Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100005394/jz1388sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100005394/jz1388Isup2.hkl |
CCDC reference: 147672
The title compound was the only isolated product from the reaction between a solution of 2,3-O-isopropylidene-5-O-(4-nitrobenzoyl)-α-D-ribofuranosyl azide (4 mmol) in dimethyl sulfoxide (5 ml) and dimethyl-3-oxoglutarate (8 mmol) together with finely ground K2CO3 (4 mmol). The heterogenous mixture was stirred at 318 K for 72 h. The precipitate was washed with water, dried in air and dissolved in CHCl3 (30 ml). The solution was washed with 1M Na2CO3 (2 x 16 ml), 0.1M HCl (16 ml) and brine (16 ml) and finally dried with Na2SO4. Solvent was removed and the residue was purified by chromatography on silica gel, first with 0.2% ethanol in CH2Cl2, followed by CH2Cl2–ether mixture. The fragile, plate-like, elongated crystals with melting point 477–479 K were obtained after several recrystallization from ethyl acetate. Details are given by Štimac et al. (1999).
All H atoms were found in the difference electron density map and were placed at the calculated positions with isotropic displacement parameters taken from those of the attached heavy atoms and multiplied by 1.5. With the absence of suitable anomalous scatterers for Mo Kα radiation, the determination of the absolute configuration was not possible. The absolute configuration was assigned to agree with the known chirality of the ribofuranose moiety and the Friedel diffraction data were merged accordingly. Three strong reflections 131, 109 and 0014 were omitted from the refinement in the final stage due to inaccuracy in measurement.
Data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1971), PLATON (Spek, 1998), ORTEP-3 (Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. ORTEPII (Johnson, 1971) view of the molecule with atomic numbering. Anisotropic displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted for clarity. |
C22H24N4O11 | Dx = 1.440 Mg m−3 Dm = 1.42 (5) Mg m−3 Dm measured by flotation |
Mr = 520.45 | Melting point = 204–206 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.845 (2) Å | Cell parameters from 28700 reflections |
b = 9.931 (2) Å | θ = 3–25° |
c = 27.325 (5) Å | µ = 0.12 mm−1 |
V = 2400.2 (8) Å3 | T = 150 K |
Z = 4 | Needles, colourless |
F(000) = 1088 | 0.35 × 0.13 × 0.13 mm |
Nonius KappaCCD diffractometer | 2111 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
301 frames in 5 sets of ω scans. Rotation/frame=2°. Crystal–detector distance=45 mm. Measuring time=200 s/°. | h = −10→10 |
