Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100019387/sk1434sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019387/sk1434Isup2.hkl |
CCDC reference: 162579
For related literature, see: Allen et al. (1987); Borch et al. (1971); Cremer & Pople (1975); Lee et al. (1987); Marchessault & Pérez (1979); Nicolaou & Dai (1991); Tronchet et al. (1989); Walker et al. (1994).
The title compound was prepared after reduction of methyl 2,3,6-tri-O-benzoyl-4-deoxy-4-methoxyimino-α-D-xylo-hexopyranoside (Tronchet et al., 1989) using sodium cyanoborohydride (Borch et al., 1971) with careful control of pH (optimum value = 3). The corresponding gluco- and galacto-methoxyamino diastereoisomers were separated by liquid chromatography and recrystallization was from diethyl ether/petroleum ether (m.p. 396 K). 1H NMR (300 MHz, CDCl3, p.p.m.): δ 8.12–7.34 (m, 15H, aromatic H), 6.17 (t, 1H, 3J2,3 = 3J3,4 = 10.0 Hz, H3), 5.91 (d, 1H, 3J4,NH = 2.1 Hz, H21), 5.20 (dd, 1H, 3J1,2 = 3.6 Hz, H2), 5.16 (d, 1H, H1), 4.76–4.72 (m, 2H, H6, H7), 4.42 (td, 1H, 3J5,6 = 3.6 Hz, 3J4,5 = 10.3 Hz, H5), 3.51 (s, 3H, H8, H9, H10), 3.44 (s, 3H, H22, H23, H24) 3.19 (bt, 1H, H4); 13C NMR (p.p.m): δ 166.7 (C═O), 166.2 (C═O), 166.0 (C═O), 133.4 [aromatic C (Car)], 133.3 (Car), 130.1 (Car), 129.9 (Car), 129.7 (Car), 129.3 (Car), 128.6 (Car), 128.5 (Car), 97.2 (C1), 73.3 (C2), 67.8 (C3), 67.3 (C5), 64.3 (C6), 62.9 (C22), 61.4 (C4), 55.6 (C7).
The s.u. of the y coordinate of the O1 atom is not given since this parameter must be fixed in the P21 space group. We measured 11 Friedels pairs since the h limits were from -11 to 11. H atoms were located from a difference map but were not refined (N—H = 0.91 Å and C—H = 0.94–1.06 Å).
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; software used to prepare material for publication: TEXSAN.
Fig. 1. ORTEPII (Johnson, 1976) molecular diagram of the title compound. Displacement ellipsoids are shown at the 40% probability level. |
C29H29NO9 | F(000) = 564 |
Mr = 535.55 | Dx = 1.284 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
a = 8.026 (2) Å | Cell parameters from 24 reflections |
b = 12.359 (3) Å | θ = 10.2–13.3° |
c = 14.056 (3) Å | µ = 0.10 mm−1 |
β = 96.63 (2)° | T = 293 K |
V = 1384.9 (5) Å3 | Monoclinic prism, colorless |
Z = 2 | 0.35 × 0.30 × 0.29 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
Radiation source: X-ray tube | θmax = 30.0°, θmin = 2.2° |
Graphite monochromator | h = −11→11 |
ω scans | k = 0→17 |
