Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016091/qa0187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016091/qa0187Isup2.hkl |
CCDC reference: 140865
Une solution de 1.4 g (7 mmol) de la 1,4-diazépine 1 e t de l'oxyde de mésitonitrile (IV) dans 15 ml d'éther diéthylique anhydre est agitée à température ambiante pendant une semaine. Après évaporation du solvant, le résidu obtenu est chromatographié sur colonne de gel de silice (éluant: hexane-chloroforme 1/1). Le dicycloadduit (II) isolé est recristallisé dans l'heptane. PF = 184–186°C.
Les cristaux, trés petits, donnent lieu à des images de diffraction de mauvaize qualité, avec une limite de résolution voisine de 24°. En outre, les cartes de fourier-différence montrent que les atomes d'hydrogène des groupements méthyle attachés aux atomes C16, C17, C48 et C50 ont 2 positions d'équilibre avec un même degré d'occupation égal á 0.5.
Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: maXus (Mackay et al., 1998); program(s) used to solve structure: maXus; program(s) used to refine structure: maXus; molecular graphics: maXus; software used to prepare material for publication: maXus.
C33H38N4O2 | Dx = 1.20 Mg m−3 |
Mr = 522.69 | Mo Kα radiation, λ = 0.71073 Å |
Monoclinic, P21/c | Cell parameters from 11268 reflections |
a = 22.9235 (7) Å | θ = 1–25.2° |
b = 9.9309 (5) Å | µ = 0.08 mm−1 |
c = 12.8363 (7) Å | T = 298 K |
β = 101.078 (3)° | Thin plate, colourless |
V = 2867.8 (4) Å3 | 0.30 × 0.25 × 0.10 mm |
Z = 4 |
KappaCCD diffractometer | Rint = 0.071 |
ϕ scans | θmax = 24.2° |
4771 measured reflections | h = −25→25 |
4280 independent reflections | k = −11→0 |
3640 reflections with refl observed if I > 1.75σ(I) | l = 0→15 |
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.073 | w = 1/[σ2(Fo2) + 0.03Fo2] |
wR(F2) = 0.083 | (Δ/σ)max = 0.004 |
S = 1.58 | Δρmax = 0.21 e Å−3 |
3640 reflections | Δρmin = −0.33 e Å−3 |
352 parameters |
C33H38N4O2 | V = 2867.8 (4) Å3 |
Mr = 522.69 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 22.9235 (7) Å | µ = 0.08 mm−1 |
b = 9.9309 (5) Å | T = 298 K |
c = 12.8363 (7) Å | 0.30 × 0.25 × 0.10 mm |
β = 101.078 (3)° |
KappaCCD diffractometer | 3640 reflections with refl observed if I > 1.75σ(I) |
4771 measured reflections | Rint = 0.071 |
4280 independent reflections |
R[F2 > 2σ(F2)] = 0.073 | 352 parameters |
wR(F2) = 0.083 | H-atom parameters not refined |
