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

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 hy-droxy 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 hy-droxy 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 mol-ecules has hydrogen bonds to sulfonate O atoms of two different anions and is the acceptor of bonds from hy-droxy groups of two further anions; the second lattice water mol-ecule donates to the carbonyl and a hy-droxy O atom in different anions, and accepts from a hy-droxy O atom in a further anion. Thus, through K-O coordination and hydrogen bonds, the potassium cations, sulfonate anions and water mol-ecules are linked in a three-dimensional network.

Related literature

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

Crystal data

K+·C6H7O9S−·2H2O

M = 330.31

Orthorhombic,

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 ▶) T min = 0.851, T max = 1.000

15452 measured reflections

2022 independent reflections

2012 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 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 ▶), 806 Friedel pairs

Flack parameter: 0.00 (4)

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis CCD; 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 and WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812048672/wm2701sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048672/wm2701Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812048672/wm2701Isup3.cdx

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812048672/wm2701Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

K+·C6H7O9S−·2H2O	F(000) = 680
Mr = 330.31	Dx = 1.903 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9940 reflections
a = 6.21040 (15) Å	θ = 3.6–32.6°
b = 6.93014 (16) Å	µ = 0.70 mm−1
c = 26.7851 (7) Å	T = 140 K
V = 1152.80 (5) Å3	Plate, colourless
Z = 4	0.80 × 0.40 × 0.10 mm

Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer	2022 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 16.0050 pixels mm-1	θmax = 25.0°, θmin = 3.6°
Thin slice φ and ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −8→8
Tmin = 0.851, Tmax = 1.000	l = −31→31
15452 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018	All 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 reflections	Δρmax = 0.22 e Å−3
214 parameters	Δρmin = −0.24 e Å−3
0 restraints	Absolute structure: Flack (1983), 806 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (4)

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.

	x	y	z	Uiso*/Ueq
K	0.43096 (6)	0.06331 (5)	0.592707 (13)	0.01341 (10)
C1	0.7395 (3)	0.4927 (2)	0.64787 (6)	0.0130 (4)
C2	0.7781 (3)	0.6005 (2)	0.59853 (6)	0.0101 (3)
C3	0.9401 (3)	0.7544 (2)	0.61585 (6)	0.0101 (3)
C4	1.0569 (3)	0.6623 (2)	0.66013 (6)	0.0118 (4)
H4	1.179 (3)	0.591 (3)	0.6515 (7)	0.014*
C5	1.0939 (3)	0.8288 (2)	0.69651 (7)	0.0143 (4)
H5	1.068 (3)	0.790 (3)	0.7284 (8)	0.017*
C6	0.9307 (3)	0.9816 (3)	0.68001 (7)	0.0163 (4)
O1	0.5875 (2)	0.39178 (19)	0.65771 (5)	0.0213 (3)
O2	0.5917 (2)	0.68214 (18)	0.57932 (5)	0.0152 (3)
O3	1.0843 (2)	0.82586 (17)	0.58160 (5)	0.0132 (3)
O4	0.8989 (2)	0.52687 (17)	0.68067 (4)	0.0146 (3)
O5	1.3044 (2)	0.9069 (2)	0.69025 (5)	0.0168 (3)
O6	0.81153 (19)	0.90096 (17)	0.63873 (4)	0.0133 (3)
S2	0.89769 (6)	0.42594 (6)	0.555030 (14)	0.01075 (10)
O21	1.0867 (2)	0.35166 (17)	0.58032 (5)	0.0163 (3)
O22	0.7275 (2)	0.28416 (18)	0.54814 (4)	0.0170 (3)
O23	0.9402 (2)	0.53401 (17)	0.50966 (4)	0.0144 (3)
O8	0.8855 (2)	0.9517 (2)	0.50022 (5)	0.0136 (3)
O9	0.4146 (3)	0.2464 (2)	0.74597 (5)	0.0243 (3)
H6A	1.006 (4)	1.106 (3)	0.6699 (7)	0.018 (5)*
H6B	0.828 (4)	1.008 (3)	0.7059 (8)	0.023 (6)*
H2O	0.548 (4)	0.623 (4)	0.5572 (9)	0.034 (7)*
H3O	1.013 (4)	0.860 (4)	0.5587 (9)	0.036 (7)*
H5O	1.375 (5)	0.847 (4)	0.7033 (10)	0.032 (8)*
H8OA	0.856 (4)	1.063 (5)	0.5060 (10)	0.049 (9)*
H8OB	0.775 (4)	0.904 (4)	0.4948 (9)	0.028 (7)*
H9OA	0.377 (5)	0.146 (5)	0.7374 (11)	0.048 (9)*
H9OB	0.468 (5)	0.296 (4)	0.7205 (11)	0.042 (8)*

