2-Phenyl­ethyl 1-thio-β-d-galactopyran­oside hemihydrate

Brito, I.; Szilágyi, L.; Kumar, A.A.; Albanez, J.; Bolte, M.

doi:10.1107/S1600536811031667

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages o2308-o2309

doi:10.1107/S1600536811031667

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2-Phenylethyl 1-thio-β-D-galactopyranoside hemihydrate

Iván Brito,^a ^* László Szilágyi,^b Ambati Ashok Kumar,^b Joselyn Albanez ^a and Michael Bolte ^c

^aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, ^bDepartment of Organic Chemistry, University of Debrecen, H-4010 Debrecen Pf 20., Hungary, and ^cInstitut für Anorganische Chemie der Goethe–Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 25 July 2011; accepted 5 August 2011; online 11 August 2011)

The title compound, C₁₄H₂₀O₅S·0.5H₂O, crystallizes with two organic molecules and a solvent water molecule in the asymmetric unit. In both molecules, the hexapyranosyl rings adopt a slightly distorted chair conformation (⁵C₂) with four substituents in equatorial positions and one substituent in an axial position. The main difference between the organic molecules is the dihedral angle between the phenyl ring and the best plane defined by the O—C₁—C₂—C₃ atoms (r.m.s deviations = 0.003 and 0.043 Å) of the hexapyranosyl rings [47.4 (4) and 86.5 (4)°]. In the asymmetric unit, molecules are linked by two strong O—H⋯O hydrogen bonds. In the crystal, the components are linked by a total of 10 distinct O—H⋯O hydrogen bonds, resulting in the formation of a two-dimensional network parallel to the ab plane.

Related literature

For synthetic methods see: Helferich & Türk (1956 ). For pharmacological properties of the title compound, see: De Bruyne et al. (1977 ); Choi et al. (2003 ). Gutiérrez et al. (2011 ). For puckering parameters see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₄H₂₀O₅S·0.5H₂O
M_r = 309.37
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.8358 (4) Å
b = 14.8218 (16) Å
c = 41.390 (3) Å
V = 2966.6 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 173 K
0.20 × 0.09 × 0.08 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 200; Blessing, 1995 ) T_min = 0.954, T_max = 0.981
14206 measured reflections
5217 independent reflections
2395 reflections with I > 2σ(I)
R_int = 0.169

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.117
S = 0.68
5217 reflections
377 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 2269 Friedel pairs
Flack parameter: −0.25 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O31—H31⋯O1W	0.84	1.92	2.759 (7)	179
O41—H41⋯O41A	0.84	1.95	2.779 (7)	169
O51—H51⋯O1Wⁱ	0.84	1.98	2.773 (6)	156
O61—H61⋯O31Aⁱⁱ	0.84	1.86	2.697 (7)	172
O31A—H31A⋯O61ⁱⁱⁱ	0.84	1.92	2.650 (7)	145
O41A—H41A⋯O41^iv	0.84	2.05	2.788 (7)	147
O51A—H51A⋯O61A^v	0.84	2.10	2.785 (7)	138
O61A—H61A⋯O31ⁱⁱ	0.84	2.02	2.744 (6)	145
O1W—H1WA⋯O31^v	0.84	2.23	2.989 (8)	150
O1W—H1WB⋯O41A^v	0.84	2.43	3.270 (6)	180
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x+1, y, z; (v) x-1, y, z.

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009)'.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031667/om2454sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031667/om2454Isup2.hkl

checkCIF report

Comment top

2-Phenylethyl-1-thio-β-D-galactopyranoside is one of the most potent inhibitors of β-galactosidase (EC 3.2.1.23) (De Bruyne, et al., 1977) and a radiologically labeled derivative has also been used for imaging of LacZ gene expression. (Choi et al., 2003). It was recently found to be moderately active in tests against Trypanosoma cruzi, the causal agent of Chagas disease (Gutiérrez et al., 2011). In the title compound, it crystallizes with two organic molecules and a solvent water molecule in the asymmetric unit, Fig. 1. In both molecules the hexapyranosyl rings adopts a slightly distorted chair conformation (⁵C₂) (Q_T= 0.574 (6) Å, θ= 3.4 (6)°, ϕ₂ = 8(9)°; Q_T= 0.587 (6) Å, θ= 9.2 (7)°, ϕ₂ = 299 (4)° for both molecules respectively), (Cremer & Pople, 1975) with four substituents in equatorial positions and one substituent in an axial position. The main difference between the organic molecules is the dihedral angle between the phenyl ring and the best plane defined by the atoms O1/C2/C3/C4 and O1A/C2A/C3A/C4A (r.m.s deviation 0.003 Å; 0.043Å respectively), of the hexapyranosyl rings [47.4 (4) and 86.5 (4)°]. The max. deviation for the best planes of the hexapyranosyl rings are: 0.290 (7)Å and 0.050 (6) Å) for molecules A and B respectively. The mean bond distances are: C—O 1.425 (7) Å, Csp3—Csp3 1.524 (9)Å and aromatic C—C 1.386 (11) Å. In the asymmetric unit the three molecules are linked by two strong O— H···O hydrogen bonds and the crystal packing is stabilized by eight O— H···O hydrogen bonding leading to the formation of a two-dimensional network parallel to the ab plane, Fig. 2, Table 1.

