Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011689/qa0297sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011689/qa0297IIIasup2.hkl |
CCDC reference: 152666
Une solution de 1,5-benzodiazépinone (1 g, 4.7 mmol) et l'oxyde de mésitonitrile (0.76 g, 4.7 mmol) dans d'éther diéthylique anhydre (30 ml) 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–acétate d'éthyle 7:3). Le cycloadduit isolé est recristallisé dans un mélange CHCl3/éthanol (1/9) (p.f.: 518–519 K).
Les cartes de densité électronique différence, calculées en fin d'affinement, montrent que chaque atome d'hydrogène des groupes méthyle portés par les atomes de carbone C20, C21, C22 et C23, occupe statistiquement deux positions avec un degré d'occupation 0.5.
Data collection: KappaCCD Software (Nonius, 1997); data reduction: DENZO and Scalepak (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999); software used to prepare material for publication: maXus.
C23H25N3O2 | F(000) = 800 |
Mr = 375.47 | Dx = 1.241 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.4861 (5) Å | Cell parameters from 14430 reflections |
b = 16.872 (1) Å | θ = 1–25.6° |
c = 17.9161 (6) Å | µ = 0.08 mm−1 |
β = 152.698 (2)° | T = 298 K |
V = 2008.5 (3) Å3 | Cuboid, colourless |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
KappaCCD diffractometer | Rint = 0.056 |
Radiation source: fine-focus sealed tube | θmax = 25.8° |
ϕ scan | h = −15→17 |
3885 measured reflections | k = −20→0 |
3745 independent reflections | l = −22→15 |
2838 reflections with I > 3σ(I) |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom, diff |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters not refined |
wR(F2) = 0.057 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2) + 0.03Fo2] |
S = 1.45 | (Δ/σ)max = 0.011 |
2838 reflections | Δρmax = 0.17 e Å−3 |
253 parameters | Δρmin = −0.20 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C23H25N3O2 | V = 2008.5 (3) Å3 |
Mr = 375.47 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.4861 (5) Å | µ = 0.08 mm−1 |
b = 16.872 (1) Å | T = 298 K |
c = 17.9161 (6) Å | 0.30 × 0.25 × 0.20 mm |
β = 152.698 (2)° |
KappaCCD diffractometer | 2838 reflections with I > 3σ(I) |
3885 measured reflections | Rint = 0.056 |
3745 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 253 parameters |
wR(F2) = 0.057 | H-atom parameters not refined |
S = 1.45 | Δρmax = 0.17 e Å−3 |
2838 reflections | Δρmin = −0.20 e Å−3 |
Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are estimated using the full covariance matrix. The standard uncertainties in cell dimensions are are used in calculating the standard uncertainties of bond distances, angles and torsion angles. Angles between l.s. planes have standard uncertainties calculated from atomic positional standard uncertainties; the errors in cell dimensions are not used in this case. |