24551 measured reflections | k = −11→11 |
2358 independent reflections | l = −32→31 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.122 | Calculated w = 1/[σ2(Fo2) + (0.0546P)2 + 1.5179P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.038 |
2358 reflections | Δρmax = 0.54 e Å−3 |
335 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0067 (16) |
C22H24N4O11 | V = 2400.2 (8) Å3 |
Mr = 520.45 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.845 (2) Å | µ = 0.12 mm−1 |
b = 9.931 (2) Å | T = 150 K |
c = 27.325 (5) Å | 0.35 × 0.13 × 0.13 mm |
Nonius KappaCCD diffractometer | 2111 reflections with I > 2σ(I) |
24551 measured reflections | Rint = 0.057 |
2358 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.54 e Å−3 |
2358 reflections | Δρmin = −0.24 e Å−3 |
335 parameters |
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 | ||
C1' | −0.6307 (4) | −0.8855 (4) | −0.18894 (14) | 0.0376 (9) | |
H1 | −0.6961 | −0.8915 | −0.2187 | 0.056* | |
C2' | −0.4774 (4) | −0.8216 (4) | −0.20306 (14) | 0.0378 (9) | |
H2 | −0.4650 | −0.8148 | −0.2393 | 0.057* | |
C3' | −0.4820 (4) | −0.6825 (4) | −0.17878 (14) | 0.0392 (9) | |
H3 | −0.4540 | −0.6089 | −0.2020 | 0.059* | |
C4' | −0.6409 (5) | −0.6661 (4) | −0.15912 (15) | 0.0379 (9) | |
H4 | −0.6346 | −0.6251 | −0.1258 | 0.057* | |
O4' | −0.7006 (3) | −0.8011 (3) | −0.15439 (9) | 0.0373 (7) | |
C5' | −0.7432 (5) | −0.5803 (4) | −0.19017 (14) | 0.0417 (10) | |
H5 | −0.8449 | −0.5739 | −0.1752 | 0.063* | |
H6 | −0.7013 | −0.4883 | −0.1936 | 0.063* | |
O2 | −0.3545 (3) | −0.8892 (3) | −0.18087 (11) | 0.0440 (7) | |
C1 | −0.2650 (5) | −0.7883 (4) | −0.15631 (16) | 0.0453 (10) | |
O3 | −0.3766 (3) | −0.6952 (3) | −0.13990 (10) | 0.0454 (7) | |
C2 | −0.1880 (5) | −0.8498 (6) | −0.11333 (18) | 0.0622 (13) | |
H7 | −0.1128 | −0.9152 | −0.1247 | 0.093* | |
H8 | −0.2630 | −0.8955 | −0.0928 | 0.093* | |
H9 | −0.1377 | −0.7793 | −0.0943 | 0.093* | |
C3 | −0.1558 (5) | −0.7230 (5) | −0.19226 (19) | 0.0545 (12) | |
H10 | −0.0810 | −0.7896 | −0.2029 | 0.082* | |
H11 | −0.1041 | −0.6476 | −0.1763 | 0.082* | |
H12 | −0.2120 | −0.6898 | −0.2207 | 0.082* | |
O11 | −0.7515 (3) | −0.6456 (3) | −0.23720 (9) | 0.0403 (7) | |
O12 | −0.9497 (3) | −0.5140 (3) | −0.25665 (10) | 0.0470 (7) | |
C10 | −0.8659 (4) | −0.6053 (4) | −0.26637 (14) | 0.0387 (9) | |
C11 | −0.8791 (4) | −0.6907 (4) | −0.31113 (15) | 0.0380 (9) | |
C12 | −1.0027 (5) | −0.6691 (5) | −0.34182 (16) | 0.0482 (11) | |
H13 | −1.0718 | −0.5988 | −0.3345 | 0.072* | |
