F(000) = 600

Data collection top

Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer	3062 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3008 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 16.0050 pixels mm^-1	θ_max = 30.0°, θ_min = 3.5°
Thin slice φ and ω scans	h = −32→32
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→12
T_min = 0.914, T_max = 1.000	l = −7→7
20712 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.018	w = 1/[σ²(F_o²) + (0.0253P)² + 0.2102P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.048	(Δ/σ)_max = 0.001
S = 1.12	Δρ_max = 0.30 e Å⁻³
3062 reflections	Δρ_min = −0.34 e Å⁻³
198 parameters	Absolute structure: Flack x determined using 1229 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.023 (11)
Primary atom site location: structure-invariant direct methods

Special details top

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.21 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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

	x	y	z	U_iso*/U_eq
K1	0.5000	1.0000	0.67598 (9)	0.01296 (9)
K2	0.5000	0.5000	0.70830 (10)	0.01438 (9)
C1	0.37190 (6)	0.69370 (16)	0.3668 (3)	0.0102 (3)
C2	0.32071 (6)	0.69562 (16)	0.1730 (3)	0.0099 (2)
C3	0.26543 (6)	0.67837 (15)	0.3346 (3)	0.0104 (3)
C4	0.21277 (6)	0.65562 (16)	0.1567 (3)	0.0112 (3)
C5	0.15984 (6)	0.63560 (19)	0.3308 (3)	0.0150 (3)
O1	0.38531 (5)	0.55224 (13)	0.4618 (2)	0.0142 (2)
O2	0.32388 (5)	0.57866 (13)	−0.0172 (2)	0.0129 (2)
O3	0.26007 (5)	0.81265 (13)	0.4827 (3)	0.0138 (2)
O4	0.20578 (5)	0.77316 (14)	−0.0315 (2)	0.0136 (2)
O5	0.10823 (5)	0.62153 (13)	0.1783 (3)	0.0156 (2)
S1	0.43316 (2)	0.78331 (4)	0.21337 (7)	0.00910 (8)
O11	0.43680 (5)	0.73320 (13)	−0.0636 (2)	0.0145 (2)
O12	0.48337 (4)	0.74113 (13)	0.3723 (2)	0.0132 (2)
O13	0.42133 (5)	0.94196 (12)	0.2349 (3)	0.0153 (2)
O9	0.42697 (5)	0.37107 (14)	1.0868 (3)	0.0188 (2)
H1	0.3619 (8)	0.756 (2)	0.520 (4)	0.008 (4)*
H2	0.3170 (9)	0.786 (2)	0.088 (4)	0.014 (5)*
H3	0.2694 (9)	0.598 (2)	0.456 (5)	0.015 (5)*
H4	0.2190 (9)	0.573 (2)	0.044 (5)	0.017 (5)*
H5A	0.1557 (9)	0.718 (3)	0.447 (5)	0.019 (5)*
H5B	0.1647 (9)	0.553 (3)	0.444 (5)	0.019 (6)*
H1O	0.3898 (10)	0.496 (3)	0.338 (5)	0.029 (6)*
H2O	0.3515 (10)	0.585 (3)	−0.100 (5)	0.021 (6)*
H3O	0.2443 (11)	0.793 (3)	0.633 (5)	0.029 (7)*
H4O	0.2011 (12)	0.848 (3)	0.035 (6)	0.037 (8)*
H5O	0.1126 (10)	0.557 (3)	0.075 (5)	0.023 (6)*
H9A	0.4115 (12)	0.304 (3)	1.008 (7)	0.042 (8)*
H9B	0.4524 (13)	0.326 (3)	1.175 (7)	0.048 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.01062 (18)	0.01409 (18)	0.0142 (2)	−0.00037 (15)	0.000	0.000
K2	0.0152 (2)	0.01494 (19)	0.01297 (19)	0.00403 (16)	0.000	0.000
C1	0.0088 (6)	0.0117 (6)	0.0101 (6)	0.0001 (5)	0.0004 (5)	0.0014 (5)
C2	0.0087 (6)	0.0110 (6)	0.0100 (6)	0.0001 (5)	0.0000 (5)	0.0008 (5)
C3	0.0092 (6)	0.0104 (6)	0.0117 (7)	−0.0003 (5)	0.0008 (5)	0.0005 (5)
C4	0.0090 (6)	0.0116 (6)	0.0129 (7)	−0.0005 (5)	0.0004 (5)	0.0010 (6)
C5	0.0096 (6)	0.0205 (7)	0.0151 (7)	−0.0016 (5)	0.0001 (6)	0.0022 (6)
O1	0.0163 (5)	0.0135 (5)	0.0128 (5)	0.0002 (4)	−0.0024 (4)	0.0041 (4)
O2	0.0099 (5)	0.0172 (5)	0.0118 (5)	−0.0010 (4)	0.0020 (4)	−0.0032 (4)
O3	0.0140 (5)	0.0139 (5)	0.0133 (5)	−0.0014 (4)	0.0028 (4)	−0.0036 (4)
O4	0.0147 (5)	0.0146 (5)	0.0116 (5)	0.0015 (4)	−0.0002 (4)	0.0012 (4)
O5	0.0083 (5)	0.0201 (5)	0.0184 (6)	−0.0014 (4)	−0.0008 (4)	−0.0038 (5)
S1	0.00803 (14)	0.01074 (14)	0.00852 (15)	−0.00035 (11)	0.00023 (12)	0.00024 (12)
O11	0.0150 (5)	0.0200 (5)	0.0084 (5)	−0.0009 (5)	0.0011 (4)	−0.0014 (4)
O12	0.0091 (4)	0.0182 (5)	0.0124 (5)	0.0006 (4)	−0.0011 (4)	0.0013 (4)
O13	0.0160 (5)	0.0107 (4)	0.0191 (6)	−0.0006 (4)	−0.0015 (4)	0.0003 (4)
O9	0.0141 (5)	0.0159 (6)	0.0263 (6)	0.0020 (5)	−0.0060 (5)	−0.0015 (5)

