Crystal structure of potassium (1S)-d-lyxit-1-yl-sulfonate monohydrate.

The title compound, K(+)·C5H11O8S(-)·H2O [systematic name: potassium (1S,2S,3S,4R)-1,2,3,4,5-penta-hydroxy-pentane-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 hy-droxy-methyl 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 inter-molecular O-H⋯O hydrogen bonding.

Chemical context

In aqueous solution, the bis­ulfite anion HSO3 − exists in a complex, pH-dependent equilibrium with sulfurous acid H2SO3 and the sulfite anion SO3 2−. 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.

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.

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 + , −y + , −z + 1; (3) −x + , y + , −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 + , y − , −z + 1; (11) −x + , y + , −z; (12) −x + , y − , −z.]

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1OO9i	0.80(3)	1.90(3)	2.6716(19)	160(2)
O2H2OO1i	0.77(3)	2.35(3)	2.9810(17)	141(2)
O2H2OO11	0.77(3)	2.41(2)	2.9935(16)	134(2)
O3H3OO4ii	0.85(3)	1.91(3)	2.7609(17)	173(3)
O4H4OO2iii	0.76(3)	2.17(3)	2.8586(17)	151(3)
O5H5OO13iv	0.78(3)	2.03(3)	2.7152(17)	146(2)
O9H9AO5v	0.81(3)	1.95(3)	2.7426(18)	167(3)
O9H9BO12vi	0.84(3)	1.90(3)	2.7289(17)	170(3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

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.

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.

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 (δC 82.20) and minor (δC 84.26) adducts in the ratios of 17.05 : 5.43 : 71.32 : 6.20, respectively.

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 Me 3COH at δH 1.24): δH 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: δH 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: δH 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 Me 3COH at δC 30.29): δC 94.86 (C1, β-pyran­ose), 94.70 (C1, α-pyran­ose); signals for the major acyclic sulfonate: δC 82.20 (C1), 70.45, 69.88, 69.35 (C2, C3, C4), 63.80 (C5); the minor acyclic sulfonate showed a peak at δC 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.

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+C5H11O8SH2O
M r	288.31
Crystal system, space group	Orthorhombic, P21212
Temperature (K)	140
a, b, c ()	23.3536(5), 9.0434(2), 4.9939(1)
V (3)	1054.69(4)
Z	4
Radiation type	Mo K
(mm1)	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 > 2(I)] reflections	20712, 3062, 3008
R int	0.023
(sin /)max (1)	0.703
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.018, 0.048, 1.12
No. of reflections	3062
No. of parameters	198
H-atom treatment	All H-atom parameters refined
max, min (e 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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015014139/lh5775sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014139/lh5775Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015014139/lh5775Isup3.cml

CCDC reference: 1415264

Additional supporting information: crystallographic information; 3D view; checkCIF report

K+·C5H11O8S−·H2O	Dx = 1.816 Mg m−3
Mr = 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

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	Rint = 0.023
Detector resolution: 16.0050 pixels mm-1	θmax = 30.0°, θmin = 3.5°
Thin slice φ and ω scans	h = −32→32
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→12
Tmin = 0.914, Tmax = 1.000	l = −7→7
20712 measured reflections

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(Fo2) + (0.0253P)2 + 0.2102P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.048	(Δ/σ)max = 0.001
S = 1.12	Δρmax = 0.30 e Å−3
3062 reflections	Δρmin = −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

