Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047150/sj2366sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047150/sj2366Isup2.hkl |
CCDC reference: 667263
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.039
- wR factor = 0.110
- Data-to-parameter ratio = 11.3
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT220_ALERT_2_A Large Non-Solvent O Ueq(max)/Ueq(min) ... 4.95 Ratio
Author Response: This is a dynamic disorder of the carbonyl oxygen quite normal for a protected saccharide without strong intermolecular hydrogen bonds. Most probably the whole acetate group is involved in the dynamic disorder but it is most clearly visible at this carbonyl oxygen atom. The movement is perpendicular to the C=O bond direction which is also physically sound. |
PLAT220_ALERT_2_A Large Non-Solvent O Ueq(max)/Ueq(min) ... 4.87 Ratio
Author Response: This is a dynamic disorder of the carbonyl oxygen quite normal for a protected saccharide without strong intermolecular hydrogen bonds. Most probably the whole acetate group is involved in the dynamic disorder but it is most clearly visible at this carbonyl oxygen atom. The movement is perpendicular to the C=O bond direction which is also physically sound. |
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C16A
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C24A
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C14A
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
Alert level C PLAT213_ALERT_2_C Atom O24B has ADP max/min Ratio ............. 3.60 prola PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.88 Ratio
Author Response: This is a dynamic disorder of the carbonyl oxygen quite normal for a protected saccharide without strong intermolecular hydrogen bonds. Most probably the whole acetate group is involved in the dynamic disorder but it is most clearly visible at this carbonyl oxygen atom. The movement is perpendicular to the C=O bond direction which is also physically sound. |
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.56 Ratio
Author Response: This is a dynamic disorder of the carbonyl oxygen quite normal for a protected saccharide without strong intermolecular hydrogen bonds. Most probably the whole acetate group is involved in the dynamic disorder but it is most clearly visible at this carbonyl oxygen atom. The movement is perpendicular to the C=O bond direction which is also physically sound. |
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.60 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.21 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12A
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for O21
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C22A
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C26A
Author Response: This is also related to the dynamic disorder of the acetate groups when intermolecular bonding is weak, as it is in this protected saccharide. The C16A is the carbonyl carbon where the oxygen is exhibiting a large movement. |
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.992 Tmax scaled 0.992 Tmin scaled 0.942 REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 25.68 From the CIF: _reflns_number_total 4492 Count of symmetry unique reflns 3391 Completeness (_total/calc) 132.47% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1101 Fraction of Friedel pairs measured 0.325 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C12 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C15 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C22 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C23 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C24 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C25 = . R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
4 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 13 ALERT level G = General alerts; check 10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 12 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound (I) was prepared from the trifluoromethanesulfonate derivative (III) (Grandjean & Lukacs, 1996) as follows: sodium sulfide nonahydrate (475 mg, 2.0 mmol) was dried by heating under vacuum and then allowed to cool to RT. Molecular sieves 4Å (ca 500 mg) and acetonitrile (6 ml) were added, followed by trifluoromethanesulfonate (III) (500 mg, 1.0 mmol). The mixture was stirred at 50°C for 3 h, after which time it was diluted with dichloromethane (50 ml) and filtered through Celite. The filtrate was washed with HCl (1M, 50 ml) then NaHCO3 (sat. 50 ml), then dried (Na2SO4), filtered and concentrated. The residue was purified by flash column chromatography (3:1 pentane:ethyl acetate) to give the thioether (II) (331 mg, 90%). Thioether (II) (214 mg) was dissolved in THF (3 ml) and cooled to -78 C, while ammonia (ca 20 ml) was condensed in. Sodium (ca 140 mg) was added to give a deep blue solution, followed by MeOH (0.04 ml). After 2 min, NH4Cl was added until the blue colour disappeared and the solvents were allowed to evaporate. The crude material was then acetylated with acetic anhydride (3 + 1.6 ml) and pyridine (3 + 1.6 ml) overnight. Methanol (8 ml) and ethyl acetate (40 ml) were then added and the mixture was washed with HCl (1M, 30 ml) then NaHCO3 (sat. 30 ml), then dried (Na2SO4), filtered and concentrated. The residue was purified by flash column chromatography (2:1 toluene:ethyl acetate) to give the title compound (I) (131 mg, 71%). Crystals were grown from methanol solution by slow evaporation of the solvent.
Several of the O-acyl groups showed substantial disorder most clearly shown by the elongated ellipsoids especially of O14B, O16B and O24B. This disorder most probably occurs due to the absence of strong intermolecular hydrogen bonding interactions. Attempts to model the disorder did not improve the fit, thus it is represented only by the elongated ellipsoids. All hydrogen atoms were geometrically positioned and refined with riding motion, d(C—H)=0.96, 0.97,0.98 Å for CH3, CH2 and CH respectivly. The Uiso(H) = 1.5Ueq(C) for CH3 and 1.2Ueq(C) for CH2 and CH. The transformation for the overlay (Fig. 3) was calculated with the program ROTERA (Norrestam, 1991).
