Phenyl 2,3,4-tri-O-benzyl-1-thio-α-d-mannopyran­oside monohydrate

Durka, M.; Norberg, B.; Roué, Y.; Vincent, S.P.; Wouters, J.

doi:10.1107/S1600536810019604

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1525

doi:10.1107/S1600536810019604

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Phenyl 2,3,4-tri-O-benzyl-1-thio-α-D-mannopyranoside monohydrate

Maxime Durka,^a Bernadette Norberg,^a Yvain Roué,^a Stéphane P. Vincent ^a and Johan Wouters ^a ^*

^aDepartment of Chemistry, University of Namur, 61 Rue de Bruxelles, B-5000 Namur, Belgium
^*Correspondence e-mail: johan.wouters@fundp.ac.be

(Received 27 April 2010; accepted 25 May 2010; online 5 June 2010)

In the title compound, C₃₃H₃₄O₅S·H₂O, the mannopyranoside ring adopts a chair conformation with the 2-α-thiophenyl group occupying an axial position. One of the pendant benzyl groups is disordered over two sets of sites in a 0.5:0.5 ratio. In the crystal, the water molecule makes two O—H⋯O hydrogen bonds to an adjacent sugar molecule with the O atoms of the primary alcohol and ether groups acting as acceptors. At the same time, the OH group of the sugar makes a hydrogen bond to a water molecule.

Related literature

For background to the synthesis and properties of mannopyranosides, see: Boons (1991 ); Szurmai et al. (1994 ); Caravano et al. (2003 ); Grizot et al. (2006 ); Dohi et al. (2008 ). For ring conformation analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₃₃H₃₄O₅S·H₂O
M_r = 560.69
Monoclinic, P 2₁
a = 12.628 (1) Å
b = 8.084 (1) Å
c = 14.832 (2) Å
β = 101.380 (5)°
V = 1484.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 150 K
0.35 × 0.30 × 0.17 mm

Data collection

Oxford Diffraction Gemini Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.948, T_max = 0.974
12650 measured reflections
5205 independent reflections
4333 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.062
S = 0.97
5205 reflections
400 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 2381 Friedel pairs
Flack parameter: 0.01 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW—HW1⋯O2	0.88 (3)	2.00 (3)	2.861 (2)	166 (2)
OW—HW2⋯O6	0.78 (2)	2.07 (2)	2.827 (2)	165 (2)
O6—H6⋯OWⁱ	0.87 (2)	1.89 (2)	2.745 (2)	169 (2)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+2]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810019604/hb5424sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810019604/hb5424Isup2.hkl

checkCIF report

Comment top

Oligosaccharides are natural ligands of lectins, which are important receptors involved in key biological processes. Efficient strategies for the regioselective transformations of monosaccharides to achieve glycosylation reactions or further functionalizations are of paramount importance. Furthermore, the knowledge of the conformations of carbohydrates alone or bound to protein gives access to key informations that can be exploited to understand biocatalytic processes or stereoelectronic effects (Caravano et al., 2003).

Numerous strategies of protections of mannopyranosides have been described in the litterature (e.g. Boons, 1991; Szurmai et al., 1994) in order to derivatise the primary alcohol. The title compound is also a key intermediate for the synthesis of heptosyl transferase inhibitors (Dohi et al., 2008; Grizot et al., 2006).

Crystal structure of the title compound confirms the expected relative stereochemistry : C1 R, C2 S, C3 S, C4 R, C5 R. The mannopyranoside adopts a chair conformation with puckering amplitude (Q) = 0.522 (3) Å, Theta = 3.6 (3) °, and Phi = 60 (5) ° (Cremer & Pople, 1975).

The 2-alpha-thiophenyl group on C1 and the O-benzyl group on C2 occupy an axial position, the two other O-benzyl groups (on C3 and C4) and carbon atom C6 occupying an equatorial position.

Thiophenyl-2,3,4-O-tri-benzyl-alpha-D-mannopyranoside co-crystallized with one water molecule (O_W). This water molecule is part of a H bond network involving the primary alcohol O6 and also secondary alcohol O2 (Table 1). Packing is further reinforced by van der Waals interactions involving the aromatic rings.

Related literature top

For background to the synthesis and properties of mannopyranosides, see: Boons (1991); Szurmai et al. (1994); Caravano et al. (2003); Grizot et al. (2006); Dohi et al. (2008). For ring conformation analysis, see: Cremer & Pople (1975).

