Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003377/da1176sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003377/da1176Isup2.hkl |
CCDC reference: 164689
Reductive acetylation of the azide O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D– galactopyranosyl)-N-hydroxysuccinimide [prepared following the procedure of Cao et al. (1995)] under Pd/C hydrogenation in MeOH/Ac2O 9:1 provided the title compound after recrystallization from methylene chloride/diethyl ether (Rodriguez et al., 1998). Spectroscopic data: 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 6.07 (bs, 1H, 3J2,NH = 9.6 Hz, H15), 5.48 (dd, 1H, 3J4,5 = 1.3 Hz, 3J3,4 = 3.0 Hz, H4), 5.28 (d, 1H, 3J1,2 = 3.5 Hz, H1), 5.26 (m, 1H, H3), 4.95 (td, 1H, 3J5,6 or 7 = 6.1 Hz, 3J5,7 or 6 = 6.6 Hz, H5), 4.71 (ddd, 1H, 3J2,3 = 11.8 Hz, H2), 4.23 (dd, 1H, 2J6,7 = 11.5 Hz, H6 or H7), 3.91 (dd, 1H, H7 or H6), 2.71 (s, 4H, H8, H9, H10, H11), 2.13, 2.03, 2.02, 1.99 (4 s, 12H, H12, H13, H14; H16, H17, H18; H19, H20, H21; H22, H23, H24); 13C NMR (δ, p.p.m.): 170.9 (C═O), 170.7 (C═O), 170.6 (C═O), 170.4 (C═O), 170.1 (C═O), 104.2 (C1), 69.2, 67.3, 67.1 (C3, C4, C5), 61.6 (C6), 47.2 (C2), 25.4 (C8, C9), 23.2 (C12), 20.7 (C14, C16, C18).
The y s.u. of O1 is not given, since this parameter must be fixed in space group P21. H atoms were located geometrically.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992-1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Fig. 1. The molecular structure of (I) showing the atom-numbering scheme and with displacement ellipsoids drawn at the 35% probability level. H atoms have been omitted for clarity. |
C18H24N2O11 | F(000) = 468 |
Mr = 444.39 | Dx = 1.331 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.556 (4) Å | Cell parameters from 25 reflections |
b = 9.191 (1) Å | θ = 20.2–26.8° |
c = 12.536 (6) Å | µ = 0.11 mm−1 |
β = 114.28 (5)° | T = 293 K |
V = 1108.6 (7) Å3 | Monoclinic prism, colourless |
Z = 2 | 0.38 × 0.35 × 0.34 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.009 |
Radiation source: X-ray tube | θmax = 30.0°, θmin = 2.1° |
Graphite monochromator | h = −14→14 |
ω scans | k = 0→12 |
3547 measured reflections | l = 0→17 |
3470 independent reflections | 2 standard reflections every 120 reflections |
2900 reflections with I > 0.07σ(I) | intensity decay: 5.5% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters not refined |
wR(F2) = 0.055 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.0002|Fo|2] |
S = 1.94 | (Δ/σ)max = 0.030 |