Refinement. Refinement on F2. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.01575 (6) | 0.20732 (2) | 0.82585 (5) | 0.0765 (2) | |
C10 | 0.65380 (7) | 0.05314 (3) | 1.34939 (5) | 0.1128 (3) | |
C11 | 0.59220 (7) | 0.11625 (3) | 1.34723 (5) | 0.1115 (3) | |
C12 | 0.44881 (7) | 0.16724 (3) | 1.21626 (5) | 0.0970 (3) | |
C14 | −0.05861 (6) | 0.18849 (3) | 0.84819 (5) | 0.0763 (2) | |
C15 | −0.12205 (6) | 0.11154 (3) | 0.81863 (5) | 0.0984 (3) | |
C16 | −0.19260 (7) | 0.09550 (3) | 0.83939 (6) | 0.1126 (3) | |
C17 | −0.20355 (6) | 0.15337 (3) | 0.88625 (5) | 0.0932 (3) | |
C18 | −0.13857 (6) | 0.22879 (3) | 0.91552 (5) | 0.0940 (3) | |
C19 | −0.06629 (6) | 0.24786 (3) | 0.89751 (5) | 0.0809 (2) | |
C20 | −0.11507 (8) | 0.04681 (3) | 0.76543 (7) | 0.1697 (3) | |
C21 | −0.28675 (8) | 0.13418 (3) | 0.90272 (6) | 0.1551 (3) | |
C22 | 0.00252 (8) | 0.33114 (3) | 0.93069 (6) | 0.1480 (3) | |
C24 | 0.25826 (7) | −0.01524 (3) | 0.88832 (6) | 0.1276 (3) | |
C31 | 0.22932 (6) | 0.24250 (3) | 0.88597 (5) | 0.0744 (2) | |
C4 | 0.28700 (7) | 0.32921 (3) | 0.92105 (5) | 0.1127 (3) | |
C5 | 0.33756 (8) | 0.33963 (3) | 0.87436 (6) | 0.1426 (3) | |
C6 | 0.37874 (7) | 0.25648 (3) | 0.87261 (6) | 0.1162 (3) | |
C61 | 0.37277 (6) | 0.20100 (3) | 0.93607 (5) | 0.0837 (2) | |
C7 | 0.30728 (7) | 0.11744 (3) | 0.87522 (5) | 0.0983 (3) | |
C81 | 0.41957 (6) | 0.08752 (3) | 1.08448 (5) | 0.0809 (2) | |
C82 | 0.36296 (6) | 0.15397 (2) | 1.08494 (5) | 0.0704 (2) | |
C9 | 0.56898 (7) | 0.03848 (3) | 1.21969 (5) | 0.1102 (3) | |
N13 | 0.21889 (5) | 0.21023 (2) | 0.95396 (4) | 0.07439 (19) | |
N2 | −0.10249 (5) | 0.22414 (2) | 0.68673 (4) | 0.0891 (2) | |
N8 | 0.32335 (5) | 0.06712 (2) | 0.94612 (4) | 0.1027 (2) | |
O23 | 0.23976 (5) | 0.09452 (2) | 0.76676 (4) | 0.1650 (2) | |
O3 | 0.02435 (4) | 0.232618 (17) | 0.71268 (3) | 0.08205 (16) | |
H10 | 0.755802 | 0.018140 | 1.441592 | 0.0500* | |
H11 | 0.650702 | 0.125753 | 1.437435 | 0.0500* | |
H12 | 0.405714 | 0.212139 | 1.214058 | 0.0500* | |
H16 | −0.234699 | 0.042498 | 0.820993 | 0.0500* | |
H18 | −0.144074 | 0.269589 | 0.948924 | 0.0500* | |
H20A | −0.063659 | 0.068388 | 0.756625 | 0.0500* | 0.50 |
H20B | −0.247259 | 0.025688 | 0.662025 | 0.0500* | 0.50 |
H20C | −0.027559 | 0.005288 | 0.845425 | 0.0500* | 0.50 |
H20D | −0.159259 | −0.007312 | 0.763325 | 0.0500* | 0.50 |
H20E | 0.030241 | 0.035788 | 0.859725 | 0.0500* | 0.50 |
H20F | −0.195359 | 0.064688 | 0.663625 | 0.0500* | 0.50 |
H21A | −0.323523 | 0.079154 | 0.877660 | 0.0500* | 0.50 |
H21B | −0.403123 | 0.166154 | 0.829060 | 0.0500* | 0.50 |
H21C | −0.185823 | 0.144354 | 1.012361 | 0.0500* | 0.50 |
H21D | −0.430147 | 0.118970 | 0.790609 | 0.0500* | 0.50 |
H21E | −0.289741 | 0.176083 | 0.940036 | 0.0500* | 0.50 |
H21F | −0.220828 | 0.081158 | 0.967355 | 0.0500* | 0.50 |