4363 measured reflections | l = 0→19 |
4225 independent reflections | 2 standard reflections every 120 reflections |
3518 reflections with I > 0.05σ(I) | intensity decay: 4.2% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.068 | H-atom parameters not refined |
wR(F2) = 0.040 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00008|Fo|2] |
S = 1.90 | (Δ/σ)max = 0.022 |
3518 reflections | Δρmax = 0.16 e Å−3 |
351 parameters | Δρmin = −0.20 e Å−3 |
C29H29NO9 | V = 1384.9 (5) Å3 |
Mr = 535.55 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.026 (2) Å | µ = 0.10 mm−1 |
b = 12.359 (3) Å | T = 293 K |
c = 14.056 (3) Å | 0.35 × 0.30 × 0.29 mm |
β = 96.63 (2)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
4363 measured reflections | 2 standard reflections every 120 reflections |
4225 independent reflections | intensity decay: 4.2% |
3518 reflections with I > 0.05σ(I) |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.040 | H-atom parameters not refined |
S = 1.90 | Δρmax = 0.16 e Å−3 |
3518 reflections | Δρmin = −0.20 e Å−3 |
351 parameters |
Refinement. The decay correction has been applied. H atoms have been located by difference-Fourier syntheses |
x | y | z | Uiso*/Ueq | ||
O1 | 0.5814 (1) | 0.2268 | 0.54634 (9) | 0.0658 (4) | |
O2 | 0.3181 (2) | 0.1688 (1) | 0.41260 (9) | 0.0611 (4) | |
O3 | 0.0850 (1) | 0.3243 (1) | 0.46179 (8) | 0.0557 (3) | |
O4 | 0.2644 (2) | 0.5096 (1) | 0.6053 (1) | 0.0839 (5) | |
O5 | 0.4243 (2) | 0.1894 (1) | 0.67208 (9) | 0.0659 (4) | |
O6 | 0.2258 (2) | 0.2590 (1) | 0.81754 (9) | 0.0793 (5) | |
O7 | 0.2091 (2) | 0.0041 (1) | 0.4192 (1) | 0.0867 (5) | |
O8 | 0.2176 (2) | 0.4078 (2) | 0.3499 (1) | 0.0841 (5) | |
O9 | 0.2720 (3) | 0.3301 (2) | 0.9620 (1) | 0.1271 (7) | |
N4 | 0.1551 (2) | 0.4329 (2) | 0.6445 (1) | 0.0695 (5) | |
C1 | 0.4522 (3) | 0.1654 (2) | 0.5771 (1) | 0.0629 (6) | |
C2 | 0.2928 (2) | 0.1888 (2) | 0.5107 (1) | 0.0557 (5) | |
C3 | 0.2428 (2) | 0.3051 (2) | 0.5202 (1) | 0.0524 (5) | |
C4 | 0.2167 (2) | 0.3263 (2) | 0.6238 (1) | 0.0560 (5) | |
C5 | 0.3794 (2) | 0.2999 (2) | 0.6870 (1) | 0.0610 (6) | |
C6 | 0.3719 (3) | 0.3175 (2) | 0.7915 (1) | 0.0757 (7) | |
C7 | 0.7427 (3) | 0.2016 (2) | 0.5953 (2) | 0.0921 (8) | |
C8 | 0.2657 (2) | 0.0737 (2) | 0.3738 (1) | 0.0587 (6) | |
C9 | 0.2868 (2) | 0.0672 (2) | 0.2716 (1) | 0.0585 (5) | |
C10 | 0.3621 (3) | 0.1485 (2) | 0.2250 (1) | 0.0774 (7) | |
C11 | 0.3851 (3) | 0.1371 (2) | 0.1300 (2) | 0.1010 (9) | |