Related literature top

For synthetic methods see: Helferich & Türk (1956). For pharmacological properties of the title compound, see: De Bruyne et al. (1977); Choi et al. (2003). Gutiérrez et al. (2011). For puckering parameters see: Cremer & Pople (1975).

Experimental top

1-thio-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose(0.364 g,1 mmol) was dissolved in acetonitrile (2 ml) and 1-bromo-2-phenylethane (0.185 g, 1 mmol) and triethyl amine (242µl, 2 mmol) added. The reaction mixture was stirred at RT until disappearence of the starting materials (TLC, 60 min). The solvent was removed under reduced pressure, and the residue purified by column chromatography (EtOAc: hexane - 8: 2) to give 2-phenylethyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside (1). Syrup, 402 mg (86%). [α]_D -22.9(CHCl₃,c 0.15), Lit. (Helferich & Türk, 1956). [α]_D -19.2 (CHCl₃). HR—MS:m/z calcd. for C₂₂H₂₈O₉S[M+Na]⁺: 491.135. Found: 491.138. ¹H-NMR (CDCl₃, 500 MHz): δ 7.20–7.35 (m,5H, Phenyl-H); 5.44 (br.s, 1H, H-4); 5.26 (t, 1H, H-2, J_2,3 9.9 Hz); 5.03 (br.d, 1H, H-3); 4.44 (d, 1H, H-1, J_1,2 10.1 Hz); 4.10–4.20 (m,2H, H-6a,b); 3.90 (m, 1H, H-5); 2.92 (m, 1H, S-CH_2a); 2.94 (m, 2H, Ph-CH₂); 3.00 (m, 1H, S-CH_{2 b});2.16, 2.06, 2.04,1.99 (s, 4x3H, 4x COCH₃);¹³C-NMR (CDCl₃, 125 MHz): δ 130.5 (Phenyl-C); 85.6 (C-1); 76.5(C-5); 73.3 (C-3); 69.0 (C-4); 68.7 (C-2); 62.2 (C-6); 38.2 (Ph-CH₂); 33.1 (S-CH₂); 22.3 (4xCOCH₃). The product (0.300 g, 0.64 mmol) was deacetylated by treatment with catalytic amount of NaOMe in methanol. The reaction mixture was stirred at room temperature until completion (TLC 20 min). After neutralization with a cation exchanger (Amberlyst 15) the solvent was removed under reduced pressure and the title molecule, 2-phenylethyl- 1-thio-β-D-galactopyranoside, was isolated as a white solid (MeOH: EtOAc - 2:8), 185 mg (96.3%). [α]_D -22.4 (MeOH, c 0.11). Lit. (Helferich &Türk,1956) [α]_D -32.2 (MeOH). HR—MS: m/z calcd. for C₁₄H₂₀O₅S [M+Na]⁺:323.094. Found: 323.094.

¹H-NMR(CD₃OD, 500 MHz): δ 7.15–7.30 (m, 5H, Phenyl-H); 4.34 (d, 1H, H-1, J_1,2 9.6 Hz); 3.90 (dd, 1H,H-4, J_4,5 ~ 1 Hz); 3.77(dd, 1H, H-6a, J_{6a,6 b} 11.5 Hz, J_5,6a 6.6 Hz); 3.71(dd, 1H, H-6 b, J_{5,6 b} 5.3 Hz); 3.57 (t, 1H, H-2, J_2,3 9.6 Hz); 3.53(m, 1H, H-5); 3.46 (1H, dd, H-3, J_3,4 3.4 Hz);2.92 (m, 1H, S-CH_2a);2.95 (m, 2H, Ph-CH₂); 3.02(m, 1H, S-CH_{2 b}); ¹³C-NMR (CDCl₃, 125 MHz): δ 131.3, 131.0, 128.9 (Phenyl-C); 88.4 (C-1); 81.5 (C-5); 77.1 (C-3);72.3 (C-2); 71.3 (C-4); 63.5 (C-6); 38.6 (Ph-CH₂); 33.2 (S-CH₂). Colourless single crystals suitable for X-ray analysis were obtained by slow evaporation of an aqueous solution.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009)'.

Figures top

	Fig. 1. Perspective view of the asymmetric unit of the title compound, with the atom numbering. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. A Packing diagram, viewed down the c axis.

