2,3,4,6-Tetra-O-acetyl-β-d-galacto­pyranosyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl disulfide tetra­hydro­furan solvate

Brito, I.; Szilágyi, L.; López-Rodríguez, M.

doi:10.1107/S1600536808039494

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Pages o2472-o2473

doi:10.1107/S1600536808039494

Open

access

2,3,4,6-Tetra-O-acetyl-β-D-galactopyranosyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl disulfide tetrahydrofuran solvate

Iván Brito,^a ^* Lászlo Szilágyi ^b and Matías López-Rodríguez ^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 ^cInstituto de Bio-Orgánica 'Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez N°2, La Laguna, Tenerife, Spain
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 17 November 2008; accepted 24 November 2008; online 29 November 2008)

The asymmetric unit of title compound, C₂₈H₃₈O₁₈S₂·C₄H₈O, comprises one disulfide-bridged sugar molecule and one solvent molecule. No significant differences in structural parameters are found between the present structure and the previously determined unsolvated form [Brito, López-Rodríguez, Bényei & Szilagyi (2006 ). Carbohydr. Res. 341, 2967–2972]. The compounds are characterized by a compact structure with spatial proximity of the two pyranosyl rings. One of the carbonyl atoms is disordered over two sites [site occupancy = 0.69 (7) for major component] and the displacement parameters for the THF species are unsually large.

Related literature

For analysis of conformation, see: Cremer & Pople (1975 ). For the synthesis, see: Szilágyi et al. (2001 ). For background to disulfide linkage and diglycosyl disulfides, see: André et al. (2006 ); Chakka et al. (2005 ); Pérez et al. (1978 ); Szilágyi & Varela (2006 ). For the structure of the unsolvated form, see: Brito et al. (2006).

Experimental

Crystal data

C₂₈H₃₈O₁₈S₂·C₄H₈O
M_r = 798.81
Monoclinic, P 2₁
a = 14.6499 (14) Å
b = 10.0096 (10) Å
c = 15.4029 (15) Å
β = 113.573 (2)°
V = 2070.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 298 (2) K
0.40 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.920, T_max = 0.960
13257 measured reflections
7410 independent reflections
4763 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.151
S = 0.85
7410 reflections
497 parameters
45 restraints
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack, (1983 ), 3438 Friedel pairs
Flack parameter: 0.02 (9)

Table 1
Selected torsion angle (°)

C1—S1—S2—C21	−80.25 (19)

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039494/tk2332sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039494/tk2332Isup2.hkl

checkCIF report

Comment top

The disulfide linkage which plays an essential role in stabilizing the tertiary structure of proteins, was not known in carbohydrate chemistry until recently when it was introduced as a new interglycosidic connecting element (Szilágyi & Varela, 2006). Diglycosyl disulfides were proposed as novel carbohydrate scaffolds with potential biological activity (Szilágyi & Varela, 2006, Chakka et al., 2005). This has recently been demonstrated in binding studies with galectins and in assays with tumor cells (André et al., 2006). We report herein the crystal and molecular structure of the title compound, (I), Fig. 1. The averaged bond lengths [C—O 1.429 (6), O—C 1.341 (8), C=O 1.181 (8), C—C 1.478 (10) Å] and other parameters, Table 1, compare well with those for the previously determined unsolvated form (Brito et al., 2006). The pyranosyl rings adopt chair conformations with Cremer & Pople (1975) puckering parameters: Q_T= 0.604 (6) (Glc) and 0.566 (5) Å (Gal), θ = 2.4 (5) (Glc) and 9.6 (6)°(Gal), ϕ = 15 (11) (Glc) and 9(4)° (Gal); these parameters are similar to those for the unsolvated form. The conformations of the acetyl groups are in agreement with the observation that in acetylated pyranoses, the carbonyl C=O bonds tend to align so that they nearly eclipse the axial-H atoms atoms on the common ring C atoms.

Related literature top

For analysis of conformation, see: Cremer & Pople (1975). For the synthesis, see: Szilágyi et al. (2001). For background to disulfide linkage and diglycosyl disulfides, see: André et al. (2006); Chakka et al. (2005); Pérez et al. (1978); Szilágyi & Varela (2006). For the structure of the unsolvated form, see: Brito et al. (2006).

Experimental top

Compound (I) was synthesized as described by Szilágyi et al. (2001).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN(Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.