Experimental top

The title compound was obtained by a six-step synthetic route that will be described in details elsewhere. Overall yield is 70%. Colourless prisms of (I) were obtained by evaporation of a solution in ethyl acetate.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of (I): C-bound H atoms are omitted and disorder is not presented for clarity. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Phenyl 2,3,4-tri-O-benzyl-1-thio-α-D-mannopyranoside monohydrate top

Crystal data top

C₃₃H₃₄O₅S·H₂O	F(000) = 596.0
M_r = 560.69	D_x = 1.255 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7534 reflections
a = 12.628 (1) Å	θ = 3.0–28.2°
b = 8.084 (1) Å	µ = 0.15 mm⁻¹
c = 14.832 (2) Å	T = 150 K
β = 101.380 (5)°	Prism, colourless
V = 1484.4 (2) Å³	0.35 × 0.30 × 0.17 mm
Z = 2

Data collection top

Oxford Diffraction Gemini Ruby CCD diffractometer	5205 independent reflections
Radiation source: Enhanced fine-focus sealed tube	4333 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −15→14
T_min = 0.948, T_max = 0.974	k = −9→9
12650 measured reflections	l = −17→17

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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0359P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.001
5205 reflections	Δρ_max = 0.13 e Å⁻³
400 parameters	Δρ_min = −0.17 e Å⁻³
17 restraints	Absolute structure: Flack (1983), 2381 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (5)

Crystal data top

C₃₃H₃₄O₅S·H₂O	V = 1484.4 (2) Å³
M_r = 560.69	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 12.628 (1) Å	µ = 0.15 mm⁻¹
b = 8.084 (1) Å	T = 150 K
c = 14.832 (2) Å	0.35 × 0.30 × 0.17 mm
β = 101.380 (5)°