C12 | 0.3311 (3) | 0.0472 (3) | 0.0814 (2) | 0.107 (1) | |
C13 | 0.2542 (3) | −0.0332 (2) | 0.1261 (2) | 0.0966 (9) | |
C14 | 0.2326 (3) | −0.0244 (2) | 0.2212 (2) | 0.0777 (7) | |
C15 | 0.0904 (2) | 0.3769 (2) | 0.3779 (1) | 0.0601 (6) | |
C16 | −0.0787 (2) | 0.3888 (2) | 0.3238 (1) | 0.0581 (5) | |
C17 | −0.2247 (2) | 0.3869 (2) | 0.3665 (1) | 0.0639 (6) | |
C18 | −0.3773 (3) | 0.3985 (2) | 0.3117 (2) | 0.0797 (7) | |
C19 | −0.3855 (3) | 0.4098 (3) | 0.2156 (2) | 0.111 (1) | |
C20 | −0.2420 (4) | 0.4085 (4) | 0.1723 (2) | 0.146 (1) | |
C21 | −0.0898 (3) | 0.4006 (3) | 0.2265 (2) | 0.112 (1) | |
C22 | 0.2431 (3) | 0.6103 (2) | 0.6494 (2) | 0.1023 (9) | |
C23 | 0.1875 (3) | 0.2736 (2) | 0.9056 (2) | 0.0825 (8) | |
C24 | 0.0341 (3) | 0.2145 (2) | 0.9234 (2) | 0.0852 (8) | |
C25 | −0.0146 (4) | 0.2180 (3) | 1.0146 (2) | 0.134 (1) | |
C26 | −0.1551 (4) | 0.1584 (4) | 1.0330 (2) | 0.156 (1) | |
C27 | −0.2445 (4) | 0.1023 (4) | 0.9636 (3) | 0.159 (1) | |
C28 | −0.1994 (4) | 0.1008 (4) | 0.8735 (3) | 0.160 (1) | |
C29 | −0.0588 (4) | 0.1556 (3) | 0.8544 (2) | 0.117 (1) | |
H1 | 0.4757 | 0.0817 | 0.5807 | 0.076* | |
H2 | 0.1931 | 0.1395 | 0.5280 | 0.067* | |
H3 | 0.3239 | 0.3557 | 0.4990 | 0.063* | |
H4 | 0.1294 | 0.2687 | 0.6433 | 0.067* | |
H5 | 0.4737 | 0.3507 | 0.6684 | 0.075* | |
H6 | 0.4761 | 0.2774 | 0.8276 | 0.094* | |
H7 | 0.3454 | 0.3972 | 0.8044 | 0.094* | |
H8 | 0.7486 | 0.2259 | 0.6600 | 0.111* | |
H9 | 0.7603 | 0.1254 | 0.5954 | 0.111* | |
H10 | 0.8288 | 0.2360 | 0.5647 | 0.111* | |
H11 | 0.3969 | 0.2129 | 0.2587 | 0.092* | |
H12 | 0.4387 | 0.1934 | 0.0980 | 0.121* | |
H13 | 0.3455 | 0.0398 | 0.0154 | 0.126* | |
H14 | 0.2136 | −0.0962 | 0.0914 | 0.114* | |
H15 | 0.1786 | −0.0817 | 0.2532 | 0.092* | |
H16 | −0.2182 | 0.3771 | 0.4342 | 0.076* | |
H17 | −0.4779 | 0.3979 | 0.3419 | 0.093* | |
H18 | −0.4903 | 0.4196 | 0.1778 | 0.131* | |
H19 | −0.2442 | 0.4158 | 0.1040 | 0.179* | |
H20 | 0.0127 | 0.4042 | 0.1976 | 0.132* | |
H21 | 0.0552 | 0.4392 | 0.6074 | 0.084* | |
H22 | 0.2562 | 0.6016 | 0.7177 | 0.122* | |
H23 | 0.3200 | 0.6613 | 0.6314 | 0.122* | |
H24 | 0.1290 | 0.6372 | 0.6311 | 0.122* | |
H25 | 0.0492 | 0.2634 | 1.0630 | 0.158* | |
H26 | −0.1833 | 0.1623 | 1.0979 | 0.190* | |
H27 | −0.3395 | 0.0654 | 0.9797 | 0.189* | |
H28 | −0.2594 | 0.0575 | 0.8260 | 0.190* | |
H29 | −0.0208 | 0.1535 | 0.7927 | 0.139* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0539 (7) | 0.0685 (9) | 0.0760 (8) | 0.0034 (7) | 0.0113 (6) | 0.0104 (7) |