2,3,4,6-Tetra-O-acetyl-β-D-galactopyranosyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl disulfide tetrahydrofuran solvate top

Crystal data top

C₂₈H₃₈O₁₈S₂·C₄H₈O	F(000) = 844
M_r = 798.81	D_x = 1.281 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4312 reflections
a = 14.6499 (14) Å	θ = 2.4–25.0°
b = 10.0096 (10) Å	µ = 0.20 mm⁻¹
c = 15.4029 (15) Å	T = 298 K
β = 113.573 (2)°	Prism, yellow
V = 2070.2 (4) Å³	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection top

Nonius KappaCCD area-detector diffractometer	7410 independent reflections
Radiation source: fine-focus sealed tube	4763 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ scans, and ω scans with κ offsets	θ_max = 25.2°, θ_min = 2.5°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −17→16
T_min = 0.920, T_max = 0.960	k = −12→11
13257 measured reflections	l = −18→18

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)] = 0.054	H-atom parameters constrained
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.0875P)²] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max = 0.042
7410 reflections	Δρ_max = 0.34 e Å⁻³
497 parameters	Δρ_min = −0.19 e Å⁻³
45 restraints	Absolute structure: Flack, (1983), 3438 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (9)

Crystal data top

C₂₈H₃₈O₁₈S₂·C₄H₈O	V = 2070.2 (4) Å³
M_r = 798.81	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 14.6499 (14) Å	µ = 0.20 mm⁻¹
b = 10.0096 (10) Å	T = 298 K
c = 15.4029 (15) Å	0.40 × 0.30 × 0.20 mm
β = 113.573 (2)°