Data collection top

Oxford Diffraction Gemini Ruby CCD diffractometer	5205 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	4333 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.974	R_int = 0.022
12650 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.062	Δρ_max = 0.13 e Å⁻³
S = 0.97	Δρ_min = −0.17 e Å⁻³
5205 reflections	Absolute structure: Flack (1983), 2381 Friedel pairs
400 parameters	Absolute structure parameter: 0.01 (5)
17 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
C1	0.28677 (14)	0.7097 (2)	0.89516 (11)	0.0300 (4)
H1	0.3281	0.7834	0.9416	0.036*
C2	0.32672 (13)	0.7370 (2)	0.80557 (11)	0.0334 (4)
H2	0.3072	0.8487	0.7825	0.040*
C3	0.27664 (14)	0.6105 (2)	0.73342 (11)	0.0337 (4)
H3	0.1995	0.6349	0.7142	0.040*
C4	0.28925 (14)	0.4357 (2)	0.77082 (10)	0.0297 (4)
H4	0.3641	0.3989	0.7759	0.036*
C5	0.25565 (14)	0.4210 (2)	0.86404 (10)	0.0276 (4)
H5	0.1771	0.4349	0.8547	0.033*
C6	0.28498 (13)	0.2565 (2)	0.90995 (11)	0.0323 (4)
H6A	0.2635	0.2547	0.9692	0.039*
H6B	0.2466	0.1688	0.8725	0.039*
C8	0.11808 (13)	0.7620 (2)	0.98996 (11)	0.0308 (4)
C9	0.02534 (15)	0.6816 (2)	1.00193 (13)	0.0370 (5)
H9	−0.0181	0.6284	0.9525	0.044*
C10	−0.00307 (16)	0.6802 (2)	1.08781 (14)	0.0448 (5)
H10	−0.0665	0.6283	1.0954	0.054*
C11	0.06208 (17)	0.7552 (3)	1.16149 (13)	0.0489 (5)
H11	0.0431	0.7537	1.2190	0.059*
C12	0.15545 (18)	0.8325 (3)	1.14995 (13)	0.0453 (5)
H12	0.2004	0.8810	1.2002	0.054*
C13	0.18316 (15)	0.8388 (2)	1.06442 (13)	0.0378 (5)
H13	0.2453	0.8945	1.0568	0.045*
C14	0.50097 (18)	0.8655 (2)	0.81855 (16)	0.0507 (6)
H14A	0.5083	0.9246	0.8764	0.061*
H14B	0.4635	0.9367	0.7699	0.061*
C15	0.61013 (15)	0.8228 (2)	0.80096 (11)	0.0322 (4)
C16	0.62073 (15)	0.7141 (2)	0.73104 (11)	0.0367 (4)
H16	0.5595	0.6650	0.6961	0.044*
C17	0.72045 (17)	0.6782 (3)	0.71287 (13)	0.0478 (5)
H17	0.7264	0.6048	0.6659	0.057*
C18	0.81128 (17)	0.7497 (3)	0.76340 (17)	0.0603 (6)
H18	0.8787	0.7253	0.7505	0.072*
C19	0.80278 (18)	0.8570 (3)	0.83291 (16)	0.0578 (7)
H19	0.8647	0.9052	0.8673	0.069*
C20	0.70225 (17)	0.8946 (2)	0.85263 (12)	0.0434 (5)
H20	0.6968	0.9673	0.9001	0.052*
O3	0.32582 (10)	0.61829 (18)	0.65476 (8)	0.0464 (4)
C21	0.2578 (3)	0.6608 (6)	0.5714 (2)	0.0441 (11)	0.50
H21A	0.2135	0.7550	0.5805	0.053*	0.50
H21B	0.2102	0.5689	0.5495	0.053*	0.50
C22	0.3247 (5)	0.7026 (7)	0.5018 (4)	0.0280 (18)	0.50
C23	0.4047 (6)	0.8186 (9)	0.5201 (3)	0.043 (2)	0.50
H23	0.4207	0.8676	0.5779	0.051*	0.50
C24	0.4617 (5)	0.8638 (7)	0.4547 (5)	0.0407 (15)	0.50
H24	0.5178	0.9396	0.4692	0.049*	0.50
C25	0.4364 (5)	0.7974 (10)	0.3673 (5)	0.0456 (16)	0.50
H25	0.4748	0.8301	0.3229	0.055*	0.50