C13 | −1.0260 (5) | −0.7470 (5) | −0.38204 (17) | 0.0510 (11) | |
H14 | −1.1100 | −0.7316 | −0.4030 | 0.076* | |
C14 | −0.9246 (5) | −0.8488 (4) | −0.39157 (15) | 0.0442 (10) | |
C15 | −0.8003 (5) | −0.8719 (4) | −0.36319 (15) | 0.0469 (10) | |
H15 | −0.7304 | −0.9409 | −0.3715 | 0.070* | |
C16 | −0.7779 (5) | −0.7930 (4) | −0.32216 (15) | 0.0428 (10) | |
H16 | −0.6932 | −0.8087 | −0.3015 | 0.064* | |
N11 | −0.9517 (5) | −0.9355 (4) | −0.43481 (15) | 0.0591 (11) | |
O111 | −0.8537 (5) | −1.0111 (4) | −0.44807 (15) | 0.0944 (14) | |
O112 | −1.0716 (5) | −0.9275 (5) | −0.45604 (16) | 0.0865 (12) | |
N1 | −0.6159 (4) | −1.0186 (3) | −0.16730 (11) | 0.0373 (8) | |
N2 | −0.6226 (4) | −1.1245 (4) | −0.19845 (13) | 0.0483 (9) | |
N3 | −0.6018 (4) | −1.2321 (4) | −0.17292 (16) | 0.0529 (10) | |
C4 | −0.5828 (5) | −1.1970 (4) | −0.12519 (18) | 0.0493 (11) | |
C5 | −0.5904 (4) | −1.0568 (4) | −0.12095 (14) | 0.0361 (9) | |
C20 | −0.5770 (5) | −0.9642 (4) | −0.07831 (14) | 0.0386 (9) | |
H17 | −0.5166 | −0.8846 | −0.0879 | 0.058* | |
H18 | −0.5226 | −1.0108 | −0.0516 | 0.058* | |
C21 | −0.7284 (5) | −0.9183 (4) | −0.05990 (13) | 0.0394 (10) | |
O21 | −0.8440 (3) | −0.9786 (3) | −0.06469 (10) | 0.0489 (8) | |
O22 | −0.7165 (4) | −0.8023 (3) | −0.03613 (10) | 0.0545 (8) | |
C22 | −0.8542 (7) | −0.7580 (6) | −0.0119 (2) | 0.0814 (19) | |
H19 | −0.8351 | −0.6730 | 0.0052 | 0.122* | |
H20 | −0.8865 | −0.8265 | 0.0117 | 0.122* | |
H21 | −0.9339 | −0.7446 | −0.0363 | 0.122* | |
C31 | −0.5648 (7) | −1.3016 (6) | −0.0904 (2) | 0.0708 (15) | |
O31 | −0.5500 (5) | −1.4199 (3) | −0.0977 (2) | 0.0924 (14) | |
O32 | −0.5689 (8) | −1.2559 (4) | −0.04509 (18) | 0.119 (2) | |
C32 | −0.5566 (18) | −1.3652 (8) | −0.0091 (3) | 0.194 (6) | |
H22 | −0.5566 | −1.3272 | 0.0240 | 0.291* | |
H23 | −0.4622 | −1.4148 | −0.0145 | 0.291* | |
H24 | −0.6426 | −1.4265 | −0.0128 | 0.291* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1' | 0.034 (2) | 0.046 (2) | 0.033 (2) | −0.006 (2) | 0.0025 (17) | −0.0025 (18) |
C2' | 0.035 (2) | 0.042 (2) | 0.0363 (19) | −0.0078 (19) | 0.0037 (17) | −0.0011 (18) |
C3' | 0.033 (2) | 0.041 (2) | 0.043 (2) | −0.0055 (19) | 0.0012 (18) | −0.0012 (19) |
C4' | 0.034 (2) | 0.036 (2) | 0.044 (2) | −0.0064 (18) | 0.0032 (18) | −0.0044 (19) |
O4' | 0.0333 (14) | 0.0381 (15) | 0.0405 (14) | −0.0030 (13) | 0.0074 (12) | 0.0011 (13) |
C5' | 0.036 (2) | 0.043 (2) | 0.046 (2) | −0.003 (2) | 0.0047 (19) | −0.0060 (19) |
O2 | 0.0284 (13) | 0.0425 (16) | 0.0610 (17) | −0.0063 (13) | 0.0026 (13) | 0.0015 (15) |