Data collection top

Nonius KappaCCD area-detector diffractometer	7410 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	4763 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.960	R_int = 0.046
13257 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.151	Δρ_max = 0.34 e Å⁻³
S = 0.85	Δρ_min = −0.19 e Å⁻³
7410 reflections	Absolute structure: Flack, (1983), 3438 Friedel pairs
497 parameters	Absolute structure parameter: 0.02 (9)
45 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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)
S1	0.94859 (8)	0.98543 (12)	0.93468 (8)	0.0609 (3)
O1	0.8235 (2)	1.1214 (3)	0.98368 (19)	0.0587 (7)
O2	0.5745 (2)	1.1063 (3)	0.7358 (2)	0.0692 (8)
O3	0.5648 (4)	1.2681 (6)	0.6357 (3)	0.146 (2)
O4	0.7645 (2)	1.0285 (3)	0.7398 (2)	0.0644 (8)
O5	0.6752 (4)	0.8414 (4)	0.7054 (3)	0.1135 (14)
O6	0.8497 (3)	1.2956 (4)	1.1307 (2)	0.0822 (9)
O7	0.8713 (4)	1.0964 (5)	1.2001 (3)	0.1132 (14)
O8	0.5850 (2)	1.2941 (3)	0.8764 (2)	0.0684 (8)
O9	0.5145 (3)	1.1965 (4)	0.9648 (3)	0.1042 (13)
C1	0.8424 (3)	1.0964 (4)	0.9008 (3)	0.0546 (10)
H1	0.8612	1.1814	0.8809	0.066*
C2	0.7471 (3)	1.0494 (4)	0.8225 (3)	0.0548 (10)
H2	0.7253	0.9658	0.8412	0.066*
C3	0.6682 (3)	1.1554 (4)	0.8047 (3)	0.0580 (11)
H3	0.6874	1.2365	0.7806	0.07*
C4	0.6549 (3)	1.1872 (5)	0.8953 (3)	0.0624 (11)
H4	0.6301	1.1083	0.9166	0.075*
C5	0.7552 (3)	1.2286 (4)	0.9704 (3)	0.0601 (11)
H5	0.7793	1.3079	0.9487	0.072*
C6	0.5307 (4)	1.1702 (7)	0.6531 (4)	0.0865 (16)
C7	0.4395 (5)	1.1036 (8)	0.5895 (4)	0.116 (2)
H7A	0.3886	1.1144	0.6135	0.174*
H7B	0.4524	1.0102	0.5859	0.174*
H7C	0.4175	1.1426	0.5275	0.174*
C8	0.7260 (4)	0.9197 (6)	0.6875 (4)	0.0773 (14)
C9	0.7533 (5)	0.9114 (8)	0.6047 (4)	0.116 (2)
H9A	0.7772	0.8231	0.6009	0.175*
H9B	0.8046	0.9754	0.6117	0.175*
H9C	0.6959	0.9302	0.5478	0.175*
C10	0.7520 (4)	1.2569 (6)	1.0644 (3)	0.0802 (15)
H10A	0.7049	1.3282	1.058	0.096*
H10B	0.7302	1.1779	1.0873	0.096*
C11	0.9038 (5)	1.2052 (7)	1.1941 (4)	0.0896 (17)
C12	1.0060 (5)	1.2548 (8)	1.2510 (4)	0.122 (2)
H12A	1.0442	1.1855	1.2929	0.183*
H12B	1.0025	1.3309	1.2875	0.183*
H12C	1.0374	1.2801	1.2094	0.183*
C13	0.5199 (3)	1.2900 (6)	0.9193 (3)	0.0704 (12)
C14	0.4608 (4)	1.4138 (5)	0.9033 (4)	0.0890 (16)
H14A	0.4028	1.3978	0.9161	0.133*
H14B	0.4408	1.4417	0.8386	0.133*
H14C	0.5005	1.4826	0.9447	0.133*
S2	0.89370 (8)	0.80485 (11)	0.95029 (7)	0.0611 (3)
O21	0.98609 (19)	0.7760 (3)	1.13641 (18)	0.0584 (7)
O22	0.7552 (2)	0.5961 (3)	1.1697 (2)	0.0684 (8)
O23	0.6851 (3)	0.7007 (4)	1.2553 (3)	0.0950 (11)
O24	0.7182 (2)	0.7573 (3)	1.0062 (2)	0.0678 (8)
O25	0.6962 (4)	0.5714 (5)	0.9230 (3)	0.1235 (16)
O26	1.1652 (2)	0.8389 (4)	1.2729 (2)	0.0751 (9)
O27	1.1690 (4)	0.9965 (5)	1.3749 (4)	0.1336 (17)
O28	0.9183 (2)	0.7190 (4)	1.3348 (2)	0.0803 (9)
O29A	0.988 (5)	0.519 (4)	1.3922 (18)	0.103 (15)	0.31 (7)
O29B	0.921 (4)	0.5063 (16)	1.3697 (18)	0.155 (9)	0.69 (7)
C21	0.8909 (3)	0.8131 (4)	1.0674 (3)	0.0531 (9)
H21	0.8739	0.9037	1.0799	0.064*
C22	0.8144 (3)	0.7149 (4)	1.0712 (3)	0.0576 (10)
H22	0.8288	0.626	1.0531	0.069*
C23	0.8154 (3)	0.7094 (5)	1.1694 (3)	0.0601 (11)
H23	0.7853	0.791	1.1815	0.072*
C24	0.9198 (3)	0.6941 (4)	1.2442 (3)	0.0593 (11)
H24	0.943	0.6028	1.2424	0.071*
C25	0.9914 (3)	0.7911 (5)	1.2309 (3)	0.0593 (10)
H25	0.974	0.8827	1.2407	0.071*
C26	0.6918 (4)	0.6043 (5)	1.2123 (4)	0.0740 (13)
C27	0.6347 (5)	0.4806 (6)	1.2017 (5)	0.1028 (18)
H27A	0.584	0.494	1.2256	0.154*
H27B	0.6785	0.4103	1.2367	0.154*
H27C	0.6042	0.4566	1.136	0.154*
C28	0.6681 (4)	0.6785 (6)	0.9334 (4)	0.0798 (14)
C29	0.5757 (4)	0.7449 (7)	0.8683 (4)	0.105 (2)
H29A	0.5918	0.8306	0.8502	0.157*
H29B	0.5313	0.7564	0.8997	0.157*
H29C	0.5441	0.6907	0.8129	0.157*
C210	1.0967 (3)	0.7613 (5)	1.2966 (3)	0.0708 (13)
H21A	1.1056	0.7808	1.3612	0.085*
H21B	1.1102	0.6671	1.2928	0.085*
C211	1.1968 (4)	0.9552 (5)	1.3177 (4)	0.0830 (15)
C212	1.2625 (6)	1.0235 (7)	1.2826 (6)	0.128 (2)
H21C	1.2737	1.1132	1.3067	0.191*
H21D	1.2324	1.0257	1.2146	0.191*
H21E	1.3249	0.9769	1.3032	0.191*
C213	0.9328 (8)	0.6160 (10)	1.3954 (5)	0.115 (3)
C214	0.9212 (7)	0.6644 (11)	1.4834 (5)	0.174 (4)
H21F	0.9701	0.6219	1.5381	0.261*
H21G	0.8557	0.6426	1.4792	0.261*
H21H	0.9304	0.7595	1.4888	0.261*