C26	0.3545 (7)	0.6830 (9)	0.3456 (3)	0.0481 (19)	0.50
H26	0.3372	0.6388	0.2866	0.058*	0.50
C27	0.2978 (6)	0.6338 (10)	0.4127 (4)	0.044 (2)	0.50
H27	0.2427	0.5562	0.3988	0.053*	0.50
C21'	0.2980 (4)	0.7526 (6)	0.5997 (2)	0.0413 (7)	0.50
H21C	0.3253	0.8515	0.6334	0.050*	0.50
H21D	0.2199	0.7608	0.5844	0.050*	0.50
C22'	0.3411 (10)	0.7456 (13)	0.5118 (7)	0.0413 (7)	0.50
C23'	0.4273 (9)	0.8369 (12)	0.4994 (6)	0.0413 (7)	0.50
H23'	0.4617	0.9043	0.5471	0.050*	0.50
C24'	0.4653 (6)	0.8333 (8)	0.4192 (7)	0.0413 (7)	0.50
H24'	0.5225	0.9015	0.4122	0.050*	0.50
C25'	0.4206 (7)	0.7315 (9)	0.3503 (6)	0.0413 (7)	0.50
H25'	0.4465	0.7287	0.2958	0.050*	0.50
C26'	0.3361 (8)	0.6316 (8)	0.3617 (6)	0.0413 (7)	0.50
H26'	0.3052	0.5596	0.3149	0.050*	0.50
C27'	0.2970 (8)	0.6377 (14)	0.4420 (8)	0.0413 (7)	0.50
H27'	0.2405	0.5687	0.4494	0.050*	0.50
C28	0.26726 (15)	0.2153 (3)	0.66005 (13)	0.0451 (5)
H28A	0.3146	0.1422	0.7016	0.054*
H28B	0.3101	0.2731	0.6224	0.054*
C29	0.17992 (15)	0.1171 (2)	0.60016 (12)	0.0376 (5)
C30	0.17758 (17)	0.1035 (3)	0.50676 (13)	0.0445 (5)
H30	0.2310	0.1538	0.4812	0.053*
C31	0.09579 (19)	0.0151 (3)	0.45124 (14)	0.0540 (6)
H31	0.0945	0.0064	0.3885	0.065*
C32	0.01714 (19)	−0.0592 (3)	0.48815 (15)	0.0570 (6)
H32	−0.0373	−0.1189	0.4506	0.068*
C33	0.01817 (17)	−0.0461 (3)	0.58167 (15)	0.0516 (6)
H33	−0.0359	−0.0957	0.6067	0.062*
C34	0.09947 (16)	0.0405 (3)	0.63681 (13)	0.0430 (5)
H34	0.1007	0.0480	0.6996	0.052*
O1	0.30602 (9)	0.54559 (13)	0.92705 (7)	0.0281 (3)
O2	0.44079 (9)	0.71853 (15)	0.82204 (8)	0.0383 (3)
O4	0.21835 (9)	0.32927 (16)	0.71031 (8)	0.0385 (3)
O6	0.39918 (10)	0.22905 (16)	0.92224 (9)	0.0376 (3)
OW	0.55620 (12)	0.4829 (2)	0.94836 (10)	0.0379 (3)
S1	0.14464 (4)	0.77358 (5)	0.87681 (3)	0.03636 (13)
HW1	0.528 (2)	0.551 (4)	0.9035 (18)	0.084 (9)*
HW2	0.5117 (18)	0.417 (3)	0.9508 (13)	0.047 (7)*
H6	0.4137 (16)	0.142 (3)	0.9571 (13)	0.050 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0308 (10)	0.0249 (9)	0.0353 (10)	0.0021 (8)	0.0090 (8)	0.0008 (7)
C2	0.0287 (10)	0.0296 (10)	0.0436 (10)	0.0051 (8)	0.0111 (8)	0.0099 (8)
C3	0.0279 (10)	0.0449 (11)	0.0295 (9)	0.0067 (9)	0.0089 (8)	0.0063 (8)
C4	0.0231 (10)	0.0371 (11)	0.0284 (9)	0.0003 (8)	0.0037 (7)	−0.0026 (8)
C5	0.0255 (10)	0.0274 (10)	0.0303 (9)	−0.0021 (8)	0.0061 (7)	−0.0032 (8)
C6	0.0313 (10)	0.0333 (10)	0.0333 (8)	−0.0040 (9)	0.0088 (7)	−0.0021 (8)
C8	0.0266 (10)	0.0275 (9)	0.0394 (9)	0.0041 (8)	0.0093 (7)	−0.0005 (9)
C9	0.0277 (11)	0.0346 (11)	0.0477 (11)	0.0026 (8)	0.0048 (8)	0.0003 (8)
C10	0.0356 (11)	0.0380 (12)	0.0662 (14)	0.0049 (9)	0.0232 (10)	0.0098 (10)
C11	0.0597 (14)	0.0457 (12)	0.0468 (11)	0.0112 (12)	0.0238 (10)	0.0057 (11)