O2 | 0.0713 (8) | 0.0544 (8) | 0.0601 (7) | −0.0096 (7) | 0.0177 (6) | −0.0067 (6) |
O3 | 0.0473 (6) | 0.0663 (8) | 0.0545 (7) | −0.0050 (6) | 0.0096 (5) | 0.0073 (7) |
O4 | 0.099 (1) | 0.0622 (9) | 0.095 (1) | 0.0017 (9) | 0.0331 (8) | −0.0067 (8) |
O5 | 0.0741 (8) | 0.0618 (8) | 0.0616 (7) | −0.0012 (7) | 0.0065 (6) | 0.0104 (7) |
O6 | 0.0895 (9) | 0.093 (1) | 0.0578 (7) | −0.0114 (9) | 0.0181 (7) | −0.0032 (8) |
O7 | 0.118 (1) | 0.0729 (9) | 0.0685 (9) | −0.0392 (9) | 0.0081 (8) | 0.0021 (8) |
O8 | 0.0592 (8) | 0.108 (1) | 0.0881 (9) | −0.0051 (8) | 0.0239 (7) | 0.0355 (9) |
O9 | 0.167 (2) | 0.148 (2) | 0.070 (1) | −0.026 (2) | 0.027 (1) | −0.018 (1) |
N4 | 0.062 (1) | 0.072 (1) | 0.077 (1) | 0.0025 (9) | 0.0186 (8) | −0.002 (1) |
C1 | 0.073 (1) | 0.053 (1) | 0.065 (1) | 0.004 (1) | 0.013 (1) | 0.004 (1) |
C2 | 0.058 (1) | 0.053 (1) | 0.057 (1) | −0.0077 (9) | 0.0121 (8) | −0.0004 (9) |
C3 | 0.0465 (9) | 0.056 (1) | 0.055 (1) | −0.0027 (9) | 0.0073 (8) | 0.0008 (9) |
C4 | 0.053 (1) | 0.059 (1) | 0.058 (1) | −0.003 (1) | 0.0134 (8) | 0.000 (1) |
C5 | 0.061 (1) | 0.061 (1) | 0.060 (1) | −0.003 (1) | 0.0072 (9) | 0.002 (1) |
C6 | 0.079 (1) | 0.088 (2) | 0.060 (1) | −0.009 (1) | 0.006 (1) | −0.001 (1) |
C7 | 0.064 (1) | 0.105 (2) | 0.105 (2) | 0.016 (1) | 0.001 (1) | 0.011 (2) |
C8 | 0.051 (1) | 0.054 (1) | 0.069 (1) | −0.005 (1) | −0.0025 (9) | −0.001 (1) |
C9 | 0.053 (1) | 0.062 (1) | 0.059 (1) | 0.001 (1) | 0.0000 (9) | −0.004 (1) |
C10 | 0.084 (1) | 0.086 (2) | 0.063 (1) | −0.019 (1) | 0.010 (1) | −0.007 (1) |
C11 | 0.123 (2) | 0.112 (2) | 0.071 (1) | −0.027 (2) | 0.022 (1) | 0.001 (1) |
C12 | 0.113 (2) | 0.144 (3) | 0.066 (1) | −0.018 (2) | 0.016 (1) | −0.023 (2) |
C13 | 0.108 (2) | 0.103 (2) | 0.077 (1) | −0.018 (2) | 0.009 (1) | −0.031 (1) |
C14 | 0.081 (1) | 0.074 (2) | 0.077 (1) | −0.010 (1) | 0.006 (1) | −0.011 (1) |
C15 | 0.061 (1) | 0.059 (1) | 0.062 (1) | 0.003 (1) | 0.0168 (9) | 0.007 (1) |
C16 | 0.060 (1) | 0.056 (1) | 0.060 (1) | 0.005 (1) | 0.0110 (8) | 0.009 (1) |
C17 | 0.060 (1) | 0.062 (1) | 0.071 (1) | 0.000 (1) | 0.0114 (9) | −0.012 (1) |
C18 | 0.057 (1) | 0.070 (1) | 0.112 (2) | 0.006 (1) | 0.005 (1) | −0.013 (1) |
C19 | 0.091 (2) | 0.114 (2) | 0.118 (2) | 0.026 (2) | −0.026 (2) | 0.019 (2) |
C20 | 0.120 (2) | 0.229 (4) | 0.085 (2) | 0.022 (3) | −0.010 (2) | 0.066 (2) |
C21 | 0.085 (2) | 0.176 (3) | 0.076 (1) | 0.022 (2) | 0.011 (1) | 0.050 (2) |
C22 | 0.105 (2) | 0.069 (2) | 0.133 (2) | −0.004 (2) | 0.016 (2) | −0.023 (2) |