	U11	U22	U33	U12	U13	U23
K	0.01291 (17)	0.01296 (18)	0.01436 (18)	−0.00271 (16)	0.00075 (14)	−0.00059 (14)
C1	0.0148 (8)	0.0111 (8)	0.0130 (8)	0.0003 (7)	0.0025 (7)	−0.0026 (7)
C2	0.0099 (7)	0.0094 (8)	0.0111 (8)	0.0005 (7)	0.0002 (6)	−0.0016 (7)
C3	0.0109 (8)	0.0088 (8)	0.0107 (7)	−0.0001 (7)	0.0014 (7)	−0.0007 (6)
C4	0.0121 (9)	0.0111 (8)	0.0121 (8)	−0.0016 (8)	−0.0005 (7)	0.0008 (6)
C5	0.0165 (9)	0.0167 (9)	0.0099 (8)	−0.0046 (8)	−0.0013 (8)	−0.0007 (7)
C6	0.0160 (9)	0.0157 (9)	0.0174 (9)	−0.0009 (8)	−0.0012 (8)	−0.0078 (7)
O1	0.0230 (7)	0.0234 (7)	0.0174 (6)	−0.0114 (7)	0.0046 (6)	0.0005 (5)
O2	0.0115 (6)	0.0157 (6)	0.0183 (6)	0.0036 (6)	−0.0058 (5)	−0.0063 (5)
O3	0.0132 (6)	0.0137 (6)	0.0127 (6)	−0.0036 (6)	−0.0014 (5)	0.0029 (5)
O4	0.0188 (6)	0.0121 (6)	0.0129 (6)	−0.0036 (6)	−0.0004 (5)	0.0021 (4)
O5	0.0132 (6)	0.0164 (7)	0.0208 (7)	−0.0017 (6)	−0.0064 (5)	0.0006 (6)
O6	0.0139 (6)	0.0109 (6)	0.0152 (6)	0.0020 (5)	−0.0032 (5)	−0.0045 (5)
S2	0.0124 (2)	0.00826 (19)	0.01156 (19)	−0.00009 (19)	0.00120 (15)	−0.00172 (16)
O21	0.0160 (6)	0.0148 (6)	0.0183 (6)	0.0044 (6)	−0.0009 (6)	−0.0006 (5)
O22	0.0191 (7)	0.0127 (6)	0.0192 (7)	−0.0032 (6)	0.0028 (5)	−0.0036 (5)
O23	0.0178 (6)	0.0140 (6)	0.0115 (6)	−0.0013 (5)	0.0032 (5)	−0.0011 (5)
O8	0.0131 (7)	0.0118 (7)	0.0158 (6)	−0.0009 (6)	−0.0007 (5)	−0.0020 (5)
O9	0.0335 (8)	0.0240 (8)	0.0154 (7)	−0.0131 (7)	0.0015 (7)	−0.0031 (6)