S = 1.58 | Δρmax = 0.21 e Å−3 |
3640 reflections | Δρmin = −0.33 e Å−3 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | −0.17658 (4) | −0.1811 (1) | −0.81897 (6) | 0.0481 (5) | |
O11 | −0.31419 (4) | 0.0716 (1) | −0.72296 (8) | 0.0609 (5) | |
N4 | −0.16773 (4) | −0.2042 (1) | −0.64187 (8) | 0.0421 (5) | |
C91 | −0.16641 (5) | −0.1016 (1) | −0.72308 (9) | 0.0431 (6) | |
N21 | −0.36212 (5) | 0.0935 (1) | −0.8087 (1) | 0.0580 (6) | |
C5 | −0.18798 (6) | −0.1722 (2) | −0.5448 (1) | 0.0511 (7) | |
N2 | −0.17360 (5) | −0.3240 (1) | −0.79071 (9) | 0.0496 (6) | |
N7 | −0.28569 (5) | −0.1557 (1) | −0.67058 (9) | 0.0567 (6) | |
C11 | −0.11917 (6) | −0.4771 (2) | −0.5471 (1) | 0.0522 (7) | |
C43 | −0.43471 (6) | −0.0847 (2) | −1.0309 (1) | 0.0543 (7) | |
C10 | −0.16936 (5) | −0.4524 (1) | −0.6276 (1) | 0.0459 (6) | |
C31 | −0.35796 (5) | 0.0115 (2) | −0.8837 (1) | 0.0486 (7) | |
C20 | −0.10415 (5) | −0.0395 (2) | −0.7055 (1) | 0.0480 (7) | |
C8 | −0.27863 (6) | −0.0489 (2) | −0.7437 (1) | 0.0475 (7) | |
C9 | −0.21548 (6) | 0.0032 (2) | −0.7280 (1) | 0.0473 (6) | |
C47 | −0.39271 (6) | 0.1363 (2) | −1.0527 (1) | 0.0598 (8) | |
C3 | −0.17134 (5) | −0.3269 (1) | −0.6900 (1) | 0.0421 (6) | |
C41 | −0.30602 (5) | −0.0815 (2) | −0.8591 (1) | 0.0488 (7) | |
C15 | −0.21680 (6) | −0.5434 (2) | −0.6449 (1) | 0.0549 (7) | |
C42 | −0.39734 (5) | 0.0217 (2) | −0.9897 (1) | 0.0501 (7) | |
C13 | −0.16629 (8) | −0.6781 (2) | −0.4956 (1) | 0.0637 (9) | |
C45 | −0.45790 (7) | 0.0273 (2) | −1.2010 (1) | 0.068 (1) | |
C12 | −0.11922 (7) | −0.5886 (2) | −0.4828 (1) | 0.0619 (8) | |
C16 | −0.06649 (7) | −0.3850 (2) | −0.5300 (1) | 0.0692 (9) | |
C21 | −0.08979 (7) | 0.0783 (2) | −0.6507 (2) | 0.074 (1) | |
C44 | −0.46501 (6) | −0.0779 (2) | −1.1350 (1) | 0.0632 (8) | |
C48 | −0.44429 (7) | −0.2029 (2) | −0.9636 (1) | 0.0662 (9) | |
C14 | −0.21390 (7) | −0.6554 (2) | −0.5777 (1) | 0.0663 (9) | |
C50 | −0.35824 (8) | 0.2580 (2) | −1.0101 (2) | 0.081 (1) | |
C6 | −0.25360 (7) | −0.1340 (2) | −0.5618 (1) | 0.0664 (9) | |
C46 | −0.42256 (7) | 0.1352 (2) | −1.1580 (1) | 0.069 (1) | |
C18 | −0.27030 (7) | −0.5229 (2) | −0.7302 (2) | 0.075 (1) | |
C25 | −0.05881 (7) | −0.1095 (2) | −0.7393 (2) | 0.0722 (9) | |
C23 | 0.01282 (8) | 0.0525 (3) | −0.6606 (2) | 0.089 (1) | |
C17 | −0.1661 (1) | −0.7961 (2) | −0.4220 (2) | 0.084 (1) | |
C19 | −0.34725 (8) | −0.1940 (3) | −0.6727 (2) | 0.087 (1) | |