C23 | 0.105 (2) | 0.088 (2) | 0.055 (1) | 0.012 (1) | 0.013 (1) | 0.004 (1) |
C24 | 0.101 (2) | 0.088 (2) | 0.072 (1) | 0.026 (1) | 0.030 (1) | 0.021 (1) |
C25 | 0.133 (2) | 0.184 (3) | 0.094 (2) | 0.012 (2) | 0.057 (1) | 0.010 (2) |
C26 | 0.139 (2) | 0.232 (5) | 0.111 (2) | 0.018 (3) | 0.070 (2) | 0.032 (3) |
C27 | 0.149 (2) | 0.178 (4) | 0.167 (3) | −0.007 (3) | 0.086 (2) | 0.026 (3) |
C28 | 0.147 (2) | 0.184 (4) | 0.163 (3) | −0.053 (3) | 0.076 (2) | −0.003 (3) |
C29 | 0.123 (2) | 0.133 (3) | 0.104 (2) | −0.020 (2) | 0.045 (2) | 0.003 (2) |
O1—C1 | 1.393 (2) | C10—H11 | 0.95 |
O2—C2 | 1.438 (2) | C11—C12 | 1.349 (4) |
O3—C3 | 1.447 (2) | C11—H12 | 0.96 |
O4—N4 | 1.443 (2) | C12—C13 | 1.361 (4) |
O5—C1 | 1.411 (2) | C12—H13 | 0.95 |
O5—C5 | 1.433 (2) | C13—C14 | 1.372 (3) |
O6—C6 | 1.459 (3) | C13—H14 | 0.96 |
C1—C2 | 1.521 (3) | C14—H15 | 0.97 |
N4—C4 | 1.449 (3) | C15—C16 | 1.485 (2) |
C2—C3 | 1.503 (3) | C16—C17 | 1.377 (3) |
C3—C4 | 1.517 (2) | C16—C21 | 1.368 (3) |
C4—C5 | 1.528 (3) | C17—C18 | 1.377 (3) |
C5—C6 | 1.493 (3) | C17—H16 | 0.95 |
O1—C7 | 1.429 (2) | C18—C19 | 1.353 (3) |
O2—C8 | 1.343 (2) | C18—H17 | 0.95 |
O3—C15 | 1.352 (2) | C19—C20 | 1.363 (4) |
O4—C22 | 1.410 (3) | C19—H18 | 0.95 |
O6—C23 | 1.321 (2) | C20—C21 | 1.366 (4) |
O7—C8 | 1.192 (2) | C20—H19 | 0.96 |
O8—C15 | 1.198 (2) | C21—H20 | 0.96 |
O9—C23 | 1.206 (3) | C22—H22 | 0.96 |
N4—H21 | 0.91 | C22—H23 | 0.94 |
C1—H1 | 1.05 | C22—H24 | 0.98 |
C2—H2 | 1.06 | C23—C24 | 1.477 (3) |
C3—H3 | 0.97 | C24—C25 | 1.382 (3) |
C4—H4 | 1.06 | C24—C29 | 1.364 (4) |
C5—H5 | 1.04 | C25—C26 | 1.397 (5) |
C6—H6 | 1.05 | C25—H25 | 0.98 |
C6—H7 | 1.03 | C26—C27 | 1.335 (5) |
C7—H8 | 0.95 | C26—H26 | 0.97 |
C7—H9 | 0.95 | C27—C28 | 1.357 (4) |
C7—H10 | 0.95 | C27—H27 | 0.94 |
C8—C9 | 1.468 (2) | C28—C29 | 1.369 (4) |
C9—C10 | 1.377 (3) | C28—H28 | 0.94 |
C9—C14 | 1.379 (3) | C29—H29 | 0.95 |
C10—C11 | 1.376 (3) | ||
N4—O4—C22 | 107.6 (2) | C10—C11—C12 | 120.2 (2) |
C1—O5—C5 | 114.1 (1) | C10—C11—H12 | 120.0 |
C6—O6—C23 | 116.6 (2) | C12—C11—H12 | 119.8 |
O4—N4—C4 | 106.5 (1) | C11—C12—C13 | 120.3 (2) |
O1—C1—O5 | 112.6 (2) | C11—C12—H13 | 120.2 |
O1—C1—C2 | 108.1 (1) | C13—C12—H13 | 119.5 |
O5—C1—C2 | 109.1 (2) | C12—C13—C14 | 120.5 (2) |
O2—C2—C1 | 110.7 (1) | C12—C13—H14 | 120.3 |
O2—C2—C3 | 108.6 (1) | C14—C13—H14 | 119.2 |
C1—C2—C3 | 109.9 (2) | C9—C14—C13 | 119.8 (2) |
O3—C3—C2 | 109.3 (1) | C9—C14—H15 | 119.5 |
O3—C3—C4 | 107.9 (1) | C13—C14—H15 | 120.7 |
