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Potassium (1R,4R,5S,8S)-4,5,8-trihy­dr­oxy-3-oxo-2,6-dioxabi­cyclo­[3.3.0]octane-4-sulfonate dihydrate

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

(Received 8 November 2012; accepted 27 November 2012; online 5 December 2012)

The title salt, K+·C6H7O9S·2H2O, formed by reaction of dehydro-L-ascorbic acid with potassium hydrogen sulfite in water, crystallizes as colourless plates. The potassium ion is coordinated by eight O atoms arising from hy­droxy or sulfonate groups. The sulfonate group is bonded to the C atom neighbouring that of the lactone carbonyl group. As is commonly observed in crystalline L-ascorbic acid derivatives, the O atom of the primary hy­droxy group is linked to the second C atom from the lactone C atom, forming a hemi-acetal function, thereby creating a bicyclic system of two fused five-membered rings, both of which have envelope conformations with one of the shared C atoms as the flap. Addition of the sulfur nucleophile occurs from the less hindered face. One of the two independent lattice water mol­ecules has hydrogen bonds to sulfonate O atoms of two different anions and is the acceptor of bonds from hy­droxy groups of two further anions; the second lattice water mol­ecule donates to the carbonyl and a hy­droxy O atom in different anions, and accepts from a hy­droxy O atom in a further anion. Thus, through K—O coordination and hydrogen bonds, the potassium cations, sulfonate anions and water mol­ecules are linked in a three-dimensional network.

Related literature

For the first synthesis of the title compound, see: Ingles (1961[Ingles, D. L. (1961). Aust. J. Chem. 14, 302-307.]). For related studies on crystalline properties of hydrogen sulfite addition products of carbohydrates and their structures, see: Cole et al. (2001[Cole, E. R., Craig, D. C., Fitzpatrick, L. J., Hibbert, D. B. & Stevens, J. D. (2001). Carbohydr. Res. 335, 1-10.]); Haines & Hughes (2010[Haines, A. H. & Hughes, D. L. (2010). Carbohydr. Res. 345, 2705-2708.], 2012[Haines, A. H. & Hughes, D. L. (2012). Acta Cryst. E68, m377-m378.]). For examples of related bicyclic structures based on dehydro-L-ascorbic acid, see: Hvoslef (1972[Hvoslef, J. (1972). Acta Cryst. B28, 916-923.]); Yvin et al. (1982[Yvin, J.-C., Chevolot-Magueur, A.-M., Chevolot, L., Lallemand, J.-Y., Potier, P. & Guilhem, J. (1982). J. Am. Chem. Soc. 104, 4497-4498.]).

[Scheme 1]

Experimental

Crystal data
  • K+·C6H7O9S·2H2O

  • Mr = 330.31

  • Orthorhombic, P 21 21 21

  • a = 6.21040 (15) Å

  • b = 6.93014 (16) Å

  • c = 26.7851 (7) Å

  • V = 1152.80 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.70 mm−1

  • T = 140 K

  • 0.80 × 0.40 × 0.10 mm

Data collection
  • Oxford Diffraction Xcalibur Sapphire3 CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.851, Tmax = 1.000

  • 15452 measured reflections

  • 2022 independent reflections

  • 2012 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.018

  • wR(F2) = 0.048

  • S = 1.13

  • 2022 reflections

  • 214 parameters

  • All H-atom parameters refined

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.24 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 806 Friedel pairs

  • Flack parameter: 0.00 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2O⋯O8i 0.77 (3) 1.91 (3) 2.6533 (18) 162 (3)
O3—H3O⋯O8 0.79 (3) 1.87 (3) 2.6525 (18) 171 (3)
O5—H5O⋯O9ii 0.70 (3) 2.01 (3) 2.684 (2) 162 (3)
O8—H8OA⋯O22iii 0.81 (3) 2.07 (3) 2.8141 (18) 155 (3)
O8—H8OB⋯O23i 0.78 (3) 2.13 (3) 2.7798 (18) 142 (2)
O9—H9OA⋯O5iv 0.77 (3) 2.13 (3) 2.869 (2) 161 (3)
O9—H9OB⋯O1 0.83 (3) 1.95 (3) 2.7852 (19) 175 (3)
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (ii) [-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) x, y+1, z; (iv) x-1, y-1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPIII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]) and ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Comment top