C12	0.0497 (13)	0.0427 (12)	0.0427 (11)	0.0021 (10)	0.0073 (9)	−0.0073 (9)
C13	0.0318 (11)	0.0327 (10)	0.0501 (12)	0.0001 (8)	0.0105 (9)	−0.0028 (9)
C14	0.0534 (14)	0.0313 (12)	0.0750 (14)	−0.0061 (10)	0.0314 (11)	−0.0078 (10)
C15	0.0386 (11)	0.0282 (10)	0.0313 (9)	−0.0064 (8)	0.0103 (8)	0.0023 (8)
C16	0.0331 (11)	0.0442 (11)	0.0312 (9)	−0.0001 (9)	0.0024 (8)	0.0017 (8)
C17	0.0458 (13)	0.0565 (14)	0.0441 (11)	0.0070 (11)	0.0165 (10)	0.0045 (10)
C18	0.0344 (13)	0.0552 (15)	0.0942 (17)	0.0017 (12)	0.0198 (12)	0.0163 (14)
C19	0.0390 (14)	0.0482 (14)	0.0751 (16)	−0.0134 (11)	−0.0160 (12)	0.0203 (12)
C20	0.0600 (15)	0.0312 (10)	0.0345 (10)	−0.0123 (10)	−0.0011 (10)	0.0050 (8)
O3	0.0426 (8)	0.0664 (9)	0.0334 (7)	0.0167 (7)	0.0157 (6)	0.0184 (7)
C21	0.031 (2)	0.065 (3)	0.032 (2)	−0.020 (2)	−0.0058 (17)	0.002 (2)
C22	0.036 (3)	0.022 (4)	0.025 (3)	0.011 (3)	0.007 (3)	0.010 (3)
C23	0.049 (5)	0.065 (4)	0.011 (2)	0.006 (4)	0.001 (2)	−0.004 (2)
C24	0.033 (3)	0.046 (3)	0.041 (4)	−0.012 (2)	0.000 (3)	−0.004 (3)
C25	0.052 (4)	0.052 (4)	0.041 (4)	0.009 (3)	0.030 (3)	0.010 (3)
C26	0.080 (5)	0.047 (4)	0.017 (2)	0.012 (4)	0.008 (3)	−0.002 (2)
C27	0.038 (3)	0.036 (3)	0.052 (6)	−0.011 (2)	−0.007 (4)	−0.002 (4)
C21'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C22'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C23'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C24'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C25'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C26'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C27'	0.0536 (15)	0.0354 (13)	0.0370 (14)	0.0045 (11)	0.0144 (11)	0.0001 (11)
C28	0.0364 (11)	0.0497 (13)	0.0494 (11)	0.0013 (10)	0.0092 (9)	−0.0137 (10)
C29	0.0362 (11)	0.0329 (10)	0.0443 (12)	0.0027 (9)	0.0097 (9)	−0.0077 (9)
C30	0.0488 (13)	0.0425 (12)	0.0447 (12)	−0.0036 (10)	0.0152 (10)	−0.0046 (9)
C31	0.0657 (15)	0.0514 (14)	0.0423 (12)	−0.0035 (12)	0.0040 (11)	−0.0069 (10)
C32	0.0486 (15)	0.0532 (15)	0.0629 (14)	−0.0103 (11)	−0.0046 (12)	−0.0147 (11)
C33	0.0439 (14)	0.0417 (13)	0.0709 (15)	−0.0084 (10)	0.0157 (11)	−0.0053 (11)
C34	0.0427 (12)	0.0416 (11)	0.0464 (11)	0.0025 (10)	0.0124 (9)	−0.0043 (9)
O1	0.0309 (7)	0.0244 (6)	0.0286 (6)	−0.0002 (5)	0.0054 (5)	0.0000 (5)
O2	0.0307 (7)	0.0340 (7)	0.0521 (7)	−0.0014 (6)	0.0127 (6)	0.0108 (6)
O4	0.0283 (7)	0.0484 (8)	0.0378 (7)	0.0024 (6)	0.0042 (5)	−0.0151 (6)
O6	0.0350 (8)	0.0285 (8)	0.0494 (7)	0.0019 (6)	0.0082 (6)	0.0079 (6)
OW	0.0299 (8)	0.0340 (8)	0.0469 (8)	−0.0020 (7)	0.0005 (6)	0.0019 (6)
S1	0.0316 (3)	0.0396 (3)	0.0383 (2)	0.0082 (2)	0.00785 (19)	0.0010 (2)