2900 reflections | Δρmax = 0.25 e Å−3 |
279 parameters | Δρmin = −0.19 e Å−3 |
C18H24N2O11 | V = 1108.6 (7) Å3 |
Mr = 444.39 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.556 (4) Å | µ = 0.11 mm−1 |
b = 9.191 (1) Å | T = 293 K |
c = 12.536 (6) Å | 0.38 × 0.35 × 0.34 mm |
β = 114.28 (5)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.009 |
3547 measured reflections | 2 standard reflections every 120 reflections |
3470 independent reflections | intensity decay: 5.5% |
2900 reflections with I > 0.07σ(I) |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters not refined |
S = 1.94 | Δρmax = 0.25 e Å−3 |
2900 reflections | Δρmin = −0.19 e Å−3 |
279 parameters |
Refinement. The decay correction has been applied. H atoms were located by geometry. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.2804 (1) | −0.5525 | −0.98523 (9) | 0.0574 (3) | |
O3 | 0.1246 (1) | −0.6080 (1) | −0.72175 (9) | 0.0529 (3) | |
O4 | 0.0209 (1) | −0.3635 (1) | −0.65250 (9) | 0.0560 (3) | |
O5 | −0.2342 (1) | −0.3564 (1) | −0.85519 (8) | 0.0510 (3) | |
O6 | −0.4031 (1) | −0.3098 (2) | −0.7315 (1) | 0.0692 (4) | |
O7 | −0.5199 (2) | −0.5766 (3) | −0.9433 (2) | 0.1307 (7) | |
O8 | −0.3494 (2) | −0.4554 (3) | −1.2095 (1) | 0.1364 (7) | |
O9 | 0.0420 (2) | −0.3547 (1) | −1.0389 (1) | 0.0851 (4) | |
O10 | 0.0822 (1) | −0.7987 (2) | −0.6300 (1) | 0.0754 (4) | |
O11 | 0.1505 (2) | −0.4715 (2) | −0.4817 (1) | 0.0993 (5) | |
O12 | −0.4488 (2) | −0.5150 (2) | −0.6609 (2) | 0.1043 (5) | |
N1 | −0.4113 (2) | −0.5083 (2) | −1.0598 (1) | 0.0722 (4) | |
N2 | −0.0150 (1) | −0.5564 (1) | −0.9704 (1) | 0.0490 (3) | |
C1 | −0.1936 (2) | −0.4268 (2) | −0.9345 (1) | 0.0487 (4) | |
C2 | −0.0467 (2) | −0.4825 (2) | −0.8826 (1) | 0.0453 (4) | |
C3 | −0.0214 (2) | −0.5760 (2) | −0.7760 (1) | 0.0458 (4) | |
C4 | −0.0653 (2) | −0.4917 (2) | −0.6920 (1) | 0.0479 (4) | |
C5 | −0.2139 (2) | −0.4398 (2) | −0.7522 (1) | 0.0502 (4) | |
C6 | −0.2567 (2) | −0.3432 (2) | −0.6766 (1) | 0.0613 (5) | |
C7 | −0.5232 (2) | −0.5258 (3) | −1.0315 (2) | 0.1035 (8) | |
C8 | −0.6434 (3) | −0.4686 (4) | −1.1371 (3) | 0.156 (1) | |
C9 | −0.5863 (4) | −0.4200 (4) | −1.2241 (3) | 0.164 (1) | |
C10 | −0.4367 (3) | −0.4611 (3) | −1.1721 (2) | 0.1064 (7) | |
C11 | 0.0160 (2) | −0.4850 (2) | −1.0480 (1) | 0.0563 (4) | |
C12 | 0.0113 (3) | −0.5700 (2) | −1.1514 (2) | 0.0858 (6) | |
C13 | 0.1639 (2) | −0.7240 (2) | −0.6477 (1) | 0.0578 (4) | |
C14 | 0.3160 (2) | −0.7380 (3) | −0.5940 (2) | 0.0814 (6) | |