The addition of hydrogen sulfite (bisulfite) anion to carbonyl compounds to form sulfonic acid salts has found use in the purification of aldehydes and some ketones. Certain carbohydrates, despite existing preponderately in a hemi-acetal form, also give such adducts and the crystalline structures of the potassium sulfonic acid salts of D-glucose and D-mannose (Cole et al., 2001), D-galactose (Haines & Hughes, 2010) and the sodium sulfonic salt of D-glucose (Haines & Hughes, 2012) have been determined by X-ray crystallographic studies and all shown to exist in an acyclic form.

Ingles (1961) reported the preparation of an addition product between potassium hydrogen sulfite and dehydro-L-ascorbic acid. This compound, with carbonyl functionality at C1, C2 and C3, has potentially three sites of attack by the anion, but the carbonyl group at C1 is incorporated in a lactone structure and therefore is the least likely to undergo nucleophilic attack by the sulfur but the question of formation of a C2 or C3 adduct remained open. Our present study was undertaken to determine the structure of this compound.

Preparation of the adduct by reaction of potassium hydrogen sulfite (generated in aqueous solution from potassium metabisulfite) and dehydro-L-ascorbic acid in water by the published procedure gave, as reported, the adduct as a dihydrate with properties (m.p. and [α]D) in agreement with those described (Ingles, 1961). HRESIMS (negative ion mode, methanol solution) did not show an expected peak at m/e 254.9816 for [C6H7O9S]- but showed peaks at 173.0089 for the dehydro-L-ascorbic acid anion (calculated for [C6H5O6]-: m/z 173.0092) and the ion of the methanol adduct at 205.0349 (calcd for [C7H9O7]-: m/z 205.0354), indicating instability of the adduct in the methanol solution.

The crystal structure indicates attachment of the sulfur at C2 on the opposite side of the fused ring formed by attack of O6 on the C3 carbonyl function (Figure 1). This bicyclic motif for L-ascorbic acid derivatives in which the two rings share the C3—C4 bond is a common feature revealed in many crystal structures determined by X-ray crystallography, for example the dehydro-L-ascorbic acid dimer (Hvoslef, 1972) and the marine natural product delesserine (Yvin et al., 1982). Both rings have envelope conformations and C3 is the flap out-of-plane atom in each. The potassium ions are eight-coordinate (Figures 1 and 2) with a coordination sphere between that of a square antiprism (in which one of the square planes is O22, O23ii, O2iii, and O6iii; for symmetry codes, see: 'Geometric parameters Table') and dodecahedral (in which the pairs of `pseudo-equatorial' B-site atoms are O22, O5i and O21iv, O2iii). Each potassium ion is bonded to O atoms of five different anions with K—O bond lengths in the range 2.6757 (13) – 3.0265 (13) Å. Of the two lattice water molecules, that containing O8 has hydrogen bonds to oxygen atoms in different sulfonate groups (Table1, Figure 3) and is the acceptor of two hydrogen bonds, from H2O and H3O in different anions, leading to an approximately tetrahedral arrangement about the O8 atom. The water molecule of O9 accepts a single hydrogen bond from an H5O atom and donates two hydrogen bonds, to O1 and O5, in different anions (Figure 3); the trigonal arrangement at the O9 atom has an umbrella shape. Thus, through K—O coordination and hydrogen bonds, potassium cations, sulfonate anions and water molecules are linked in a three-dimensional network.

Related literature top

For the first synthesis of the title compound, see: Ingles (1961). For related studies on crystalline properties of hydrogen sulfite addition products of carbohydrates and their structures, see: Cole et al. (2001); Haines & Hughes (2010, 2012). For examples of related bicyclic structures based on dehydro-L-ascorbic acid, see: Hvoslef (1972); Yvin et al. (1982).