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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—O11iv	3.1131 (12)	C4—O4	1.4281 (18)
K1—O11v	3.1131 (12)	C4—C5	1.522 (2)
K1—O13iv	3.3824 (13)	C4—H4	0.95 (2)
K1—O13v	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—O12vi	2.7787 (12)	O2—H2O	0.77 (3)
K2—O9	2.8002 (14)	O3—H3O	0.85 (3)
K2—O9vi	2.8003 (14)	O4—H4O	0.76 (3)
K2—O11v	2.8149 (12)	O5—K1x	2.8505 (11)
K2—O11vii	2.8149 (12)	O5—H5O	0.78 (3)
K2—O1	2.9854 (12)	S1—O11	1.4579 (11)
K2—O1vi	2.9855 (12)	S1—O13	1.4650 (11)
K2—K1viii	4.5246 (1)	S1—O12	1.4665 (11)
K2—K2v	4.9939 (1)	S1—K1ix	3.6713 (5)
K2—K2ix	4.9939 (1)	O11—K2ix	2.8149 (12)
K2—H9B	3.02 (3)	O11—K1ix	3.1131 (12)
C1—O1	1.3998 (18)	O13—K1ix	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)	O9vi—K2—K1viii	116.12 (3)
O12i—K1—O5ii	109.61 (3)	O11v—K2—K1viii	139.74 (2)
O12—K1—O5ii	86.51 (3)	O11vii—K2—K1viii	42.75 (2)
O12i—K1—O5iii	86.51 (3)	O1—K2—K1viii	98.25 (2)
O12—K1—O5iii	109.61 (3)	O1vi—K2—K1viii	80.05 (2)
O5ii—K1—O5iii	150.43 (6)	K1—K2—K1viii	175.911 (17)
O12i—K1—O13	80.20 (3)	O12—K2—K2v	127.14 (3)
O12—K1—O13	49.96 (3)	O12vi—K2—K2v	127.14 (3)
O5ii—K1—O13	133.00 (4)	O9—K2—K2v	47.55 (3)
O5iii—K1—O13	72.75 (3)	O9vi—K2—K2v	47.55 (3)
O12i—K1—O13i	49.96 (3)	O11v—K2—K2v	66.13 (2)
O12—K1—O13i	80.20 (3)	O11vii—K2—K2v	66.13 (2)
O5ii—K1—O13i	72.76 (3)	O1—K2—K2v	114.35 (3)
O5iii—K1—O13i	133.00 (4)	O1vi—K2—K2v	114.35 (3)
O13—K1—O13i	81.87 (5)	K1—K2—K2v	92.044 (9)
O12i—K1—O11iv	61.01 (3)	K1viii—K2—K2v	92.044 (9)
O12—K1—O11iv	159.17 (3)	O12—K2—K2ix	52.86 (3)
O5ii—K1—O11iv	76.81 (3)	O12vi—K2—K2ix	52.86 (3)
O5iii—K1—O11iv	90.86 (3)	O9—K2—K2ix	132.45 (3)
O13—K1—O11iv	138.92 (3)	O9vi—K2—K2ix	132.45 (3)
O13i—K1—O11iv	82.96 (3)	O11v—K2—K2ix	113.87 (2)
O12i—K1—O11v	159.16 (3)	O11vii—K2—K2ix	113.87 (2)
O12—K1—O11v	61.01 (3)	O1—K2—K2ix	65.65 (3)
O5ii—K1—O11v	90.86 (3)	O1vi—K2—K2ix	65.65 (3)
O5iii—K1—O11v	76.81 (3)	K1—K2—K2ix	87.956 (9)
O13—K1—O11v	82.96 (3)	K1viii—K2—K2ix	87.956 (9)
O13i—K1—O11v	138.92 (3)	K2v—K2—K2ix	180.0
O11iv—K1—O11v	130.61 (4)	O12—K2—H9B	145.3 (6)
O12i—K1—O13iv	103.91 (3)	O12vi—K2—H9B	96.3 (6)
O12—K1—O13iv	130.41 (3)	O9—K2—H9B	16.1 (6)
O5ii—K1—O13iv	50.78 (3)	O9vi—K2—H9B	85.4 (6)
O5iii—K1—O13iv	102.19 (3)	O11v—K2—H9B	83.3 (6)
O13—K1—O13iv	173.46 (3)	O11vii—K2—H9B	59.4 (6)
O13i—K1—O13iv	104.67 (3)	O1—K2—H9B	94.0 (6)
O11iv—K1—O13iv	43.74 (3)	O1vi—K2—H9B	124.5 (6)
O11v—K1—O13iv	91.89 (3)	K1—K2—H9B	123.1 (6)
O12i—K1—O13v	130.41 (3)	K1viii—K2—H9B	60.6 (6)
O12—K1—O13v	103.91 (3)	K2v—K2—H9B	39.5 (6)
O5ii—K1—O13v	102.19 (3)	K2ix—K2—H9B	140.5 (6)
O5iii—K1—O13v	50.78 (3)	O1—C1—C2	113.41 (12)
O13—K1—O13v	104.67 (3)	O1—C1—S1	112.02 (10)
O13i—K1—O13v	173.46 (3)	C2—C1—S1	110.00 (10)
O11iv—K1—O13v	91.89 (3)	O1—C1—H1	108.2 (12)
O11v—K1—O13v	43.74 (3)	C2—C1—H1	107.6 (11)
O13iv—K1—O13v	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)
O11iv—K1—S1i	67.69 (2)	O3—C3—C2	105.10 (11)
O11v—K1—S1i	161.09 (2)	O3—C3—C4	110.15 (12)
O13iv—K1—S1i	102.79 (2)	C2—C3—C4	112.67 (12)
O13v—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)
O11iv—K1—S1	161.09 (2)	C5—C4—H4	111.7 (14)
O11v—K1—S1	67.69 (2)	C3—C4—H4	109.1 (13)