The title compound (I) was synthesized as part of a program towards the synthesis of thioether-linked disaccharides as new glycomimetics (Cumpstey, 2006). The title compound crystallizes with two unique half molecules in the asymmetric unit. Both molecules are shown in Fig. 1. Both of the sulfur atoms are positioned on a two fold axis whereby the second half of each molecule is generated through the two fold rotation. A packing view of the structure is shown in Fig 2. The conformations of the sugar rings in the two molecules are very similar as can be seen from corresponding geometrical parameters for the two rings. The Cremer Pople parameters (Cremer & Pople, 1975) for the ring O15→ C11→ C12→ C13→ C14→ C15 are: Q=0.587 (3) Å, θ=0.0 (3)° and φ=159 (9)° while for the ring O25→ C21→ C22→ C23→ C24→ C25 they are: Q=0.597 (3) Å, θ=1.3 (3)° and φ=244 (7)°. Both rings are on C-form. The major conformational difference between the molecules is shown in an overlay of the two unique half molecules (Fig. 3), the acetyl group starting at O16 in one of the molecules deviates significantly from the corresponding acetyl group, beginning with O26 in the other molecule. The rest of the atoms, except for these two acetyl groups, have an average deviation of 0.06 (6)Å between the atoms of one residue and the overlaid residue.
For general background, see: Cumpstey (2006). For synthesis of the trifluoromethanesulfonate precursor to the title compound, see: Grandjean & Lukacs (1996). For geometrical calculations, see: Cremer & Pople (1975); Norrestam (1991).
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 2003).
C26H38O16S | F(000) = 1352 |
Mr = 638.62 | Dx = 1.292 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 5794 reflections |
a = 22.6458 (13) Å | θ = 3.8–32.1° |
b = 7.2018 (3) Å | µ = 0.17 mm−1 |
c = 21.3260 (12) Å | T = 293 K |
β = 109.258 (7)° | Prism, colourless |
V = 3283.4 (3) Å3 | 0.30 × 0.05 × 0.05 mm |
Z = 4 |
Oxford Diffraction Xcalibur-II with Sapphire-III CCD diffractometer | 4492 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3486 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 16.5467 pixels mm-1 | θmax = 25.7°, θmin = 3.9° |
ω scans at different θ | h = −27→25 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | k = −5→8 |
Tmin = 0.95, Tmax = 1.00 | l = −25→26 |
10820 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0718P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.110 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.24 e Å−3 |
4492 reflections | Δρmin = −0.27 e Å−3 |
398 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0036 (7) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1101 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.03 (9) |
C26H38O16S | V = 3283.4 (3) Å3 |
Mr = 638.62 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 22.6458 (13) Å | µ = 0.17 mm−1 |
b = 7.2018 (3) Å | T = 293 K |
c = 21.3260 (12) Å | 0.30 × 0.05 × 0.05 mm |
β = 109.258 (7)° |
Oxford Diffraction Xcalibur-II with Sapphire-III CCD diffractometer | 4492 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 3486 reflections with I > 2σ(I) |