Experimental top

The title compound was prepared by a procedure similar to that described (Ingles, 1961). L-Ascorbic acid (1.76 g) was oxidized by shaking with iodine (2.48 g) in MeOH (15 ml) and the solution neutralized with basic lead carbonate (7 g), then filtered through kieselguhr. The syrup obtained on evaporation of the solution was dissolved in water (1.2 ml) and added to a solution of potassium hydrogen sulfite made by dissolving potassium metabisulfite (1.11 g) in water (1.6 ml). The crystals that formed were collected, washed with 95% EtOH and dried under vacuum over P2O5, m.p. (with swelling) 401–403 K with gradual decomposition to 473 K [lit. slow decomposition above 423 K (Ingles, 1961)]; [α]D24 +38.5 (c, 0.74, 9:1 H2O:HOAc), lit. [α]D +35 (c 1.5, 9:1 H2O:HOAc). 1H NMR (D2O, 400 MHz, reference Me3COH at δH 1.24): δ 4.95 (br s, H-4), 4.63 (ddd, J5,6a = 5, J5,6 b = 2.5, J4,5 = 0.6 Hz, H-5), 4.24 (dd, J6a,6b = 10.4 Hz, H-6a), 4.18 (dd, H-6 b). 13C NMR (D2O, 100 MHz, referenced to Me3COH at δC 30.29): δ 172.33 (C1), 107.17 (C3), 88.88 (C2), 88.70 (C4), 76.06 (C6), 73.64 (C5).

HRESIMS (negative ion mode, measured in MeOH solution) gave no peak at the expected m/z [C6H7O9S1]- but predominant peaks were observed at m/z 173.0089 ([C6H5O6]-), and 205.0349 ([C7H9O7]-) which indicated (i) decomposition of the sulfonate in solution to dehydro-L-ascorbic acid, and (ii) addition of methanol to this decomposition product.