C15 | 0.1261 (2) | −0.3677 (3) | −0.5452 (2) | 0.0722 (5) | |
C16 | 0.2027 (3) | −0.2266 (3) | −0.5205 (2) | 0.1112 (8) | |
C17 | −0.4899 (2) | −0.4077 (3) | −0.7189 (2) | 0.0777 (6) | |
C18 | −0.6375 (2) | −0.3638 (4) | −0.7819 (2) | 0.1043 (8) | |
H1 | −0.2032 | −0.3608 | −0.9957 | 0.059* | |
H2 | 0.0133 | −0.4008 | −0.8570 | 0.055* | |
H3 | −0.0731 | −0.6636 | −0.7991 | 0.055* | |
H4 | −0.0549 | −0.5513 | −0.6269 | 0.058* | |
H5 | −0.2736 | −0.5222 | −0.7746 | 0.060* | |
H6 | −0.2054 | −0.2554 | −0.6626 | 0.073* | |
H7 | −0.2373 | −0.3913 | −0.6045 | 0.073* | |
H8 | −0.6842 | −0.3880 | −1.1158 | 0.190* | |
H9 | −0.7104 | −0.5427 | −1.1701 | 0.190* | |
H10 | −0.5965 | −0.3187 | −1.2365 | 0.198* | |
H11 | −0.6333 | −0.4697 | −1.2968 | 0.198* | |
H12 | −0.0130 | −0.6677 | −1.1447 | 0.105* | |
H13 | −0.0556 | −0.5282 | −1.2210 | 0.105* | |
H14 | 0.1003 | −0.5671 | −1.1535 | 0.105* | |
H15 | −0.0295 | −0.6452 | −0.9790 | 0.115* | |
H16 | 0.3560 | −0.6524 | −0.5509 | 0.099* | |
H17 | 0.3418 | −0.8196 | −0.5428 | 0.099* | |
H18 | 0.3488 | −0.7513 | −0.6535 | 0.099* | |
H19 | 0.1410 | −0.1497 | −0.5241 | 0.135* | |
H20 | 0.2391 | −0.2104 | −0.5776 | 0.135* | |
H21 | 0.2768 | −0.2294 | −0.4451 | 0.135* | |
H22 | −0.6958 | −0.4358 | −0.7715 | 0.127* | |
H23 | −0.6523 | −0.2734 | −0.7521 | 0.127* | |
H24 | −0.6588 | −0.3538 | −0.8631 | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0593 (6) | 0.0465 (6) | 0.0500 (6) | −0.0088 (5) | 0.0061 (5) | −0.0044 (6) |
O3 | 0.0549 (5) | 0.0443 (6) | 0.0534 (5) | 0.0026 (5) | 0.0163 (4) | 0.0087 (5) |
O4 | 0.0584 (6) | 0.0501 (6) | 0.0474 (5) | −0.0068 (6) | 0.0096 (4) | −0.0073 (5) |
O5 | 0.0567 (6) | 0.0435 (6) | 0.0468 (5) | 0.0040 (5) | 0.0150 (4) | 0.0013 (5) |
O6 | 0.0630 (6) | 0.0717 (9) | 0.0715 (7) | 0.0117 (6) | 0.0261 (5) | 0.0094 (7) |
O7 | 0.090 (1) | 0.188 (2) | 0.120 (1) | −0.043 (1) | 0.0493 (8) | −0.038 (1) |
O8 | 0.166 (2) | 0.161 (2) | 0.0608 (8) | −0.034 (2) | 0.0249 (9) | 0.022 (1) |
O9 | 0.155 (1) | 0.0272 (5) | 0.1010 (8) | −0.0100 (7) | 0.0808 (6) | 0.0012 (6) |
O10 | 0.0874 (8) | 0.0574 (8) | 0.0747 (7) | 0.0017 (7) | 0.0267 (6) | 0.0233 (7) |
O11 | 0.098 (1) | 0.103 (1) | 0.0586 (7) | 0.006 (1) | −0.0071 (7) | 0.0016 (8) |
O12 | 0.0809 (9) | 0.103 (1) | 0.121 (1) | 0.0064 (9) | 0.0335 (8) | 0.0488 (9) |
N1 | 0.0636 (8) | 0.070 (1) | 0.0560 (7) | −0.0052 (8) | −0.0028 (6) | −0.0086 (8) |
N2 | 0.0730 (8) | 0.0255 (6) | 0.0500 (6) | −0.0002 (6) | 0.0268 (5) | −0.0014 (5) |