Geometric parameters (Å, º) top

K1—O12ⁱ	2.8161 (12)	C2—O2	1.4233 (18)
K1—O12	2.8162 (12)	C2—C3	1.530 (2)
K1—O5ⁱⁱ	2.8505 (11)	C2—H2	0.93 (2)
K1—O5ⁱⁱⁱ	2.8505 (11)	C3—O3	1.4274 (18)
K1—O13	2.9160 (12)	C3—C4	1.531 (2)
K1—O13ⁱ	2.9160 (12)	C3—H3	0.95 (2)
K1—O11^iv	3.1131 (12)	C4—O4	1.4281 (18)
K1—O11^v	3.1131 (12)	C4—C5	1.522 (2)
K1—O13^iv	3.3824 (13)	C4—H4	0.95 (2)
K1—O13^v	3.3824 (13)	C5—O5	1.4313 (18)
K1—S1ⁱ	3.4078 (5)	C5—H5A	0.95 (2)
K1—S1	3.4079 (5)	C5—H5B	0.94 (2)
K2—O12	2.7787 (12)	O1—H1O	0.80 (3)
K2—O12^vi	2.7787 (12)	O2—H2O	0.77 (3)
K2—O9	2.8002 (14)	O3—H3O	0.85 (3)
K2—O9^vi	2.8003 (14)	O4—H4O	0.76 (3)
K2—O11^v	2.8149 (12)	O5—K1^x	2.8505 (11)
K2—O11^vii	2.8149 (12)	O5—H5O	0.78 (3)
K2—O1	2.9854 (12)	S1—O11	1.4579 (11)
K2—O1^vi	2.9855 (12)	S1—O13	1.4650 (11)
K2—K1^viii	4.5246 (1)	S1—O12	1.4665 (11)
K2—K2^v	4.9939 (1)	S1—K1^ix	3.6713 (5)
K2—K2^ix	4.9939 (1)	O11—K2^ix	2.8149 (12)
K2—H9B	3.02 (3)	O11—K1^ix	3.1131 (12)
C1—O1	1.3998 (18)	O13—K1^ix	3.3824 (13)
C1—C2	1.538 (2)	O9—H9A	0.81 (3)
C1—S1	1.8141 (15)	O9—H9B	0.84 (3)
C1—H1	0.98 (2)