2-Phenylethyl 1-thio-β-D-galactopyranoside monohydrate top

Crystal data top

C₁₄H₂₀O₅S·0.5H₂O	F(000) = 1320
M_r = 309.37	D_x = 1.385 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3425 reflections
a = 4.8358 (4) Å	θ = 2.8–25.6°
b = 14.8218 (16) Å	µ = 0.24 mm⁻¹
c = 41.390 (3) Å	T = 173 K
V = 2966.6 (5) Å³	Needle, colourless
Z = 8	0.20 × 0.09 × 0.08 mm

Data collection top

Stoe IPDS II two-circle diffractometer	5217 independent reflections
Radiation source: fine-focus sealed tube	2395 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.169
ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (MULABS; Spek, 200; Blessing, 1995)	h = −4→5
T_min = 0.954, T_max = 0.981	k = −17→17
14206 measured reflections	l = −49→47

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0007P)²] where P = (F_o² + 2F_c²)/3
S = 0.68	(Δ/σ)_max = 0.001
5217 reflections	Δρ_max = 0.28 e Å⁻³
377 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2269 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.25 (16)

Crystal data top

C₁₄H₂₀O₅S·0.5H₂O	V = 2966.6 (5) Å³
M_r = 309.37	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.8358 (4) Å	µ = 0.24 mm⁻¹
b = 14.8218 (16) Å	T = 173 K
c = 41.390 (3) Å	0.20 × 0.09 × 0.08 mm