Tmin = 0.95, Tmax = 1.00 | Rint = 0.021 |
10820 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.110 | Δρmax = 0.24 e Å−3 |
S = 1.05 | Δρmin = −0.27 e Å−3 |
4492 reflections | Absolute structure: Flack (1983), 1101 Friedel pairs |
398 parameters | Absolute structure parameter: −0.03 (9) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.0000 | 0.92953 (13) | 0.5000 | 0.0534 (3) | |
C13 | 0.06297 (12) | 0.7707 (4) | 0.49958 (13) | 0.0444 (6) | |
H13 | 0.0447 | 0.6545 | 0.4777 | 0.053* | |
C14 | 0.10871 (13) | 0.7272 (4) | 0.56881 (13) | 0.0473 (7) | |
H14 | 0.1396 | 0.6380 | 0.5639 | 0.057* | |
C15 | 0.14320 (13) | 0.8986 (5) | 0.60214 (13) | 0.0520 (7) | |
H15 | 0.1131 | 0.9893 | 0.6078 | 0.062* | |
O15 | 0.17528 (8) | 0.9763 (3) | 0.56093 (9) | 0.0549 (5) | |
C11 | 0.13600 (12) | 1.0308 (4) | 0.49624 (13) | 0.0479 (7) | |
H11 | 0.1064 | 1.1268 | 0.4992 | 0.057* | |
C12 | 0.10163 (12) | 0.8597 (4) | 0.46103 (13) | 0.0465 (7) | |
H12 | 0.1324 | 0.7692 | 0.4567 | 0.056* | |
O14 | 0.07742 (10) | 0.6447 (3) | 0.61058 (10) | 0.0607 (6) | |
C14A | 0.08051 (18) | 0.4616 (6) | 0.6179 (2) | 0.0791 (10) | |
O14B | 0.1048 (3) | 0.3678 (5) | 0.5886 (3) | 0.173 (2) | |
C14C | 0.0512 (3) | 0.3921 (8) | 0.6656 (3) | 0.127 (2) | |
H14A | 0.0396 | 0.2643 | 0.6561 | 0.191* | |
H14B | 0.0146 | 0.4643 | 0.6620 | 0.191* | |
H14C | 0.0804 | 0.4024 | 0.7099 | 0.191* | |
C16 | 0.19207 (16) | 0.8600 (6) | 0.66876 (16) | 0.0745 (10) | |
H16A | 0.2140 | 0.9738 | 0.6869 | 0.089* | |
H16B | 0.1722 | 0.8132 | 0.6995 | 0.089* | |
O16 | 0.23542 (11) | 0.7255 (5) | 0.66035 (11) | 0.0822 (8) | |
C16A | 0.2510 (2) | 0.5855 (8) | 0.6984 (2) | 0.1022 (15) | |
O16B | 0.2344 (4) | 0.5756 (11) | 0.7444 (3) | 0.272 (5) | |
C16C | 0.2925 (2) | 0.4510 (10) | 0.6811 (3) | 0.1246 (19) | |
H16C | 0.3351 | 0.4924 | 0.6992 | 0.187* | |
H16D | 0.2810 | 0.4416 | 0.6337 | 0.187* | |
H16E | 0.2885 | 0.3316 | 0.6993 | 0.187* | |
O11 | 0.17385 (10) | 1.0956 (4) | 0.46204 (11) | 0.0665 (6) | |
C11A | 0.1962 (3) | 1.2802 (7) | 0.4788 (3) | 0.1078 (17) | |
H11A | 0.1622 | 1.3661 | 0.4625 | 0.162* | |
H11B | 0.2276 | 1.3073 | 0.4589 | 0.162* | |
H11C | 0.2140 | 1.2914 | 0.5262 | 0.162* | |
O12 | 0.06299 (9) | 0.9156 (3) | 0.39597 (9) | 0.0605 (6) | |
C12A | 0.05499 (17) | 0.7933 (6) | 0.34735 (16) | 0.0647 (9) | |
O12B | 0.07856 (16) | 0.6436 (5) | 0.35551 (13) | 0.1047 (10) | |
C12C | 0.0102 (2) | 0.8648 (7) | 0.28403 (17) | 0.0952 (14) | |
H12A | 0.0015 | 0.7691 | 0.2509 | 0.143* | |
H12B | 0.0281 | 0.9701 | 0.2694 | 0.143* | |
H12C | −0.0280 | 0.9012 | 0.2910 | 0.143* | |
S2 | 0.5000 | 0.97527 (14) | 0.0000 | 0.0504 (3) | |
C23 | 0.46337 (14) | 0.8177 (4) | 0.04313 (13) | 0.0484 (7) | |
H23 | 0.4889 | 0.7050 | 0.0555 | 0.058* | |
C24 | 0.39672 (15) | 0.7633 (4) | 0.00179 (14) | 0.0545 (8) | |
H24 | 0.3807 | 0.6756 | 0.0274 | 0.065* | |
C25 | 0.35471 (13) | 0.9327 (5) | −0.01386 (14) | 0.0555 (7) | |
H25 | 0.3706 | 1.0234 | −0.0386 | 0.067* | |
O25 | 0.35581 (8) | 1.0108 (3) | 0.04826 (9) | 0.0588 (6) | |
C21 | 0.41579 (12) | 1.0751 (5) | 0.08979 (13) | 0.0510 (7) | |