Refinement top

Hydrogen atoms were located in difference maps and were all refined freely except, in the final cycles, the Uiso parameters of the methine hydrogen atoms were set at 1.2.Ueq of the parent carbon atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis CCD (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. View of the expanded asymmetric unit of K+.C6H7O9S-.2H2O, showing the conformation of the anion, the coordination of the potassium cation and the locations of the water molecules; all the potassium ions bonded to the anion are included. In all the figures, thermal ellipsoids are drawn at the 50% probability level, and hydrogen atoms are drawn as spheres of arbitrary size. Superscripts in the atom labels denote symmetry operations as defined in the Tables of molecular dimensions and hydrogen bonds.
[Figure 2] Fig. 2. A section through the unit cell, showing the linking of the different moieties through K—O coordination bonds.
[Figure 3] Fig. 3. A section through the unit cell (as Figure 2), showing the linking of the different moieties through hydrogen bonds (dashed lines).
Potassium (1R,4R,5S,8S)-4,5,8-trihydroxy-3-oxo-2,6-dioxabicyclo[3.3.0]octane-4-sulfonate dihydrate top
Crystal data top
K+·C6H7O9S·2H2OF(000) = 680
Mr = 330.31Dx = 1.903 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 9940 reflections
a = 6.21040 (15) Åθ = 3.6–32.6°
b = 6.93014 (16) ŵ = 0.70 mm1
c = 26.7851 (7) ÅT = 140 K
V = 1152.80 (5) Å3Plate, colourless
Z = 40.80 × 0.40 × 0.10 mm
Data collection top
Oxford Diffraction Xcalibur 3/Sapphire3 CCD
diffractometer
2022 independent reflections
Radiation source: Enhance (Mo) X-ray Source2012 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 16.0050 pixels mm-1θmax = 25.0°, θmin = 3.6°
Thin slice ϕ and ω scansh = 77
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
k = 88
Tmin = 0.851, Tmax = 1.000l = 3131
15452 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018All H-atom parameters refined
wR(F2) = 0.048 w = 1/[σ2(Fo2) + (0.0259P)2 + 0.3818P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.002
2022 reflectionsΔρmax = 0.22 e Å3
214 parametersΔρmin = 0.24 e Å3
0 restraintsAbsolute structure: Flack (1983), 806 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (4)
Crystal data top
K+·C6H7O9S·2H2OV = 1152.80 (5) Å3
Mr = 330.31Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.21040 (15) ŵ = 0.70 mm1
b = 6.93014 (16) ÅT = 140 K
c = 26.7851 (7) Å0.80 × 0.40 × 0.10 mm
Data collection top
Oxford Diffraction Xcalibur 3/Sapphire3 CCD
diffractometer
2022 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
2012 reflections with I > 2σ(I)
Tmin = 0.851, Tmax = 1.000Rint = 0.026
15452 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.018All H-atom parameters refined
wR(F2) = 0.048Δρmax = 0.22 e Å3
S = 1.13Δρmin = 0.24 e Å3
2022 reflectionsAbsolute structure: Flack (1983), 806 Friedel pairs
214 parametersAbsolute structure parameter: 0.00 (4)
0 restraints
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