Data collection top

Stoe IPDS II two-circle diffractometer	5217 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 200; Blessing, 1995)	2395 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.981	R_int = 0.169
14206 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.117	Δρ_max = 0.28 e Å⁻³
S = 0.68	Δρ_min = −0.30 e Å⁻³
5217 reflections	Absolute structure: Flack (1983), 2269 Friedel pairs
377 parameters	Absolute structure parameter: −0.25 (16)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	0.3816 (4)	0.92470 (10)	0.85163 (4)	0.0217 (4)
O1	0.2305 (9)	0.7771 (2)	0.82113 (11)	0.0186 (11)
C2	0.1463 (14)	0.8684 (3)	0.82448 (14)	0.0171 (14)
H2	−0.0432	0.8697	0.8341	0.020*
C3	0.1355 (15)	0.9128 (3)	0.79134 (14)	0.0192 (15)
H3	0.3253	0.9114	0.7818	0.023*
C4	−0.0578 (14)	0.8611 (4)	0.76924 (14)	0.0150 (14)
H4	−0.2469	0.8656	0.7789	0.018*
C5	0.0165 (15)	0.7603 (4)	0.76836 (16)	0.0206 (17)
H5	−0.1313	0.7263	0.7566	0.025*
C6	0.0370 (14)	0.7259 (4)	0.80286 (15)	0.0176 (15)
H6	−0.1488	0.7321	0.8132	0.021*
C7	0.1644 (18)	0.9413 (4)	0.88681 (16)	0.0298 (18)
H7A	0.2706	0.9759	0.9031	0.036*
H7B	0.0036	0.9785	0.8804	0.036*
C8	0.0570 (17)	0.8546 (4)	0.90277 (18)	0.0335 (19)
H8A	−0.0909	0.8706	0.9183	0.040*
H8B	−0.0258	0.8156	0.8859	0.040*
C11	0.2787 (17)	0.8018 (4)	0.92039 (17)	0.0302 (19)
C12	0.3759 (19)	0.8276 (4)	0.95047 (17)	0.036 (2)
H12	0.3035	0.8805	0.9603	0.043*
C13	0.5745 (19)	0.7786 (5)	0.96658 (19)	0.040 (2)
H13	0.6369	0.7982	0.9872	0.049*
C14	0.684 (2)	0.7011 (4)	0.9531 (2)	0.044 (2)
H14	0.8212	0.6671	0.9641	0.053*
C15	0.588 (2)	0.6744 (5)	0.9230 (2)	0.050 (3)
H15	0.6588	0.6205	0.9137	0.060*
C16	0.395 (2)	0.7234 (4)	0.90633 (19)	0.042 (2)
H16	0.3392	0.7048	0.8854	0.050*
O31	0.0486 (12)	1.0048 (3)	0.79387 (11)	0.0352 (14)
H31	−0.0953	1.0262	0.7855	0.053*
O41	−0.0739 (10)	0.8992 (3)	0.73781 (10)	0.0234 (11)
H41	0.0863	0.9052	0.7303	0.035*
O51	0.2726 (10)	0.7497 (2)	0.75186 (12)	0.0239 (12)
H51	0.3191	0.6951	0.7521	0.036*
C61	0.1245 (16)	0.6275 (4)	0.80496 (16)	0.0254 (16)
H61B	0.0055	0.5902	0.7908	0.030*
H61C	0.3182	0.6210	0.7976	0.030*
O61	0.0999 (11)	0.5973 (3)	0.83768 (11)	0.0276 (11)
H61	0.2498	0.5739	0.8436	0.041*
S1A	0.1800 (4)	0.92289 (11)	0.58806 (4)	0.0207 (4)
O1A	0.4361 (10)	0.7963 (2)	0.62109 (10)	0.0185 (11)
C2A	0.4278 (15)	0.8930 (4)	0.61866 (14)	0.0174 (15)
H2A	0.6142	0.9150	0.6118	0.021*
C3A	0.3507 (14)	0.9383 (3)	0.65050 (15)	0.0162 (14)
H3A	0.1519	0.9264	0.6556	0.019*
C4A	0.5327 (14)	0.9033 (4)	0.67780 (14)	0.0166 (15)
H4A	0.7246	0.9268	0.6747	0.020*
C5A	0.5420 (14)	0.8010 (4)	0.67805 (16)	0.0170 (15)
H5A	0.6784	0.7805	0.6947	0.020*
C6A	0.6377 (15)	0.7696 (3)	0.64495 (15)	0.0171 (14)
H6A	0.8174	0.7998	0.6398	0.021*
C7A	0.3763 (16)	0.8986 (4)	0.55177 (15)	0.0246 (16)
H7A1	0.5560	0.9305	0.5526	0.030*
H7A2	0.4135	0.8330	0.5504	0.030*
C8A	0.2146 (16)	0.9289 (5)	0.52203 (15)	0.0298 (18)
H8A1	0.0333	0.8979	0.5216	0.036*
H8A2	0.1805	0.9946	0.5233	0.036*
C11A	0.3715 (16)	0.9077 (4)	0.49135 (15)	0.0265 (16)
C12A	0.5655 (18)	0.9652 (5)	0.47895 (18)	0.0323 (19)
H12A	0.6040	1.0207	0.4896	0.039*
C13A	0.7059 (17)	0.9425 (5)	0.45085 (19)	0.042 (2)
H13A	0.8432	0.9822	0.4426	0.050*
C14A	0.650 (2)	0.8640 (6)	0.43483 (19)	0.046 (2)
H14A	0.7484	0.8492	0.4157	0.055*
C15A	0.4537 (19)	0.8077 (5)	0.44622 (19)	0.039 (2)
H15A	0.4146	0.7536	0.4348	0.047*
C16A	0.3062 (18)	0.8271 (4)	0.47450 (17)	0.034 (2)