O31	0.7418 (11)	0.0601 (14)	0.3640 (9)	0.306 (5)
C31	0.6827 (15)	0.2535 (13)	0.4405 (8)	0.301 (9)
H31A	0.6559	0.3386	0.4113	0.361*
H31B	0.71	0.265	0.5087	0.361*
C32	0.7705 (12)	0.2047 (18)	0.4071 (10)	0.291 (7)
H32A	0.7751	0.2654	0.3599	0.349*
H32B	0.8343	0.203	0.4608	0.349*
C33	0.6337 (11)	0.0251 (15)	0.3603 (6)	0.235 (5)
H33A	0.5878	0.0138	0.2947	0.282*
H33B	0.637	−0.059	0.3927	0.282*
C34	0.5917 (12)	0.1382 (19)	0.4080 (8)	0.281 (6)
H34A	0.5818	0.1036	0.4624	0.337*
H34B	0.5293	0.1746	0.363	0.337*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0625 (6)	0.0635 (6)	0.0677 (7)	0.0038 (6)	0.0377 (5)	0.0038 (6)
O1	0.0704 (18)	0.0570 (17)	0.0581 (17)	0.0048 (13)	0.0358 (15)	0.0102 (15)
O2	0.0641 (19)	0.0688 (19)	0.071 (2)	−0.0002 (16)	0.0228 (16)	−0.0020 (16)
O3	0.132 (4)	0.165 (5)	0.098 (3)	0.056 (3)	0.001 (3)	−0.036 (4)
O4	0.081 (2)	0.0657 (19)	0.0530 (17)	−0.0031 (15)	0.0335 (15)	−0.0036 (16)
O5	0.157 (4)	0.073 (3)	0.121 (3)	−0.025 (2)	0.066 (3)	−0.029 (3)
O6	0.110 (3)	0.070 (2)	0.0621 (19)	0.0011 (18)	0.0296 (19)	0.023 (2)
O7	0.144 (4)	0.103 (3)	0.106 (3)	0.029 (3)	0.064 (3)	0.023 (3)
O8	0.0714 (19)	0.0543 (17)	0.089 (2)	0.0138 (16)	0.0425 (17)	0.0106 (16)
O9	0.117 (3)	0.098 (3)	0.135 (3)	0.041 (3)	0.090 (3)	0.031 (2)
C1	0.063 (3)	0.051 (2)	0.059 (2)	0.004 (2)	0.033 (2)	0.000 (2)
C2	0.061 (3)	0.053 (2)	0.055 (2)	0.0059 (19)	0.028 (2)	−0.002 (2)
C3	0.056 (3)	0.054 (2)	0.062 (3)	0.002 (2)	0.021 (2)	−0.002 (2)
C4	0.063 (3)	0.058 (3)	0.073 (3)	0.011 (2)	0.034 (2)	0.007 (2)
C5	0.075 (3)	0.048 (2)	0.066 (3)	0.004 (2)	0.037 (2)	0.008 (2)
C6	0.088 (4)	0.098 (4)	0.071 (4)	0.003 (3)	0.030 (3)	0.001 (3)
C7	0.092 (4)	0.161 (6)	0.077 (4)	−0.009 (4)	0.016 (3)	−0.015 (4)
C8	0.090 (4)	0.069 (3)	0.067 (3)	−0.005 (3)	0.025 (3)	0.003 (3)
C9	0.137 (6)	0.140 (6)	0.069 (4)	−0.033 (4)	0.039 (4)	0.000 (5)
C10	0.087 (4)	0.087 (4)	0.071 (3)	0.001 (3)	0.036 (3)	0.020 (3)
C11	0.125 (5)	0.082 (4)	0.076 (4)	0.014 (3)	0.054 (4)	0.030 (4)
C12	0.116 (5)	0.149 (7)	0.079 (4)	0.012 (4)	0.017 (4)	0.024 (5)
C13	0.069 (3)	0.075 (3)	0.074 (3)	0.000 (3)	0.036 (2)	0.006 (3)
C14	0.084 (4)	0.081 (4)	0.108 (4)	−0.003 (3)	0.046 (3)	0.013 (3)
S2	0.0789 (7)	0.0549 (6)	0.0570 (6)	0.0025 (5)	0.0350 (5)	0.0060 (6)
O21	0.0597 (17)	0.0695 (19)	0.0547 (16)	0.0044 (13)	0.0320 (14)	0.0082 (14)
O22	0.080 (2)	0.0643 (18)	0.080 (2)	−0.0035 (16)	0.0514 (18)	−0.0061 (17)
O23	0.105 (3)	0.095 (3)	0.118 (3)	−0.019 (2)	0.079 (2)	−0.014 (2)
O24	0.0570 (18)	0.079 (2)	0.0675 (18)	−0.0007 (16)	0.0246 (16)	0.0021 (16)
O25	0.129 (4)	0.086 (3)	0.124 (4)	−0.026 (3)	0.017 (3)	−0.016 (3)
O26	0.070 (2)	0.091 (3)	0.0701 (19)	−0.0123 (18)	0.0342 (16)	−0.0047 (18)
O27	0.186 (5)	0.107 (3)	0.133 (4)	−0.030 (3)	0.090 (4)	0.005 (4)
O28	0.095 (2)	0.097 (2)	0.0640 (19)	0.0000 (19)	0.0475 (18)	0.002 (2)
O29A	0.14 (3)	0.077 (17)	0.066 (10)	0.025 (8)	0.016 (13)	0.010 (13)
O29B	0.23 (3)	0.128 (9)	0.093 (8)	0.030 (6)	0.052 (14)	−0.045 (10)
C21	0.056 (2)	0.054 (2)	0.052 (2)	0.005 (2)	0.0246 (19)	0.012 (2)
C22	0.064 (3)	0.055 (2)	0.060 (2)	0.005 (2)	0.031 (2)	0.009 (2)
C23	0.067 (3)	0.058 (3)	0.068 (3)	0.005 (2)	0.041 (2)	0.010 (2)
C24	0.078 (3)	0.061 (3)	0.051 (2)	0.006 (2)	0.038 (2)	0.011 (2)
C25	0.062 (3)	0.069 (3)	0.054 (2)	0.002 (2)	0.031 (2)	0.006 (2)
C26	0.081 (3)	0.070 (3)	0.092 (3)	−0.006 (3)	0.055 (3)	−0.001 (3)
C27	0.124 (5)	0.090 (4)	0.130 (5)	−0.011 (4)	0.088 (4)	−0.024 (4)
C28	0.074 (4)	0.075 (4)	0.087 (4)	0.000 (3)	0.028 (3)	−0.024 (3)
C29	0.073 (3)	0.137 (5)	0.086 (4)	0.028 (4)	0.013 (3)	−0.014 (4)
C210	0.067 (3)	0.091 (4)	0.062 (3)	0.005 (2)	0.034 (2)	0.007 (3)
C211	0.094 (4)	0.072 (4)	0.082 (4)	−0.001 (3)	0.035 (3)	0.016 (3)
C212	0.145 (6)	0.086 (4)	0.176 (7)	−0.019 (4)	0.089 (6)	−0.021 (4)
C213	0.156 (8)	0.133 (7)	0.066 (4)	0.007 (5)	0.055 (4)	−0.037 (7)
C214	0.240 (10)	0.230 (11)	0.092 (5)	−0.013 (6)	0.109 (6)	−0.051 (8)
O31	0.397 (14)	0.285 (12)	0.252 (10)	0.024 (9)	0.148 (11)	0.016 (11)
C31	0.48 (2)	0.171 (9)	0.103 (7)	0.016 (6)	−0.034 (11)	0.121 (11)
C32	0.372 (14)	0.227 (12)	0.150 (11)	0.082 (9)	−0.024 (10)	0.003 (12)
C33	0.352 (13)	0.214 (10)	0.069 (5)	0.032 (5)	0.011 (7)	0.003 (10)
C34	0.376 (13)	0.332 (17)	0.094 (7)	0.074 (8)	0.050 (9)	0.126 (12)