H21 | 0.4316 | 1.1737 | 0.0679 | 0.061* | |
C22 | 0.45988 (13) | 0.9110 (5) | 0.10616 (13) | 0.0495 (7) | |
H22 | 0.4447 | 0.8204 | 0.1315 | 0.059* | |
O21 | 0.40895 (10) | 1.1376 (4) | 0.14776 (10) | 0.0702 (7) | |
C21A | 0.3779 (2) | 1.3135 (9) | 0.1412 (2) | 0.124 (2) | |
H21A | 0.4072 | 1.4111 | 0.1424 | 0.186* | |
H21B | 0.3616 | 1.3296 | 0.1771 | 0.186* | |
H21C | 0.3442 | 1.3177 | 0.0997 | 0.186* | |
O22 | 0.52012 (8) | 0.9780 (3) | 0.14720 (8) | 0.0509 (5) | |
C22A | 0.55538 (16) | 0.8637 (6) | 0.19447 (15) | 0.0627 (9) | |
O22B | 0.53879 (16) | 0.7114 (5) | 0.20135 (15) | 0.1117 (11) | |
C22C | 0.61622 (14) | 0.9470 (7) | 0.23186 (15) | 0.0776 (11) | |
H22A | 0.6287 | 0.9063 | 0.2772 | 0.116* | |
H22B | 0.6126 | 1.0798 | 0.2302 | 0.116* | |
H22C | 0.6470 | 0.9090 | 0.2125 | 0.116* | |
O24 | 0.39636 (12) | 0.6743 (3) | −0.05891 (11) | 0.0684 (6) | |
C24A | 0.3899 (2) | 0.4933 (6) | −0.06424 (18) | 0.0844 (11) | |
O24B | 0.3825 (4) | 0.4096 (5) | −0.0215 (2) | 0.248 (4) | |
C24C | 0.3930 (3) | 0.4115 (7) | −0.1262 (2) | 0.1039 (14) | |
H24A | 0.3988 | 0.2797 | −0.1208 | 0.156* | |
H24B | 0.4274 | 0.4647 | −0.1368 | 0.156* | |
H24C | 0.3547 | 0.4366 | −0.1616 | 0.156* | |
C26 | 0.28733 (15) | 0.8875 (6) | −0.05192 (17) | 0.0718 (10) | |
H26A | 0.2854 | 0.8141 | −0.0907 | 0.086* | |
H26B | 0.2701 | 0.8136 | −0.0241 | 0.086* | |
O26 | 0.25050 (9) | 1.0513 (4) | −0.07258 (10) | 0.0655 (6) | |
C26A | 0.24722 (15) | 1.1191 (6) | −0.13217 (16) | 0.0696 (10) | |
O26B | 0.27403 (14) | 1.0533 (6) | −0.16579 (13) | 0.1082 (11) | |
C26C | 0.2064 (2) | 1.2840 (9) | −0.1493 (2) | 0.1140 (19) | |
H26C | 0.2038 | 1.3269 | −0.1928 | 0.171* | |
H26D | 0.2236 | 1.3805 | −0.1174 | 0.171* | |
H26E | 0.1654 | 1.2520 | −0.1489 | 0.171* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0376 (5) | 0.0389 (6) | 0.0859 (7) | 0.000 | 0.0233 (5) | 0.000 |
C13 | 0.0406 (14) | 0.0391 (15) | 0.0542 (15) | 0.0011 (12) | 0.0165 (13) | −0.0042 (13) |
C14 | 0.0430 (15) | 0.0508 (17) | 0.0515 (15) | 0.0151 (13) | 0.0202 (13) | 0.0019 (14) |
C15 | 0.0488 (15) | 0.061 (2) | 0.0486 (15) | 0.0013 (15) | 0.0193 (13) | −0.0055 (14) |
O15 | 0.0415 (9) | 0.0675 (14) | 0.0551 (11) | −0.0040 (10) | 0.0153 (8) | −0.0043 (11) |
C11 | 0.0423 (14) | 0.0547 (18) | 0.0510 (15) | −0.0002 (13) | 0.0211 (13) | −0.0010 (14) |
C12 | 0.0439 (15) | 0.0516 (17) | 0.0445 (14) | 0.0054 (13) | 0.0154 (12) | −0.0029 (13) |
O14 | 0.0732 (13) | 0.0534 (14) | 0.0690 (12) | 0.0163 (11) | 0.0415 (11) | 0.0114 (11) |
C14A | 0.097 (3) | 0.051 (2) | 0.107 (3) | 0.014 (2) | 0.059 (2) | 0.012 (2) |
O14B | 0.297 (6) | 0.0479 (18) | 0.278 (5) | 0.008 (3) | 0.233 (5) | −0.002 (3) |
C14C | 0.173 (5) | 0.080 (3) | 0.176 (5) | 0.033 (3) | 0.120 (4) | 0.059 (4) |
C16 | 0.070 (2) | 0.094 (3) | 0.0546 (19) | 0.008 (2) | 0.0140 (17) | −0.009 (2) |
O16 | 0.0631 (14) | 0.117 (2) | 0.0610 (13) | 0.0220 (15) | 0.0127 (12) | 0.0186 (16) |
C16A | 0.123 (4) | 0.104 (4) | 0.086 (3) | 0.003 (3) | 0.043 (3) | 0.030 (3) |
O16B | 0.424 (10) | 0.215 (7) | 0.290 (7) | 0.180 (7) | 0.271 (8) | 0.177 (6) |
C16C | 0.123 (4) | 0.121 (5) | 0.118 (3) | 0.048 (4) | 0.023 (3) | 0.018 (4) |