C1 | 0.0624 (8) | 0.0353 (8) | 0.0405 (7) | −0.0026 (7) | 0.0133 (6) | 0.0033 (7) |
C2 | 0.0572 (8) | 0.0297 (7) | 0.0454 (7) | −0.0078 (7) | 0.0174 (6) | −0.0004 (6) |
C3 | 0.0510 (7) | 0.0354 (8) | 0.0431 (7) | −0.0048 (7) | 0.0113 (6) | 0.0023 (6) |
C4 | 0.0521 (8) | 0.0452 (9) | 0.0417 (7) | −0.0047 (7) | 0.0145 (6) | 0.0023 (7) |
C5 | 0.0516 (8) | 0.0505 (9) | 0.0428 (7) | −0.0056 (7) | 0.0135 (6) | 0.0009 (7) |
C6 | 0.0613 (8) | 0.066 (1) | 0.0545 (8) | 0.0022 (9) | 0.0212 (7) | −0.0032 (9) |
C7 | 0.065 (1) | 0.118 (2) | 0.111 (1) | −0.024 (1) | 0.020 (1) | −0.048 (1) |
C8 | 0.070 (2) | 0.145 (3) | 0.176 (2) | 0.011 (2) | −0.027 (1) | −0.051 (2) |
C9 | 0.129 (2) | 0.109 (2) | 0.132 (2) | −0.009 (2) | −0.068 (2) | 0.015 (2) |
C10 | 0.127 (2) | 0.084 (2) | 0.055 (1) | −0.013 (2) | −0.016 (1) | 0.000 (1) |
C11 | 0.081 (1) | 0.0288 (7) | 0.0647 (8) | 0.0099 (8) | 0.0361 (7) | 0.0070 (7) |
C12 | 0.154 (2) | 0.045 (1) | 0.086 (1) | 0.012 (1) | 0.0771 (9) | 0.0004 (9) |
C13 | 0.0785 (9) | 0.0475 (9) | 0.0432 (7) | 0.0152 (8) | 0.0207 (7) | 0.0082 (7) |
C14 | 0.084 (1) | 0.083 (1) | 0.077 (1) | 0.029 (1) | 0.0323 (9) | 0.023 (1) |
C15 | 0.061 (1) | 0.083 (1) | 0.0563 (9) | −0.002 (1) | 0.0072 (7) | −0.0239 (9) |
C16 | 0.107 (2) | 0.089 (2) | 0.106 (2) | −0.030 (1) | 0.011 (1) | −0.039 (1) |
C17 | 0.0674 (9) | 0.089 (1) | 0.079 (1) | 0.002 (1) | 0.0328 (8) | 0.006 (1) |
C18 | 0.068 (1) | 0.112 (2) | 0.132 (2) | 0.015 (1) | 0.040 (1) | 0.023 (2) |
O1—N1 | 1.373 (2) | C11—C12 | 1.496 (4) |
O1—C1 | 1.449 (2) | C13—C14 | 1.469 (4) |
O3—C3 | 1.436 (3) | C15—C16 | 1.492 (5) |
O3—C13 | 1.362 (3) | C17—C18 | 1.484 (4) |
O4—C4 | 1.446 (3) | N2—H15 | 0.83 |
O4—C15 | 1.347 (3) | C1—H1 | 0.95 |
O5—C1 | 1.394 (3) | C2—H2 | 0.95 |
O5—C5 | 1.440 (3) | C3—H3 | 0.95 |
O6—C6 | 1.443 (3) | C4—H4 | 0.95 |
O6—C17 | 1.339 (4) | C5—H5 | 0.95 |
O7—C7 | 1.189 (5) | C6—H6 | 0.95 |
O8—C10 | 1.195 (5) | C6—H7 | 0.95 |
O9—C11 | 1.223 (3) | C8—H8 | 0.95 |
O10—C13 | 1.192 (3) | C8—H9 | 0.95 |
O11—C15 | 1.201 (4) | C9—H10 | 0.94 |
O12—C17 | 1.196 (4) | C9—H11 | 0.96 |
N1—C7 | 1.375 (5) | C12—H12 | 0.95 |
N1—C10 | 1.390 (4) | C12—H13 | 0.95 |
N2—C2 | 1.444 (3) | C12—H14 | 0.95 |
N2—C11 | 1.322 (3) | C14—H16 | 0.95 |
C1—C2 | 1.503 (3) | C14—H17 | 0.95 |
C2—C3 | 1.518 (3) | C14—H18 | 0.95 |
C3—C4 | 1.525 (3) | C16—H19 | 0.95 |
C4—C5 | 1.511 (3) | C16—H20 | 0.95 |
C5—C6 | 1.497 (4) | C16—H21 | 0.95 |
C7—C8 | 1.502 (5) | C18—H22 | 0.95 |
C8—C9 | 1.514 (8) | C18—H23 | 0.95 |
C9—C10 | 1.488 (6) | C18—H24 | 0.95 |