C1 | 0.032 (2) | 0.047 (2) | 0.057 (2) | −0.003 (2) | 0.004 (2) | −0.003 (2) |
O3 | 0.0318 (14) | 0.0539 (17) | 0.0505 (16) | −0.0021 (15) | −0.0034 (13) | −0.0108 (15) |
C2 | 0.043 (2) | 0.073 (3) | 0.070 (3) | 0.006 (3) | −0.006 (2) | 0.001 (3) |
C3 | 0.034 (2) | 0.049 (3) | 0.081 (3) | −0.011 (2) | 0.009 (2) | −0.005 (2) |
O11 | 0.0367 (14) | 0.0422 (15) | 0.0420 (14) | 0.0053 (13) | 0.0012 (12) | −0.0004 (13) |
O12 | 0.0396 (16) | 0.0448 (16) | 0.0566 (16) | 0.0098 (15) | 0.0042 (14) | 0.0007 (14) |
C10 | 0.031 (2) | 0.037 (2) | 0.048 (2) | −0.001 (2) | 0.0067 (19) | 0.0085 (19) |
C11 | 0.0276 (19) | 0.042 (2) | 0.045 (2) | 0.0009 (18) | 0.0039 (17) | 0.0087 (19) |
C12 | 0.033 (2) | 0.052 (3) | 0.059 (2) | 0.011 (2) | 0.001 (2) | −0.004 (2) |
C13 | 0.036 (2) | 0.060 (3) | 0.057 (3) | 0.003 (2) | −0.009 (2) | −0.003 (2) |
C14 | 0.040 (2) | 0.046 (2) | 0.046 (2) | −0.002 (2) | 0.0027 (19) | 0.000 (2) |
C15 | 0.047 (2) | 0.046 (2) | 0.048 (2) | 0.012 (2) | 0.001 (2) | 0.005 (2) |
C16 | 0.037 (2) | 0.047 (2) | 0.045 (2) | 0.005 (2) | 0.0008 (19) | 0.006 (2) |
N11 | 0.067 (3) | 0.055 (2) | 0.055 (2) | 0.006 (2) | −0.004 (2) | −0.001 (2) |
O111 | 0.104 (3) | 0.095 (3) | 0.084 (3) | 0.044 (3) | −0.024 (2) | −0.037 (2) |
O112 | 0.078 (3) | 0.093 (3) | 0.089 (3) | 0.005 (3) | −0.029 (2) | −0.021 (2) |
N1 | 0.0351 (18) | 0.0349 (17) | 0.0420 (18) | −0.0102 (15) | 0.0050 (15) | −0.0060 (15) |
N2 | 0.0409 (19) | 0.048 (2) | 0.056 (2) | −0.0089 (19) | 0.0123 (18) | −0.022 (2) |
N3 | 0.040 (2) | 0.042 (2) | 0.077 (3) | −0.0011 (17) | 0.008 (2) | −0.022 (2) |
C4 | 0.039 (2) | 0.037 (2) | 0.072 (3) | 0.004 (2) | 0.006 (2) | 0.000 (2) |
C5 | 0.029 (2) | 0.034 (2) | 0.045 (2) | −0.0032 (17) | 0.0036 (18) | 0.0001 (17) |
C20 | 0.040 (2) | 0.039 (2) | 0.037 (2) | −0.0070 (19) | −0.0032 (18) | 0.0010 (18) |
C21 | 0.049 (2) | 0.039 (2) | 0.0308 (19) | 0.001 (2) | −0.0069 (18) | −0.0023 (18) |
O21 | 0.0463 (17) | 0.0527 (18) | 0.0478 (16) | −0.0078 (16) | 0.0087 (14) | −0.0090 (15) |
O22 | 0.069 (2) | 0.0442 (17) | 0.0509 (17) | 0.0097 (17) | −0.0159 (16) | −0.0172 (14) |
C22 | 0.080 (4) | 0.084 (4) | 0.081 (4) | 0.036 (4) | −0.018 (3) | −0.047 (3) |
C31 | 0.057 (3) | 0.064 (4) | 0.092 (4) | 0.008 (3) | −0.007 (3) | 0.000 (3) |
O31 | 0.080 (3) | 0.0356 (19) | 0.161 (4) | 0.0039 (19) | −0.006 (3) | 0.012 (2) |
O32 | 0.214 (7) | 0.048 (2) | 0.096 (3) | 0.018 (3) | −0.034 (4) | 0.032 (2) |
C32 | 0.39 (2) | 0.087 (5) | 0.104 (6) | 0.012 (10) | −0.081 (9) | 0.030 (5) |
C1'—O4' | 1.406 (5) | C13—C14 | 1.377 (6) |
C1'—N1 | 1.454 (5) | C14—C15 | 1.365 (6) |