C24 | −0.00100 (7) | −0.0632 (3) | −0.7169 (2) | 0.087 (1) | |
C22 | −0.0315 (1) | 0.1238 (3) | −0.6279 (2) | 0.103 (1) | |
C49 | −0.4882 (1) | 0.0276 (3) | −1.3161 (2) | 0.101 (1) | |
H5A | −0.16408 | −0.09882 | −0.51193 | 0.05000* | |
H5B | −0.18098 | −0.25022 | −0.49993 | 0.05000* | |
H41A | −0.27722 | −0.06507 | −0.90296 | 0.05000* | |
H41B | −0.31772 | −0.17437 | −0.86466 | 0.05000* | |
H12 | −0.08502 | −0.60353 | −0.42794 | 0.05000* | |
H16A | −0.07359 | −0.31296 | −0.58083 | 0.05000* | 0.50 |
H16B | −0.03179 | −0.43436 | −0.53923 | 0.05000* | 0.50 |
H16C | −0.06029 | −0.34836 | −0.45953 | 0.05000* | 0.50 |
H21 | −0.12059 | 0.12918 | −0.62781 | 0.05000* | |
H44 | −0.49151 | −0.15057 | −1.16080 | 0.05000* | |
H48A | −0.42059 | −0.19367 | −0.89363 | 0.05000* | 0.50 |
H48B | −0.43329 | −0.28387 | −0.99583 | 0.05000* | 0.50 |
H48C | −0.48559 | −0.20717 | −0.95903 | 0.05000* | 0.50 |
H14 | −0.24670 | −0.71728 | −0.59027 | 0.05000* | |
H50A | −0.34044 | 0.24308 | −0.93704 | 0.05000* | 0.50 |
H50B | −0.38434 | 0.33438 | −1.01554 | 0.05000* | 0.50 |
H50C | −0.32764 | 0.27468 | −1.05014 | 0.05000* | 0.50 |
H6A | −0.25550 | −0.04051 | −0.54389 | 0.05000* | |
H6B | −0.27130 | −0.18711 | −0.51369 | 0.05000* | |
H46 | −0.41806 | 0.21184 | −1.20143 | 0.05000* | |
H18A | −0.26590 | −0.44263 | −0.76960 | 0.05000* | |
H18B | −0.30470 | −0.51483 | −0.69830 | 0.05000* | |
H18C | −0.27490 | −0.59903 | −0.77710 | 0.05000* | |
H25 | −0.06831 | −0.19088 | −0.77930 | 0.05000* | |
H23 | 0.05302 | 0.08476 | −0.64323 | 0.05000* | |
H17A | −0.12980 | −0.79617 | −0.37020 | 0.05000* | 0.50 |
H17B | −0.16900 | −0.87807 | −0.46220 | 0.05000* | 0.50 |
H17C | −0.19930 | −0.78937 | −0.38670 | 0.05000* | 0.50 |
H19A | −0.36725 | −0.20757 | −0.74476 | 0.05000* | |
H19B | −0.36675 | −0.12337 | −0.64126 | 0.05000* | |
H19C | −0.34845 | −0.27567 | −0.63316 | 0.05000* | |
H24 | 0.02940 | −0.11367 | −0.74151 | 0.05000* | |
H22 | −0.02282 | 0.20644 | −0.58914 | 0.05000* | |
H49A | −0.51079 | −0.05370 | −1.33272 | 0.05000* | |
H49B | −0.45879 | 0.03380 | −1.35992 | 0.05000* | |
H49C | −0.51429 | 0.10390 | −1.32912 | 0.05000* | |
H50D | −0.37654 | 0.30558 | −0.95574 | 0.05000* | 0.50 |
H48D | −0.47759 | −0.25787 | −1.00093 | 0.05000* | 0.50 |
H50E | −0.31984 | 0.20888 | −0.98694 | 0.05000* | 0.50 |
H16D | −0.07449 | −0.28716 | −0.51103 | 0.05000* | 0.50 |
H17D | −0.13170 | −0.85947 | −0.42560 | 0.05000* | 0.50 |