O12ⁱ—K1—O12	114.84 (5)	O9^vi—K2—K1^viii	116.12 (3)
O12ⁱ—K1—O5ⁱⁱ	109.61 (3)	O11^v—K2—K1^viii	139.74 (2)
O12—K1—O5ⁱⁱ	86.51 (3)	O11^vii—K2—K1^viii	42.75 (2)
O12ⁱ—K1—O5ⁱⁱⁱ	86.51 (3)	O1—K2—K1^viii	98.25 (2)
O12—K1—O5ⁱⁱⁱ	109.61 (3)	O1^vi—K2—K1^viii	80.05 (2)
O5ⁱⁱ—K1—O5ⁱⁱⁱ	150.43 (6)	K1—K2—K1^viii	175.911 (17)
O12ⁱ—K1—O13	80.20 (3)	O12—K2—K2^v	127.14 (3)
O12—K1—O13	49.96 (3)	O12^vi—K2—K2^v	127.14 (3)
O5ⁱⁱ—K1—O13	133.00 (4)	O9—K2—K2^v	47.55 (3)
O5ⁱⁱⁱ—K1—O13	72.75 (3)	O9^vi—K2—K2^v	47.55 (3)
O12ⁱ—K1—O13ⁱ	49.96 (3)	O11^v—K2—K2^v	66.13 (2)
O12—K1—O13ⁱ	80.20 (3)	O11^vii—K2—K2^v	66.13 (2)
O5ⁱⁱ—K1—O13ⁱ	72.76 (3)	O1—K2—K2^v	114.35 (3)
O5ⁱⁱⁱ—K1—O13ⁱ	133.00 (4)	O1^vi—K2—K2^v	114.35 (3)
O13—K1—O13ⁱ	81.87 (5)	K1—K2—K2^v	92.044 (9)
O12ⁱ—K1—O11^iv	61.01 (3)	K1^viii—K2—K2^v	92.044 (9)
O12—K1—O11^iv	159.17 (3)	O12—K2—K2^ix	52.86 (3)
O5ⁱⁱ—K1—O11^iv	76.81 (3)	O12^vi—K2—K2^ix	52.86 (3)
O5ⁱⁱⁱ—K1—O11^iv	90.86 (3)	O9—K2—K2^ix	132.45 (3)
O13—K1—O11^iv	138.92 (3)	O9^vi—K2—K2^ix	132.45 (3)
O13ⁱ—K1—O11^iv	82.96 (3)	O11^v—K2—K2^ix	113.87 (2)
O12ⁱ—K1—O11^v	159.16 (3)	O11^vii—K2—K2^ix	113.87 (2)
O12—K1—O11^v	61.01 (3)	O1—K2—K2^ix	65.65 (3)
O5ⁱⁱ—K1—O11^v	90.86 (3)	O1^vi—K2—K2^ix	65.65 (3)
O5ⁱⁱⁱ—K1—O11^v	76.81 (3)	K1—K2—K2^ix	87.956 (9)
O13—K1—O11^v	82.96 (3)	K1^viii—K2—K2^ix	87.956 (9)
O13ⁱ—K1—O11^v	138.92 (3)	K2^v—K2—K2^ix	180.0
O11^iv—K1—O11^v	130.61 (4)	O12—K2—H9B	145.3 (6)
O12ⁱ—K1—O13^iv	103.91 (3)	O12^vi—K2—H9B	96.3 (6)
O12—K1—O13^iv	130.41 (3)	O9—K2—H9B	16.1 (6)
O5ⁱⁱ—K1—O13^iv	50.78 (3)	O9^vi—K2—H9B	85.4 (6)
O5ⁱⁱⁱ—K1—O13^iv	102.19 (3)	O11^v—K2—H9B	83.3 (6)
O13—K1—O13^iv	173.46 (3)	O11^vii—K2—H9B	59.4 (6)
O13ⁱ—K1—O13^iv	104.67 (3)	O1—K2—H9B	94.0 (6)
O11^iv—K1—O13^iv	43.74 (3)	O1^vi—K2—H9B	124.5 (6)
O11^v—K1—O13^iv	91.89 (3)	K1—K2—H9B	123.1 (6)
O12ⁱ—K1—O13^v	130.41 (3)	K1^viii—K2—H9B	60.6 (6)
O12—K1—O13^v	103.91 (3)	K2^v—K2—H9B	39.5 (6)
O5ⁱⁱ—K1—O13^v	102.19 (3)	K2^ix—K2—H9B	140.5 (6)
O5ⁱⁱⁱ—K1—O13^v	50.78 (3)	O1—C1—C2	113.41 (12)
O13—K1—O13^v	104.67 (3)	O1—C1—S1	112.02 (10)
O13ⁱ—K1—O13^v	173.46 (3)	C2—C1—S1	110.00 (10)
O11^iv—K1—O13^v	91.89 (3)	O1—C1—H1	108.2 (12)
O11^v—K1—O13^v	43.74 (3)	C2—C1—H1	107.6 (11)
O13^iv—K1—O13^v	68.79 (4)	S1—C1—H1	105.2 (11)
O12ⁱ—K1—S1ⁱ	25.01 (2)	O2—C2—C3	108.66 (11)
O12—K1—S1ⁱ	100.14 (3)	O2—C2—C1	111.77 (11)
O5ⁱⁱ—K1—S1ⁱ	89.35 (3)	C3—C2—C1	108.82 (12)
O5ⁱⁱⁱ—K1—S1ⁱ	110.94 (3)	O2—C2—H2	110.9 (13)
O13—K1—S1ⁱ	83.10 (3)	C3—C2—H2	104.6 (13)
O13ⁱ—K1—S1ⁱ	25.29 (2)	C1—C2—H2	111.7 (13)