O11 | 0.0615 (13) | 0.0736 (16) | 0.0782 (13) | −0.0127 (12) | 0.0416 (11) | −0.0053 (13) |
C11A | 0.131 (4) | 0.090 (3) | 0.133 (4) | −0.048 (3) | 0.085 (3) | −0.014 (3) |
O12 | 0.0692 (12) | 0.0607 (14) | 0.0450 (11) | 0.0031 (11) | 0.0101 (9) | −0.0033 (11) |
C12A | 0.074 (2) | 0.073 (3) | 0.0491 (18) | −0.009 (2) | 0.0232 (17) | −0.0021 (18) |
O12B | 0.138 (3) | 0.097 (3) | 0.0672 (15) | 0.026 (2) | 0.0173 (16) | −0.0258 (17) |
C12C | 0.115 (3) | 0.100 (3) | 0.057 (2) | −0.021 (3) | 0.011 (2) | 0.004 (2) |
S2 | 0.0613 (6) | 0.0382 (5) | 0.0579 (6) | 0.000 | 0.0282 (5) | 0.000 |
C23 | 0.0598 (18) | 0.0373 (16) | 0.0488 (15) | −0.0016 (13) | 0.0190 (14) | 0.0019 (13) |
C24 | 0.071 (2) | 0.0448 (17) | 0.0457 (15) | −0.0159 (16) | 0.0166 (15) | 0.0003 (14) |
C25 | 0.0516 (15) | 0.061 (2) | 0.0480 (15) | −0.0126 (15) | 0.0085 (13) | −0.0003 (15) |
O25 | 0.0420 (10) | 0.0770 (16) | 0.0533 (11) | −0.0082 (10) | 0.0100 (9) | −0.0079 (11) |
C21 | 0.0415 (15) | 0.0599 (18) | 0.0476 (15) | 0.0003 (14) | 0.0093 (12) | −0.0031 (14) |
C22 | 0.0518 (15) | 0.0502 (17) | 0.0466 (14) | −0.0089 (14) | 0.0164 (12) | 0.0023 (14) |
O21 | 0.0554 (12) | 0.097 (2) | 0.0535 (11) | 0.0139 (13) | 0.0119 (10) | −0.0157 (12) |
C21A | 0.102 (3) | 0.154 (5) | 0.091 (3) | 0.076 (4) | −0.001 (3) | −0.036 (3) |
O22 | 0.0438 (9) | 0.0566 (12) | 0.0459 (9) | 0.0004 (10) | 0.0060 (8) | 0.0055 (10) |
C22A | 0.066 (2) | 0.076 (3) | 0.0431 (16) | 0.0171 (19) | 0.0140 (16) | 0.0132 (17) |
O22B | 0.119 (2) | 0.087 (2) | 0.100 (2) | −0.007 (2) | −0.0042 (18) | 0.044 (2) |
C22C | 0.0615 (19) | 0.111 (3) | 0.0533 (17) | 0.012 (2) | 0.0090 (15) | 0.004 (2) |
O24 | 0.1048 (17) | 0.0452 (13) | 0.0560 (11) | −0.0225 (12) | 0.0276 (12) | −0.0062 (10) |
C24A | 0.143 (3) | 0.047 (2) | 0.066 (2) | −0.011 (2) | 0.037 (2) | 0.0012 (19) |
O24B | 0.606 (13) | 0.048 (2) | 0.171 (4) | −0.011 (4) | 0.237 (6) | −0.003 (3) |
C24C | 0.156 (4) | 0.069 (3) | 0.088 (3) | −0.025 (3) | 0.042 (3) | −0.024 (2) |
C26 | 0.062 (2) | 0.074 (3) | 0.068 (2) | −0.0157 (19) | 0.0062 (17) | 0.0081 (19) |
O26 | 0.0550 (12) | 0.0881 (17) | 0.0511 (11) | −0.0059 (12) | 0.0145 (9) | 0.0006 (12) |
C26A | 0.062 (2) | 0.091 (3) | 0.0586 (19) | 0.0005 (19) | 0.0241 (17) | 0.0071 (19) |
O26B | 0.126 (2) | 0.138 (3) | 0.0759 (16) | 0.043 (2) | 0.0538 (17) | 0.0097 (18) |
C26C | 0.118 (4) | 0.132 (5) | 0.106 (3) | 0.047 (4) | 0.055 (3) | 0.041 (3) |
S1—C13i | 1.831 (3) | S2—C23 | 1.824 (3) |
S1—C13 | 1.831 (3) | S2—C23ii | 1.824 (3) |
C13—C12 | 1.526 (4) | C23—C24 | 1.527 (4) |
C13—C14 | 1.530 (4) | C23—C22 | 1.528 (4) |
C13—H13 | 0.9800 | C23—H23 | 0.9800 |
C14—O14 | 1.437 (3) | C24—O24 | 1.442 (4) |
C14—C15 | 1.508 (5) | C24—C25 | 1.515 (5) |
C14—H14 | 0.9800 | C24—H24 | 0.9800 |
C15—O15 | 1.426 (3) | C25—O25 | 1.432 (4) |
C15—C16 | 1.511 (4) | C25—C26 | 1.509 (4) |
C15—H15 | 0.9800 | C25—H25 | 0.9800 |
O15—C11 | 1.428 (3) | O25—C21 | 1.432 (3) |
C11—O11 | 1.377 (3) | C21—O21 | 1.372 (3) |
C11—C12 | 1.517 (4) | C21—C22 | 1.511 (4) |
C11—H11 | 0.9800 | C21—H21 | 0.9800 |
C12—O12 | 1.432 (3) | C22—O22 | 1.439 (3) |
C12—H12 | 0.9800 | C22—H22 | 0.9800 |
O14—C14A | 1.327 (5) | O21—C21A | 1.432 (6) |
C14A—O14B | 1.173 (5) | C21A—H21A | 0.9600 |
C14A—C14C | 1.474 (5) | C21A—H21B | 0.9600 |
C14C—H14A | 0.9600 | C21A—H21C | 0.9600 |
C14C—H14B | 0.9600 | O22—C22A | 1.342 (4) |
C14C—H14C | 0.9600 | C22A—O22B | 1.184 (5) |
C16—O16 | 1.432 (5) | C22A—C22C | 1.473 (5) |
C16—H16A | 0.9700 | C22C—H22A | 0.9600 |
C16—H16B | 0.9700 | C22C—H22B | 0.9600 |
O16—C16A | 1.269 (6) | C22C—H22C | 0.9600 |
C16A—O16B | 1.163 (5) | O24—C24A | 1.313 (5) |
C16A—C16C | 1.478 (8) | C24A—O24B | 1.151 (5) |
C16C—H16C | 0.9600 | C24A—C24C | 1.470 (6) |
C16C—H16D | 0.9600 | C24C—H24A | 0.9600 |
C16C—H16E | 0.9600 | C24C—H24B | 0.9600 |
O11—C11A | 1.425 (6) | C24C—H24C | 0.9600 |
C11A—H11A | 0.9600 | C26—O26 | 1.428 (5) |
C11A—H11B | 0.9600 | C26—H26A | 0.9700 |
C11A—H11C | 0.9600 | C26—H26B | 0.9700 |
O12—C12A | 1.327 (4) | O26—C26A | 1.340 (4) |
C12A—O12B | 1.190 (5) | C26A—O26B | 1.181 (4) |
C12A—C12C | 1.488 (5) | C26A—C26C | 1.474 (7) |
C12C—H12A | 0.9600 | C26C—H26C | 0.9600 |
C12C—H12B | 0.9600 | C26C—H26D | 0.9600 |
C12C—H12C | 0.9600 | C26C—H26E | 0.9600 |
C13i—S1—C13 | 102.64 (18) | C23—S2—C23ii | 103.03 (19) |
C12—C13—C14 | 106.2 (2) | C24—C23—C22 | 107.0 (2) |
C12—C13—S1 | 109.04 (19) | C24—C23—S2 | 113.33 (19) |
C14—C13—S1 | 113.80 (18) | C22—C23—S2 | 109.5 (2) |
C12—C13—H13 | 109.2 | C24—C23—H23 | 109.0 |
C14—C13—H13 | 109.2 | C22—C23—H23 | 109.0 |
S1—C13—H13 | 109.2 | S2—C23—H23 | 109.0 |
O14—C14—C15 | 109.3 (2) | O24—C24—C25 | 110.0 (2) |
O14—C14—C13 | 111.6 (2) | O24—C24—C23 | 110.1 (2) |
C15—C14—C13 | 111.6 (2) | C25—C24—C23 | 110.5 (2) |
O14—C14—H14 | 108.1 | O24—C24—H24 | 108.7 |
C15—C14—H14 | 108.1 | C25—C24—H24 | 108.7 |
C13—C14—H14 | 108.1 | C23—C24—H24 | 108.7 |
O15—C15—C14 | 108.7 (2) | O25—C25—C26 | 106.8 (2) |
O15—C15—C16 | 106.7 (2) | O25—C25—C24 | 107.1 (2) |
C14—C15—C16 | 113.4 (3) | C26—C25—C24 | 113.2 (3) |
O15—C15—H15 | 109.3 | O25—C25—H25 | 109.9 |
C14—C15—H15 | 109.3 | C26—C25—H25 | 109.9 |
C16—C15—H15 | 109.3 | C24—C25—H25 | 109.9 |
C15—O15—C11 | 114.94 (19) | C25—O25—C21 | 115.02 (19) |
O11—C11—O15 | 107.9 (2) | O21—C21—O25 | 107.3 (2) |
O11—C11—C12 | 108.7 (2) | O21—C21—C22 | 108.1 (2) |
O15—C11—C12 | 108.0 (2) | O25—C21—C22 | 108.0 (3) |
O11—C11—H11 | 110.7 | O21—C21—H21 | 111.1 |
O15—C11—H11 | 110.7 | O25—C21—H21 | 111.1 |
C12—C11—H11 | 110.7 | C22—C21—H21 | 111.1 |
O12—C12—C11 | 107.5 (2) | O22—C22—C21 | 107.4 (2) |
O12—C12—C13 | 111.4 (2) | O22—C22—C23 | 111.6 (2) |
C11—C12—C13 | 111.5 (2) | C21—C22—C23 | 111.3 (2) |
O12—C12—H12 | 108.8 | O22—C22—H22 | 108.8 |
C11—C12—H12 | 108.8 | C21—C22—H22 | 108.8 |
C13—C12—H12 | 108.8 | C23—C22—H22 | 108.8 |
C14A—O14—C14 | 117.8 (2) | C21—O21—C21A | 113.5 (3) |
O14B—C14A—O14 | 121.7 (3) | O21—C21A—H21A | 109.5 |
O14B—C14A—C14C | 124.7 (4) | O21—C21A—H21B | 109.5 |
O14—C14A—C14C | 113.6 (3) | H21A—C21A—H21B | 109.5 |
C14A—C14C—H14A | 109.5 | O21—C21A—H21C | 109.5 |
C14A—C14C—H14B | 109.5 | H21A—C21A—H21C | 109.5 |
H14A—C14C—H14B | 109.5 | H21B—C21A—H21C | 109.5 |
C14A—C14C—H14C | 109.5 | C22A—O22—C22 | 117.4 (3) |
H14A—C14C—H14C | 109.5 | O22B—C22A—O22 | 121.8 (3) |
H14B—C14C—H14C | 109.5 | O22B—C22A—C22C | 126.1 (3) |
O16—C16—C15 | 109.1 (3) | O22—C22A—C22C | 112.0 (3) |
O16—C16—H16A | 109.9 | C22A—C22C—H22A | 109.5 |
C15—C16—H16A | 109.9 | C22A—C22C—H22B | 109.5 |
O16—C16—H16B | 109.9 | H22A—C22C—H22B | 109.5 |
C15—C16—H16B | 109.9 | C22A—C22C—H22C | 109.5 |
H16A—C16—H16B | 108.3 | H22A—C22C—H22C | 109.5 |
C16A—O16—C16 | 121.0 (3) | H22B—C22C—H22C | 109.5 |
O16B—C16A—O16 | 119.3 (6) | C24A—O24—C24 | 119.1 (3) |
O16B—C16A—C16C | 125.4 (5) | O24B—C24A—O24 | 119.5 (4) |
O16—C16A—C16C | 115.3 (4) | O24B—C24A—C24C | 124.4 (4) |
C16A—C16C—H16C | 109.5 | O24—C24A—C24C | 116.1 (3) |
C16A—C16C—H16D | 109.5 | C24A—C24C—H24A | 109.5 |
H16C—C16C—H16D | 109.5 | C24A—C24C—H24B | 109.5 |
C16A—C16C—H16E | 109.5 | H24A—C24C—H24B | 109.5 |
H16C—C16C—H16E | 109.5 | C24A—C24C—H24C | 109.5 |
H16D—C16C—H16E | 109.5 | H24A—C24C—H24C | 109.5 |
C11—O11—C11A | 114.5 (3) | H24B—C24C—H24C | 109.5 |
O11—C11A—H11A | 109.5 | O26—C26—C25 | 111.8 (3) |
O11—C11A—H11B | 109.5 | O26—C26—H26A | 109.2 |
H11A—C11A—H11B | 109.5 | C25—C26—H26A | 109.2 |
O11—C11A—H11C | 109.5 | O26—C26—H26B | 109.2 |
H11A—C11A—H11C | 109.5 | C25—C26—H26B | 109.2 |
H11B—C11A—H11C | 109.5 | H26A—C26—H26B | 107.9 |
C12A—O12—C12 | 116.9 (3) | C26A—O26—C26 | 116.0 (3) |
O12B—C12A—O12 | 123.2 (3) | O26B—C26A—O26 | 123.4 (4) |
O12B—C12A—C12C | 125.8 (4) | O26B—C26A—C26C | 125.3 (4) |
O12—C12A—C12C | 110.9 (4) | O26—C26A—C26C | 111.3 (3) |
C12A—C12C—H12A | 109.5 | C26A—C26C—H26C | 109.5 |
C12A—C12C—H12B | 109.5 | C26A—C26C—H26D | 109.5 |
H12A—C12C—H12B | 109.5 | H26C—C26C—H26D | 109.5 |
C12A—C12C—H12C | 109.5 | C26A—C26C—H26E | 109.5 |
H12A—C12C—H12C | 109.5 | H26C—C26C—H26E | 109.5 |
H12B—C12C—H12C | 109.5 | H26D—C26C—H26E | 109.5 |
C13i—S1—C13—C12 | 147.8 (2) | C23ii—S2—C23—C22 | 151.4 (2) |
C13i—S1—C13—C14 | −93.8 (2) | C23ii—S2—C23—C24 | −89.2 (2) |
C12—C13—C14—O14 | 179.1 (2) | C22—C23—C24—O24 | 179.8 (2) |
S1—C13—C14—O14 | 59.1 (3) | S2—C23—C24—O24 | 59.0 (3) |
C12—C13—C14—C15 | 56.5 (3) | C22—C23—C24—C25 | 58.1 (3) |
S1—C13—C14—C15 | −63.5 (3) | S2—C23—C24—C25 | −62.8 (3) |
O14—C14—C15—O15 | 178.6 (2) | O24—C24—C25—O25 | 178.4 (2) |
C13—C14—C15—O15 | −57.6 (3) | C23—C24—C25—O25 | −59.8 (3) |
O14—C14—C15—C16 | 60.0 (3) | O24—C24—C25—C26 | 60.9 (3) |
C13—C14—C15—C16 | −176.1 (2) | C23—C24—C25—C26 | −177.2 (2) |
C14—C15—O15—C11 | 60.2 (3) | C26—C25—O25—C21 | −175.8 (3) |
C16—C15—O15—C11 | −177.1 (3) | C24—C25—O25—C21 | 62.6 (3) |
C15—O15—C11—O11 | −177.7 (3) | C25—O25—C21—O21 | −177.5 (3) |
C15—O15—C11—C12 | −60.4 (3) | C25—O25—C21—C22 | −61.2 (3) |
O11—C11—C12—O12 | −62.6 (3) | O21—C21—C22—O22 | −64.9 (3) |
O15—C11—C12—O12 | −179.32 (19) | O25—C21—C22—O22 | 179.29 (18) |
O11—C11—C12—C13 | 175.1 (2) | O21—C21—C22—C23 | 172.7 (2) |
O15—C11—C12—C13 | 58.4 (3) | O25—C21—C22—C23 | 56.8 (3) |
C14—C13—C12—O12 | −177.0 (2) | C24—C23—C22—O22 | −176.6 (2) |
S1—C13—C12—O12 | −54.0 (3) | S2—C23—C22—O22 | −53.4 (3) |
C14—C13—C12—C11 | −56.9 (3) | C24—C23—C22—C21 | −56.6 (3) |
S1—C13—C12—C11 | 66.1 (3) | S2—C23—C22—C21 | 66.6 (3) |