C2—C3—C4 | 108.6 (2) | O3—C15—O8 | 123.7 (2) |
N4—C4—C3 | 116.0 (2) | O3—C15—C16 | 112.0 (2) |
N4—C4—C5 | 111.5 (2) | O8—C15—C16 | 124.3 (2) |
C3—C4—C5 | 108.5 (1) | C15—C16—C17 | 123.3 (2) |
O5—C5—C4 | 109.4 (2) | C15—C16—C21 | 118.2 (2) |
O5—C5—C6 | 108.8 (2) | C17—C16—C21 | 118.5 (2) |
C4—C5—C6 | 114.3 (2) | C16—C17—C18 | 120.1 (2) |
O6—C6—C5 | 107.4 (2) | C16—C17—H16 | 119.1 |
C1—O1—C7 | 113.4 (2) | C18—C17—H16 | 120.9 |
C2—O2—C8 | 117.8 (1) | C17—C18—C19 | 120.5 (2) |
C3—O3—C15 | 117.4 (1) | C17—C18—H17 | 119.6 |
O4—N4—H21 | 105.1 | C19—C18—H17 | 119.9 |
C4—N4—H21 | 105.2 | C18—C19—C20 | 119.9 (2) |
O1—C1—H1 | 114.5 | C18—C19—H18 | 120.7 |
O5—C1—H1 | 102.0 | C20—C19—H18 | 119.4 |
C2—C1—H1 | 110.5 | C19—C20—C21 | 120.0 (2) |
O2—C2—H2 | 108.4 | C19—C20—H19 | 121.6 |
C1—C2—H2 | 110.8 | C21—C20—H19 | 118.4 |
C3—C2—H2 | 108.3 | C16—C21—C20 | 121.1 (2) |
O3—C3—H3 | 107.1 | C16—C21—H20 | 117.9 |
C2—C3—H3 | 113.1 | C20—C21—H20 | 121.0 |
C4—C3—H3 | 110.7 | O4—C22—H22 | 109.7 |
N4—C4—H4 | 108.0 | O4—C22—H23 | 111.0 |
C3—C4—H4 | 107.5 | O4—C22—H24 | 109.9 |
C5—C4—H4 | 104.6 | H22—C22—H23 | 110.2 |
O5—C5—H5 | 109.6 | H22—C22—H24 | 106.9 |
C4—C5—H5 | 108.8 | H23—C22—H24 | 108.9 |
C6—C5—H5 | 105.8 | O6—C23—O9 | 121.4 (2) |
O6—C6—H6 | 105.3 | O6—C23—C24 | 112.4 (2) |
O6—C6—H7 | 104.0 | O9—C23—C24 | 126.2 (2) |
C5—C6—H6 | 106.6 | C23—C24—C25 | 118.2 (2) |
C5—C6—H7 | 110.2 | C23—C24—C29 | 122.7 (2) |
H6—C6—H7 | 122.4 | C25—C24—C29 | 119.1 (3) |
O1—C7—H8 | 109.4 | C24—C25—C26 | 118.4 (3) |
O1—C7—H9 | 110.0 | C24—C25—H25 | 118.8 |
O1—C7—H10 | 110.4 | C26—C25—H25 | 122.8 |
H8—C7—H9 | 108.7 | C25—C26—C27 | 121.0 (3) |
H8—C7—H10 | 109.4 | C25—C26—H26 | 115.5 |
H9—C7—H10 | 108.9 | C27—C26—H26 | 123.4 |
O2—C8—O7 | 122.3 (2) | C26—C27—C28 | 120.7 (4) |
O2—C8—C9 | 112.3 (2) | C26—C27—H27 | 117.3 |
O7—C8—C9 | 125.4 (2) | C28—C27—H27 | 122.0 |
C8—C9—C10 | 122.1 (2) | C27—C28—C29 | 119.4 (4) |
C8—C9—C14 | 118.9 (2) | C27—C28—H28 | 119.9 |
C10—C9—C14 | 119.0 (2) | C29—C28—H28 | 120.4 |
C9—C10—C11 | 120.2 (2) | C24—C29—C28 | 121.3 (3) |
C9—C10—H11 | 119.5 | C24—C29—H29 | 117.2 |
C11—C10—H11 | 120.3 | C28—C29—H29 | 121.5 |
O1—C1—O5—C5 | 60.0 (2) | C1—C2—C3—C4 | −58.6 (2) |
O1—C1—C2—O2 | 55.3 (2) | C2—O2—C8—C9 | 175.5 (1) |
O1—C1—C2—C3 | −64.6 (2) | C2—C1—O1—C7 | −172.4 (2) |
O2—C2—C1—O5 | 178.0 (1) | C2—C1—O5—C5 | −59.9 (2) |
O2—C2—C3—O3 | 62.7 (2) | C2—C3—O3—C15 | −103.4 (2) |
O2—C2—C3—C4 | −179.8 (1) | C2—C3—C4—C5 | 58.2 (2) |