Geometric parameters (Å, º) top

C1—O1	1.414 (2)	O3—C21	1.403 (3)
C1—C2	1.528 (2)	C21—C22	1.496 (6)
C1—S1	1.8355 (17)	C21—H21A	0.9700
C1—H1	0.9800	C21—H21B	0.9700
C2—O2	1.421 (2)	C22—C23	1.366 (8)
C2—C3	1.524 (2)	C22—C27	1.412 (7)
C2—H2	0.9800	C23—C24	1.366 (7)
C3—O3	1.427 (2)	C23—H23	0.9300
C3—C4	1.515 (3)	C24—C25	1.382 (7)
C3—H3	0.9800	C24—H24	0.9300
C4—O4	1.425 (2)	C25—C26	1.377 (8)
C4—C5	1.529 (2)	C25—H25	0.9300
C4—H4	0.9800	C26—C27	1.393 (8)
C5—O1	1.4347 (18)	C26—H26	0.9300
C5—C6	1.506 (2)	C27—H27	0.9300
C5—H5	0.9800	C21'—C22'	1.510 (8)
C6—O6	1.435 (2)	C21'—H21C	0.9700
C6—H6A	0.9700	C21'—H21D	0.9700
C6—H6B	0.9700	C22'—C23'	1.356 (10)
C8—C9	1.381 (2)	C22'—C27'	1.384 (10)
C8—C13	1.386 (2)	C23'—C24'	1.370 (9)
C8—S1	1.7777 (17)	C23'—H23'	0.9300
C9—C10	1.390 (3)	C24'—C25'	1.346 (9)
C9—H9	0.9300	C24'—H24'	0.9300
C10—C11	1.372 (3)	C25'—C26'	1.375 (9)
C10—H10	0.9300	C25'—H25'	0.9300
C11—C12	1.375 (3)	C26'—C27'	1.377 (9)
C11—H11	0.9300	C26'—H26'	0.9300
C12—C13	1.382 (3)	C27'—H27'	0.9300
C12—H12	0.9300	C28—O4	1.403 (2)
C13—H13	0.9300	C28—C29	1.500 (3)
C14—O2	1.417 (2)	C28—H28A	0.9700
C14—C15	1.493 (3)	C28—H28B	0.9700
C14—H14A	0.9700	C29—C30	1.384 (3)
C14—H14B	0.9700	C29—C34	1.389 (3)
C15—C16	1.386 (2)	C30—C31	1.386 (3)
C15—C20	1.388 (3)	C30—H30	0.9300
C16—C17	1.370 (3)	C31—C32	1.365 (3)
C16—H16	0.9300	C31—H31	0.9300
C17—C18	1.368 (3)	C32—C33	1.389 (3)
C17—H17	0.9300	C32—H32	0.9300
C18—C19	1.368 (3)	C33—C34	1.372 (3)
C18—H18	0.9300	C33—H33	0.9300
C19—C20	1.392 (3)	C34—H34	0.9300
C19—H19	0.9300	O6—H6	0.87 (2)
C20—H20	0.9300	OW—HW1	0.88 (3)
O3—C21'	1.362 (4)	OW—HW2	0.78 (2)