H48E | −0.4496 | −0.145 | −0.899 | 0.050* | 0.50 |
H16E | −0.03229 | −0.41166 | −0.46923 | 0.05000* | 0.50 |
H17E | −0.15670 | −0.75227 | −0.35510 | 0.05000* | 0.50 |
H50F | −0.35324 | 0.33658 | −1.05264 | 0.05000* | 0.50 |
H17F | −0.20570 | −0.84187 | −0.43710 | 0.05000* | 0.50 |
H48F | −0.40669 | −0.25477 | −0.96083 | 0.05000* | 0.50 |
H16F | −0.05109 | −0.37946 | −0.59763 | 0.05000* | 0.50 |
H9A | −0.20728 | 0.05562 | −0.65929 | 0.05000* | |
H9B | −0.21308 | 0.06572 | −0.78909 | 0.05000* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0658 (6) | 0.0498 (6) | 0.0274 (4) | −0.0023 (4) | 0.0106 (3) | −0.0036 (4) |
O11 | 0.0679 (6) | 0.0630 (7) | 0.0495 (6) | 0.0118 (5) | 0.0113 (4) | −0.0148 (5) |
N4 | 0.0586 (6) | 0.0390 (7) | 0.0279 (5) | −0.0048 (5) | 0.0122 (4) | −0.0019 (4) |
C91 | 0.0584 (7) | 0.0419 (8) | 0.0277 (6) | −0.0044 (6) | 0.0107 (5) | −0.0020 (5) |
N21 | 0.0576 (7) | 0.0593 (9) | 0.0557 (8) | 0.0100 (5) | 0.0155 (5) | −0.0041 (6) |
C5 | 0.0790 (9) | 0.0466 (8) | 0.0263 (6) | −0.0023 (7) | 0.0133 (6) | −0.0025 (6) |
N2 | 0.0631 (7) | 0.0467 (7) | 0.0376 (7) | −0.0034 (5) | 0.0119 (5) | −0.0064 (5) |
N7 | 0.0544 (7) | 0.0640 (9) | 0.0512 (7) | −0.0067 (5) | 0.0187 (5) | 0.0065 (6) |
C11 | 0.0620 (8) | 0.0425 (9) | 0.0489 (8) | 0.0006 (6) | 0.0058 (6) | −0.0059 (6) |
C43 | 0.0484 (7) | 0.056 (1) | 0.0571 (9) | 0.0074 (6) | 0.0132 (6) | −0.0033 (7) |
C10 | 0.0582 (8) | 0.0380 (8) | 0.0401 (7) | −0.0016 (6) | 0.0116 (5) | −0.0066 (6) |
C31 | 0.0514 (7) | 0.0463 (8) | 0.0476 (8) | −0.0008 (6) | 0.0170 (5) | −0.0006 (7) |
C20 | 0.0540 (8) | 0.0514 (9) | 0.0371 (7) | −0.0059 (6) | 0.0088 (5) | 0.0058 (6) |
C8 | 0.0553 (7) | 0.0460 (8) | 0.0407 (7) | 0.0019 (6) | 0.0152 (5) | −0.0037 (6) |
C9 | 0.0572 (8) | 0.0435 (8) | 0.0396 (7) | −0.0051 (6) | 0.0098 (5) | 0.0005 (6) |
C47 | 0.0537 (8) | 0.059 (1) | 0.066 (1) | 0.0070 (7) | 0.0163 (7) | 0.0097 (8) |
C3 | 0.0448 (7) | 0.0436 (8) | 0.0360 (7) | −0.0032 (5) | 0.0072 (5) | −0.0063 (6) |
C41 | 0.0513 (7) | 0.0500 (9) | 0.0437 (7) | 0.0022 (6) | 0.0107 (5) | −0.0048 (6) |
C15 | 0.0677 (9) | 0.0432 (9) | 0.0517 (8) | −0.0082 (6) | 0.0130 (6) | −0.0111 (7) |
C42 | 0.0448 (7) | 0.0533 (9) | 0.0516 (8) | 0.0072 (6) | 0.0148 (5) | 0.0010 (7) |
C13 | 0.095 (1) | 0.0346 (8) | 0.060 (1) | 0.0046 (8) | 0.0206 (8) | −0.0019 (7) |
C45 | 0.070 (1) | 0.074 (1) | 0.056 (1) | 0.0263 (9) | 0.0000 (7) | 0.0007 (9) |