O2—C8—C9—C10 | 3.8 (3) | C3—O3—C15—C16 | 178.5 (2) |
O2—C8—C9—C14 | −177.6 (2) | C3—C2—O2—C8 | −140.9 (2) |
O3—C3—C2—C1 | −176.1 (1) | C3—C4—C5—C6 | 179.8 (2) |
O3—C3—C4—N4 | −57.0 (2) | C4—N4—O4—C22 | −161.6 (2) |
O3—C3—C4—C5 | 176.6 (2) | C4—C3—O3—C15 | 138.6 (2) |
O3—C15—C16—C17 | 23.9 (3) | C5—C6—O6—C23 | −173.3 (2) |
O3—C15—C16—C21 | −155.1 (2) | C6—O6—C23—C24 | 177.7 (2) |
O4—N4—C4—C3 | −51.6 (2) | C8—C9—C10—C11 | 177.5 (2) |
O4—N4—C4—C5 | 73.2 (2) | C8—C9—C14—C13 | −178.7 (2) |
O5—C1—O1—C7 | 67.1 (2) | C9—C10—C11—C12 | 1.3 (4) |
O5—C1—C2—C3 | 58.1 (2) | C9—C14—C13—C12 | 1.0 (4) |
O5—C5—C4—N4 | 173.1 (1) | C10—C9—C14—C13 | 0.0 (3) |
O5—C5—C4—C3 | −57.9 (2) | C10—C11—C12—C13 | −0.3 (5) |
O5—C5—C6—O6 | −70.1 (2) | C11—C10—C9—C14 | −1.1 (3) |
O6—C6—C5—C4 | 52.5 (2) | C11—C12—C13—C14 | −0.8 (4) |
O6—C23—C24—C25 | 176.4 (2) | C15—C16—C17—C18 | 179.9 (2) |
O6—C23—C24—C29 | −2.3 (3) | C15—C16—C21—C20 | 177.9 (3) |
O7—C8—O2—C2 | −4.5 (3) | C16—C17—C18—C19 | 1.3 (4) |
O7—C8—C9—C10 | −176.2 (2) | C16—C21—C20—C19 | 3.1 (6) |
O7—C8—C9—C14 | 2.4 (3) | C17—C16—C21—C20 | −1.2 (5) |
O8—C15—O3—C3 | 0.2 (3) | C17—C18—C19—C20 | 0.7 (5) |
O8—C15—C16—C17 | −157.8 (2) | C18—C17—C16—C21 | −1.0 (4) |
O8—C15—C16—C21 | 23.1 (4) | C18—C19—C20—C21 | −2.9 (6) |
O9—C23—O6—C6 | −1.9 (3) | C23—C24—C25—C26 | −177.1 (3) |
O9—C23—C24—C25 | −4.0 (4) | C23—C24—C29—C28 | 179.3 (3) |
O9—C23—C24—C29 | 177.2 (3) | C24—C25—C26—C27 | −2.4 (6) |
N4—C4—C3—C2 | −175.4 (2) | C24—C29—C28—C27 | −2.2 (6) |
N4—C4—C5—C6 | 50.9 (2) | C25—C24—C29—C28 | 0.6 (5) |
C1—O5—C5—C4 | 60.6 (2) | C25—C26—C27—C28 | 0.9 (7) |
C1—O5—C5—C6 | −173.9 (2) | C26—C25—C24—C29 | 1.6 (5) |
C1—C2—O2—C8 | 98.3 (2) | C26—C27—C28—C29 | 1.4 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H21···O3 | 0.91 | 2.53 | 2.895 (2) | 105 |
N4—H21···O7i | 0.91 | 2.26 | 3.085 (2) | 151 |
Symmetry code: (i) −x, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C29H29NO9 |
Mr | 535.55 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 8.026 (2), 12.359 (3), 14.056 (3) |
β (°) | 96.63 (2) |
V (Å3) | 1384.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.35 × 0.30 × 0.29 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 0.05σ(I)] reflections | 4363, 4225, 3518 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.040, 1.90 |
No. of reflections | 3518 |
No. of parameters | 351 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, TEXSAN (Molecular Structure Corporation, 1992-1997), SIR92 (Altomare et al., 1993), TEXSAN.