Geometric parameters (Å, º) top

S1—C1	1.810 (4)	O24—C22	1.429 (5)
S1—S2	2.0313 (16)	O25—C28	1.182 (7)
O1—C5	1.425 (5)	O26—C211	1.339 (6)
O1—C1	1.432 (4)	O26—C210	1.427 (5)
O2—C6	1.338 (7)	O27—C211	1.183 (6)
O2—C3	1.445 (5)	O28—C213	1.349 (8)
O3—C6	1.178 (7)	O28—C24	1.427 (5)
O4—C8	1.337 (6)	O29A—C213	1.27 (3)
O4—C2	1.410 (5)	O29B—C213	1.156 (17)
O5—C8	1.187 (6)	C21—C22	1.509 (6)
O6—C11	1.335 (6)	C21—H21	0.98
O6—C10	1.440 (6)	C22—C23	1.509 (6)
O7—C11	1.207 (7)	C22—H22	0.98
O8—C13	1.361 (5)	C23—C24	1.510 (6)
O8—C4	1.428 (5)	C23—H23	0.98
O9—C13	1.191 (6)	C24—C25	1.503 (6)
C1—C2	1.510 (6)	C24—H24	0.98
C1—H1	0.98	C25—C210	1.497 (6)
C2—C3	1.511 (6)	C25—H25	0.98
C2—H2	0.98	C26—C27	1.466 (7)
C3—C4	1.517 (6)	C27—H27A	0.96
C3—H3	0.98	C27—H27B	0.96
C4—C5	1.520 (6)	C27—H27C	0.96
C4—H4	0.98	C28—C29	1.481 (7)
C5—C10	1.495 (6)	C29—H29A	0.96
C5—H5	0.98	C29—H29B	0.96
C6—C7	1.463 (8)	C29—H29C	0.96
C7—H7A	0.96	C210—H21A	0.97
C7—H7B	0.96	C210—H21B	0.97
C7—H7C	0.96	C211—C212	1.450 (9)
C8—C9	1.484 (8)	C212—H21C	0.96
C9—H9A	0.96	C212—H21D	0.96
C9—H9B	0.96	C212—H21E	0.96
C9—H9C	0.96	C213—C214	1.513 (9)
C10—H10A	0.97	C214—H21F	0.96
C10—H10B	0.97	C214—H21G	0.96
C11—C12	1.486 (9)	C214—H21H	0.96
C12—H12A	0.96	O31—C32	1.578 (16)
C12—H12B	0.96	O31—C33	1.601 (14)
C12—H12C	0.96	C31—C32	1.640 (17)
C13—C14	1.475 (7)	C31—C34	1.68 (2)
C14—H14A	0.96	C31—H31A	0.97
C14—H14B	0.96	C31—H31B	0.97
C14—H14C	0.96	C32—H32A	0.97
S2—C21	1.823 (4)	C32—H32B	0.97
O21—C21	1.424 (4)	C33—C34	1.601 (15)
O21—C25	1.434 (4)	C33—H33A	0.97
O22—C26	1.337 (5)	C33—H33B	0.97
O22—C23	1.437 (5)	C34—H34A	0.97
O23—C26	1.196 (6)	C34—H34B	0.97
O24—C28	1.326 (6)