H22A | 0.048316 | 0.334063 | 0.912853 | 0.0500* | 0.50 |
H22B | 0.110716 | 0.345063 | 1.041454 | 0.0500* | 0.50 |
H22C | −0.107384 | 0.367363 | 0.858754 | 0.0500* | 0.50 |
H22D | 0.145174 | 0.332052 | 1.015408 | 0.0500* | 0.50 |
H22E | −0.055482 | 0.355881 | 0.843764 | 0.0500* | 0.50 |
H22F | −0.021894 | 0.365401 | 0.957782 | 0.0500* | 0.50 |
H24A | 0.277171 | −0.044380 | 0.947397 | 0.0500* | 0.50 |
H24B | 0.336602 | −0.039183 | 0.905488 | 0.0500* | 0.50 |
H24C | 0.118465 | −0.016172 | 0.774280 | 0.0500* | 0.50 |
H24D | 0.164153 | −0.033449 | 0.860754 | 0.0500* | 0.50 |
H24E | 0.393875 | −0.031522 | 1.004498 | 0.0500* | 0.50 |
H24F | 0.176892 | −0.013944 | 0.782920 | 0.0500* | 0.50 |
H4A | 0.404401 | 0.341605 | 1.034353 | 0.0500* | |
H4B | 0.179001 | 0.364005 | 0.857453 | 0.0500* | |
H5A | 0.454059 | 0.372525 | 0.951257 | 0.0500* | |
H5B | 0.225159 | 0.362626 | 0.767757 | 0.0500* | |
H66 | 0.503272 | 0.198598 | 1.052766 | 0.0500* | |
H6A | 0.275839 | 0.242677 | 0.763405 | 0.0500* | |
H6B | 0.507440 | 0.256176 | 0.940705 | 0.0500* | |
H9 | 0.612980 | −0.006418 | 1.222686 | 0.0500* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0325 (2) | 0.0405 (3) | 0.0328 (2) | 0.00319 (19) | 0.0287 (2) | 0.00036 (19) |
C10 | 0.0514 (3) | 0.0658 (4) | 0.0401 (3) | 0.0134 (3) | 0.0384 (3) | 0.0166 (2) |
C11 | 0.0552 (3) | 0.0678 (3) | 0.0362 (3) | 0.0013 (3) | 0.0397 (3) | 0.0014 (2) |
C12 | 0.0457 (3) | 0.0507 (3) | 0.0378 (2) | −0.0009 (2) | 0.0371 (2) | −0.0040 (2) |
C14 | 0.0305 (2) | 0.0455 (3) | 0.0328 (2) | 0.00421 (19) | 0.0279 (2) | 0.00376 (19) |
C15 | 0.0405 (3) | 0.0458 (3) | 0.0456 (3) | 0.0015 (2) | 0.0379 (2) | −0.0002 (2) |
C16 | 0.0475 (3) | 0.0490 (3) | 0.0517 (3) | −0.0036 (2) | 0.0432 (3) | 0.0025 (2) |
C17 | 0.0369 (3) | 0.0672 (3) | 0.0369 (2) | 0.0015 (2) | 0.0328 (2) | 0.0046 (2) |
C18 | 0.0398 (3) | 0.0559 (3) | 0.0396 (2) | 0.0034 (2) | 0.0358 (2) | 0.0017 (2) |
C19 | 0.0344 (2) | 0.0452 (3) | 0.0341 (2) | 0.00463 (19) | 0.0303 (2) | 0.0046 (2) |
C20 | 0.0761 (4) | 0.0499 (3) | 0.0852 (4) | −0.0026 (3) | 0.0728 (4) | −0.0063 (3) |
C21 | 0.0671 (3) | 0.0851 (4) | 0.0688 (3) | −0.0073 (3) | 0.0629 (3) | −0.0011 (3) |
C22 | 0.0713 (3) | 0.0499 (3) | 0.0705 (3) | 0.0013 (2) | 0.0663 (3) | 0.0001 (2) |
C24 | 0.0593 (3) | 0.0604 (3) | 0.0525 (3) | 0.0000 (3) | 0.0495 (3) | −0.0073 (3) |
C31 | 0.0307 (2) | 0.0498 (3) | 0.0285 (2) | −0.00057 (19) | 0.0257 (2) | 0.00068 (19) |
C4 | 0.0516 (3) | 0.0548 (3) | 0.0452 (3) | −0.0065 (2) | 0.0419 (3) | −0.0029 (2) |
C5 | 0.0620 (3) | 0.0721 (4) | 0.0611 (3) | −0.0101 (3) | 0.0543 (3) | 0.0012 (3) |
C6 | 0.0419 (3) | 0.0902 (4) | 0.0490 (3) | 0.0062 (3) | 0.0411 (3) | 0.0141 (3) |
C61 | 0.0320 (2) | 0.0612 (3) | 0.0337 (2) | 0.0054 (2) | 0.0289 (2) | 0.0074 (2) |
C7 | 0.0407 (3) | 0.0652 (3) | 0.0402 (2) | 0.0144 (2) | 0.0367 (2) | 0.0093 (2) |