O1—C1 | 1.393 (2) | C1—C2 | 1.521 (3) |
O2—C2 | 1.438 (2) | N4—C4 | 1.449 (3) |
O3—C3 | 1.447 (2) | C2—C3 | 1.503 (3) |
O4—N4 | 1.443 (2) | C3—C4 | 1.517 (2) |
O5—C1 | 1.411 (2) | C4—C5 | 1.528 (3) |
O5—C5 | 1.433 (2) | C5—C6 | 1.493 (3) |
O6—C6 | 1.459 (3) | ||
N4—O4—C22 | 107.6 (2) | O3—C3—C2 | 109.3 (1) |
C1—O5—C5 | 114.1 (1) | O3—C3—C4 | 107.9 (1) |
C6—O6—C23 | 116.6 (2) | C2—C3—C4 | 108.6 (2) |
O4—N4—C4 | 106.5 (1) | N4—C4—C3 | 116.0 (2) |
O1—C1—O5 | 112.6 (2) | N4—C4—C5 | 111.5 (2) |
O1—C1—C2 | 108.1 (1) | C3—C4—C5 | 108.5 (1) |
O5—C1—C2 | 109.1 (2) | O5—C5—C4 | 109.4 (2) |
O2—C2—C1 | 110.7 (1) | O5—C5—C6 | 108.8 (2) |
O2—C2—C3 | 108.6 (1) | C4—C5—C6 | 114.3 (2) |
C1—C2—C3 | 109.9 (2) | O6—C6—C5 | 107.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H21···O3 | 0.91 | 2.53 | 2.895 (2) | 104.9 |
N4—H21···O7i | 0.91 | 2.26 | 3.085 (2) | 151.2 |
Symmetry code: (i) −x, y+1/2, −z+1. |
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Hydroxylamine-substituted sugars are found in an important class of antitumor antibiotic, such as calicheamicin or esperamicin that cleaves DNA specifically (Nicolaou & Dai, 1991). Conformational study has demonstrated a key role for this unusual N—O linkage in maintaining the oligosaccharide core in the minor groove of the DNA (Walker et al., 1994). In this context, the structure of sugars containing the hydroxylamine linkage, such as the title compound, (I), are of interest to assess and validate the latter theoretical studies. Reduction of methyl 2,3,6-tri-O-benzoyl-4-deoxy-4-methoxyimino-α-D-xylo-hexopyranoside with NaBH3CN at pH = 3 afforded a mixture of the corresponding gluco- and galacto-methoxyamino diastereoisomers. Recrystallization of the mixture from diethyl ether/petroleum ether allowed the separation of each epimer. The structure of (I) displays interatomic bond distances and angles (Table 1) in good agreement with those given by Allen et al. (1987). The configuration at C4 is R, which implies the gluco configuration. The ring adops a quasi-perfect 4C1 chair conformation, as defined by the Cremer & Pople (1975) parameters, Q = 0.593 (3) Å, Θ = 2.6 (2)° and Φ2 = 195 (4)°. This conformation is also adopted in solution, as outlined by the large values of the coupling constant (~10 Hz) in NMR. The exocyclic hydroxymethyl group adopted a staggered gg conformation [ω = O5—C5—C6—O6 = -70.1 (2)°, C4—C5—C6—O6 = -52.5 (2)°], which is the conformation usually observed in other structures containing gluco residues (Marchessault & Pérez, 1979).
The α (C3—C4—N4—O4) and β (C22—O4—N4—C4) torsion angles have values of -51.6 (2) and -160.6 (2)°, respectively, close to those of the global minimum calculated by Walker et al. (1994). However, the β value is decreased in comparison with the value of -120° calculated by Walker et al. (1994) in monosaccharide, as well as in comparison with the value of -134° reported by Lee et al. (1987) for the crystal structure of calicheamicin γ1I derivative. Moreover, NMR measurements in chloroform indicated a small value of 3J'4,NH (2.1 Hz) for the hydroxylamino H atom, which is consistent with an average conformation in which the hydroxylamine H atom is gauche to the C4 H atom.
Two kinds of hydrogen bonds co-exist in the stucture. The first assumes the crystal packing, forming an infinite chain of molecules running along the b axis. The second is intramolecular, linking the N4 atom to the benzoyl O3 atom. The hydrogen-bond details are given in Table 2.