C1'—C2' | 1.546 (5) | C14—N11 | 1.481 (6) |
C2'—O2 | 1.415 (5) | C15—C16 | 1.382 (6) |
C2'—C3' | 1.533 (6) | N11—O111 | 1.203 (5) |
C3'—O3 | 1.419 (5) | N11—O112 | 1.212 (5) |
C3'—C4' | 1.513 (5) | N1—C5 | 1.341 (5) |
C4'—O4' | 1.446 (5) | N1—N2 | 1.354 (4) |
C4'—C5' | 1.505 (6) | N2—N3 | 1.289 (5) |
C5'—O11 | 1.441 (4) | N3—C4 | 1.360 (6) |
O2—C1 | 1.443 (5) | C4—C5 | 1.399 (6) |
C1—O3 | 1.425 (5) | C4—C31 | 1.417 (7) |
C1—C2 | 1.489 (6) | C5—C20 | 1.489 (5) |
C1—C3 | 1.522 (6) | C20—C21 | 1.501 (6) |
O11—C10 | 1.348 (5) | C21—O21 | 1.192 (5) |
O12—C10 | 1.201 (4) | C21—O22 | 1.327 (5) |
C10—C11 | 1.493 (6) | O22—C22 | 1.455 (6) |
C11—C16 | 1.387 (6) | C31—O31 | 1.199 (6) |
C11—C12 | 1.394 (6) | C31—O32 | 1.319 (7) |
C12—C13 | 1.360 (6) | O32—C32 | 1.469 (8) |
O4'—C1'—N1 | 108.0 (3) | C12—C13—C14 | 118.1 (4) |
O4'—C1'—C2' | 108.0 (3) | C15—C14—C13 | 122.8 (4) |
N1—C1'—C2' | 113.3 (3) | C15—C14—N11 | 119.1 (4) |
O2—C2'—C3' | 105.2 (3) | C13—C14—N11 | 118.1 (4) |
O2—C2'—C1' | 111.9 (3) | C14—C15—C16 | 118.8 (4) |
C3'—C2'—C1' | 103.8 (3) | C15—C16—C11 | 119.9 (4) |
O3—C3'—C4' | 110.7 (3) | O111—N11—O112 | 121.8 (4) |
O3—C3'—C2' | 103.1 (3) | O111—N11—C14 | 119.1 (4) |
C4'—C3'—C2' | 106.0 (3) | O112—N11—C14 | 119.1 (4) |
O4'—C4'—C5' | 110.8 (3) | C5—N1—N2 | 112.4 (3) |
O4'—C4'—C3' | 105.7 (3) | C5—N1—C1' | 131.0 (3) |
C5'—C4'—C3' | 114.8 (3) | N2—N1—C1' | 116.5 (3) |
C1'—O4'—C4' | 109.4 (3) | N3—N2—N1 | 107.3 (3) |
O11—C5'—C4' | 106.2 (3) | N2—N3—C4 | 108.9 (3) |
C2'—O2—C1 | 106.9 (3) | N3—C4—C5 | 109.2 (4) |
O3—C1—O2 | 102.5 (3) | N3—C4—C31 | 118.0 (4) |
O3—C1—C2 | 109.6 (4) | C5—C4—C31 | 132.8 (5) |
O2—C1—C2 | 109.4 (4) | N1—C5—C4 | 102.2 (4) |
O3—C1—C3 | 111.5 (4) | N1—C5—C20 | 125.3 (3) |
O2—C1—C3 | 110.1 (3) | C4—C5—C20 | 132.5 (4) |
C2—C1—C3 | 113.2 (4) | C5—C20—C21 | 112.3 (3) |
C3'—O3—C1 | 106.1 (3) | O21—C21—O22 | 123.9 (4) |
C10—O11—C5' | 115.6 (3) | O21—C21—C20 | 125.1 (3) |
O12—C10—O11 | 123.8 (4) | O22—C21—C20 | 110.9 (4) |
O12—C10—C11 | 124.2 (4) | C21—O22—C22 | 114.8 (4) |
O11—C10—C11 | 112.0 (3) | O31—C31—O32 | 119.7 (6) |
C16—C11—C12 | 119.2 (4) | O31—C31—C4 | 128.3 (6) |
C16—C11—C10 | 122.9 (4) | O32—C31—C4 | 112.0 (5) |
C12—C11—C10 | 117.8 (4) | C31—O32—C32 | 111.8 (5) |
C13—C12—C11 | 121.2 (4) | ||
O4'—C1'—C2'—O2 | 104.3 (3) | C12—C13—C14—N11 | 178.8 (4) |
N1—C1'—C2'—O2 | −15.2 (4) | C13—C14—C15—C16 | 2.4 (7) |
O4'—C1'—C2'—C3' | −8.6 (4) | N11—C14—C15—C16 | −178.3 (4) |
N1—C1'—C2'—C3' | −128.2 (3) | C14—C15—C16—C11 | −1.4 (6) |
O2—C2'—C3'—O3 | −9.2 (4) | C12—C11—C16—C15 | 0.0 (6) |