C81 | 0.0356 (2) | 0.0456 (3) | 0.0333 (2) | 0.0005 (2) | 0.0309 (2) | −0.0002 (2) |
C82 | 0.0294 (2) | 0.0435 (3) | 0.0281 (2) | −0.00135 (19) | 0.0250 (2) | −0.00075 (19) |
C9 | 0.0494 (3) | 0.0501 (3) | 0.0483 (3) | 0.0112 (2) | 0.0435 (3) | 0.0094 (2) |
N13 | 0.03070 (19) | 0.0477 (2) | 0.03011 (18) | 0.00392 (16) | 0.02689 (17) | 0.00395 (16) |
N2 | 0.0337 (2) | 0.0653 (3) | 0.0368 (2) | 0.00089 (18) | 0.03142 (19) | 0.00040 (18) |
N8 | 0.0502 (2) | 0.0469 (2) | 0.0421 (2) | 0.00122 (18) | 0.0421 (2) | −0.00251 (18) |
O23 | 0.0859 (3) | 0.0822 (3) | 0.0617 (2) | 0.0235 (2) | 0.0684 (2) | 0.01248 (19) |
O3 | 0.03128 (16) | 0.0695 (2) | 0.02983 (15) | 0.00093 (14) | 0.02696 (14) | 0.00126 (14) |
C1—C14 | 1.4790 (5) | C61—C6 | 1.5333 (6) |
C11—C10 | 1.3676 (7) | C61—C7 | 1.4960 (6) |
C11—C12 | 1.3779 (6) | C81—C9 | 1.3854 (6) |
C14—C15 | 1.3949 (6) | C82—C12 | 1.3898 (5) |
C14—C19 | 1.4041 (5) | C82—C81 | 1.3934 (5) |
C15—C16 | 1.3898 (6) | C9—C10 | 1.3772 (7) |
C15—C20 | 1.5108 (6) | N13—C1 | 1.3879 (5) |
C16—C17 | 1.3856 (6) | N13—C31 | 1.4596 (5) |
C17—C18 | 1.3795 (6) | N13—C82 | 1.4352 (5) |
C17—C21 | 1.5089 (6) | N2—C1 | 1.2805 (5) |
C19—C18 | 1.3800 (6) | N8—C24 | 1.4688 (5) |
C22—C19 | 1.5060 (6) | N8—C7 | 1.3647 (5) |
C31—C4 | 1.5165 (6) | N8—C81 | 1.4372 (5) |
C4—C5 | 1.5350 (6) | O23—C7 | 1.2266 (5) |
C6—C5 | 1.5357 (7) | O3—C31 | 1.4491 (5) |
C61—C31 | 1.5164 (6) | O3—N2 | 1.4472 (4) |
C1—C14—C15 | 119.33 (4) | C7—N8—C24 | 117.43 (4) |
C1—C14—C19 | 120.08 (4) | C81—C82—C12 | 119.58 (4) |
C1—N13—C31 | 105.83 (3) | C81—C9—C10 | 120.55 (4) |
C12—C11—C10 | 119.51 (4) | C81—N8—C24 | 118.27 (3) |
C14—C15—C20 | 121.43 (4) | C81—N8—C7 | 123.94 (4) |
C14—C19—C22 | 121.27 (4) | C82—C12—C11 | 120.63 (4) |
C14—C15—C16 | 118.21 (4) | C82—C81—C9 | 118.91 (4) |
C14—C19—C18 | 118.80 (4) | C82—C81—N8 | 121.94 (3) |
C15—C14—C19 | 120.60 (4) | C82—N13—C1 | 123.12 (3) |
C15—C16—C17 | 122.16 (4) | C82—N13—C31 | 122.20 (3) |
C16—C15—C20 | 120.36 (4) | C9—C10—C11 | 120.71 (4) |
C16—C17—C21 | 120.58 (4) | N13—C1—C14 | 122.95 (3) |
C16—C17—C18 | 118.26 (4) | N13—C82—C12 | 118.36 (3) |
C18—C17—C21 | 121.15 (4) | N13—C82—C81 | 122.06 (3) |
C19—C18—C17 | 121.96 (4) | N2—C1—C14 | 122.56 (4) |
C22—C19—C18 | 119.93 (4) | N2—C1—N13 | 114.47 (3) |
C31—C4—C5 | 103.80 (4) | N2—O3—C31 | 107.40 (3) |
C31—C61—C6 | 103.28 (4) | N8—C7—C61 | 115.77 (4) |
C31—C61—C7 | 110.83 (3) | N8—C81—C9 | 119.12 (4) |
C4—C5—C6 | 106.78 (4) | O23—C7—C61 | 123.24 (4) |
C61—C31—C4 | 103.86 (3) | O23—C7—N8 | 120.98 (4) |
C61—C6—C5 | 105.29 (4) | O3—C31—N13 | 102.15 (3) |
C7—C61—C6 | 116.88 (4) | O3—N2—C1 | 106.03 (3) |
Experimental details
Crystal data | |
Chemical formula | C23H25N3O2 |
Mr | 375.47 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 14.4861 (5), 16.872 (1), 17.9161 (6) |