H16A	0.1666	0.7874	0.4822	0.041*
O31A	0.3948 (11)	1.0327 (2)	0.64734 (11)	0.0213 (10)
H31A	0.2432	1.0585	0.6437	0.032*
O41A	0.4250 (10)	0.9385 (3)	0.70761 (10)	0.0241 (11)
H41A	0.5551	0.9456	0.7208	0.036*
O51A	0.2770 (10)	0.7663 (3)	0.68599 (11)	0.0261 (12)
H51A	0.2409	0.7220	0.6740	0.039*
C61A	0.6753 (15)	0.6677 (4)	0.64172 (16)	0.0196 (15)
H61D	0.5043	0.6362	0.6484	0.023*
H61E	0.7153	0.6517	0.6190	0.023*
O61A	0.8991 (13)	0.6415 (3)	0.66183 (13)	0.0420 (15)
H61A	0.8688	0.5898	0.6693	0.063*
O1W	−0.4231 (11)	1.0767 (3)	0.76658 (13)	0.0445 (14)
H1WA	−0.5761	1.0770	0.7762	0.067*
H1WB	−0.4623	1.0412	0.7514	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0215 (10)	0.0253 (7)	0.0184 (9)	0.0002 (8)	−0.0020 (8)	−0.0018 (7)
O1	0.016 (3)	0.018 (2)	0.022 (3)	0.0012 (18)	−0.004 (2)	0.0002 (19)
C2	0.016 (4)	0.020 (3)	0.015 (4)	0.003 (3)	−0.001 (3)	0.002 (3)
C3	0.029 (4)	0.015 (3)	0.014 (3)	0.003 (3)	−0.005 (3)	−0.004 (2)
C4	0.012 (4)	0.024 (3)	0.009 (4)	0.004 (3)	0.003 (3)	0.006 (2)
C5	0.020 (4)	0.025 (3)	0.017 (4)	−0.003 (3)	0.003 (3)	−0.003 (3)
C6	0.019 (4)	0.017 (3)	0.017 (4)	−0.002 (3)	−0.001 (3)	−0.003 (3)
C7	0.038 (5)	0.035 (4)	0.017 (4)	0.004 (4)	0.000 (4)	0.000 (3)
C8	0.033 (5)	0.039 (4)	0.028 (5)	0.007 (4)	0.003 (4)	0.003 (3)
C11	0.041 (5)	0.024 (3)	0.025 (5)	−0.010 (3)	0.002 (4)	0.007 (3)
C12	0.044 (6)	0.038 (4)	0.024 (4)	0.011 (4)	0.011 (4)	0.002 (3)
C13	0.051 (6)	0.040 (4)	0.030 (5)	−0.010 (4)	0.004 (5)	0.008 (4)
C14	0.063 (7)	0.028 (4)	0.041 (5)	0.004 (4)	−0.013 (5)	0.007 (3)
C15	0.066 (7)	0.033 (4)	0.053 (6)	0.011 (5)	−0.001 (6)	−0.004 (4)
C16	0.062 (6)	0.034 (4)	0.029 (5)	−0.005 (4)	−0.013 (5)	−0.004 (3)
O31	0.055 (4)	0.021 (2)	0.029 (3)	0.020 (2)	−0.018 (3)	0.001 (2)
O41	0.021 (3)	0.029 (2)	0.021 (3)	0.000 (2)	−0.005 (2)	0.0035 (19)
O51	0.034 (3)	0.013 (2)	0.024 (3)	0.0057 (19)	0.002 (3)	0.0008 (19)
C61	0.019 (4)	0.024 (3)	0.033 (4)	−0.009 (3)	0.002 (4)	0.001 (3)
O61	0.023 (3)	0.028 (2)	0.032 (3)	0.001 (2)	0.002 (2)	0.0133 (19)
S1A	0.0180 (9)	0.0286 (8)	0.0154 (9)	0.0032 (7)	−0.0022 (7)	−0.0005 (7)
O1A	0.020 (3)	0.0161 (19)	0.020 (3)	0.0050 (19)	−0.006 (2)	0.0004 (17)
C2A	0.017 (4)	0.021 (3)	0.014 (4)	0.002 (3)	−0.003 (3)	0.004 (2)
C3A	0.015 (4)	0.015 (3)	0.019 (3)	−0.003 (3)	0.000 (3)	−0.002 (3)
C4A	0.020 (4)	0.021 (3)	0.008 (3)	−0.005 (3)	−0.007 (3)	−0.002 (3)
C5A	0.014 (4)	0.019 (3)	0.018 (4)	−0.002 (3)	−0.002 (3)	0.002 (3)
C6A	0.015 (4)	0.018 (3)	0.019 (4)	0.003 (3)	−0.003 (3)	0.002 (3)
C7A	0.029 (4)	0.033 (3)	0.012 (4)	0.004 (3)	0.003 (4)	0.007 (3)
C8A	0.043 (5)	0.031 (3)	0.016 (4)	0.014 (4)	−0.003 (3)	−0.003 (3)
C11A	0.026 (4)	0.035 (4)	0.018 (4)	0.007 (4)	−0.006 (3)	0.001 (3)
C12A	0.034 (5)	0.035 (4)	0.028 (4)	0.002 (4)	−0.004 (4)	0.002 (3)
C13A	0.025 (5)	0.067 (5)	0.032 (5)	−0.001 (4)	0.004 (4)	0.016 (4)
C14A	0.042 (6)	0.074 (5)	0.022 (5)	0.023 (5)	0.000 (4)	0.000 (4)
C15A	0.044 (6)	0.042 (4)	0.032 (5)	0.013 (4)	0.005 (5)	−0.011 (4)
C16A	0.051 (6)	0.031 (4)	0.022 (4)	0.007 (4)	0.002 (4)	0.005 (3)
O31A	0.022 (3)	0.0197 (19)	0.023 (3)	−0.002 (2)	−0.008 (3)	0.002 (2)
O41A	0.032 (3)	0.027 (2)	0.014 (2)	−0.005 (2)	−0.003 (2)	−0.0025 (19)
O51A	0.029 (3)	0.028 (2)	0.021 (3)	−0.012 (2)	0.003 (2)	−0.001 (2)
C61A	0.020 (4)	0.021 (3)	0.018 (4)	0.001 (3)	0.003 (3)	0.000 (3)
O61A	0.050 (4)	0.019 (2)	0.057 (4)	0.005 (3)	−0.021 (3)	0.007 (2)
O1W	0.026 (3)	0.049 (3)	0.058 (4)	−0.015 (3)	0.005 (3)	−0.002 (3)