O11^iv—K1—S1ⁱ	67.69 (2)	O3—C3—C2	105.10 (11)
O11^v—K1—S1ⁱ	161.09 (2)	O3—C3—C4	110.15 (12)
O13^iv—K1—S1ⁱ	102.79 (2)	C2—C3—C4	112.67 (12)
O13^v—K1—S1ⁱ	153.82 (2)	O3—C3—H3	109.2 (14)
O12ⁱ—K1—S1	100.14 (3)	C2—C3—H3	109.4 (14)
O12—K1—S1	25.01 (2)	C4—C3—H3	110.2 (13)
O5ⁱⁱ—K1—S1	110.94 (3)	O4—C4—C5	111.81 (12)
O5ⁱⁱⁱ—K1—S1	89.34 (3)	O4—C4—C3	111.94 (12)
O13—K1—S1	25.29 (2)	C5—C4—C3	109.69 (12)
O13ⁱ—K1—S1	83.11 (3)	O4—C4—H4	102.4 (14)
O11^iv—K1—S1	161.09 (2)	C5—C4—H4	111.7 (14)
O11^v—K1—S1	67.69 (2)	C3—C4—H4	109.1 (13)
O13^iv—K1—S1	153.82 (2)	O5—C5—C4	113.00 (13)
O13^v—K1—S1	102.79 (2)	O5—C5—H5A	108.0 (13)
S1ⁱ—K1—S1	94.639 (16)	C4—C5—H5A	109.8 (13)
O12—K2—O12^vi	105.71 (5)	O5—C5—H5B	110.5 (13)
O12—K2—O9	130.48 (3)	C4—C5—H5B	109.7 (13)
O12^vi—K2—O9	99.55 (3)	H5A—C5—H5B	105.5 (19)
O12—K2—O9^vi	99.55 (3)	C1—O1—K2	119.01 (9)
O12^vi—K2—O9^vi	130.48 (3)	C1—O1—H1O	110.1 (19)
O9—K2—O9^vi	95.09 (6)	K2—O1—H1O	95.8 (18)
O12—K2—O11^v	65.36 (3)	C2—O2—H2O	110.5 (18)
O12^vi—K2—O11^v	154.90 (3)	C3—O3—H3O	108.4 (18)
O9—K2—O11^v	73.70 (4)	C4—O4—H4O	113 (2)
O9^vi—K2—O11^v	74.59 (4)	C5—O5—K1^x	130.19 (10)
O12—K2—O11^vii	154.90 (3)	C5—O5—H5O	107.9 (17)
O12^vi—K2—O11^vii	65.36 (3)	K1^x—O5—H5O	89.8 (17)
O9—K2—O11^vii	74.59 (4)	O11—S1—O13	112.64 (7)
O9^vi—K2—O11^vii	73.70 (4)	O11—S1—O12	112.71 (7)
O11^v—K2—O11^vii	132.26 (5)	O13—S1—O12	111.46 (7)
O12—K2—O1	60.09 (3)	O11—S1—C1	107.93 (7)
O12^vi—K2—O1	90.03 (3)	O13—S1—C1	104.94 (7)
O9—K2—O1	78.33 (4)	O12—S1—C1	106.60 (7)
O9^vi—K2—O1	139.37 (4)	O11—S1—K1	142.67 (5)
O11^v—K2—O1	65.03 (3)	O13—S1—K1	58.23 (5)
O11^vii—K2—O1	139.10 (3)	O12—S1—K1	54.30 (5)
O12—K2—O1^vi	90.03 (3)	C1—S1—K1	109.38 (5)
O12^vi—K2—O1^vi	60.10 (3)	O11—S1—K1^ix	56.47 (5)
O9—K2—O1^vi	139.37 (4)	O13—S1—K1^ix	67.11 (5)
O9^vi—K2—O1^vi	78.33 (4)	O12—S1—K1^ix	101.22 (5)
O11^v—K2—O1^vi	139.10 (3)	C1—S1—K1^ix	151.95 (5)
O11^vii—K2—O1^vi	65.03 (3)	K1—S1—K1^ix	89.650 (8)
O1—K2—O1^vi	131.29 (5)	S1—O11—K2^ix	130.34 (7)
O12—K2—K1	36.31 (2)	S1—O11—K1^ix	100.55 (6)
O12^vi—K2—K1	139.71 (3)	K2^ix—O11—K1^ix	99.38 (3)
O9—K2—K1	116.12 (3)	S1—O12—K2	130.00 (6)
O9^vi—K2—K1	66.92 (3)	S1—O12—K1	100.69 (6)
O11^v—K2—K1	42.75 (2)	K2—O12—K1	107.94 (4)
O11^vii—K2—K1	139.74 (2)	S1—O13—K1	96.48 (6)
O1—K2—K1	80.05 (2)	S1—O13—K1^ix	89.37 (5)
O1^vi—K2—K1	98.25 (2)	K1—O13—K1^ix	104.67 (3)
O12—K2—K1^viii	139.71 (3)	K2—O9—H9A	105 (2)
O12^vi—K2—K1^viii	36.31 (2)	K2—O9—H9B	97 (2)
O9—K2—K1^viii	66.92 (3)	H9A—O9—H9B	102 (3)