K—O22	2.6757 (13)	C5—C6	1.531 (3)
K—O3i	2.7259 (13)	C5—H5	0.91 (2)
K—O23ii	2.8243 (12)	C6—O6	1.443 (2)
K—O2iii	2.8466 (13)	C6—H6A	1.02 (2)
K—O6iii	2.8934 (12)	C6—H6B	0.96 (2)
K—O5i	2.9356 (14)	O2—Kv	2.8466 (13)
K—O21iv	2.9455 (13)	O2—H2O	0.77 (3)
K—O1	3.0265 (13)	O3—Kvi	2.7259 (13)
C1—O1	1.204 (2)	O3—H3O	0.79 (3)
C1—O4	1.344 (2)	O5—Kvi	2.9356 (14)
C1—C2	1.537 (2)	O5—H5O	0.70 (3)
C2—O2	1.387 (2)	O6—Kv	2.8934 (12)
C2—C3	1.538 (2)	S2—O21	1.4495 (13)
C2—S2	1.8364 (17)	S2—O23	1.4517 (12)
C3—O3	1.374 (2)	S2—O22	1.4547 (13)
C3—O6	1.430 (2)	O21—Kvii	2.9455 (13)
C3—C4	1.529 (2)	O23—Kviii	2.8243 (12)
C4—O4	1.465 (2)	O8—H8OA	0.81 (3)
C4—C5	1.528 (2)	O8—H8OB	0.78 (3)
C4—H4	0.94 (2)	O9—H9OA	0.77 (3)
C5—O5	1.425 (2)	O9—H9OB	0.83 (3)
O22—K—O3i	147.16 (4)	O4—C4—C5	110.19 (13)
O22—K—O23ii	71.91 (4)	O4—C4—C3	103.95 (13)
O3i—K—O23ii	76.47 (4)	C5—C4—C3	104.51 (14)
O22—K—O2iii	103.48 (4)	O4—C4—H4	107.4 (12)
O3i—K—O2iii	72.73 (4)	C5—C4—H4	115.7 (12)
O23ii—K—O2iii	69.45 (4)	C3—C4—H4	114.5 (12)
O22—K—O6iii	81.39 (4)	O5—C5—C4	110.47 (15)
O3i—K—O6iii	117.19 (4)	O5—C5—C6	108.10 (14)
O23ii—K—O6iii	107.71 (4)	C4—C5—C6	103.82 (14)
O2iii—K—O6iii	53.58 (4)	O5—C5—H5	112.8 (13)
O22—K—O5i	142.42 (4)	C4—C5—H5	110.3 (13)
O3i—K—O5i	70.30 (4)	C6—C5—H5	110.9 (13)
O23ii—K—O5i	141.38 (4)	O6—C6—C5	107.03 (13)
O2iii—K—O5i	82.15 (4)	O6—C6—H6A	111.1 (11)
O6iii—K—O5i	72.30 (4)	C5—C6—H6A	111.1 (12)
O22—K—O21iv	93.52 (4)	O6—C6—H6B	106.8 (13)
O3i—K—O21iv	79.86 (4)	C5—C6—H6B	111.2 (13)
O23ii—K—O21iv	93.87 (3)	H6A—C6—H6B	109.5 (18)
O2iii—K—O21iv	150.46 (4)	C1—O1—K	124.25 (11)
O6iii—K—O21iv	154.80 (4)	C2—O2—Kv	128.65 (10)
O5i—K—O21iv	98.99 (4)	C2—O2—H2O	111.5 (19)
O22—K—O1	66.75 (4)	Kv—O2—H2O	117.6 (19)
O3i—K—O1	140.41 (4)	C3—O3—Kvi	131.24 (10)
O23ii—K—O1	137.02 (4)	C3—O3—H3O	105.2 (19)
O2iii—K—O1	131.13 (4)	Kvi—O3—H3O	110.0 (19)
O6iii—K—O1	77.58 (4)	C1—O4—C4	111.14 (13)
O5i—K—O1	81.47 (4)	C5—O5—Kvi	119.38 (10)
O21iv—K—O1	77.75 (4)	C5—O5—H5O	107 (2)
O1—C1—O4	122.44 (16)	Kvi—O5—H5O	120 (2)
O1—C1—C2	126.35 (16)	C3—O6—C6	108.47 (13)
O4—C1—C2	111.20 (14)	C3—O6—Kv	123.35 (9)
O2—C2—C1	112.80 (14)	C6—O6—Kv	126.50 (10)
O2—C2—C3	112.01 (14)	O21—S2—O23	115.28 (8)
C1—C2—C3	100.35 (13)	O21—S2—O22	114.05 (8)
O2—C2—S2	111.76 (11)	O23—S2—O22	112.00 (7)
C1—C2—S2	106.78 (11)	O21—S2—C2	105.36 (7)
C3—C2—S2	112.53 (11)	O23—S2—C2	105.37 (7)
O3—C3—O6	113.20 (13)	O22—S2—C2	103.37 (7)
O3—C3—C4	111.05 (14)	S2—O21—Kvii	151.80 (7)
O6—C3—C4	103.23 (12)	S2—O22—K	146.08 (7)
O3—C3—C2	118.36 (13)	S2—O23—Kviii	133.30 (7)
O6—C3—C2	104.85 (13)	H8OA—O8—H8OB	104 (3)