Geometric parameters (Å, º) top

S1—C2	1.804 (7)	S1A—C7A	1.813 (7)
S1—C7	1.812 (7)	O1A—C2A	1.437 (6)
O1—C2	1.420 (7)	O1A—C6A	1.443 (8)
O1—C6	1.422 (7)	C2A—C3A	1.526 (8)
C2—C3	1.522 (8)	C2A—H2A	1.0000
C2—H2	1.0000	C3A—O31A	1.421 (6)
C3—O31	1.432 (7)	C3A—C4A	1.523 (8)
C3—C4	1.516 (9)	C3A—H3A	1.0000
C3—H3	1.0000	C4A—O41A	1.437 (7)
C4—O41	1.420 (7)	C4A—C5A	1.517 (8)
C4—C5	1.537 (8)	C4A—H4A	1.0000
C4—H4	1.0000	C5A—O51A	1.419 (8)
C5—O51	1.423 (8)	C5A—C6A	1.519 (9)
C5—C6	1.519 (9)	C5A—H5A	1.0000
C5—H5	1.0000	C6A—C61A	1.527 (7)
C6—C61	1.521 (8)	C6A—H6A	1.0000
C6—H6	1.0000	C7A—C8A	1.525 (9)
C7—C8	1.535 (9)	C7A—H7A1	0.9900
C7—H7A	0.9900	C7A—H7A2	0.9900
C7—H7B	0.9900	C8A—C11A	1.512 (9)
C8—C11	1.515 (10)	C8A—H8A1	0.9900
C8—H8A	0.9900	C8A—H8A2	0.9900
C8—H8B	0.9900	C11A—C12A	1.368 (11)
C11—C12	1.385 (10)	C11A—C16A	1.419 (9)
C11—C16	1.416 (10)	C12A—C13A	1.388 (10)
C12—C13	1.376 (11)	C12A—H12A	0.9500
C12—H12	0.9500	C13A—C14A	1.366 (11)
C13—C14	1.383 (10)	C13A—H13A	0.9500
C13—H13	0.9500	C14A—C15A	1.348 (12)
C14—C15	1.386 (11)	C14A—H14A	0.9500
C14—H14	0.9500	C15A—C16A	1.400 (10)
C15—C16	1.371 (12)	C15A—H15A	0.9500
C15—H15	0.9500	C16A—H16A	0.9500
C16—H16	0.9500	O31A—H31A	0.8400
O31—H31	0.8395	O41A—H41A	0.8400
O41—H41	0.8400	O51A—H51A	0.8400
O51—H51	0.8400	C61A—O61A	1.420 (8)
C61—O61	1.431 (8)	C61A—H61D	0.9900
C61—H61B	0.9900	C61A—H61E	0.9900
C61—H61C	0.9900	O61A—H61A	0.8400
O61—H61	0.8400	O1W—H1WA	0.8394
S1A—C2A	1.799 (7)	O1W—H1WB	0.8399