O1—C1—C2—O2	−44.09 (16)	O13—S1—O11—K2^ix	150.63 (7)
S1—C1—C2—O2	82.24 (13)	O12—S1—O11—K2^ix	23.46 (10)
O1—C1—C2—C3	75.92 (15)	C1—S1—O11—K2^ix	−93.99 (9)
S1—C1—C2—C3	−157.75 (10)	K1—S1—O11—K2^ix	83.82 (10)
O2—C2—C3—O3	−169.41 (11)	K1^ix—S1—O11—K2^ix	112.07 (8)
C1—C2—C3—O3	68.67 (14)	O13—S1—O11—K1^ix	38.57 (7)
O2—C2—C3—C4	−49.45 (15)	O12—S1—O11—K1^ix	−88.61 (6)
C1—C2—C3—C4	−171.36 (11)	C1—S1—O11—K1^ix	153.94 (5)
O3—C3—C4—O4	60.33 (15)	K1—S1—O11—K1^ix	−28.25 (9)
C2—C3—C4—O4	−56.67 (16)	O11—S1—O12—K2	−95.90 (9)
O3—C3—C4—C5	−64.38 (15)	O13—S1—O12—K2	136.30 (8)
C2—C3—C4—C5	178.61 (12)	C1—S1—O12—K2	22.33 (10)
O4—C4—C5—O5	52.08 (17)	K1—S1—O12—K2	124.57 (9)
C3—C4—C5—O5	176.87 (12)	K1^ix—S1—O12—K2	−154.07 (6)
C2—C1—O1—K2	162.60 (8)	O11—S1—O12—K1	139.53 (6)
S1—C1—O1—K2	37.34 (13)	O13—S1—O12—K1	11.73 (7)
C4—C5—O5—K1^x	159.72 (9)	C1—S1—O12—K1	−102.24 (6)
O1—C1—S1—O11	84.07 (12)	K1^ix—S1—O12—K1	81.36 (3)
C2—C1—S1—O11	−43.04 (11)	O11—S1—O13—K1	−139.03 (6)
O1—C1—S1—O13	−155.59 (11)	O12—S1—O13—K1	−11.20 (7)
C2—C1—S1—O13	77.30 (11)	C1—S1—O13—K1	103.80 (6)
O1—C1—S1—O12	−37.26 (12)	K1^ix—S1—O13—K1	−104.69 (4)
C2—C1—S1—O12	−164.36 (10)	O11—S1—O13—K1^ix	−34.34 (6)
O1—C1—S1—K1	−94.52 (10)	O12—S1—O13—K1^ix	93.50 (6)
C2—C1—S1—K1	138.37 (8)	C1—S1—O13—K1^ix	−151.50 (5)
O1—C1—S1—K1^ix	135.22 (9)	K1—S1—O13—K1^ix	104.69 (4)
C2—C1—S1—K1^ix	8.11 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O9^ix	0.80 (3)	1.90 (3)	2.6716 (19)	160 (2)
O2—H2O···O1^ix	0.77 (3)	2.35 (3)	2.9810 (17)	141 (2)
O2—H2O···O11	0.77 (3)	2.41 (2)	2.9935 (16)	134 (2)
O3—H3O···O4^v	0.85 (3)	1.91 (3)	2.7609 (17)	173 (3)
O4—H4O···O2^xi	0.76 (3)	2.17 (3)	2.8586 (17)	151 (3)
O5—H5O···O13^xii	0.78 (3)	2.03 (3)	2.7152 (17)	146 (2)
O9—H9A···O5^x	0.81 (3)	1.95 (3)	2.7426 (18)	167 (3)
O9—H9B···O12^vii	0.84 (3)	1.90 (3)	2.7289 (17)	170 (3)