C1—S1—S2	104.17 (14)	C21—C22—C23	110.7 (4)
C5—O1—C1	112.2 (3)	O24—C22—H22	109.5
C6—O2—C3	119.4 (4)	C21—C22—H22	109.5
C8—O4—C2	118.8 (4)	C23—C22—H22	109.5
C11—O6—C10	117.9 (5)	O22—C23—C22	105.8 (3)
C13—O8—C4	117.6 (3)	O22—C23—C24	110.7 (4)
O1—C1—C2	108.7 (3)	C22—C23—C24	111.6 (3)
O1—C1—S1	107.5 (3)	O22—C23—H23	109.6
C2—C1—S1	116.9 (3)	C22—C23—H23	109.6
O1—C1—H1	107.8	C24—C23—H23	109.6
C2—C1—H1	107.8	O28—C24—C25	107.8 (3)
S1—C1—H1	107.8	O28—C24—C23	108.8 (3)
O4—C2—C1	109.0 (3)	C25—C24—C23	112.4 (3)
O4—C2—C3	110.0 (3)	O28—C24—H24	109.3
C1—C2—C3	108.8 (3)	C25—C24—H24	109.3
O4—C2—H2	109.7	C23—C24—H24	109.3
C1—C2—H2	109.7	O21—C25—C210	106.7 (3)
C3—C2—H2	109.7	O21—C25—C24	108.2 (3)
O2—C3—C2	109.1 (3)	C210—C25—C24	111.5 (4)
O2—C3—C4	108.3 (3)	O21—C25—H25	110.1
C2—C3—C4	110.6 (3)	C210—C25—H25	110.1
O2—C3—H3	109.6	C24—C25—H25	110.1
C2—C3—H3	109.6	O23—C26—O22	123.2 (5)
C4—C3—H3	109.6	O23—C26—C27	125.0 (4)
O8—C4—C3	108.4 (3)	O22—C26—C27	111.8 (4)
O8—C4—C5	110.3 (3)	C26—C27—H27A	109.5
C3—C4—C5	108.4 (3)	C26—C27—H27B	109.5
O8—C4—H4	109.9	H27A—C27—H27B	109.5
C3—C4—H4	109.9	C26—C27—H27C	109.5
C5—C4—H4	109.9	H27A—C27—H27C	109.5
O1—C5—C10	107.2 (3)	H27B—C27—H27C	109.5
O1—C5—C4	108.3 (3)	O25—C28—O24	123.3 (5)
C10—C5—C4	113.1 (4)	O25—C28—C29	126.1 (6)
O1—C5—H5	109.4	O24—C28—C29	110.6 (5)
C10—C5—H5	109.4	C28—C29—H29A	109.5
C4—C5—H5	109.4	C28—C29—H29B	109.5
O3—C6—O2	121.9 (6)	H29A—C29—H29B	109.5
O3—C6—C7	125.7 (6)	C28—C29—H29C	109.5
O2—C6—C7	112.4 (6)	H29A—C29—H29C	109.5
C6—C7—H7A	109.5	H29B—C29—H29C	109.5
C6—C7—H7B	109.5	O26—C210—C25	111.0 (4)
H7A—C7—H7B	109.5	O26—C210—H21A	109.4
C6—C7—H7C	109.5	C25—C210—H21A	109.4
H7A—C7—H7C	109.5	O26—C210—H21B	109.4
H7B—C7—H7C	109.5	C25—C210—H21B	109.4
O5—C8—O4	123.3 (5)	H21A—C210—H21B	108
O5—C8—C9	124.9 (6)	O27—C211—O26	122.4 (6)
O4—C8—C9	111.8 (5)	O27—C211—C212	126.2 (6)
C8—C9—H9A	109.5	O26—C211—C212	111.2 (5)
C8—C9—H9B	109.5	C211—C212—H21C	109.5
H9A—C9—H9B	109.5	C211—C212—H21D	109.5
C8—C9—H9C	109.5	H21C—C212—H21D	109.5
H9A—C9—H9C	109.5	C211—C212—H21E	109.5
H9B—C9—H9C	109.5	H21C—C212—H21E	109.5
O6—C10—C5	109.3 (4)	H21D—C212—H21E	109.5
O6—C10—H10A	109.8	O29B—C213—O29A	43.8 (10)
C5—C10—H10A	109.8	O29B—C213—O28	121.9 (11)
O6—C10—H10B	109.8	O29A—C213—O28	118.7 (18)
C5—C10—H10B	109.8	O29B—C213—C214	123.7 (11)
H10A—C10—H10B	108.3	O29A—C213—C214	125.3 (12)
O7—C11—O6	122.0 (6)	O28—C213—C214	109.4 (8)
O7—C11—C12	126.3 (6)	C213—C214—H21F	109.5
O6—C11—C12	111.6 (6)	C213—C214—H21G	109.5
C11—C12—H12A	109.5	H21F—C214—H21G	109.5
C11—C12—H12B	109.5	C213—C214—H21H	109.5
H12A—C12—H12B	109.5	H21F—C214—H21H	109.5
C11—C12—H12C	109.5	H21G—C214—H21H	109.5
H12A—C12—H12C	109.5	C32—O31—C33	108.0 (14)
H12B—C12—H12C	109.5	C32—C31—C34	109.3 (9)
O9—C13—O8	122.3 (4)	C32—C31—H31A	109.8
O9—C13—C14	125.9 (4)	C34—C31—H31A	109.8
O8—C13—C14	111.8 (5)	C32—C31—H31B	109.8
C13—C14—H14A	109.5	C34—C31—H31B	109.8
C13—C14—H14B	109.5	H31A—C31—H31B	108.3
H14A—C14—H14B	109.5	O31—C32—C31	107.2 (12)
C13—C14—H14C	109.5	O31—C32—H32A	110.3
H14A—C14—H14C	109.5	C31—C32—H32A	110.3
H14B—C14—H14C	109.5	O31—C32—H32B	110.3
C21—S2—S1	104.10 (15)	C31—C32—H32B	110.3
C21—O21—C25	111.7 (3)	H32A—C32—H32B	108.5
C26—O22—C23	120.0 (4)	C34—C33—O31	112.7 (12)
C28—O24—C22	118.2 (4)	C34—C33—H33A	109.1
C211—O26—C210	118.4 (4)	O31—C33—H33A	109
C213—O28—C24	118.9 (5)	C34—C33—H33B	109.1
O21—C21—C22	108.8 (3)	O31—C33—H33B	109
O21—C21—S2	108.9 (2)	H33A—C33—H33B	107.8
C22—C21—S2	108.6 (3)	C33—C34—C31	102.6 (10)
O21—C21—H21	110.2	C33—C34—H34A	111.2
C22—C21—H21	110.2	C31—C34—H34A	111.3
S2—C21—H21	110.2	C33—C34—H34B	111.2
O24—C22—C21	108.6 (3)	C31—C34—H34B	111.3
O24—C22—C23	108.9 (3)	H34A—C34—H34B	109.2