C12 | 0.084 (1) | 0.0430 (9) | 0.0541 (9) | 0.0092 (7) | 0.0037 (7) | −0.0023 (7) |
C16 | 0.0616 (9) | 0.062 (1) | 0.076 (1) | −0.0038 (7) | −0.0121 (7) | 0.0109 (9) |
C21 | 0.0637 (9) | 0.071 (1) | 0.085 (1) | −0.0165 (8) | 0.0161 (8) | −0.017 (1) |
C44 | 0.0584 (9) | 0.063 (1) | 0.064 (1) | 0.0117 (7) | 0.0022 (7) | −0.0105 (8) |
C48 | 0.0681 (9) | 0.062 (1) | 0.066 (1) | −0.0124 (7) | 0.0106 (7) | −0.0077 (8) |
C14 | 0.084 (1) | 0.0388 (9) | 0.075 (1) | −0.0151 (7) | 0.0241 (8) | −0.0113 (8) |
C50 | 0.084 (1) | 0.070 (1) | 0.088 (1) | −0.0111 (9) | 0.0215 (9) | 0.019 (1) |
C6 | 0.084 (1) | 0.077 (1) | 0.0399 (8) | 0.0026 (8) | 0.0301 (7) | 0.0026 (7) |
C46 | 0.071 (1) | 0.071 (1) | 0.063 (1) | 0.0209 (8) | 0.0160 (8) | 0.0204 (9) |
C18 | 0.071 (1) | 0.068 (1) | 0.081 (1) | −0.0219 (8) | 0.0037 (8) | −0.0056 (9) |
C25 | 0.061 (1) | 0.076 (1) | 0.078 (1) | −0.0078 (8) | 0.0212 (8) | −0.0094 (9) |
C23 | 0.059 (1) | 0.095 (2) | 0.107 (2) | −0.022 (1) | 0.0020 (9) | 0.017 (1) |
C17 | 0.127 (2) | 0.046 (1) | 0.077 (1) | −0.0002 (9) | 0.022 (1) | 0.0041 (9) |
C19 | 0.065 (1) | 0.100 (2) | 0.097 (1) | −0.0102 (9) | 0.0283 (9) | 0.029 (1) |
C24 | 0.057 (1) | 0.101 (2) | 0.101 (1) | −0.003 (1) | 0.0251 (8) | 0.007 (1) |
C22 | 0.083 (1) | 0.087 (2) | 0.130 (2) | −0.035 (1) | 0.000 (1) | −0.024 (1) |
C49 | 0.121 (2) | 0.102 (2) | 0.071 (1) | 0.034 (1) | −0.011 (1) | 0.002 (1) |
O1—C91 | 1.443 (2) | C10—C15 | 1.399 (2) |
O1—N2 | 1.463 (2) | C31—C41 | 1.492 (2) |
O11—N21 | 1.414 (2) | C31—C42 | 1.485 (2) |
O11—C8 | 1.501 (2) | C20—C21 | 1.372 (3) |
N4—C91 | 1.461 (2) | C20—C25 | 1.387 (3) |
N4—C5 | 1.446 (2) | C8—C9 | 1.514 (2) |
N4—C3 | 1.362 (2) | C8—C41 | 1.527 (2) |
C91—C20 | 1.531 (2) | C47—C42 | 1.412 (3) |
C91—C9 | 1.525 (2) | C47—C50 | 1.489 (3) |
N21—C31 | 1.279 (2) | C47—C46 | 1.393 (3) |
C5—C6 | 1.526 (3) | C15—C14 | 1.402 (3) |
N2—C3 | 1.284 (2) | C15—C18 | 1.493 (3) |
N7—C8 | 1.446 (2) | C13—C12 | 1.383 (3) |
N7—C6 | 1.464 (2) | C13—C14 | 1.382 (3) |
N7—C19 | 1.457 (3) | C13—C17 | 1.505 (3) |
C11—C10 | 1.412 (2) | C45—C44 | 1.374 (3) |
C11—C12 | 1.382 (3) | C45—C46 | 1.392 (3) |
C11—C16 | 1.497 (3) | C45—C49 | 1.507 (3) |
C43—C42 | 1.398 (3) | C21—C22 | 1.387 (3) |
C43—C44 | 1.385 (3) | C25—C24 | 1.380 (3) |
C43—C48 | 1.498 (3) | C23—C24 | 1.361 (4) |
C10—C3 | 1.477 (2) | C23—C22 | 1.370 (4) |
C91—O1—N2 | 109.1 (1) | O11—C8—C41 | 101.8 (2) |