C2—S1—C7	101.4 (4)	C2A—O1A—C6A	109.8 (4)
C2—O1—C6	111.8 (5)	O1A—C2A—C3A	112.7 (5)
O1—C2—C3	109.5 (5)	O1A—C2A—S1A	108.3 (4)
O1—C2—S1	108.7 (4)	C3A—C2A—S1A	109.7 (4)
C3—C2—S1	112.5 (4)	O1A—C2A—H2A	108.7
O1—C2—H2	108.7	C3A—C2A—H2A	108.7
C3—C2—H2	108.7	S1A—C2A—H2A	108.7
S1—C2—H2	108.7	O31A—C3A—C4A	108.5 (5)
O31—C3—C4	110.2 (5)	O31A—C3A—C2A	108.5 (5)
O31—C3—C2	110.9 (5)	C4A—C3A—C2A	110.4 (5)
C4—C3—C2	110.2 (5)	O31A—C3A—H3A	109.8
O31—C3—H3	108.5	C4A—C3A—H3A	109.8
C4—C3—H3	108.5	C2A—C3A—H3A	109.8
C2—C3—H3	108.5	O41A—C4A—C5A	111.6 (5)
O41—C4—C3	112.7 (5)	O41A—C4A—C3A	107.7 (5)
O41—C4—C5	112.2 (5)	C5A—C4A—C3A	111.3 (5)
C3—C4—C5	111.2 (5)	O41A—C4A—H4A	108.7
O41—C4—H4	106.8	C5A—C4A—H4A	108.7
C3—C4—H4	106.8	C3A—C4A—H4A	108.7
C5—C4—H4	106.8	O51A—C5A—C4A	109.7 (5)
O51—C5—C6	110.9 (6)	O51A—C5A—C6A	111.9 (5)
O51—C5—C4	108.8 (5)	C4A—C5A—C6A	108.0 (5)
C6—C5—C4	108.6 (5)	O51A—C5A—H5A	109.1
O51—C5—H5	109.5	C4A—C5A—H5A	109.1
C6—C5—H5	109.5	C6A—C5A—H5A	109.1
C4—C5—H5	109.5	O1A—C6A—C5A	109.1 (5)
O1—C6—C5	111.3 (5)	O1A—C6A—C61A	106.9 (5)
O1—C6—C61	107.4 (5)	C5A—C6A—C61A	114.7 (5)
C5—C6—C61	113.2 (5)	O1A—C6A—H6A	108.6
O1—C6—H6	108.3	C5A—C6A—H6A	108.6
C5—C6—H6	108.3	C61A—C6A—H6A	108.6
C61—C6—H6	108.3	C8A—C7A—S1A	110.0 (5)
C8—C7—S1	115.4 (5)	C8A—C7A—H7A1	109.7
C8—C7—H7A	108.4	S1A—C7A—H7A1	109.7
S1—C7—H7A	108.4	C8A—C7A—H7A2	109.7
C8—C7—H7B	108.4	S1A—C7A—H7A2	109.7
S1—C7—H7B	108.4	H7A1—C7A—H7A2	108.2
H7A—C7—H7B	107.5	C11A—C8A—C7A	111.1 (6)
C11—C8—C7	113.6 (7)	C11A—C8A—H8A1	109.4
C11—C8—H8A	108.8	C7A—C8A—H8A1	109.4
C7—C8—H8A	108.8	C11A—C8A—H8A2	109.4
C11—C8—H8B	108.8	C7A—C8A—H8A2	109.4
C7—C8—H8B	108.8	H8A1—C8A—H8A2	108.0
H8A—C8—H8B	107.7	C12A—C11A—C16A	119.6 (7)
C12—C11—C16	117.5 (7)	C12A—C11A—C8A	122.0 (6)
C12—C11—C8	122.0 (6)	C16A—C11A—C8A	118.4 (7)
C16—C11—C8	120.5 (7)	C11A—C12A—C13A	119.9 (7)
C13—C12—C11	121.8 (7)	C11A—C12A—H12A	120.1
C13—C12—H12	119.1	C13A—C12A—H12A	120.1
C11—C12—H12	119.1	C14A—C13A—C12A	121.1 (8)
C12—C13—C14	120.7 (8)	C14A—C13A—H13A	119.5
C12—C13—H13	119.7	C12A—C13A—H13A	119.5
C14—C13—H13	119.7	C15A—C14A—C13A	119.8 (8)
C13—C14—C15	118.2 (8)	C15A—C14A—H14A	120.1
C13—C14—H14	120.9	C13A—C14A—H14A	120.1
C15—C14—H14	120.9	C14A—C15A—C16A	121.6 (7)
C16—C15—C14	121.9 (8)	C14A—C15A—H15A	119.2
C16—C15—H15	119.0	C16A—C15A—H15A	119.2
C14—C15—H15	119.0	C15A—C16A—C11A	118.0 (8)
C15—C16—C11	119.9 (7)	C15A—C16A—H16A	121.0
C15—C16—H16	120.0	C11A—C16A—H16A	121.0
C11—C16—H16	120.0	C3A—O31A—H31A	109.5
C3—O31—H31	125.0	C4A—O41A—H41A	109.5
C4—O41—H41	109.5	C5A—O51A—H51A	109.5
C5—O51—H51	109.5	O61A—C61A—C6A	108.1 (5)
O61—C61—C6	109.3 (5)	O61A—C61A—H61D	110.1
O61—C61—H61B	109.8	C6A—C61A—H61D	110.1
C6—C61—H61B	109.8	O61A—C61A—H61E	110.1
O61—C61—H61C	109.8	C6A—C61A—H61E	110.1
C6—C61—H61C	109.8	H61D—C61A—H61E	108.4
H61B—C61—H61C	108.3	C61A—O61A—H61A	109.5
C61—O61—H61	109.5	H1WA—O1W—H1WB	99.1
C2A—S1A—C7A	100.7 (3)