C5—O1—C1—C2	−64.8 (4)	S1—S2—C21—C22	156.3 (2)
C5—O1—C1—S1	167.8 (3)	C28—O24—C22—C21	116.5 (4)
S2—S1—C1—O1	74.3 (3)	C28—O24—C22—C23	−122.8 (4)
S2—S1—C1—C2	−48.2 (3)	O21—C21—C22—O24	176.3 (3)
C8—O4—C2—C1	137.4 (4)	S2—C21—C22—O24	−65.2 (3)
C8—O4—C2—C3	−103.4 (4)	O21—C21—C22—C23	56.8 (4)
O1—C1—C2—O4	178.3 (3)	S2—C21—C22—C23	175.2 (3)
S1—C1—C2—O4	−59.9 (4)	C26—O22—C23—C22	−138.6 (4)
O1—C1—C2—C3	58.3 (4)	C26—O22—C23—C24	100.4 (4)
S1—C1—C2—C3	−179.9 (3)	O24—C22—C23—O22	71.7 (4)
C6—O2—C3—C2	−118.1 (4)	C21—C22—C23—O22	−169.0 (3)
C6—O2—C3—C4	121.5 (4)	O24—C22—C23—C24	−167.9 (4)
O4—C2—C3—O2	65.7 (4)	C21—C22—C23—C24	−48.5 (5)
C1—C2—C3—O2	−175.0 (3)	C213—O28—C24—C25	−128.2 (6)
O4—C2—C3—C4	−175.3 (3)	C213—O28—C24—C23	109.8 (6)
C1—C2—C3—C4	−56.0 (4)	O22—C23—C24—O28	−75.1 (4)
C13—O8—C4—C3	142.4 (4)	C22—C23—C24—O28	167.4 (4)
C13—O8—C4—C5	−99.0 (4)	O22—C23—C24—C25	165.7 (3)
O2—C3—C4—O8	−64.5 (4)	C22—C23—C24—C25	48.1 (5)
C2—C3—C4—O8	175.9 (3)	C21—O21—C25—C210	−175.0 (4)
O2—C3—C4—C5	175.6 (3)	C21—O21—C25—C24	64.9 (4)
C2—C3—C4—C5	56.1 (4)	O28—C24—C25—O21	−174.4 (3)
C1—O1—C5—C10	−172.6 (4)	C23—C24—C25—O21	−54.6 (4)
C1—O1—C5—C4	65.0 (4)	O28—C24—C25—C210	68.6 (4)
O8—C4—C5—O1	−177.4 (3)	C23—C24—C25—C210	−171.6 (4)
C3—C4—C5—O1	−58.8 (4)	C23—O22—C26—O23	−3.7 (8)
O8—C4—C5—C10	63.9 (5)	C23—O22—C26—C27	177.8 (4)
C3—C4—C5—C10	−177.6 (4)	C22—O24—C28—O25	5.0 (7)
C3—O2—C6—O3	−2.4 (8)	C22—O24—C28—C29	−173.7 (4)
C3—O2—C6—C7	176.9 (4)	C211—O26—C210—C25	93.8 (5)
C2—O4—C8—O5	2.4 (7)	O21—C25—C210—O26	52.3 (5)
C2—O4—C8—C9	−178.6 (4)	C24—C25—C210—O26	170.2 (4)
C11—O6—C10—C5	−102.8 (5)	C210—O26—C211—O27	−1.1 (8)
O1—C5—C10—O6	60.9 (5)	C210—O26—C211—C212	−177.6 (5)
C4—C5—C10—O6	−179.8 (4)	C24—O28—C213—O29B	−20 (3)
C10—O6—C11—O7	−3.9 (7)	C24—O28—C213—O29A	31 (3)
C10—O6—C11—C12	174.3 (4)	C24—O28—C213—C214	−176.2 (6)
C4—O8—C13—O9	−6.1 (7)	C33—O31—C32—C31	5.7 (13)
C4—O8—C13—C14	172.9 (4)	C34—C31—C32—O31	−4.8 (14)
C1—S1—S2—C21	−80.25 (19)	C32—O31—C33—C34	−4.8 (13)
C25—O21—C21—C22	−66.6 (4)	O31—C33—C34—C31	1.7 (12)
C25—O21—C21—S2	175.1 (3)	C32—C31—C34—C33	1.9 (12)
S1—S2—C21—O21	−85.4 (3)