N21—O11—C8 | 110.6 (2) | N7—C8—C9 | 112.8 (2) |
C91—N4—C5 | 121.1 (2) | N7—C8—C41 | 113.5 (2) |
C91—N4—C3 | 107.9 (1) | C9—C8—C41 | 114.0 (2) |
C5—N4—C3 | 125.8 (2) | C91—C9—C8 | 116.8 (2) |
O1—C91—N4 | 101.8 (2) | C42—C47—C50 | 122.5 (2) |
O1—C91—C20 | 109.9 (1) | C42—C47—C46 | 118.2 (2) |
O1—C91—C9 | 110.0 (1) | C50—C47—C46 | 119.3 (2) |
N4—C91—C20 | 108.8 (1) | N4—C3—N2 | 115.1 (2) |
N4—C91—C9 | 112.9 (1) | N4—C3—C10 | 121.1 (2) |
C20—C91—C9 | 113.0 (2) | N2—C3—C10 | 123.8 (2) |
O11—N21—C31 | 109.2 (2) | C31—C41—C8 | 103.7 (2) |
N4—C5—C6 | 113.7 (2) | C10—C15—C14 | 118.1 (2) |
O1—N2—C3 | 105.2 (2) | C10—C15—C18 | 122.2 (2) |
C8—N7—C6 | 114.4 (2) | C14—C15—C18 | 119.7 (2) |
C8—N7—C19 | 114.1 (2) | C43—C42—C31 | 121.0 (2) |
C6—N7—C19 | 111.3 (2) | C43—C42—C47 | 120.0 (2) |
C10—C11—C12 | 118.8 (2) | C31—C42—C47 | 118.7 (2) |
C10—C11—C16 | 121.5 (2) | C12—C13—C14 | 118.0 (2) |
C12—C11—C16 | 119.7 (2) | C12—C13—C17 | 121.2 (2) |
C42—C43—C44 | 119.0 (2) | C14—C13—C17 | 120.8 (2) |
C42—C43—C48 | 121.4 (2) | C44—C45—C46 | 118.0 (2) |
C44—C43—C48 | 119.5 (2) | C44—C45—C49 | 121.3 (2) |
C11—C10—C3 | 118.6 (2) | C46—C45—C49 | 120.7 (2) |
C11—C10—C15 | 120.2 (2) | C11—C12—C13 | 122.3 (2) |
C3—C10—C15 | 121.1 (2) | C20—C21—C22 | 120.8 (2) |
N21—C31—C41 | 114.0 (2) | C43—C44—C45 | 122.4 (2) |
N21—C31—C42 | 121.8 (2) | C15—C14—C13 | 122.4 (2) |
C41—C31—C42 | 123.8 (2) | C5—C6—N7 | 113.6 (2) |
C91—C20—C21 | 123.0 (2) | C47—C46—C45 | 122.0 (2) |
C91—C20—C25 | 119.0 (2) | C20—C25—C24 | 121.0 (2) |
C21—C20—C25 | 117.8 (2) | C24—C23—C22 | 119.2 (2) |
O11—C8—N7 | 109.7 (2) | C25—C24—C23 | 120.5 (2) |
O11—C8—C9 | 104.0 (2) | C21—C22—C23 | 120.5 (3) |
Experimental details
Crystal data | |
Chemical formula | C33H38N4O2 |
Mr | 522.69 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 22.9235 (7), 9.9309 (5), 12.8363 (7) |
β (°) | 101.078 (3) |
V (Å3) | 2867.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.25 × 0.10 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [refl observed if I > 1.75σ(I)] reflections | 4771, 4280, 3640 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.577 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.083, 1.58 |
No. of reflections | 3640 |
No. of parameters | 352 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.21, −0.33 |
Computer programs: KappaCCD Reference Manual (Nonius, 1998), maXus (Mackay et al., 1998), maXus.