O3···O9i | 3.591 (2) | O9···C2ii | 3.565 (3) |
O4···C12ii | 3.571 (3) | O9···C18iv | 3.587 (4) |
O5···C12ii | 3.509 (4) | O10···C12i | 3.533 (3) |
O6···C10iii | 3.593 (4) | O10···C6v | 3.537 (3) |
O8···C14ii | 3.301 (4) | O11···C9vi | 3.315 (4) |
O9···N2ii | 2.764 (2) | O12···C16v | 3.293 (4) |
O9···C3ii | 3.402 (3) | O12···C14vii | 3.575 (4) |
N1—O1—C1 | 109.9 (1) | C1—C2—H2 | 107.6 |
C3—O3—C13 | 116.8 (2) | C3—C2—H2 | 107.4 |
C4—O4—C15 | 117.6 (2) | O3—C3—H3 | 109.9 |
C1—O5—C5 | 114.7 (2) | C2—C3—H3 | 110.0 |
C6—O6—C17 | 116.8 (2) | C4—C3—H3 | 110.0 |
O1—N1—C7 | 121.4 (2) | O4—C4—H4 | 109.9 |
O1—N1—C10 | 120.2 (3) | C3—C4—H4 | 109.9 |
C7—N1—C10 | 118.0 (3) | C5—C4—H4 | 109.9 |
C2—N2—C11 | 122.2 (2) | O5—C5—H5 | 108.8 |
O1—C1—O5 | 111.0 (2) | C4—C5—H5 | 108.7 |
O1—C1—C2 | 105.8 (2) | C6—C5—H5 | 108.9 |
O5—C1—C2 | 114.5 (2) | O6—C6—H6 | 109.0 |
N2—C2—C1 | 110.6 (2) | O6—C6—H7 | 108.8 |
N2—C2—C3 | 113.1 (2) | C5—C6—H6 | 109.0 |
C1—C2—C3 | 110.5 (2) | C5—C6—H7 | 108.8 |
O3—C3—C2 | 107.4 (2) | H6—C6—H7 | 109.7 |
O3—C3—C4 | 110.4 (2) | C7—C8—H8 | 110.0 |
C2—C3—C4 | 109.1 (2) | C7—C8—H9 | 110.0 |
O4—C4—C3 | 108.8 (2) | C9—C8—H8 | 109.5 |
O4—C4—C5 | 106.9 (2) | C9—C8—H9 | 110.2 |
C3—C4—C5 | 111.3 (2) | H8—C8—H9 | 109.9 |
O5—C5—C4 | 110.9 (2) | C8—C9—H10 | 111.0 |
O5—C5—C6 | 106.2 (2) | C8—C9—H11 | 110.0 |
C4—C5—C6 | 113.1 (2) | C10—C9—H10 | 110.6 |
O6—C6—C5 | 111.5 (2) | C10—C9—H11 | 109.7 |
O7—C7—N1 | 125.9 (3) | H10—C9—H11 | 109.5 |
O7—C7—C8 | 130.4 (4) | C11—C12—H12 | 109.4 |
N1—C7—C8 | 103.7 (4) | C11—C12—H13 | 109.4 |
C7—C8—C9 | 107.2 (4) | C11—C12—H14 | 109.1 |
C8—C9—C10 | 105.9 (3) | H12—C12—H13 | 109.8 |
O8—C10—N1 | 123.5 (3) | H12—C12—H14 | 109.6 |
O8—C10—C9 | 131.9 (4) | H13—C12—H14 | 109.4 |
N1—C10—C9 | 104.5 (4) | C13—C14—H16 | 109.6 |
O9—C11—N2 | 122.1 (2) | C13—C14—H17 | 109.5 |
O9—C11—C12 | 121.2 (2) | C13—C14—H18 | 109.5 |
N2—C11—C12 | 116.6 (2) | H16—C14—H17 | 109.4 |
O3—C13—O10 | 122.4 (2) | H16—C14—H18 | 109.5 |
O3—C13—C14 | 110.5 (2) | H17—C14—H18 | 109.4 |
O10—C13—C14 | 127.1 (2) | C15—C16—H19 | 109.6 |
O4—C15—O11 | 123.3 (3) | C15—C16—H20 | 109.3 |
O4—C15—C16 | 109.7 (3) | C15—C16—H21 | 109.8 |
O11—C15—C16 | 127.0 (2) | H19—C16—H20 | 109.1 |
O6—C17—O12 | 122.1 (3) | H19—C16—H21 | 109.7 |
O6—C17—C18 | 111.9 (3) | H20—C16—H21 | 109.3 |
O12—C17—C18 | 125.9 (3) | C17—C18—H22 | 109.6 |
C2—N2—H15 | 118.3 | C17—C18—H23 | 109.6 |
C11—N2—H15 | 118.8 | C17—C18—H24 | 109.3 |
O1—C1—H1 | 108.5 | H22—C18—H23 | 109.5 |
O5—C1—H1 | 108.5 | H22—C18—H24 | 109.5 |