Experimental details

Crystal data
Chemical formula	C₂₈H₃₈O₁₈S₂·C₄H₈O
M_r	798.81
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	14.6499 (14), 10.0096 (10), 15.4029 (15)
β (°)	113.573 (2)
V (Å³)	2070.2 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.920, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	13257, 7410, 4763
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.151, 0.85
No. of reflections	7410
No. of parameters	497
No. of restraints	45
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.19
Absolute structure	Flack, (1983), 3438 Friedel pairs
Absolute structure parameter	0.02 (9)

Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN(Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

S1—C1	1.810 (4)	S2—C21	1.823 (4)
S1—S2	2.0313 (16)

C1—S1—S2	104.17 (14)	O1—C1—S1	107.5 (3)

C1—S1—S2—C21	−80.25 (19)

Acknowledgements

This study was supported by grants from the Hungarian National Science Fund [OTKA T48713 (to LSz)]. We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the Cambridge Structural Database.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
André, S., Pei, Z. C., Siebert, H. C., Ramström, O. & Gabius, H. J. (2006). Bioorg. Med. Chem. 14, 6314–6326. Web of Science PubMed Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brito, I., López-Rodríguez, M., Bényei, A. & Szilagyi, L. (2006). Carbohydr. Res. 341, 2967–2972. Web of Science CSD CrossRef PubMed CAS Google Scholar
Chakka, N., Johnston, B. D. & Pinto, B. M. (2005). Can. J. Chem. 83, 929–936. Web of Science CrossRef CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Pérez, S., Stpierre, J. & Marchessault, R. H. (1978). Can. J. Chem. 56, 2866–2871. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szilágyi, L., Illyés, T. Z. & Herczegh, P. (2001). Tetrahedron Lett. 42, 3901–3903. Google Scholar
Szilágyi, L. & Varela, O. (2006). Curr. Org. Chem. 10, 1745–1770. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.