C4—C3—C2	104.75 (13)	H9OA—O9—H9OB	105 (3)
O1—C1—C2—O2	40.4 (2)	C2—C3—O3—Kvi	−171.95 (10)
O4—C1—C2—O2	−138.58 (15)	O1—C1—O4—C4	−176.90 (16)
O1—C1—C2—C3	159.75 (17)	C2—C1—O4—C4	2.15 (18)
O4—C1—C2—C3	−19.25 (17)	C5—C4—O4—C1	127.76 (15)
O1—C1—C2—S2	−82.73 (19)	C3—C4—O4—C1	16.26 (17)
O4—C1—C2—S2	98.27 (14)	C4—C5—O5—Kvi	59.03 (16)
O2—C2—C3—O3	−87.94 (18)	C6—C5—O5—Kvi	−53.94 (16)
C1—C2—C3—O3	152.15 (14)	O3—C3—O6—C6	−84.25 (16)
S2—C2—C3—O3	38.98 (18)	C4—C3—O6—C6	35.89 (17)
O2—C2—C3—O6	39.38 (16)	C2—C3—O6—C6	145.34 (13)
C1—C2—C3—O6	−80.53 (14)	O3—C3—O6—Kv	81.84 (15)
S2—C2—C3—O6	166.30 (10)	C4—C3—O6—Kv	−158.02 (9)
O2—C2—C3—C4	147.71 (14)	C2—C3—O6—Kv	−48.57 (15)
C1—C2—C3—C4	27.80 (16)	C5—C6—O6—C3	−23.76 (18)
S2—C2—C3—C4	−85.37 (14)	C5—C6—O6—Kv	170.70 (10)
O3—C3—C4—O4	−156.62 (13)	O2—C2—S2—O21	−179.15 (11)
O6—C3—C4—O4	81.78 (14)	C1—C2—S2—O21	−55.36 (13)
C2—C3—C4—O4	−27.74 (16)	C3—C2—S2—O21	53.81 (13)
O3—C3—C4—C5	87.81 (16)	O2—C2—S2—O23	58.52 (13)
O6—C3—C4—C5	−33.79 (17)	C1—C2—S2—O23	−177.69 (11)
C2—C3—C4—C5	−143.31 (14)	C3—C2—S2—O23	−68.53 (12)
O4—C4—C5—O5	152.70 (14)	O2—C2—S2—O22	−59.16 (13)
C3—C4—C5—O5	−96.18 (16)	C1—C2—S2—O22	64.63 (12)
O4—C4—C5—C6	−91.63 (16)	C3—C2—S2—O22	173.79 (11)
C3—C4—C5—C6	19.50 (18)	O23—S2—O21—Kvii	−81.35 (17)
O5—C5—C6—O6	118.72 (15)	O22—S2—O21—Kvii	50.28 (18)
C4—C5—C6—O6	1.37 (18)	C2—S2—O21—Kvii	162.95 (15)
O4—C1—O1—K	−129.43 (14)	O21—S2—O22—K	67.79 (15)
C2—C1—O1—K	51.7 (2)	O23—S2—O22—K	−159.00 (12)
O22—K—O1—C1	−10.21 (13)	C2—S2—O22—K	−46.05 (15)
O3i—K—O1—C1	−166.47 (13)	O3i—K—O22—S2	170.05 (11)
O23ii—K—O1—C1	−27.09 (16)	O23ii—K—O22—S2	−173.73 (14)
O2iii—K—O1—C1	77.60 (15)	O2iii—K—O22—S2	−110.99 (14)
O6iii—K—O1—C1	75.65 (14)	O6iii—K—O22—S2	−61.82 (14)
O5i—K—O1—C1	149.28 (14)	O5i—K—O22—S2	−16.32 (18)
O21iv—K—O1—C1	−109.51 (14)	O21iv—K—O22—S2	93.35 (14)
C1—C2—O2—Kv	93.66 (15)	O1—K—O22—S2	18.29 (13)
C3—C2—O2—Kv	−18.67 (18)	O21—S2—O23—Kviii	98.09 (10)
S2—C2—O2—Kv	−146.01 (8)	O22—S2—O23—Kviii	−34.51 (11)
O6—C3—O3—Kvi	64.81 (18)	C2—S2—O23—Kviii	−146.21 (9)
C4—C3—O3—Kvi	−50.77 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O8ix	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···O9x	0.70 (3)	2.01 (3)	2.684 (2)	162 (3)
O8—H8OA···O22v	0.81 (3)	2.07 (3)	2.8141 (18)	155 (3)
O8—H8OB···O23ix	0.78 (3)	2.13 (3)	2.7798 (18)	142 (2)
O9—H9OA···O5i	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)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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) ; (ii) ; (iii) ; (iv) .