Symmetry codes: (v) x, y, z+1; (vii) −x+1, −y+1, z+1; (ix) x, y, z−1; (x) −x+1/2, y−1/2, −z+1; (xi) −x+1/2, y+1/2, −z; (xii) −x+1/2, y−1/2, −z.

Acknowledgements

We thank the EPSRC National Mass Spectrometry Facility (NMSF), Swansea, for determination of the low- and high-resolution mass spectra and Dr Sergey Nepogodiev for measurement of the NMR spectra.

References

Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Cole, E. R., Craig, D. C., Fitzpatrick, L. J., Hibbert, D. B. & Stevens, J. D. (2001). Carbohydr. Res. 335, 1–10. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gehman, H. & Osman, E. M. (1954). Adv. Food Res. 5, 53–96. CrossRef PubMed CAS Web of Science Google Scholar
Haines, A. H. & Hughes, D. L. (2010). Carbohydr. Res. 345, 2705–2708. Web of Science CSD CrossRef CAS PubMed Google Scholar
Haines, A. H. & Hughes, D. L. (2012). Acta Cryst. E68, m377–m378. CSD CrossRef IUCr Journals Google Scholar
Haines, A. H. & Hughes, D. L. (2013). Acta Cryst. E69, m7–m8. CSD CrossRef IUCr Journals Google Scholar
Haines, A. H. & Hughes, D. L. (2014). Acta Cryst. E70, 406–409. CSD CrossRef IUCr Journals Google Scholar
Ingles, D. L. (1959). Aust. J. Chem. 12, 97–101. CAS Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar