Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101000609/bj1013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101000609/bj1013Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101000609/bj1013IIsup3.hkl |
CCDC references: 164646; 164647
For related literature, see: Avalos et al. (1990); Cremer & Pople (1975); Ferrier (1963); Garg & Jeanloz (1985); Lee et al. (1995); Mostad (1978); Mukerjee & Ashare (1991); Tyms et al. (1990); Varki (1993); Yasuo et al. (1999).
A solution of 2,3,4,6-tetra-O-acetyl-β-D-glycosyl isothiocyanate (0.3 g) in ethanol (20 ml) and methanol (20 ml) for (I) and (II), respectively, was added dropwise to boiling ethanol (20 ml) for (I) and methanol (20 ml) for (II). The boiling solution was stirred for 2 h while refluxing. After filtration, the clear colourless filtrate was left at room temperature until single crystals suitable for X-ray analysis were obtained.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their parent atoms. C—H distances? However, the H atom on N15 in both structures, which is involved in intermolecular hydrogen bonding, was located from a difference Fourier map and refined isotropically. The C7, C11 and C13 methyl groups for (I) were refined using rotating-group refinement. Please check - C13 not a methyl carbon. Should it be C14?
For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
C17H25NO10S | F(000) = 460 |
Mr = 435.44 | Dx = 1.264 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7492 (2) Å | Cell parameters from 4350 reflections |
b = 10.4470 (3) Å | θ = 1.4–28.5° |
c = 14.3852 (3) Å | µ = 0.19 mm−1 |
β = 100.810 (1)° | T = 293 K |
V = 1143.90 (5) Å3 | Parallelepiped, colourless |
Z = 2 | 0.44 × 0.34 × 0.30 mm |
Siemens SMART CCD area-detector diffractometer | 5034 independent reflections |
Radiation source: fine-focus sealed tube | 2780 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
Detector resolution: 8.33 pixels mm-1 | θmax = 27.9°, θmin = 1.4° |
ω scans | h = −8→10 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −13→13 |
Tmin = 0.921, Tmax = 0.945 | l = −18→18 |
7784 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.062 | w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.168 | (Δ/σ)max < 0.001 |
S = 0.88 | Δρmax = 0.34 e Å−3 |
5034 reflections | Δρmin = −0.31 e Å−3 |
267 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.055 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.10 (13) |
C17H25NO10S | V = 1143.90 (5) Å3 |
Mr = 435.44 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.7492 (2) Å | µ = 0.19 mm−1 |
b = 10.4470 (3) Å | T = 293 K |
c = 14.3852 (3) Å | 0.44 × 0.34 × 0.30 mm |
β = 100.810 (1)° |
Siemens SMART CCD area-detector diffractometer | 5034 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2780 reflections with I > 2σ(I) |
Tmin = 0.921, Tmax = 0.945 | Rint = 0.084 |
7784 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.168 | Δρmax = 0.34 e Å−3 |
S = 0.88 | Δρmin = −0.31 e Å−3 |
5034 reflections | Absolute structure: Flack (1983) |
267 parameters | Absolute structure parameter: −0.10 (13) |
3 restraints |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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 | Occ. (<1) | |
S1 | 0.54892 (17) | 0.41399 (11) | 0.68914 (9) | 0.0918 (4) | |
O1 | 0.4248 (3) | 0.7520 (2) | 0.67308 (15) | 0.0507 (6) | |
O2 | 0.4085 (4) | 0.6917 (3) | 0.92413 (18) | 0.0676 (7) | |
O3 | 0.5855 (7) | 0.8385 (5) | 1.0070 (2) | 0.148 (2) | |
O4 | 0.1738 (3) | 0.9040 (3) | 0.87532 (16) | 0.0582 (6) | |
O5 | −0.0952 (5) | 0.8271 (5) | 0.8781 (3) | 0.1202 (15) | |
O6 | −0.0114 (3) | 0.8894 (2) | 0.67380 (16) | 0.0533 (6) | |
O7 | 0.0183 (5) | 1.1020 (3) | 0.6976 (4) | 0.1301 (17) | |
O8 | 0.2991 (3) | 0.9635 (2) | 0.54130 (18) | 0.0623 (7) | |
O9 | 0.0417 (4) | 1.0440 (4) | 0.4639 (3) | 0.1103 (13) | |
C1 | 0.4486 (4) | 0.6790 (3) | 0.7602 (2) | 0.0502 (8) | |
H1A | 0.3712 | 0.6041 | 0.7513 | 0.060* | |
C2 | 0.3987 (4) | 0.7655 (3) | 0.8376 (2) | 0.0503 (8) | |
H2A | 0.4778 | 0.8394 | 0.8488 | 0.060* | |
C3 | 0.2075 (4) | 0.8103 (3) | 0.8068 (2) | 0.0483 (8) | |
H3A | 0.1282 | 0.7372 | 0.8070 | 0.058* | |
C4 | 0.1765 (4) | 0.8705 (3) | 0.7081 (2) | 0.0481 (8) | |
H4A | 0.2381 | 0.9526 | 0.7102 | 0.058* | |
C5 | 0.2428 (4) | 0.7787 (3) | 0.6370 (2) | 0.0491 (8) | |
H5A | 0.1763 | 0.6985 | 0.6336 | 0.059* | |
C6 | 0.5073 (6) | 0.7404 (5) | 1.0049 (3) | 0.0703 (11) | |
C7 | 0.4978 (7) | 0.6552 (5) | 1.0893 (3) | 0.0891 (15) | |
H7A | 0.4821 | 0.5678 | 1.0686 | 0.134* | |
H7B | 0.4005 | 0.6809 | 1.1175 | 0.134* | |
H7C | 0.6048 | 0.6628 | 1.1349 | 0.134* | |
H7D | 0.5103 | 0.7073 | 1.1451 | 0.134* | 0.00 |
H7E | 0.5913 | 0.5936 | 1.0965 | 0.134* | 0.00 |
H7F | 0.3870 | 0.6114 | 1.0800 | 0.134* | 0.00 |
C8 | 0.0176 (5) | 0.9053 (5) | 0.9042 (3) | 0.0702 (11) | |
C9 | 0.0058 (8) | 1.0167 (7) | 0.9677 (4) | 0.113 (2) | |
H9A | 0.1140 | 1.0639 | 0.9770 | 0.169* | |
H9B | −0.0149 | 0.9865 | 1.0277 | 0.169* | |
H9C | −0.0892 | 1.0714 | 0.9394 | 0.169* | |
C10 | −0.0754 (5) | 1.0119 (4) | 0.6721 (3) | 0.0715 (11) | |
C11 | −0.2685 (6) | 1.0154 (5) | 0.6351 (4) | 0.0993 (16) | |
H11A | −0.2998 | 0.9483 | 0.5894 | 0.149* | |
H11B | −0.2999 | 1.0967 | 0.6055 | 0.149* | |
H11C | −0.3302 | 1.0035 | 0.6864 | 0.149* | |
H11D | −0.3203 | 1.0840 | 0.6648 | 0.149* | 0.00 |
H11E | −0.3198 | 0.9356 | 0.6487 | 0.149* | 0.00 |
H11F | −0.2898 | 1.0288 | 0.5679 | 0.149* | 0.00 |
C12 | 0.2244 (5) | 0.8342 (4) | 0.5378 (3) | 0.0611 (10) | |
H12A | 0.2846 | 0.7794 | 0.4998 | 0.073* | |
H12B | 0.1012 | 0.8372 | 0.5083 | 0.073* | |
C13 | 0.1950 (6) | 1.0590 (4) | 0.4987 (3) | 0.0714 (11) | |
C14 | 0.2937 (6) | 1.1830 (5) | 0.5060 (4) | 0.0982 (17) | |
H14A | 0.3959 | 1.1769 | 0.5552 | 0.147* | |
H14B | 0.2194 | 1.2507 | 0.5206 | 0.147* | |
H14C | 0.3290 | 1.2009 | 0.4468 | 0.147* | |
H14D | 0.2336 | 1.2422 | 0.4600 | 0.147* | 0.00 |
H14E | 0.4102 | 1.1685 | 0.4944 | 0.147* | 0.00 |
H14F | 0.3004 | 1.2179 | 0.5683 | 0.147* | 0.00 |
N15 | 0.6291 (4) | 0.6375 (3) | 0.7831 (2) | 0.0607 (8) | |
C16 | 0.6819 (5) | 0.5210 (4) | 0.7519 (2) | 0.0595 (10) | |
O17 | 0.8546 (4) | 0.5099 (3) | 0.7795 (2) | 0.0864 (9) | |
C18 | 0.9330 (6) | 0.3859 (6) | 0.7584 (4) | 0.1087 (19) | |
H18A | 0.8999 | 0.3659 | 0.6916 | 0.130* | |
H18B | 0.8925 | 0.3174 | 0.7944 | 0.130* | |
C19 | 1.1273 (7) | 0.4004 (8) | 0.7855 (7) | 0.168 (3) | |
H19A | 1.1832 | 0.3221 | 0.7725 | 0.252* | |
H19B | 1.1584 | 0.4196 | 0.8517 | 0.252* | |
H19C | 1.1655 | 0.4687 | 0.7496 | 0.252* | |
H15A | 0.711 (4) | 0.695 (3) | 0.807 (3) | 0.097 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0850 (9) | 0.0737 (8) | 0.1087 (9) | 0.0072 (6) | −0.0027 (7) | −0.0385 (7) |
O1 | 0.0303 (13) | 0.0560 (13) | 0.0617 (14) | 0.0111 (10) | −0.0016 (9) | −0.0068 (11) |
O2 | 0.0764 (19) | 0.0550 (15) | 0.0611 (16) | −0.0001 (13) | −0.0139 (13) | 0.0018 (12) |
O3 | 0.170 (4) | 0.181 (5) | 0.071 (2) | −0.106 (4) | −0.038 (2) | 0.018 (2) |
O4 | 0.0429 (15) | 0.0624 (14) | 0.0667 (14) | −0.0031 (12) | 0.0036 (10) | −0.0150 (13) |
O5 | 0.063 (2) | 0.177 (4) | 0.128 (3) | −0.050 (2) | 0.037 (2) | −0.045 (3) |
O6 | 0.0282 (12) | 0.0520 (13) | 0.0735 (14) | 0.0059 (10) | −0.0062 (10) | −0.0030 (11) |
O7 | 0.060 (2) | 0.0587 (19) | 0.254 (5) | 0.0127 (16) | −0.016 (3) | −0.039 (3) |
O8 | 0.0381 (14) | 0.0723 (17) | 0.0712 (15) | 0.0046 (12) | −0.0032 (10) | 0.0120 (13) |
O9 | 0.051 (2) | 0.098 (3) | 0.162 (3) | 0.0101 (17) | −0.0326 (19) | 0.026 (2) |
C1 | 0.037 (2) | 0.0466 (18) | 0.061 (2) | 0.0003 (15) | −0.0080 (14) | 0.0001 (16) |
C2 | 0.042 (2) | 0.0503 (18) | 0.0512 (19) | 0.0025 (15) | −0.0088 (13) | −0.0019 (15) |
C3 | 0.0349 (19) | 0.0472 (17) | 0.059 (2) | −0.0026 (14) | 0.0001 (13) | −0.0060 (15) |
C4 | 0.0294 (17) | 0.0507 (18) | 0.0593 (19) | −0.0007 (14) | −0.0041 (13) | −0.0102 (15) |
C5 | 0.0303 (18) | 0.0511 (18) | 0.060 (2) | 0.0040 (14) | −0.0067 (13) | −0.0078 (16) |
C6 | 0.057 (3) | 0.087 (3) | 0.061 (2) | −0.011 (2) | −0.0037 (17) | −0.006 (2) |
C7 | 0.107 (4) | 0.094 (3) | 0.061 (3) | 0.005 (3) | 0.001 (2) | 0.000 (2) |
C8 | 0.037 (2) | 0.100 (3) | 0.072 (2) | −0.007 (2) | 0.0088 (17) | −0.008 (2) |
C9 | 0.091 (4) | 0.153 (5) | 0.101 (4) | 0.003 (4) | 0.036 (3) | −0.049 (4) |
C10 | 0.047 (2) | 0.061 (2) | 0.102 (3) | 0.018 (2) | 0.001 (2) | −0.005 (2) |
C11 | 0.045 (3) | 0.093 (4) | 0.154 (4) | 0.025 (3) | 0.003 (3) | 0.011 (3) |
C12 | 0.043 (2) | 0.072 (2) | 0.064 (2) | 0.0073 (18) | −0.0034 (16) | −0.0057 (19) |
C13 | 0.053 (3) | 0.076 (3) | 0.078 (3) | 0.016 (2) | −0.0061 (19) | 0.018 (2) |
C14 | 0.063 (3) | 0.083 (3) | 0.141 (5) | −0.002 (3) | 0.000 (3) | 0.040 (3) |
N15 | 0.0380 (19) | 0.0536 (17) | 0.081 (2) | 0.0081 (14) | −0.0122 (14) | −0.0122 (16) |
C16 | 0.056 (3) | 0.055 (2) | 0.062 (2) | 0.0209 (18) | −0.0045 (16) | −0.0016 (17) |
O17 | 0.0607 (19) | 0.0795 (19) | 0.107 (2) | 0.0341 (16) | −0.0151 (15) | −0.0197 (18) |
C18 | 0.084 (4) | 0.112 (4) | 0.119 (4) | 0.057 (3) | −0.010 (3) | −0.028 (3) |
C19 | 0.088 (5) | 0.122 (5) | 0.287 (10) | 0.020 (5) | 0.021 (5) | −0.067 (7) |
S1—C16 | 1.667 (4) | C1—N15 | 1.442 (4) |
O1—C5 | 1.436 (4) | C1—C2 | 1.538 (5) |
O1—C1 | 1.449 (4) | C2—C3 | 1.538 (5) |
O2—C6 | 1.365 (5) | C3—C4 | 1.530 (5) |
O2—C2 | 1.454 (4) | C4—C5 | 1.558 (4) |
O3—C6 | 1.188 (6) | C5—C12 | 1.521 (5) |
O4—C8 | 1.352 (4) | C6—C7 | 1.517 (7) |
O4—C3 | 1.447 (4) | C8—C9 | 1.493 (7) |
O5—C8 | 1.204 (6) | C10—C11 | 1.492 (6) |
O6—C10 | 1.371 (5) | C13—C14 | 1.498 (7) |
O6—C4 | 1.461 (4) | N15—C16 | 1.385 (5) |
O7—C10 | 1.204 (5) | C16—O17 | 1.328 (4) |
O8—C13 | 1.355 (5) | O17—C18 | 1.486 (6) |
O8—C12 | 1.467 (5) | C18—C19 | 1.490 (8) |
O9—C13 | 1.209 (5) | ||
C5—O1—C1 | 111.8 (2) | O3—C6—O2 | 123.0 (4) |
C6—O2—C2 | 117.5 (3) | O3—C6—C7 | 126.0 (4) |
C8—O4—C3 | 120.1 (3) | O2—C6—C7 | 111.0 (4) |
C10—O6—C4 | 117.8 (3) | O5—C8—O4 | 122.5 (4) |
C13—O8—C12 | 117.7 (3) | O5—C8—C9 | 126.6 (4) |
N15—C1—O1 | 108.4 (3) | O4—C8—C9 | 110.9 (4) |
N15—C1—C2 | 112.1 (3) | O7—C10—O6 | 122.0 (4) |
O1—C1—C2 | 108.0 (2) | O7—C10—C11 | 126.6 (4) |
O2—C2—C1 | 109.2 (3) | O6—C10—C11 | 111.4 (4) |
O2—C2—C3 | 107.5 (3) | O8—C12—C5 | 110.6 (3) |
C1—C2—C3 | 109.2 (2) | O9—C13—O8 | 123.2 (4) |
O4—C3—C4 | 109.7 (3) | O9—C13—C14 | 126.1 (4) |
O4—C3—C2 | 107.3 (2) | O8—C13—C14 | 110.6 (4) |
C4—C3—C2 | 111.5 (3) | C16—N15—C1 | 121.6 (3) |
O6—C4—C3 | 110.0 (3) | O17—C16—N15 | 108.8 (3) |
O6—C4—C5 | 107.0 (2) | O17—C16—S1 | 126.1 (3) |
C3—C4—C5 | 110.0 (3) | N15—C16—S1 | 125.1 (3) |
O1—C5—C12 | 109.0 (3) | C16—O17—C18 | 116.3 (4) |
O1—C5—C4 | 107.7 (2) | O17—C18—C19 | 106.9 (5) |
C12—C5—C4 | 113.4 (3) | ||
C5—O1—C1—N15 | 170.3 (3) | O6—C4—C5—O1 | −176.1 (3) |
C5—O1—C1—C2 | −68.1 (3) | C3—C4—C5—O1 | −56.6 (3) |
C6—O2—C2—C1 | 127.3 (3) | O6—C4—C5—C12 | 63.2 (3) |
C6—O2—C2—C3 | −114.3 (4) | C3—C4—C5—C12 | −177.3 (3) |
N15—C1—C2—O2 | −64.9 (4) | C2—O2—C6—O3 | −0.8 (7) |
O1—C1—C2—O2 | 175.7 (3) | C2—O2—C6—C7 | 177.6 (4) |
N15—C1—C2—C3 | 177.8 (3) | C3—O4—C8—O5 | 3.2 (6) |
O1—C1—C2—C3 | 58.4 (3) | C3—O4—C8—C9 | −174.8 (4) |
C8—O4—C3—C4 | 98.4 (4) | C4—O6—C10—O7 | 0.1 (6) |
C8—O4—C3—C2 | −140.3 (3) | C4—O6—C10—C11 | 179.8 (3) |
O2—C2—C3—O4 | 69.0 (3) | C13—O8—C12—C5 | −125.7 (3) |
C1—C2—C3—O4 | −172.6 (3) | O1—C5—C12—O8 | −70.0 (3) |
O2—C2—C3—C4 | −170.8 (3) | C4—C5—C12—O8 | 50.0 (4) |
C1—C2—C3—C4 | −52.5 (4) | C12—O8—C13—O9 | 5.0 (6) |
C10—O6—C4—C3 | 106.4 (3) | C12—O8—C13—C14 | −177.9 (4) |
C10—O6—C4—C5 | −134.1 (3) | O1—C1—N15—C16 | −91.0 (4) |
O4—C3—C4—O6 | −72.1 (3) | C2—C1—N15—C16 | 149.9 (3) |
C2—C3—C4—O6 | 169.2 (2) | C1—N15—C16—O17 | 177.2 (3) |
O4—C3—C4—C5 | 170.3 (2) | C1—N15—C16—S1 | −2.2 (5) |
C2—C3—C4—C5 | 51.6 (3) | N15—C16—O17—C18 | 175.6 (4) |
C1—O1—C5—C12 | −170.1 (3) | S1—C16—O17—C18 | −5.0 (6) |
C1—O1—C5—C4 | 66.5 (3) | C16—O17—C18—C19 | 173.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15A···O5i | 0.90 (3) | 2.15 (3) | 3.046 (5) | 178 (3) |
C5—H5A···O9ii | 0.98 | 2.56 | 3.431 (5) | 149 |
Symmetry codes: (i) x+1, y, z; (ii) −x, y−1/2, −z+1. |
C16H23NO10S | F(000) = 444 |
Mr = 421.41 | Dx = 1.347 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3543 (2) Å | Cell parameters from 3438 reflections |
b = 10.2555 (1) Å | θ = 1.4–28.3° |
c = 14.0142 (4) Å | µ = 0.21 mm−1 |
β = 100.684 (2)° | T = 293 K |
V = 1038.66 (4) Å3 | Needle, colourless |
Z = 2 | 0.26 × 0.12 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 4151 independent reflections |
Radiation source: fine-focus sealed tube | 2094 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 1.5° |
ω scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −10→13 |
Tmin = 0.953, Tmax = 0.985 | l = −13→18 |
7436 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.072 | w = 1/[σ2(Fo2) + (0.0843P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.184 | (Δ/σ)max < 0.001 |
S = 0.86 | Δρmax = 0.28 e Å−3 |
4151 reflections | Δρmin = −0.34 e Å−3 |
258 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.035 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.17 (17) |
C16H23NO10S | V = 1038.66 (4) Å3 |
Mr = 421.41 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.3543 (2) Å | µ = 0.21 mm−1 |
b = 10.2555 (1) Å | T = 293 K |
c = 14.0142 (4) Å | 0.26 × 0.12 × 0.08 mm |
β = 100.684 (2)° |
Siemens SMART CCD area-detector diffractometer | 4151 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2094 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 0.985 | Rint = 0.078 |
7436 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.184 | Δρmax = 0.28 e Å−3 |
S = 0.86 | Δρmin = −0.34 e Å−3 |
4151 reflections | Absolute structure: Flack (1983) |
258 parameters | Absolute structure parameter: −0.17 (17) |
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 | 0.4058 (2) | 0.47378 (15) | 0.30340 (12) | 0.0675 (5) | |
O1 | 0.5576 (4) | 0.8095 (3) | 0.3225 (2) | 0.0396 (8) | |
O2 | 0.5575 (5) | 0.7557 (4) | 0.0647 (2) | 0.0503 (9) | |
O3 | 0.4038 (6) | 0.9201 (5) | −0.0190 (3) | 0.0806 (14) | |
O4 | 0.8071 (4) | 0.9680 (4) | 0.1122 (2) | 0.0427 (8) | |
O5 | 1.0902 (6) | 0.8938 (6) | 0.1109 (4) | 0.0936 (18) | |
O6 | 1.0039 (4) | 0.9559 (3) | 0.3143 (2) | 0.0434 (8) | |
O7 | 0.9609 (6) | 1.1694 (4) | 0.2877 (4) | 0.0901 (16) | |
O8 | 0.6980 (4) | 1.0214 (4) | 0.4549 (3) | 0.0511 (10) | |
O9 | 0.9684 (5) | 1.1029 (5) | 0.5307 (3) | 0.0795 (14) | |
O17 | 0.0900 (5) | 0.5878 (4) | 0.2208 (3) | 0.0601 (10) | |
C1 | 0.5251 (6) | 0.7396 (5) | 0.2322 (3) | 0.0387 (11) | |
H1A | 0.6041 | 0.6619 | 0.2382 | 0.046* | |
C2 | 0.5748 (6) | 0.8280 (5) | 0.1541 (3) | 0.0385 (11) | |
H2A | 0.4926 | 0.9040 | 0.1450 | 0.046* | |
C3 | 0.7743 (6) | 0.8717 (5) | 0.1825 (3) | 0.0362 (10) | |
H3A | 0.8567 | 0.7969 | 0.1808 | 0.043* | |
C4 | 0.8099 (6) | 0.9309 (4) | 0.2829 (3) | 0.0331 (10) | |
H4A | 0.7411 | 1.0129 | 0.2819 | 0.040* | |
C5 | 0.7482 (6) | 0.8377 (5) | 0.3552 (3) | 0.0380 (11) | |
H5A | 0.8190 | 0.7565 | 0.3564 | 0.046* | |
C6 | 0.4684 (7) | 0.8124 (6) | −0.0183 (4) | 0.0509 (13) | |
C7 | 0.4799 (10) | 0.7301 (8) | −0.1036 (4) | 0.076 (2) | |
H7A | 0.5381 | 0.6488 | −0.0822 | 0.115* | |
H7B | 0.5514 | 0.7742 | −0.1445 | 0.115* | |
H7C | 0.3576 | 0.7140 | −0.1394 | 0.115* | |
C8 | 0.9686 (7) | 0.9711 (6) | 0.0835 (3) | 0.0517 (13) | |
C9 | 0.9858 (9) | 1.0827 (8) | 0.0198 (5) | 0.086 (2) | |
H9A | 1.1047 | 1.0804 | 0.0008 | 0.129* | |
H9B | 0.9736 | 1.1624 | 0.0540 | 0.129* | |
H9C | 0.8903 | 1.0782 | −0.0370 | 0.129* | |
C10 | 1.0628 (7) | 1.0796 (6) | 0.3143 (4) | 0.0532 (13) | |
C11 | 1.2664 (7) | 1.0899 (7) | 0.3510 (5) | 0.0754 (19) | |
H11A | 1.3163 | 1.0047 | 0.3677 | 0.113* | |
H11B | 1.2889 | 1.1449 | 0.4074 | 0.113* | |
H11C | 1.3248 | 1.1268 | 0.3014 | 0.113* | |
C12 | 0.7739 (7) | 0.8915 (6) | 0.4567 (4) | 0.0504 (13) | |
H12A | 0.7123 | 0.8355 | 0.4966 | 0.060* | |
H12B | 0.9046 | 0.8937 | 0.4851 | 0.060* | |
C13 | 0.8081 (7) | 1.1198 (6) | 0.4972 (4) | 0.0529 (14) | |
C14 | 0.7078 (9) | 1.2424 (8) | 0.4920 (6) | 0.085 (2) | |
H14A | 0.5814 | 1.2283 | 0.4614 | 0.127* | |
H14B | 0.7637 | 1.3041 | 0.4548 | 0.127* | |
H14C | 0.7120 | 1.2757 | 0.5564 | 0.127* | |
N15 | 0.3383 (6) | 0.7011 (4) | 0.2131 (3) | 0.0436 (10) | |
C16 | 0.2752 (7) | 0.5893 (5) | 0.2442 (3) | 0.0438 (12) | |
C17 | −0.0065 (9) | 0.4700 (8) | 0.2397 (5) | 0.085 (2) | |
H17A | −0.1374 | 0.4825 | 0.2195 | 0.127* | |
H17B | 0.0209 | 0.4507 | 0.3078 | 0.127* | |
H17C | 0.0332 | 0.3988 | 0.2040 | 0.127* | |
H15A | 0.266 (7) | 0.751 (7) | 0.182 (4) | 0.054 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0786 (10) | 0.0332 (8) | 0.0893 (10) | 0.0010 (8) | 0.0122 (8) | 0.0217 (8) |
O1 | 0.0426 (17) | 0.034 (2) | 0.0411 (18) | −0.0076 (15) | 0.0050 (13) | 0.0013 (14) |
O2 | 0.069 (2) | 0.032 (2) | 0.0442 (19) | −0.0083 (17) | −0.0040 (16) | −0.0023 (15) |
O3 | 0.099 (3) | 0.083 (4) | 0.055 (2) | 0.034 (3) | 0.002 (2) | 0.008 (2) |
O4 | 0.0471 (18) | 0.0334 (19) | 0.0484 (18) | −0.0001 (15) | 0.0106 (14) | 0.0134 (16) |
O5 | 0.073 (3) | 0.108 (5) | 0.112 (4) | 0.038 (3) | 0.049 (3) | 0.058 (3) |
O6 | 0.0382 (16) | 0.028 (2) | 0.0606 (19) | −0.0044 (14) | 0.0007 (14) | 0.0012 (16) |
O7 | 0.077 (3) | 0.025 (3) | 0.156 (5) | −0.013 (2) | −0.009 (3) | 0.018 (3) |
O8 | 0.0448 (19) | 0.050 (3) | 0.055 (2) | −0.0065 (17) | 0.0011 (15) | −0.0137 (17) |
O9 | 0.059 (3) | 0.063 (3) | 0.104 (3) | −0.010 (2) | −0.019 (2) | −0.020 (3) |
O17 | 0.057 (2) | 0.036 (2) | 0.082 (3) | −0.0200 (18) | −0.0024 (18) | 0.011 (2) |
C1 | 0.043 (2) | 0.025 (3) | 0.046 (3) | −0.005 (2) | 0.005 (2) | 0.001 (2) |
C2 | 0.054 (3) | 0.024 (3) | 0.036 (2) | 0.001 (2) | 0.004 (2) | 0.0009 (19) |
C3 | 0.045 (3) | 0.025 (3) | 0.037 (2) | −0.004 (2) | 0.0046 (19) | 0.0097 (19) |
C4 | 0.032 (2) | 0.021 (2) | 0.044 (2) | −0.0019 (18) | 0.0028 (18) | 0.0045 (18) |
C5 | 0.038 (2) | 0.026 (3) | 0.046 (3) | −0.002 (2) | −0.002 (2) | 0.001 (2) |
C6 | 0.055 (3) | 0.052 (4) | 0.043 (3) | −0.007 (3) | 0.002 (2) | 0.004 (3) |
C7 | 0.113 (5) | 0.067 (5) | 0.048 (3) | −0.027 (4) | 0.009 (3) | −0.007 (3) |
C8 | 0.053 (3) | 0.056 (4) | 0.048 (3) | 0.008 (3) | 0.014 (2) | 0.016 (3) |
C9 | 0.083 (4) | 0.089 (6) | 0.095 (5) | 0.008 (4) | 0.039 (4) | 0.053 (5) |
C10 | 0.057 (3) | 0.031 (3) | 0.070 (3) | −0.013 (3) | 0.007 (3) | −0.003 (3) |
C11 | 0.055 (3) | 0.057 (5) | 0.111 (5) | −0.016 (3) | 0.007 (3) | −0.009 (4) |
C12 | 0.051 (3) | 0.051 (4) | 0.045 (3) | −0.006 (3) | −0.005 (2) | 0.003 (2) |
C13 | 0.046 (3) | 0.056 (4) | 0.055 (3) | −0.011 (3) | 0.006 (2) | −0.018 (3) |
C14 | 0.077 (4) | 0.066 (5) | 0.107 (5) | 0.004 (4) | 0.008 (4) | −0.030 (4) |
N15 | 0.044 (2) | 0.025 (2) | 0.055 (3) | −0.0052 (19) | −0.0097 (19) | 0.0059 (19) |
C16 | 0.052 (3) | 0.024 (3) | 0.051 (3) | −0.004 (2) | −0.002 (2) | 0.001 (2) |
C17 | 0.081 (4) | 0.063 (5) | 0.103 (5) | −0.046 (4) | −0.001 (4) | 0.020 (4) |
S1—C16 | 1.648 (5) | O9—C13 | 1.198 (6) |
O1—C5 | 1.422 (5) | O17—C16 | 1.341 (5) |
O1—C1 | 1.436 (5) | O17—C17 | 1.450 (7) |
O2—C6 | 1.356 (6) | C1—N15 | 1.407 (6) |
O2—C2 | 1.440 (6) | C1—C2 | 1.517 (6) |
O3—C6 | 1.203 (7) | C2—C3 | 1.515 (6) |
O4—C8 | 1.323 (6) | C3—C4 | 1.510 (6) |
O4—C3 | 1.447 (5) | C4—C5 | 1.522 (6) |
O5—C8 | 1.203 (7) | C5—C12 | 1.506 (7) |
O6—C10 | 1.341 (6) | C6—C7 | 1.477 (9) |
O6—C4 | 1.436 (5) | C8—C9 | 1.472 (8) |
O7—C10 | 1.202 (7) | C10—C11 | 1.494 (8) |
O8—C13 | 1.359 (6) | C13—C14 | 1.453 (10) |
O8—C12 | 1.443 (7) | N15—C16 | 1.341 (6) |
C5—O1—C1 | 112.2 (3) | O1—C5—C4 | 108.1 (3) |
C6—O2—C2 | 118.5 (4) | C12—C5—C4 | 113.5 (4) |
C8—O4—C3 | 119.8 (4) | O3—C6—O2 | 121.8 (5) |
C10—O6—C4 | 118.1 (4) | O3—C6—C7 | 126.9 (5) |
C13—O8—C12 | 118.7 (4) | O2—C6—C7 | 111.0 (6) |
C16—O17—C17 | 118.3 (5) | O5—C8—O4 | 122.9 (5) |
N15—C1—O1 | 107.7 (4) | O5—C8—C9 | 124.3 (5) |
N15—C1—C2 | 112.8 (4) | O4—C8—C9 | 112.7 (5) |
O1—C1—C2 | 108.4 (4) | O7—C10—O6 | 122.8 (5) |
O2—C2—C3 | 107.8 (3) | O7—C10—C11 | 125.5 (6) |
O2—C2—C1 | 109.0 (4) | O6—C10—C11 | 111.7 (5) |
C3—C2—C1 | 109.7 (3) | O8—C12—C5 | 110.0 (4) |
O4—C3—C4 | 109.7 (4) | O9—C13—O8 | 121.8 (6) |
O4—C3—C2 | 107.4 (3) | O9—C13—C14 | 126.7 (6) |
C4—C3—C2 | 110.9 (4) | O8—C13—C14 | 111.4 (5) |
O6—C4—C3 | 110.4 (3) | C16—N15—C1 | 124.2 (4) |
O6—C4—C5 | 108.1 (3) | N15—C16—O17 | 109.1 (4) |
C3—C4—C5 | 110.2 (4) | N15—C16—S1 | 125.1 (4) |
O1—C5—C12 | 108.8 (3) | O17—C16—S1 | 125.8 (4) |
C5—O1—C1—N15 | 172.1 (4) | O6—C4—C5—O1 | −178.1 (3) |
C5—O1—C1—C2 | −65.6 (4) | C3—C4—C5—O1 | −57.5 (5) |
C6—O2—C2—C3 | −106.9 (5) | O6—C4—C5—C12 | 61.1 (5) |
C6—O2—C2—C1 | 134.0 (4) | C3—C4—C5—C12 | −178.3 (4) |
N15—C1—C2—O2 | −65.5 (5) | C2—O2—C6—O3 | −0.3 (7) |
O1—C1—C2—O2 | 175.3 (3) | C2—O2—C6—C7 | 174.4 (4) |
N15—C1—C2—C3 | 176.6 (4) | C3—O4—C8—O5 | 2.5 (8) |
O1—C1—C2—C3 | 57.5 (5) | C3—O4—C8—C9 | −174.1 (5) |
C8—O4—C3—C4 | 96.8 (5) | C4—O6—C10—O7 | −1.4 (7) |
C8—O4—C3—C2 | −142.7 (5) | C4—O6—C10—C11 | 178.6 (4) |
O2—C2—C3—O4 | 68.5 (5) | C13—O8—C12—C5 | −125.7 (4) |
C1—C2—C3—O4 | −172.9 (4) | O1—C5—C12—O8 | −71.4 (5) |
O2—C2—C3—C4 | −171.6 (4) | C4—C5—C12—O8 | 49.0 (5) |
C1—C2—C3—C4 | −53.1 (5) | C12—O8—C13—O9 | 4.4 (7) |
C10—O6—C4—C3 | 105.3 (5) | C12—O8—C13—C14 | −177.8 (5) |
C10—O6—C4—C5 | −134.2 (4) | O1—C1—N15—C16 | −88.5 (6) |
O4—C3—C4—O6 | −69.3 (4) | C2—C1—N15—C16 | 151.9 (5) |
C2—C3—C4—O6 | 172.3 (4) | C1—N15—C16—O17 | 174.7 (4) |
O4—C3—C4—C5 | 171.5 (3) | C1—N15—C16—S1 | −4.3 (7) |
C2—C3—C4—C5 | 53.0 (5) | C17—O17—C16—N15 | 174.3 (5) |
C1—O1—C5—C12 | −171.2 (4) | C17—O17—C16—S1 | −6.7 (7) |
C1—O1—C5—C4 | 65.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15A···O5i | 0.81 (6) | 2.08 (6) | 2.884 (7) | 175 (6) |
C5—H5A···O9ii | 0.98 | 2.55 | 3.386 (7) | 143 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C17H25NO10S | C16H23NO10S |
Mr | 435.44 | 421.41 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.7492 (2), 10.4470 (3), 14.3852 (3) | 7.3543 (2), 10.2555 (1), 14.0142 (4) |
α, β, γ (°) | 90, 100.810 (1), 90 | 90, 100.684 (2), 90 |
V (Å3) | 1143.90 (5) | 1038.66 (4) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.19 | 0.21 |
Crystal size (mm) | 0.44 × 0.34 × 0.30 | 0.26 × 0.12 × 0.08 |
Data collection | ||
Diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.921, 0.945 | 0.953, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7784, 5034, 2780 | 7436, 4151, 2094 |
Rint | 0.084 | 0.078 |
(sin θ/λ)max (Å−1) | 0.659 | 0.667 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.168, 0.88 | 0.072, 0.184, 0.86 |
No. of reflections | 5034 | 4151 |
No. of parameters | 267 | 258 |
No. of restraints | 3 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.31 | 0.28, −0.34 |
Absolute structure | Flack (1983) | Flack (1983) |
Absolute structure parameter | −0.10 (13) | −0.17 (17) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997b), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
O1—C5 | 1.436 (4) | C2—C3 | 1.538 (5) |
O1—C1 | 1.449 (4) | C3—C4 | 1.530 (5) |
C1—C2 | 1.538 (5) | C4—C5 | 1.558 (4) |
C6—O2—C2—C1 | 127.3 (3) | C10—O6—C4—C5 | −134.1 (3) |
C6—O2—C2—C3 | −114.3 (4) | O1—C5—C12—O8 | −70.0 (3) |
C8—O4—C3—C4 | 98.4 (4) | C4—C5—C12—O8 | 50.0 (4) |
C8—O4—C3—C2 | −140.3 (3) | C1—N15—C16—O17 | 177.2 (3) |
C10—O6—C4—C3 | 106.4 (3) | C1—N15—C16—S1 | −2.2 (5) |
O1—C5 | 1.422 (5) | C2—C3 | 1.515 (6) |
O1—C1 | 1.436 (5) | C3—C4 | 1.510 (6) |
C1—C2 | 1.517 (6) | C4—C5 | 1.522 (6) |
C6—O2—C2—C3 | −106.9 (5) | C10—O6—C4—C5 | −134.2 (4) |
C6—O2—C2—C1 | 134.0 (4) | O1—C5—C12—O8 | −71.4 (5) |
C8—O4—C3—C4 | 96.8 (5) | C4—C5—C12—O8 | 49.0 (5) |
C8—O4—C3—C2 | −142.7 (5) | C1—N15—C16—O17 | 174.7 (4) |
C10—O6—C4—C3 | 105.3 (5) | C1—N15—C16—S1 | −4.3 (7) |
D-H···A | D-H | H···A | D···A | D-H···A | ||
N15-H15A···O5i | (I) | 0.90 (3) | 2.15 (3) | 3.046 (5) | 178 (3) | |
N15-H15A···O5ii | (II) | 0.81 (6) | 2.08 (6) | 2.884 (7) | 175 (6) | |
C5-H5A···O9iii | (I) | 0.98 | 2.56 | 3.431 (5) | 149 | |
C5-H5A···O9iv | (II) | 0.98 | 2.55 | 3.386 (7) | 143 |
%T {σymcodesfn (i) $1+x,y,z$; (ii) $x-1,y,z$; (iii) $-x,y-{σcriptscriptstyle{1οver 2}},1-z$; (iv) $2-x,y-{σcriptscriptstyle{1οver 2}},1-z$. |
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Many nomadic (define?) sugars have important biological functions (Varki, 1993). They may control various gene expressions to adjust the growth, development, controlled reaction and biochemistry of organs (Garg & Jeanloz, 1985). Query rephrasing. Glycosyl isothiocyanates have been widely used as valuable intermediates in the synthesis of glycosyl thiourea derivatives (Yasuo et al., 1999). Isothiocyanates and glycosyl isothiocyanates have been the focus of synthetic attention in recent years and have potential pharmacological properties (Mukerjee & Ashare, 1991). 1-Deoxynojirimycin, castanospermine and some of their derivatives have also shown anti-HIV activity (Tyms et al., 1990). Many biologically important products have a sugar unit joined through an atom (O, S, N or C) or a group of atoms (Avalos et al., 1990). Here, we report the X-ray structures of O-ethyl N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)carbamothiate, (I), and O-methyl N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)carbamothiate, (II). \sch
The bond lengths and angles in (I) and (II) are normal and agree with those of D-glucopyranose (Ferrier, 1963), N-(β-D-glucopyranosyl)hydroxylamine (Mostad, 1978) and N-(β-D-glucopyranosyl)-S-phenylsulfenamide (Lee et al., 1995). The hexopyranosyl ring in both structures adopts a 4C1 conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.605 (3), q2 = 0.076 (3) and q3 = 0.601 (3) Å, and θ = 7.0 (3) and ϕ2 = 6(2)°, for (I), and Q = 0.590 (5), q2 = 0.054 (4) and q3 = 0.587 (5) Å, and θ = 5.3 (4) and ϕ2 = 2(5)°, for (II). The dihedral angle between the O-acetyl groups and the mean plane through the hexopyranosyl ring is in the range of 74.9 (2) to 89.6 (1)° in (I) and 72.6 (2) to 88.9 (2)° in (II). The anomeric substituent, meanwhile, makes a dihedral angle of 64.7 (1) and 65.2 (2)° in (I) and (II), respectively, with the same ring. All ring substituents are in the equatorial position with respect to the ring in both structures.
In both structures, the acetoxymethyl group is in a gauche-gauche conformation, with O1—C5—C12—O8 and C4—C5—C12—O8 torsion angles of -70.0 (3) and 50.0 (4)°, respectively, for (I), and -71.4 (5) and 49.0 (5)°, respectively, for (II). These values may be compared with those in N-(β-D-glucopyranosyl)-S-phenylsulfenamide (Lee et al., 1995), where the corresponding O5—C5—C6—O6 and C4—C5—C6—O6 torsion angles are 72.4 (3) and -168.2 (3)°, respectively. The S atom is in a syn-periplanar conformation with respect to atom C1, while the C1—N15—C16—O17 linkage is anti-periplanar in both structures.
In the crystals of both (I) and (II), N—H···O intermolecular hydrogen bonds (Table 3) form infinite chains along the a axis. These chains are interconnected by C—H···O interactions (Table 3) to form an elongated spring-like structure along the b axis.