C15—C14—O14—C14A | −136.4 (3) | O25—C21—O21—C21A | −74.9 (4) |
C13—C14—O14—C14A | 99.7 (3) | C22—C21—O21—C21A | 168.8 (3) |
C14—O14—C14A—O14B | −4.3 (7) | C21—C22—O22—C22A | 145.7 (2) |
C14—O14—C14A—C14C | 175.5 (4) | C23—C22—O22—C22A | −92.1 (3) |
O15—C15—C16—O16 | −62.7 (4) | C22—O22—C22A—O22B | 2.1 (5) |
C14—C15—C16—O16 | 57.0 (4) | C22—O22—C22A—C22C | 178.7 (2) |
C15—C16—O16—C16A | −132.0 (4) | C25—C24—O24—C24A | −134.0 (4) |
C16—O16—C16A—O16B | −7.2 (9) | C23—C24—O24—C24A | 104.0 (4) |
C16—O16—C16A—C16C | 175.8 (4) | C24—O24—C24A—O24B | 2.7 (8) |
O15—C11—O11—C11A | −78.7 (4) | C24—O24—C24A—C24C | −177.2 (3) |
C12—C11—O11—C11A | 164.4 (3) | O25—C25—C26—O26 | 69.2 (3) |
C11—C12—O12—C12A | 146.0 (3) | C24—C25—C26—O26 | −173.2 (3) |
C13—C12—O12—C12A | −91.5 (3) | C25—C26—O26—C26A | 89.9 (3) |
C12—O12—C12A—O12B | −0.7 (5) | C26—O26—C26A—O26B | −2.0 (5) |
C12—O12—C12A—C12C | 175.7 (3) | C26—O26—C26A—C26C | 178.1 (4) |
Symmetry codes: (i) −x, y, −z+1; (ii) −x+1, y, −z. |
Experimental details
Crystal data | |
Chemical formula | C26H38O16S |
Mr | 638.62 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 22.6458 (13), 7.2018 (3), 21.3260 (12) |
β (°) | 109.258 (7) |
V (Å3) | 3283.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.30 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur-II with Sapphire-III CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.95, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10820, 4492, 3486 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.110, 1.05 |
No. of reflections | 4492 |
No. of parameters | 398 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.27 |
Absolute structure | Flack (1983), 1101 Friedel pairs |
Absolute structure parameter | −0.03 (9) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), PLATON (Spek, 2003).
The title compound (I) was synthesized as part of a program towards the synthesis of thioether-linked disaccharides as new glycomimetics (Cumpstey, 2006). The title compound crystallizes with two unique half molecules in the asymmetric unit. Both molecules are shown in Fig. 1. Both of the sulfur atoms are positioned on a two fold axis whereby the second half of each molecule is generated through the two fold rotation. A packing view of the structure is shown in Fig 2. The conformations of the sugar rings in the two molecules are very similar as can be seen from corresponding geometrical parameters for the two rings. The Cremer Pople parameters (Cremer & Pople, 1975) for the ring O15→ C11→ C12→ C13→ C14→ C15 are: Q=0.587 (3) Å, θ=0.0 (3)° and φ=159 (9)° while for the ring O25→ C21→ C22→ C23→ C24→ C25 they are: Q=0.597 (3) Å, θ=1.3 (3)° and φ=244 (7)°. Both rings are on C-form. The major conformational difference between the molecules is shown in an overlay of the two unique half molecules (Fig. 3), the acetyl group starting at O16 in one of the molecules deviates significantly from the corresponding acetyl group, beginning with O26 in the other molecule. The rest of the atoms, except for these two acetyl groups, have an average deviation of 0.06 (6)Å between the atoms of one residue and the overlaid residue.