O1—C91 | 1.443 (2) | N21—C31 | 1.279 (2) |
O1—N2 | 1.463 (2) | C5—C6 | 1.526 (3) |
O11—N21 | 1.414 (2) | N2—C3 | 1.284 (2) |
O11—C8 | 1.501 (2) | N7—C8 | 1.446 (2) |
N4—C91 | 1.461 (2) | N7—C6 | 1.464 (2) |
N4—C5 | 1.446 (2) | C31—C41 | 1.492 (2) |
N4—C3 | 1.362 (2) | C8—C9 | 1.514 (2) |
C91—C9 | 1.525 (2) | C8—C41 | 1.527 (2) |
C91—O1—N2 | 109.1 (1) | C6—N7—C19 | 111.3 (2) |
N21—O11—C8 | 110.6 (2) | C3—C10—C15 | 121.1 (2) |
C91—N4—C5 | 121.1 (2) | N21—C31—C41 | 114.0 (2) |
C91—N4—C3 | 107.9 (1) | O11—C8—N7 | 109.7 (2) |
C5—N4—C3 | 125.8 (2) | O11—C8—C9 | 104.0 (2) |
O1—C91—N4 | 101.8 (2) | O11—C8—C41 | 101.8 (2) |
O1—C91—C9 | 110.0 (1) | N7—C8—C9 | 112.8 (2) |
N4—C91—C20 | 108.8 (1) | N7—C8—C41 | 113.5 (2) |
N4—C91—C9 | 112.9 (1) | C9—C8—C41 | 114.0 (2) |
O11—N21—C31 | 109.2 (2) | C91—C9—C8 | 116.8 (2) |
N4—C5—C6 | 113.7 (2) | N4—C3—N2 | 115.1 (2) |
O1—N2—C3 | 105.2 (2) | C31—C41—C8 | 103.7 (2) |
C8—N7—C6 | 114.4 (2) | C5—C6—N7 | 113.6 (2) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Récemment, il a été montré que les composés présentant un (ou des) hétérocycle (s) accollés à un hétérocycle azoté à sept chaînons révélaient, dans certains cas, des propriétés pharmacologiques intéressantes (Bellantuono et al., 1980; Bartsch & Erker, 1988). Dans cet objectif, notre équipe de recherche s'est intéressée à la synthèse de nouveaux systèmes hétérocycliques (Hasnaoui et al., 1991; Baouid et al., 1996; Benelbaghdadi et al., 1997, 1998; Essaber et al., 1998) possédant des structures similaires à des composés biologiquement actifs. Pour développer cet axe de recherche, nous avons effectué les réactions de cycloaddition dipolaires-1,3 des oxydes de nitrile vis-à-vis de la 1,4-diazépine (III).
En effet, la condensation de l'oxyde de mésitonitrile (IV) (Grundmann & Dean, 1965; Liu et al., 1980) avec la 1,4-diazépine (III), à température ambiante dans l'éther diéthylique anhydre, conduit à deux types de cycloadduits (I) et (II) (X ou Y). D'après les analyses spectrales, le produit (II) résulte d'une double condensation de deux moles de l'oxyde de mésitonitrile (IV) avec une mole de la 1,4-diazépine (III).
Pour déterminer la nature du dicycloadduit (II) (X ou Y ou leurs régioisomères) ainsi que sa stéréochimie, une analyse cristallographique a été réalisée. La structure cristalline d'un monocristal du composé (II) montre que la cycloaddition s'est effectuée régiosélectivement sur les deux doubles liaisons N4═C5 et C7═CH2 exocycliques obtenues par tautomérie de la double liaison C6═C7 avec le groupement méthyle en position 7 de la diazépine (III). Par conséquent, le dicycloadduit obtenu est le 3-mésityl-7-méthyl-9a-phényl-4,5,6,8,9, 9a-hexahydro-7H-[1,2,4]oxadiazolo[4,5-d][1,4]diazépine-8-spiro-5'-3'- mésityl-4',5'-dihydroisoxazole. En outre, cette structure montre que les deux hétérocycles pentagonaux accollés à la 1,4-diazépine (III) sont en position relative trans.
Le cycle à 7 chaînons et les 2 cycles à 5 chaînons porteurs d'une liaison double C—N, constituent le coeur de la molécule sur lequel les 3 autres cycles phényle ou mésityles sont rattachés. Le cycle N4C5C6N7C8C9C91 présente une conformation de type bateau, avec une partie centrale quasi-plane N4N7C8C91 (déviation r.c.m.: 0.055 Å), un segment N4C5C6N7 quasi-plan (déviation r.c.m.: 0.064 Å) incliné de 122.7 (3)° et une pointe triangulaire C8C9C91 incliné de 47.5 (3)° sur la partie centrale.