C2—C1—H1 | 108.4 | H23—C18—H24 | 109.4 |
N2—C2—H2 | 107.4 | ||
O1—N1—C7—O7 | 1.1 (6) | O12—C17—O6—C6 | 3.1 (4) |
O1—N1—C7—C8 | −178.1 (3) | N1—O1—C1—C2 | −164.7 (2) |
O1—N1—C10—O8 | −0.4 (6) | N1—C7—C8—C9 | 0.3 (5) |
O1—N1—C10—C9 | −178.7 (3) | N1—C10—C9—C8 | −7.7 (5) |
O1—C1—O5—C5 | 65.9 (2) | N2—C2—C3—C4 | −176.9 (2) |
O1—C1—C2—N2 | 56.2 (2) | C1—O1—N1—C7 | −108.8 (3) |
O1—C1—C2—C3 | −69.9 (2) | C1—O1—N1—C10 | 79.2 (3) |
O3—C3—C2—N2 | 63.4 (2) | C1—O5—C5—C4 | 53.9 (2) |
O3—C3—C2—C1 | −172.0 (2) | C1—O5—C5—C6 | 177.2 (2) |
O3—C3—C4—O4 | 54.9 (2) | C1—C2—N2—C11 | 79.0 (2) |
O3—C3—C4—C5 | 172.5 (2) | C1—C2—C3—C4 | −52.3 (2) |
O4—C4—C3—C2 | −62.9 (2) | C2—N2—C11—C12 | −165.0 (2) |
O4—C4—C5—O5 | 64.1 (2) | C2—C1—O5—C5 | −53.7 (2) |
O4—C4—C5—C6 | −55.1 (2) | C2—C3—O3—C13 | −160.5 (2) |
O5—C1—O1—N1 | 70.5 (2) | C2—C3—C4—C5 | 54.7 (2) |
O5—C1—C2—N2 | 178.7 (2) | C3—O3—C13—C14 | −176.7 (2) |
O5—C1—C2—C3 | 52.6 (2) | C3—C2—N2—C11 | −156.4 (2) |
O5—C5—C4—C3 | −54.6 (2) | C3—C4—O4—C15 | −101.4 (2) |
O5—C5—C6—O6 | 64.9 (3) | C3—C4—C5—C6 | −173.9 (2) |
O6—C6—C5—C4 | −173.2 (2) | C4—O4—C15—C16 | 179.9 (2) |
O7—C7—N1—C10 | 173.2 (4) | C4—C3—O3—C13 | 80.6 (2) |
O7—C7—C8—C9 | −178.9 (5) | C5—C4—O4—C15 | 138.3 (2) |
O8—C10—N1—C7 | −172.7 (4) | C5—C6—O6—C17 | 83.7 (3) |
O8—C10—C9—C8 | 174.2 (5) | C6—O6—C17—C18 | −178.2 (3) |
O9—C11—N2—C2 | 12.2 (4) | C7—N1—C10—C9 | 9.0 (4) |
O10—C13—O3—C3 | 1.8 (3) | C7—C8—C9—C10 | 4.7 (5) |
O11—C15—O4—C4 | −0.5 (4) | C8—C7—N1—C10 | −6.0 (4) |
Symmetry codes: (i) −x, y−1/2, −z−2; (ii) −x, y+1/2, −z−2; (iii) −x−1, y+1/2, −z−2; (iv) x+1, y, z; (v) −x, y−1/2, −z−1; (vi) x+1, y, z+1; (vii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H15···O9i | 0.83 | 1.95 | 2.764 (2) | 167 |
Symmetry code: (i) −x, y−1/2, −z−2. |
Experimental details
Crystal data | |
Chemical formula | C18H24N2O11 |
Mr | 444.39 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 10.556 (4), 9.191 (1), 12.536 (6) |
β (°) | 114.28 (5) |
V (Å3) | 1108.6 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.38 × 0.35 × 0.34 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 0.07σ(I)] reflections | 3547, 3470, 2900 |
Rint | 0.009 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.055, 1.94 |
No. of reflections | 2900 |
No. of parameters | 279 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.19 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, TEXSAN (Molecular Structure Corporation, 1992-1997), SIR92 (Altomare et al., 1993), TEXSAN, ORTEPII (Johnson, 1976).