K0.43096 (6)0.06331 (5)0.592707 (13)0.01341 (10)
C10.7395 (3)0.4927 (2)0.64787 (6)0.0130 (4)
C20.7781 (3)0.6005 (2)0.59853 (6)0.0101 (3)
C30.9401 (3)0.7544 (2)0.61585 (6)0.0101 (3)
C41.0569 (3)0.6623 (2)0.66013 (6)0.0118 (4)
H41.179 (3)0.591 (3)0.6515 (7)0.014*
C51.0939 (3)0.8288 (2)0.69651 (7)0.0143 (4)
H51.068 (3)0.790 (3)0.7284 (8)0.017*
C60.9307 (3)0.9816 (3)0.68001 (7)0.0163 (4)
O10.5875 (2)0.39178 (19)0.65771 (5)0.0213 (3)
O20.5917 (2)0.68214 (18)0.57932 (5)0.0152 (3)
O31.0843 (2)0.82586 (17)0.58160 (5)0.0132 (3)
O40.8989 (2)0.52687 (17)0.68067 (4)0.0146 (3)
O51.3044 (2)0.9069 (2)0.69025 (5)0.0168 (3)
O60.81153 (19)0.90096 (17)0.63873 (4)0.0133 (3)
S20.89769 (6)0.42594 (6)0.555030 (14)0.01075 (10)
O211.0867 (2)0.35166 (17)0.58032 (5)0.0163 (3)
O220.7275 (2)0.28416 (18)0.54814 (4)0.0170 (3)
O230.9402 (2)0.53401 (17)0.50966 (4)0.0144 (3)
O80.8855 (2)0.9517 (2)0.50022 (5)0.0136 (3)
O90.4146 (3)0.2464 (2)0.74597 (5)0.0243 (3)
H6A1.006 (4)1.106 (3)0.6699 (7)0.018 (5)*
H6B0.828 (4)1.008 (3)0.7059 (8)0.023 (6)*
H2O0.548 (4)0.623 (4)0.5572 (9)0.034 (7)*
H3O1.013 (4)0.860 (4)0.5587 (9)0.036 (7)*
H5O1.375 (5)0.847 (4)0.7033 (10)0.032 (8)*
H8OA0.856 (4)1.063 (5)0.5060 (10)0.049 (9)*
H8OB0.775 (4)0.904 (4)0.4948 (9)0.028 (7)*
H9OA0.377 (5)0.146 (5)0.7374 (11)0.048 (9)*
H9OB0.468 (5)0.296 (4)0.7205 (11)0.042 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.01291 (17)0.01296 (18)0.01436 (18)0.00271 (16)0.00075 (14)0.00059 (14)
C10.0148 (8)0.0111 (8)0.0130 (8)0.0003 (7)0.0025 (7)0.0026 (7)
C20.0099 (7)0.0094 (8)0.0111 (8)0.0005 (7)0.0002 (6)0.0016 (7)
C30.0109 (8)0.0088 (8)0.0107 (7)0.0001 (7)0.0014 (7)0.0007 (6)
C40.0121 (9)0.0111 (8)0.0121 (8)0.0016 (8)0.0005 (7)0.0008 (6)
C50.0165 (9)0.0167 (9)0.0099 (8)0.0046 (8)0.0013 (8)0.0007 (7)
C60.0160 (9)0.0157 (9)0.0174 (9)0.0009 (8)0.0012 (8)0.0078 (7)
O10.0230 (7)0.0234 (7)0.0174 (6)0.0114 (7)0.0046 (6)0.0005 (5)
O20.0115 (6)0.0157 (6)0.0183 (6)0.0036 (6)0.0058 (5)0.0063 (5)
O30.0132 (6)0.0137 (6)0.0127 (6)0.0036 (6)0.0014 (5)0.0029 (5)
O40.0188 (6)0.0121 (6)0.0129 (6)0.0036 (6)0.0004 (5)0.0021 (4)
O50.0132 (6)0.0164 (7)0.0208 (7)0.0017 (6)0.0064 (5)0.0006 (6)
O60.0139 (6)0.0109 (6)0.0152 (6)0.0020 (5)0.0032 (5)0.0045 (5)
S20.0124 (2)0.00826 (19)0.01156 (19)0.00009 (19)0.00120 (15)0.00172 (16)
O210.0160 (6)0.0148 (6)0.0183 (6)0.0044 (6)0.0009 (6)0.0006 (5)
O220.0191 (7)0.0127 (6)0.0192 (7)0.0032 (6)0.0028 (5)0.0036 (5)
O230.0178 (6)0.0140 (6)0.0115 (6)0.0013 (5)0.0032 (5)0.0011 (5)
O80.0131 (7)0.0118 (7)0.0158 (6)0.0009 (6)0.0007 (5)0.0020 (5)
O90.0335 (8)0.0240 (8)0.0154 (7)0.0131 (7)0.0015 (7)0.0031 (6)
Geometric parameters (Å, º) top
K—O222.6757 (13)C5—C61.531 (3)
K—O3i2.7259 (13)C5—H50.91 (2)
K—O23ii2.8243 (12)C6—O61.443 (2)
K—O2iii2.8466 (13)C6—H6A1.02 (2)
K—O6iii2.8934 (12)C6—H6B0.96 (2)
K—O5i2.9356 (14)O2—Kv2.8466 (13)
K—O21iv2.9455 (13)O2—H2O0.77 (3)
K—O13.0265 (13)O3—Kvi2.7259 (13)
C1—O11.204 (2)O3—H3O0.79 (3)
C1—O41.344 (2)O5—Kvi2.9356 (14)
C1—C21.537 (2)O5—H5O0.70 (3)