O13iv—K1—S1	153.82 (2)	O5—C5—C4	113.00 (13)
O13v—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—O12vi	105.71 (5)	O5—C5—H5B	110.5 (13)
O12—K2—O9	130.48 (3)	C4—C5—H5B	109.7 (13)
O12vi—K2—O9	99.55 (3)	H5A—C5—H5B	105.5 (19)
O12—K2—O9vi	99.55 (3)	C1—O1—K2	119.01 (9)
O12vi—K2—O9vi	130.48 (3)	C1—O1—H1O	110.1 (19)
O9—K2—O9vi	95.09 (6)	K2—O1—H1O	95.8 (18)
O12—K2—O11v	65.36 (3)	C2—O2—H2O	110.5 (18)
O12vi—K2—O11v	154.90 (3)	C3—O3—H3O	108.4 (18)
O9—K2—O11v	73.70 (4)	C4—O4—H4O	113 (2)
O9vi—K2—O11v	74.59 (4)	C5—O5—K1x	130.19 (10)
O12—K2—O11vii	154.90 (3)	C5—O5—H5O	107.9 (17)
O12vi—K2—O11vii	65.36 (3)	K1x—O5—H5O	89.8 (17)
O9—K2—O11vii	74.59 (4)	O11—S1—O13	112.64 (7)
O9vi—K2—O11vii	73.70 (4)	O11—S1—O12	112.71 (7)
O11v—K2—O11vii	132.26 (5)	O13—S1—O12	111.46 (7)
O12—K2—O1	60.09 (3)	O11—S1—C1	107.93 (7)
O12vi—K2—O1	90.03 (3)	O13—S1—C1	104.94 (7)
O9—K2—O1	78.33 (4)	O12—S1—C1	106.60 (7)
O9vi—K2—O1	139.37 (4)	O11—S1—K1	142.67 (5)
O11v—K2—O1	65.03 (3)	O13—S1—K1	58.23 (5)
O11vii—K2—O1	139.10 (3)	O12—S1—K1	54.30 (5)
O12—K2—O1vi	90.03 (3)	C1—S1—K1	109.38 (5)
O12vi—K2—O1vi	60.10 (3)	O11—S1—K1ix	56.47 (5)
O9—K2—O1vi	139.37 (4)	O13—S1—K1ix	67.11 (5)
O9vi—K2—O1vi	78.33 (4)	O12—S1—K1ix	101.22 (5)
O11v—K2—O1vi	139.10 (3)	C1—S1—K1ix	151.95 (5)
O11vii—K2—O1vi	65.03 (3)	K1—S1—K1ix	89.650 (8)
O1—K2—O1vi	131.29 (5)	S1—O11—K2ix	130.34 (7)
O12—K2—K1	36.31 (2)	S1—O11—K1ix	100.55 (6)
O12vi—K2—K1	139.71 (3)	K2ix—O11—K1ix	99.38 (3)
O9—K2—K1	116.12 (3)	S1—O12—K2	130.00 (6)
O9vi—K2—K1	66.92 (3)	S1—O12—K1	100.69 (6)
O11v—K2—K1	42.75 (2)	K2—O12—K1	107.94 (4)
O11vii—K2—K1	139.74 (2)	S1—O13—K1	96.48 (6)
O1—K2—K1	80.05 (2)	S1—O13—K1ix	89.37 (5)
O1vi—K2—K1	98.25 (2)	K1—O13—K1ix	104.67 (3)
O12—K2—K1viii	139.71 (3)	K2—O9—H9A	105 (2)
O12vi—K2—K1viii	36.31 (2)	K2—O9—H9B	97 (2)
O9—K2—K1viii	66.92 (3)	H9A—O9—H9B	102 (3)
O1—C1—C2—O2	−44.09 (16)	O13—S1—O11—K2ix	150.63 (7)
S1—C1—C2—O2	82.24 (13)	O12—S1—O11—K2ix	23.46 (10)
O1—C1—C2—C3	75.92 (15)	C1—S1—O11—K2ix	−93.99 (9)
S1—C1—C2—C3	−157.75 (10)	K1—S1—O11—K2ix	83.82 (10)
O2—C2—C3—O3	−169.41 (11)	K1ix—S1—O11—K2ix	112.07 (8)
C1—C2—C3—O3	68.67 (14)	O13—S1—O11—K1ix	38.57 (7)
O2—C2—C3—C4	−49.45 (15)	O12—S1—O11—K1ix	−88.61 (6)
C1—C2—C3—C4	−171.36 (11)	C1—S1—O11—K1ix	153.94 (5)
O3—C3—C4—O4	60.33 (15)	K1—S1—O11—K1ix	−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)	K1ix—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—K1x	159.72 (9)	C1—S1—O12—K1	−102.24 (6)
O1—C1—S1—O11	84.07 (12)	K1ix—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)	K1ix—S1—O13—K1	−104.69 (4)
C2—C1—S1—O12	−164.36 (10)	O11—S1—O13—K1ix	−34.34 (6)
O1—C1—S1—K1	−94.52 (10)	O12—S1—O13—K1ix	93.50 (6)
C2—C1—S1—K1	138.37 (8)	C1—S1—O13—K1ix	−151.50 (5)
O1—C1—S1—K1ix	135.22 (9)	K1—S1—O13—K1ix	104.69 (4)
C2—C1—S1—K1ix	8.11 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O9ix	0.80 (3)	1.90 (3)	2.6716 (19)	160 (2)
O2—H2O···O1ix	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···O4v	0.85 (3)	1.91 (3)	2.7609 (17)	173 (3)
O4—H4O···O2xi	0.76 (3)	2.17 (3)	2.8586 (17)	151 (3)
O5—H5O···O13xii	0.78 (3)	2.03 (3)	2.7152 (17)	146 (2)
O9—H9A···O5x	0.81 (3)	1.95 (3)	2.7426 (18)	167 (3)
O9—H9B···O12vii	0.84 (3)	1.90 (3)	2.7289 (17)	170 (3)