C1'—C2'—C3'—O3 | 108.4 (3) | C10—C11—C16—C15 | 177.3 (4) |
O2—C2'—C3'—C4' | −125.6 (3) | C15—C14—N11—O111 | −10.5 (6) |
C1'—C2'—C3'—C4' | −8.0 (4) | C13—C14—N11—O111 | 168.8 (5) |
O3—C3'—C4'—O4' | −89.7 (4) | C15—C14—N11—O112 | 170.0 (4) |
C2'—C3'—C4'—O4' | 21.4 (4) | C13—C14—N11—O112 | −10.7 (6) |
O3—C3'—C4'—C5' | 147.9 (3) | O4'—C1'—N1—C5 | −34.1 (5) |
C2'—C3'—C4'—C5' | −101.0 (4) | C2'—C1'—N1—C5 | 85.4 (5) |
N1—C1'—O4'—C4' | 145.9 (3) | O4'—C1'—N1—N2 | 148.8 (3) |
C2'—C1'—O4'—C4' | 23.1 (4) | C2'—C1'—N1—N2 | −91.7 (4) |
C5'—C4'—O4'—C1' | 96.9 (3) | C5—N1—N2—N3 | 0.0 (4) |
C3'—C4'—O4'—C1' | −28.1 (4) | C1'—N1—N2—N3 | 177.6 (3) |
O4'—C4'—C5'—O11 | −59.6 (4) | N1—N2—N3—C4 | 0.5 (5) |
C3'—C4'—C5'—O11 | 60.1 (4) | N2—N3—C4—C5 | −0.9 (5) |
C3'—C2'—O2—C1 | −15.6 (4) | N2—N3—C4—C31 | 177.3 (4) |
C1'—C2'—O2—C1 | −127.6 (3) | N2—N1—C5—C4 | −0.5 (5) |
C2'—O2—C1—O3 | 34.6 (4) | C1'—N1—C5—C4 | −177.7 (4) |
C2'—O2—C1—C2 | 150.8 (3) | N2—N1—C5—C20 | 180.0 (4) |
C2'—O2—C1—C3 | −84.2 (4) | C1'—N1—C5—C20 | 2.8 (7) |
C4'—C3'—O3—C1 | 144.0 (3) | N3—C4—C5—N1 | 0.8 (5) |
C2'—C3'—O3—C1 | 31.1 (4) | C31—C4—C5—N1 | −176.9 (5) |
O2—C1—O3—C3' | −41.1 (4) | N3—C4—C5—C20 | −179.7 (4) |
C2—C1—O3—C3' | −157.2 (4) | C31—C4—C5—C20 | 2.5 (9) |
C3—C1—O3—C3' | 76.7 (4) | N1—C5—C20—C21 | 79.4 (5) |
C4'—C5'—O11—C10 | 163.8 (3) | C4—C5—C20—C21 | −99.9 (5) |
C5'—O11—C10—O12 | 5.9 (5) | C5—C20—C21—O21 | 25.6 (6) |
C5'—O11—C10—C11 | −172.1 (3) | C5—C20—C21—O22 | −156.1 (3) |
O12—C10—C11—C16 | 178.0 (4) | O21—C21—O22—C22 | 5.4 (6) |
O11—C10—C11—C16 | −4.1 (5) | C20—C21—O22—C22 | −173.0 (4) |
O12—C10—C11—C12 | −4.7 (6) | N3—C4—C31—O31 | 7.5 (9) |
O11—C10—C11—C12 | 173.3 (3) | C5—C4—C31—O31 | −174.9 (6) |
C16—C11—C12—C13 | 0.5 (6) | N3—C4—C31—O32 | −171.1 (5) |
C10—C11—C12—C13 | −177.0 (4) | C5—C4—C31—O32 | 6.5 (9) |
C11—C12—C13—C14 | 0.4 (7) | O31—C31—O32—C32 | −1.1 (11) |
C12—C13—C14—C15 | −1.9 (7) | C4—C31—O32—C32 | 177.6 (8) |
Experimental details
Crystal data | |
Chemical formula | C22H24N4O11 |
Mr | 520.45 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 8.845 (2), 9.931 (2), 27.325 (5) |
V (Å3) | 2400.2 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.35 × 0.13 × 0.13 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24551, 2358, 2111 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.122, 1.09 |
No. of reflections | 2358 |
No. of parameters | 335 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.24 |
Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1971), PLATON (Spek, 1998), ORTEP-3 (Farrugia, 1999).