C2—O21.387 (2)O6—Kv2.8934 (12)
C2—C31.538 (2)S2—O211.4495 (13)
C2—S21.8364 (17)S2—O231.4517 (12)
C3—O31.374 (2)S2—O221.4547 (13)
C3—O61.430 (2)O21—Kvii2.9455 (13)
C3—C41.529 (2)O23—Kviii2.8243 (12)
C4—O41.465 (2)O8—H8OA0.81 (3)
C4—C51.528 (2)O8—H8OB0.78 (3)
C4—H40.94 (2)O9—H9OA0.77 (3)
C5—O51.425 (2)O9—H9OB0.83 (3)
O22—K—O3i147.16 (4)O4—C4—C5110.19 (13)
O22—K—O23ii71.91 (4)O4—C4—C3103.95 (13)
O3i—K—O23ii76.47 (4)C5—C4—C3104.51 (14)
O22—K—O2iii103.48 (4)O4—C4—H4107.4 (12)
O3i—K—O2iii72.73 (4)C5—C4—H4115.7 (12)
O23ii—K—O2iii69.45 (4)C3—C4—H4114.5 (12)
O22—K—O6iii81.39 (4)O5—C5—C4110.47 (15)
O3i—K—O6iii117.19 (4)O5—C5—C6108.10 (14)
O23ii—K—O6iii107.71 (4)C4—C5—C6103.82 (14)
O2iii—K—O6iii53.58 (4)O5—C5—H5112.8 (13)
O22—K—O5i142.42 (4)C4—C5—H5110.3 (13)
O3i—K—O5i70.30 (4)C6—C5—H5110.9 (13)
O23ii—K—O5i141.38 (4)O6—C6—C5107.03 (13)
O2iii—K—O5i82.15 (4)O6—C6—H6A111.1 (11)
O6iii—K—O5i72.30 (4)C5—C6—H6A111.1 (12)
O22—K—O21iv93.52 (4)O6—C6—H6B106.8 (13)
O3i—K—O21iv79.86 (4)C5—C6—H6B111.2 (13)
O23ii—K—O21iv93.87 (3)H6A—C6—H6B109.5 (18)
O2iii—K—O21iv150.46 (4)C1—O1—K124.25 (11)
O6iii—K—O21iv154.80 (4)C2—O2—Kv128.65 (10)
O5i—K—O21iv98.99 (4)C2—O2—H2O111.5 (19)
O22—K—O166.75 (4)Kv—O2—H2O117.6 (19)
O3i—K—O1140.41 (4)C3—O3—Kvi131.24 (10)
O23ii—K—O1137.02 (4)C3—O3—H3O105.2 (19)
O2iii—K—O1131.13 (4)Kvi—O3—H3O110.0 (19)
O6iii—K—O177.58 (4)C1—O4—C4111.14 (13)
O5i—K—O181.47 (4)C5—O5—Kvi119.38 (10)
O21iv—K—O177.75 (4)C5—O5—H5O107 (2)
O1—C1—O4122.44 (16)Kvi—O5—H5O120 (2)
O1—C1—C2126.35 (16)C3—O6—C6108.47 (13)
O4—C1—C2111.20 (14)C3—O6—Kv123.35 (9)
O2—C2—C1112.80 (14)C6—O6—Kv126.50 (10)
O2—C2—C3112.01 (14)O21—S2—O23115.28 (8)
C1—C2—C3100.35 (13)O21—S2—O22114.05 (8)
O2—C2—S2111.76 (11)O23—S2—O22112.00 (7)
C1—C2—S2106.78 (11)O21—S2—C2105.36 (7)
C3—C2—S2112.53 (11)O23—S2—C2105.37 (7)
O3—C3—O6113.20 (13)O22—S2—C2103.37 (7)
O3—C3—C4111.05 (14)S2—O21—Kvii151.80 (7)
O6—C3—C4103.23 (12)S2—O22—K146.08 (7)
O3—C3—C2118.36 (13)S2—O23—Kviii133.30 (7)
O6—C3—C2104.85 (13)H8OA—O8—H8OB104 (3)
C4—C3—C2104.75 (13)H9OA—O9—H9OB105 (3)
O1—C1—C2—O240.4 (2)C2—C3—O3—Kvi171.95 (10)
O4—C1—C2—O2138.58 (15)O1—C1—O4—C4176.90 (16)
O1—C1—C2—C3159.75 (17)C2—C1—O4—C42.15 (18)
O4—C1—C2—C319.25 (17)C5—C4—O4—C1127.76 (15)
O1—C1—C2—S282.73 (19)C3—C4—O4—C116.26 (17)
O4—C1—C2—S298.27 (14)C4—C5—O5—Kvi59.03 (16)
O2—C2—C3—O387.94 (18)C6—C5—O5—Kvi53.94 (16)
C1—C2—C3—O3152.15 (14)O3—C3—O6—C684.25 (16)
S2—C2—C3—O338.98 (18)C4—C3—O6—C635.89 (17)
O2—C2—C3—O639.38 (16)C2—C3—O6—C6145.34 (13)
C1—C2—C3—O680.53 (14)O3—C3—O6—Kv81.84 (15)
S2—C2—C3—O6166.30 (10)C4—C3—O6—Kv158.02 (9)
O2—C2—C3—C4147.71 (14)C2—C3—O6—Kv48.57 (15)
C1—C2—C3—C427.80 (16)C5—C6—O6—C323.76 (18)
S2—C2—C3—C485.37 (14)C5—C6—O6—Kv170.70 (10)
O3—C3—C4—O4156.62 (13)O2—C2—S2—O21179.15 (11)
O6—C3—C4—O481.78 (14)C1—C2—S2—O2155.36 (13)
C2—C3—C4—O427.74 (16)C3—C2—S2—O2153.81 (13)
O3—C3—C4—C587.81 (16)O2—C2—S2—O2358.52 (13)
O6—C3—C4—C533.79 (17)C1—C2—S2—O23177.69 (11)
C2—C3—C4—C5143.31 (14)C3—C2—S2—O2368.53 (12)
O4—C4—C5—O5152.70 (14)O2—C2—S2—O2259.16 (13)