O1—N1 | 1.373 (2) | N1—C7 | 1.375 (5) |
O1—C1 | 1.449 (2) | N1—C10 | 1.390 (4) |
O3—C3 | 1.436 (3) | N2—C2 | 1.444 (3) |
O3—C13 | 1.362 (3) | N2—C11 | 1.322 (3) |
O4—C4 | 1.446 (3) | C1—C2 | 1.503 (3) |
O4—C15 | 1.347 (3) | C2—C3 | 1.518 (3) |
O5—C1 | 1.394 (3) | C3—C4 | 1.525 (3) |
O5—C5 | 1.440 (3) | C4—C5 | 1.511 (3) |
O6—C6 | 1.443 (3) | C5—C6 | 1.497 (4) |
O6—C17 | 1.339 (4) | ||
N1—O1—C1 | 109.9 (1) | N2—C2—C3 | 113.1 (2) |
C3—O3—C13 | 116.8 (2) | C1—C2—C3 | 110.5 (2) |
C4—O4—C15 | 117.6 (2) | O3—C3—C2 | 107.4 (2) |
C1—O5—C5 | 114.7 (2) | O3—C3—C4 | 110.4 (2) |
C6—O6—C17 | 116.8 (2) | C2—C3—C4 | 109.1 (2) |
O1—N1—C7 | 121.4 (2) | O4—C4—C3 | 108.8 (2) |
O1—N1—C10 | 120.2 (3) | O4—C4—C5 | 106.9 (2) |
C7—N1—C10 | 118.0 (3) | C3—C4—C5 | 111.3 (2) |
C2—N2—C11 | 122.2 (2) | O5—C5—C4 | 110.9 (2) |
O1—C1—O5 | 111.0 (2) | O5—C5—C6 | 106.2 (2) |
O1—C1—C2 | 105.8 (2) | C4—C5—C6 | 113.1 (2) |
O5—C1—C2 | 114.5 (2) | O6—C6—C5 | 111.5 (2) |
N2—C2—C1 | 110.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H15···O9i | 0.83 | 1.95 | 2.764 (2) | 167.2 |
Symmetry code: (i) −x, y−1/2, −z−2. |
2-Desoxy-N-acetyl-D-galactose (GalNAc) is found within the carbohydrate moiety of tumour-associated antigens such as Tn or TF, as well as in the corresponding sialylated derivatives. These carbohydrates are abundantly expressed at the surface of tumour cells and therefore represent interesting biological targets for immunological studies and for immunotherapy. Recently, several groups have devised new synthetic routes which facilitate the chemical synthesis of the glycopeptide conjugate on the basis of chemoselective oxime bond formation (Cao et al., 1995; Rodriguez et al., 1998). In this context, the title compound, (I), a mimic of GalNAc bearing an α-glycosyloxysuccinimide linkage, has been synthesized and its structure determined. \sch
The observed interatomic bond distances and angles are essentially in good agreement with those given by Allen et al. (1987), except for the distances O1—N1, O1—C1 and O5—C1, which are discussed below, and also, somewhat surprisingly, O3—C3 and O3—C13 (Table 1). If one considers the Cremer & Pople (1975) parameters, Q = 0.532 (3) Å, θ = 4.8 (3)° and ϕ2 = 210.5 (3)°, the pyranose ring has a perfect 4C1 chair conformation. This conformation is also adopted in solution, as evidenced by the large NMR coupling constant between H2 and H3 (11.8 Hz), indicating a trans diaxial arrangement.
The exocyclic hydroxymethyl group adopts a staggered gauche-trans conformation [ω = O5—C5—C6—O6 = 64.9 (3)° and C4—C5—C6—O6 = -173.2 (2)°], which has been shown by Eriksson et al. (1996) to be the preferred conformation in crystal structures having the galacto configuration, as in (I). The torsion angle ϕ (H1—C1—O1—N1) has a value of -49°, corresponding to the staggered conformer where the exoanomeric effect contributes to energy stabilization. The anomeric C1—O1 bond length of 1.449 (2) Å is greater than the average length of such bonds [1.401 (10) Å] reported by Sheldrick (1976). The O1—N1 and O5—C1 bonds also have unusually short values, of 1.373 (2) and 1.394 (3) Å, respectively, in contrast with the literature values of 1.462 Å (Walker et al., 1994) and 1.430 (10) Å (Sheldrick, 1976). Together, these data may indicate a strong endoanomeric effect, which would result in a shortening of O5—C1 and a lengthening of C1—O1.
As shown in Table 2, an intermolecular hydrogen bond contributes to the crystal packing, forming infinite chains of molecules running along the 21 axis.