O1—C1—C2	111.21 (14)	C21—O3—C3	116.2 (2)
O1—C1—S1	114.34 (12)	O3—C21—C22	109.4 (4)
C2—C1—S1	108.15 (11)	O3—C21—H21A	109.8
O1—C1—H1	107.6	C22—C21—H21A	109.8
C2—C1—H1	107.6	O3—C21—H21B	109.8
S1—C1—H1	107.6	C22—C21—H21B	109.8
O2—C2—C3	108.46 (14)	H21A—C21—H21B	108.2
O2—C2—C1	109.45 (13)	C23—C22—C27	119.2 (6)
C3—C2—C1	110.59 (14)	C23—C22—C21	120.9 (5)
O2—C2—H2	109.4	C27—C22—C21	119.5 (5)
C3—C2—H2	109.4	C22—C23—C24	121.0 (5)
C1—C2—H2	109.4	C22—C23—H23	119.5
O3—C3—C4	108.00 (14)	C24—C23—H23	119.5
O3—C3—C2	110.94 (15)	C23—C24—C25	120.4 (4)
C4—C3—C2	111.68 (13)	C23—C24—H24	119.8
O3—C3—H3	108.7	C25—C24—H24	119.8
C4—C3—H3	108.7	C26—C25—C24	120.3 (5)
C2—C3—H3	108.7	C26—C25—H25	119.9
O4—C4—C3	108.98 (12)	C24—C25—H25	119.9
O4—C4—C5	105.68 (14)	C25—C26—C27	119.5 (5)
C3—C4—C5	112.09 (14)	C25—C26—H26	120.2
O4—C4—H4	110.0	C27—C26—H26	120.2
C3—C4—H4	110.0	C26—C27—C22	119.6 (6)
C5—C4—H4	110.0	C26—C27—H27	120.2
O1—C5—C6	106.70 (11)	C22—C27—H27	120.2
O1—C5—C4	111.58 (13)	O3—C21'—C22'	113.2 (5)
C6—C5—C4	112.98 (14)	O3—C21'—H21C	108.9
O1—C5—H5	108.5	C22'—C21'—H21C	108.9
C6—C5—H5	108.5	O3—C21'—H21D	108.9
C4—C5—H5	108.5	C22'—C21'—H21D	108.9
O6—C6—C5	110.21 (14)	H21C—C21'—H21D	107.8
O6—C6—H6A	109.6	C23'—C22'—C27'	117.2 (8)
C5—C6—H6A	109.6	C23'—C22'—C21'	122.1 (10)
O6—C6—H6B	109.6	C27'—C22'—C21'	120.6 (9)
C5—C6—H6B	109.6	C22'—C23'—C24'	122.3 (7)
H6A—C6—H6B	108.1	C22'—C23'—H23'	118.9
C9—C8—C13	119.53 (16)	C24'—C23'—H23'	118.9
C9—C8—S1	117.95 (13)	C25'—C24'—C23'	120.4 (7)
C13—C8—S1	122.40 (14)	C25'—C24'—H24'	119.8
C8—C9—C10	120.02 (17)	C23'—C24'—H24'	119.8
C8—C9—H9	120.0	C24'—C25'—C26'	119.0 (7)
C10—C9—H9	120.0	C24'—C25'—H25'	120.5
C11—C10—C9	120.23 (19)	C26'—C25'—H25'	120.5
C11—C10—H10	119.9	C25'—C26'—C27'	120.3 (8)
C9—C10—H10	119.9	C25'—C26'—H26'	119.9
C10—C11—C12	119.72 (18)	C27'—C26'—H26'	119.9
C10—C11—H11	120.1	C26'—C27'—C22'	120.7 (9)
C12—C11—H11	120.1	C26'—C27'—H27'	119.7
C11—C12—C13	120.66 (17)	C22'—C27'—H27'	119.7
C11—C12—H12	119.7	O4—C28—C29	108.24 (15)
C13—C12—H12	119.7	O4—C28—H28A	110.0
C12—C13—C8	119.79 (18)	C29—C28—H28A	110.0
C12—C13—H13	120.1	O4—C28—H28B	110.0
C8—C13—H13	120.1	C29—C28—H28B	110.0
O2—C14—C15	109.44 (16)	H28A—C28—H28B	108.4
O2—C14—H14A	109.8	C30—C29—C34	118.92 (17)
C15—C14—H14A	109.8	C30—C29—C28	120.18 (18)
O2—C14—H14B	109.8	C34—C29—C28	120.90 (17)
C15—C14—H14B	109.8	C29—C30—C31	120.1 (2)
H14A—C14—H14B	108.2	C29—C30—H30	119.9
C16—C15—C20	118.96 (19)	C31—C30—H30	119.9
C16—C15—C14	120.41 (16)	C32—C31—C30	120.32 (19)
C20—C15—C14	120.61 (18)	C32—C31—H31	119.8
C17—C16—C15	120.65 (18)	C30—C31—H31	119.8
C17—C16—H16	119.7	C31—C32—C33	120.20 (19)
C15—C16—H16	119.7	C31—C32—H32	119.9
C18—C17—C16	120.4 (2)	C33—C32—H32	119.9
C18—C17—H17	119.8	C34—C33—C32	119.5 (2)
C16—C17—H17	119.8	C34—C33—H33	120.2
C19—C18—C17	119.9 (2)	C32—C33—H33	120.2
C19—C18—H18	120.0	C33—C34—C29	120.89 (18)
C17—C18—H18	120.0	C33—C34—H34	119.6
C18—C19—C20	120.51 (19)	C29—C34—H34	119.6
C18—C19—H19	119.7	C1—O1—C5	114.61 (11)
C20—C19—H19	119.7	C14—O2—C2	116.02 (14)
C15—C20—C19	119.52 (19)	C28—O4—C4	116.34 (13)
C15—C20—H20	120.2	C6—O6—H6	106.8 (14)
C19—C20—H20	120.2	HW1—OW—HW2	106 (2)
C21'—O3—C21	40.1 (2)	C8—S1—C1	101.91 (8)
C21'—O3—C3	115.02 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW—HW1···O2	0.88 (3)	2.00 (3)	2.861 (2)	166 (2)
OW—HW2···O6	0.78 (2)	2.07 (2)	2.827 (2)	165 (2)
O6—H6···OWⁱ	0.87 (2)	1.89 (2)	2.745 (2)	169 (2)

Symmetry code: (i) −x+1, y−1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₃₃H₃₄O₅S·H₂O
M_r	560.69
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	150
a, b, c (Å)	12.628 (1), 8.084 (1), 14.832 (2)
β (°)	101.380 (5)
V (Å³)	1484.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.35 × 0.30 × 0.17

Data collection
Diffractometer	Oxford Diffraction Gemini Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.948, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	12650, 5205, 4333
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.062, 0.97
No. of reflections	5205
No. of parameters	400
No. of restraints	17
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.17
Absolute structure	Flack (1983), 2381 Friedel pairs
Absolute structure parameter	0.01 (5)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW—HW1···O2	0.88 (3)	2.00 (3)	2.861 (2)	166 (2)
OW—HW2···O6	0.78 (2)	2.07 (2)	2.827 (2)	165 (2)
O6—H6···OWⁱ	0.87 (2)	1.89 (2)	2.745 (2)	169 (2)

Symmetry code: (i) −x+1, y−1/2, −z+2.

Acknowledgements

This work was supported in part by the Fonds National de la Recherche Scientifique (FNRS, Belgium).

References

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