C3—C4—C5—O596.18 (16)C1—C2—S2—O2264.63 (12)
O4—C4—C5—C691.63 (16)C3—C2—S2—O22173.79 (11)
C3—C4—C5—C619.50 (18)O23—S2—O21—Kvii81.35 (17)
O5—C5—C6—O6118.72 (15)O22—S2—O21—Kvii50.28 (18)
C4—C5—C6—O61.37 (18)C2—S2—O21—Kvii162.95 (15)
O4—C1—O1—K129.43 (14)O21—S2—O22—K67.79 (15)
C2—C1—O1—K51.7 (2)O23—S2—O22—K159.00 (12)
O22—K—O1—C110.21 (13)C2—S2—O22—K46.05 (15)
O3i—K—O1—C1166.47 (13)O3i—K—O22—S2170.05 (11)
O23ii—K—O1—C127.09 (16)O23ii—K—O22—S2173.73 (14)
O2iii—K—O1—C177.60 (15)O2iii—K—O22—S2110.99 (14)
O6iii—K—O1—C175.65 (14)O6iii—K—O22—S261.82 (14)
O5i—K—O1—C1149.28 (14)O5i—K—O22—S216.32 (18)
O21iv—K—O1—C1109.51 (14)O21iv—K—O22—S293.35 (14)
C1—C2—O2—Kv93.66 (15)O1—K—O22—S218.29 (13)
C3—C2—O2—Kv18.67 (18)O21—S2—O23—Kviii98.09 (10)
S2—C2—O2—Kv146.01 (8)O22—S2—O23—Kviii34.51 (11)
O6—C3—O3—Kvi64.81 (18)C2—S2—O23—Kviii146.21 (9)
C4—C3—O3—Kvi50.77 (18)
Symmetry codes: (i) x1, y1, z; (ii) x1/2, y+1/2, z+1; (iii) x, y1, z; (iv) x1, y, z; (v) x, y+1, z; (vi) x+1, y+1, z; (vii) x+1, y, z; (viii) x+1/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O8ix0.77 (3)1.91 (3)2.6533 (18)162 (3)
O3—H3O···O80.79 (3)1.87 (3)2.6525 (18)171 (3)
O5—H5O···O9x0.70 (3)2.01 (3)2.684 (2)162 (3)
O8—H8OA···O22v0.81 (3)2.07 (3)2.8141 (18)155 (3)
O8—H8OB···O23ix0.78 (3)2.13 (3)2.7798 (18)142 (2)
O9—H9OA···O5i0.77 (3)2.13 (3)2.869 (2)161 (3)
O9—H9OB···O10.83 (3)1.95 (3)2.7852 (19)175 (3)
Symmetry codes: (i) x1, y1, z; (v) x, y+1, z; (ix) x1/2, y+3/2, z+1; (x) x+2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaK+·C6H7O9S·2H2O
Mr330.31
Crystal system, space groupOrthorhombic, P212121
Temperature (K)140
a, b, c (Å)6.21040 (15), 6.93014 (16), 26.7851 (7)
V3)1152.80 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.70
Crystal size (mm)0.80 × 0.40 × 0.10
Data collection
DiffractometerOxford Diffraction Xcalibur 3/Sapphire3 CCD
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2010)
Tmin, Tmax0.851, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
15452, 2022, 2012
Rint0.026
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.048, 1.13
No. of reflections2022
No. of parameters214
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.22, 0.24
Absolute structureFlack (1983), 806 Friedel pairs
Absolute structure parameter0.00 (4)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), ORTEPIII (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O8i0.77 (3)1.91 (3)2.6533 (18)162 (3)
O3—H3O···O80.79 (3)1.87 (3)2.6525 (18)171 (3)
O5—H5O···O9ii0.70 (3)2.01 (3)2.684 (2)162 (3)
O8—H8OA···O22iii0.81 (3)2.07 (3)2.8141 (18)155 (3)
O8—H8OB···O23i0.78 (3)2.13 (3)2.7798 (18)142 (2)
O9—H9OA···O5iv0.77 (3)2.13 (3)2.869 (2)161 (3)
O9—H9OB···O10.83 (3)1.95 (3)2.7852 (19)175 (3)
Symmetry codes: (i) x1/2, y+3/2, z+1; (ii) x+2, y+1/2, z+3/2; (iii) x, y+1, z; (iv) x1, y1, z.
 

Acknowledgements

We thank the EPSRC National Mass Spectrometry Service Centre at Swansea for determination of the low- and high-resolution mass spectra.

References

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