C1'—O4' | 1.406 (5) | C14—N11 | 1.481 (6) |
C1'—N1 | 1.454 (5) | N11—O111 | 1.203 (5) |
C1'—C2' | 1.546 (5) | N11—O112 | 1.212 (5) |
C2'—C3' | 1.533 (6) | N1—C5 | 1.341 (5) |
C3'—C4' | 1.513 (5) | N1—N2 | 1.354 (4) |
C4'—O4' | 1.446 (5) | N2—N3 | 1.289 (5) |
C4'—C5' | 1.505 (6) | N3—C4 | 1.360 (6) |
C5'—O11 | 1.441 (4) | C4—C5 | 1.399 (6) |
O4'—C1'—C2'—C3' | −8.6 (4) | O4'—C4'—C5'—O11 | −59.6 (4) |
C1'—C2'—C3'—C4' | −8.0 (4) | C3'—C4'—C5'—O11 | 60.1 (4) |
C2'—C3'—C4'—O4' | 21.4 (4) | O4'—C1'—N1—C5 | −34.1 (5) |
C2'—C1'—O4'—C4' | 23.1 (4) | O4'—C1'—N1—N2 | 148.8 (3) |
C3'—C4'—O4'—C1' | −28.1 (4) |
The Dimroth reaction of glycosyl azides with dimethyl-3-oxo-glutarate (DOG) was recently used to produce the intermediates for further cyclizations to various 8-aza-3-deazaguanine nucleosides. The stereochemistry followed a favourable path even with 1,2-cis glycosyl azides, in sharp contrast to the condensations with cyanoacetamide, which were reported to yield 1,2-trans nucleosides exclusively (Štimac et al., 1999). Herein, we report the crystal structure of the only product (I) between 2,3-O-isopropylidene-5-O– (4-nitrobenzoyl)-α-D-ribofuranosyl azide and DOG, which revealed the glycosidation site N1 of the 4-methoxycarbonyl-1,2,3-triazol-5-yl acetate, and the α-anomeric configuration of the nucleoside. The molecule with the atomic numbering scheme is depicted in Fig. 1. Selected geometric parameters are presented in Table 1. The absolute configuration was assigned to agree with the known chirality of the sugar moiety (α-D-ribofuranose).
A survey of the Cambridge Structural Database (Allen & Kennard, 1993) revealed 18 examples where the aglycon moiety of the nucleoside was either the 1,2,4-triazole derivative alone (BESZII, BESZOO, FULRAF, JAZVEL, JAZVIP, JAZVOV, RIBVAR, RFRTZL, VAWMIP, VAWMOV, VICFUI, VICGAP, VIRAZL), or the 1,2,4-triazole derivative as part of the bicyclic system (CAFVAJ, CAFVEN, DIHNIR, VAPZOB, VAWMEL). Only in the structure determination of 2-β-D-ribofuranosyl-1,2,3-triazole-4,5-dicarboxamide dihydrate (JAZYUE) was the 1,2,3-triazole derivative an aglycon to ribofuranose (Sanghvi et al., 1990).
The orientation of the heterocyclic base relative to the sugar moiety (defined as anti or syn) is determined by the torsion angle about the N-glycosidic bond, explicitly, for purines and pyrimidines. In the cases of modified nucleosides with e.g. a five-membered base ring system, the sequence of atoms is chosen as far as possible to correspond closely with the normal substrates (Sundaralingham, 1975; IUPAC-IUB Joint Commission on Biochemical Nomenclature, 1983). The appropriate torsion angles O4'—C1'—N1—C5 and O4'—C1'—N1—N2 in this study are −34.1 (6) and 148.8 (3)°, respectively, suggesting high anti-configuration. The conformation about the C4'—C5' bond [O4'—C4'—C5'—O11 − 59.6 (4)°] is in the gauche range. The ribofuranose moiety exists in an O4'-exo-C4'-endo pucker. The corresponding Cremer–Pople (Cremer & Pople, 1975) puckering parameters q2 and ϕ2 are 0.246 (4) Å and 161.7 (10)° (Spek, 1998; Farrugia, 2000), respectively, suggesting the twisted form around the bond C4'—O4'. The bond lengths and angles are normal and in agreement with the values for the related compounds. The bond lengths N1—C5 1.341 (5), N1—N2 1.354 (4), N2—N3 1.289 (5), N3—C4 1.360 (6) and C4—C5 1.399 (6) Å in the 1,2,3-triazole ring suggest considerable delocalization of electrons and the prevalent double bond character of N2—N3 bonds. The triazole moiety is planar to within 0.005 (3) Å, and the phenyl part of the para-nitrobenzoyl group to within 0.011 (3) Å. The dihedral angles between the para-nitro group –NO2 (N11, O111, O112), the carboxylate group –COO (C10, O11, O12), and the phenyl ring (C11–C16) are 10.8 (4) and 5.8 (3)°, respectively.
Because the –OH groups of the molecule are protected with either the para-nitrobenzoate or the isopropylidene group, the molecule is essentially hydrophobic. There are only weak C—H···O and C—H···N intra- and intermolecular interactions (Table 1), which control the packing. Although the data were collected at 150 K, there is still appreciable thermal motion of the terminal C32 atom.