β (°) | 152.698 (2) |
V (Å3) | 2008.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 3σ(I)] reflections | 3885, 3745, 2838 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.612 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.057, 1.45 |
No. of reflections | 2838 |
No. of parameters | 253 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.17, −0.20 |
Computer programs: KappaCCD Software (Nonius, 1997), DENZO and Scalepak (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), maXus (Mackay et al., 1999), maXus.
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Il a été montré que les composés possédant au moins un (ou des) hétérocycle(s) accolé(s) à un hétérocycle azoté à sept chaînons révélaient, dans la plupart des cas, des propriétés pharmacologiques intéressantes (Bellantuono et al., 1980; Bartsch & Erker, 1988). Dans cet objectif, nous développons toujours notre étude concernant la synthèse de nouveaux systèmes polyhétérocycliques (Hasnaoui et al., 1991; Baouid et al., 1996; Benelbaghdadi et al., 1997, 1998; Essaber et al., 1998). Ces systèmes peuvent ètre actifs biologiquement. Par la suite, nous avons effectué des réactions de cycloaddition dipolaires-1,3 des oxydes de nitrile vis-à-vis de la 1,5-benzodiazépin-2-one.
En effet, nous avons réalisé la condensation de l'oxyde de mésitonitrile (Grundmann & Dean, 1965; Liu et al., 1980) avec la 1,5-benzodazépin-2-one (Rossi et al., 1960) à température ambiante dans l'éther diéthylique anhydre. Selon les formes tautomères de la benzodiazépin-2-one deux cycloadduits isomères peuvent ètre obtenus. Pour déterminer la structure exacte du produit obtenu une analyse cristallographique a été réalisée. La structure cristalline composé montre que la cycloaddition s'est effectuée régiosélectivement sur la double liaison N5═C4 de la 1,5-benzodiazépin-2-one aboutissant à l'adduit 1-mésityl-8-méthyl-3a,6a-triméthylène-3a,6a,7,13 − tétrahydro- 8H-[1,2,4]oxadiazolo[5,4-d][1,5]benzodiazépin-7-one, (I), avec un rendement de 75%. Cette réaction de cycloaddition est à la fois péri et régiosélective.
Les deux cycles à 5 chaînons portés par le fragment benzodiazepine montrent deux conformations différentes; (i) le cycle C4/C5/C6/C61/C31 présente une conformation enveloppe, avec l'atome C31 situé à 0.6041 (4) Å au dessus du plan formé par les atomes C4/C5/C6/C61; (ii) le cycle C1/N2/O3/C31/N13 présente une conformation bipyramidale à base triangulaire, avec C1 à −0.0759 Å e t C31 à 0.3211 Å du plan N2/O3/N13, respectivement. Le fragment N8/C81/C9/C10/C11/C12/C82/N13 de la benzodiazepine est quasi-plan: l'angle entre les deux plans N8/C81/C82/N13 et C81/C9/C10/C11/C12/C82 est égal à 176.4 (1)°. La déformation du cycle à 7 chaînons est donnée par les angles de torsion N13/C31/C61/C7: −64.0 (1)° et C31/C61/C7/N8: −68.7 (1)°.