C6—O1—C2—C3	−63.2 (7)	C6A—O1A—C2A—C3A	−59.8 (7)
C6—O1—C2—S1	173.6 (4)	C6A—O1A—C2A—S1A	178.7 (4)
C7—S1—C2—O1	−109.5 (4)	C7A—S1A—C2A—O1A	−76.8 (5)
C7—S1—C2—C3	129.0 (5)	C7A—S1A—C2A—C3A	159.8 (4)
O1—C2—C3—O31	179.5 (5)	O1A—C2A—C3A—O31A	169.9 (5)
S1—C2—C3—O31	−59.5 (6)	S1A—C2A—C3A—O31A	−69.4 (6)
O1—C2—C3—C4	57.2 (7)	O1A—C2A—C3A—C4A	51.1 (7)
S1—C2—C3—C4	178.2 (4)	S1A—C2A—C3A—C4A	171.8 (4)
O31—C3—C4—O41	57.8 (7)	O31A—C3A—C4A—O41A	69.2 (6)
C2—C3—C4—O41	−179.5 (5)	C2A—C3A—C4A—O41A	−171.9 (5)
O31—C3—C4—C5	−175.2 (5)	O31A—C3A—C4A—C5A	−168.2 (5)
C2—C3—C4—C5	−52.5 (7)	C2A—C3A—C4A—C5A	−49.3 (7)
O41—C4—C5—O51	57.6 (7)	O41A—C4A—C5A—O51A	53.7 (7)
C3—C4—C5—O51	−69.6 (6)	C3A—C4A—C5A—O51A	−66.6 (7)
O41—C4—C5—C6	178.4 (6)	O41A—C4A—C5A—C6A	175.9 (5)
C3—C4—C5—C6	51.3 (7)	C3A—C4A—C5A—C6A	55.6 (7)
C2—O1—C6—C5	63.8 (7)	C2A—O1A—C6A—C5A	66.0 (6)
C2—O1—C6—C61	−171.8 (5)	C2A—O1A—C6A—C61A	−169.4 (5)
O51—C5—C6—O1	63.5 (6)	O51A—C5A—C6A—O1A	57.2 (6)
C4—C5—C6—O1	−56.0 (7)	C4A—C5A—C6A—O1A	−63.6 (6)
O51—C5—C6—C61	−57.5 (7)	O51A—C5A—C6A—C61A	−62.7 (7)
C4—C5—C6—C61	−177.1 (5)	C4A—C5A—C6A—C61A	176.5 (6)
C2—S1—C7—C8	61.9 (6)	C2A—S1A—C7A—C8A	−174.0 (5)
S1—C7—C8—C11	71.3 (7)	S1A—C7A—C8A—C11A	−178.9 (5)
C7—C8—C11—C12	77.3 (9)	C7A—C8A—C11A—C12A	−86.0 (8)
C7—C8—C11—C16	−102.6 (8)	C7A—C8A—C11A—C16A	96.4 (8)
C16—C11—C12—C13	−1.1 (12)	C16A—C11A—C12A—C13A	−3.0 (11)
C8—C11—C12—C13	179.0 (8)	C8A—C11A—C12A—C13A	179.5 (7)
C11—C12—C13—C14	−0.1 (13)	C11A—C12A—C13A—C14A	1.4 (12)
C12—C13—C14—C15	0.0 (13)	C12A—C13A—C14A—C15A	0.5 (12)
C13—C14—C15—C16	1.4 (14)	C13A—C14A—C15A—C16A	−0.7 (13)
C14—C15—C16—C11	−2.7 (14)	C14A—C15A—C16A—C11A	−0.9 (12)
C12—C11—C16—C15	2.5 (12)	C12A—C11A—C16A—C15A	2.7 (11)
C8—C11—C16—C15	−177.7 (8)	C8A—C11A—C16A—C15A	−179.6 (7)
O1—C6—C61—O61	65.0 (7)	O1A—C6A—C61A—O61A	172.2 (5)
C5—C6—C61—O61	−171.8 (6)	C5A—C6A—C61A—O61A	−66.6 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···O1W	0.84	1.92	2.759 (7)	179
O41—H41···O41A	0.84	1.95	2.779 (7)	169
O51—H51···O1Wⁱ	0.84	1.98	2.773 (6)	156
O61—H61···O31Aⁱⁱ	0.84	1.86	2.697 (7)	172
O31A—H31A···O61ⁱⁱⁱ	0.84	1.92	2.650 (7)	145
O41A—H41A···O41^iv	0.84	2.05	2.788 (7)	147
O51A—H51A···O61A^v	0.84	2.10	2.785 (7)	138
O61A—H61A···O31ⁱⁱ	0.84	2.02	2.744 (6)	145
O1W—H1WA···O31^v	0.84	2.23	2.989 (8)	150
O1W—H1WB···O41A^v	0.84	2.43	3.270 (6)	180

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

Experimental details

Crystal data
Chemical formula	C₁₄H₂₀O₅S·0.5H₂O
M_r	309.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	4.8358 (4), 14.8218 (16), 41.390 (3)
V (Å³)	2966.6 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.20 × 0.09 × 0.08

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 200; Blessing, 1995)
T_min, T_max	0.954, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	14206, 5217, 2395
R_int	0.169
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.117, 0.68
No. of reflections	5217
No. of parameters	377
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.30
Absolute structure	Flack (1983), 2269 Friedel pairs
Absolute structure parameter	−0.25 (16)

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009)'.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···O1W	0.84	1.92	2.759 (7)	179.3
O41—H41···O41A	0.84	1.95	2.779 (7)	168.6
O51—H51···O1Wⁱ	0.84	1.98	2.773 (6)	156.4
O61—H61···O31Aⁱⁱ	0.84	1.86	2.697 (7)	172.1
O31A—H31A···O61ⁱⁱⁱ	0.84	1.92	2.650 (7)	145.1
O41A—H41A···O41^iv	0.84	2.05	2.788 (7)	146.9
O51A—H51A···O61A^v	0.84	2.10	2.785 (7)	138.4
O61A—H61A···O31ⁱⁱ	0.84	2.02	2.744 (6)	144.5
O1W—H1WA···O31^v	0.84	2.23	2.989 (8)	150.4
O1W—H1WB···O41A^v	0.84	2.43	3.270 (6)	179.9

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

Acknowledgements

We thank OTKA, the Hungarian Scientific Research Fund (grant Nos. IN-79731 and NK-68578) for financial support. IB thanks the Spanish Research Council (CSIC) for the provision of a free-of-charge license to the Cambridge Structural Database.

References

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