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Condensation of mesito­nitrile oxide with 1,7-di­methyl-5-phenyl-2,3-di­hydro-1H-1,4-diazepine leads to two cycloadducts (I) and (II). The structure and stereochemistry of the dicyclo­adduct (II) was established by X-ray crystallographic analysis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016091/qa0187sup1.cif
Contains datablocks default, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016091/qa0187Isup2.hkl
Contains datablock I

CCDC reference: 140865

Comment top

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 N4C5 et C7CH2 exocycliques obtenues par tautomérie de la double liaison C6C7 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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

(I) top
Crystal data top
C33H38N4O2Dx = 1.20 Mg m3
Mr = 522.69Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/cCell parameters from 11268 reflections
a = 22.9235 (7) Åθ = 1–25.2°
b = 9.9309 (5) ŵ = 0.08 mm1
c = 12.8363 (7) ÅT = 298 K
β = 101.078 (3)°Thin plate, colourless
V = 2867.8 (4) Å30.30 × 0.25 × 0.10 mm
Z = 4
Data collection top
KappaCCD
diffractometer
Rint = 0.071
ϕ scansθmax = 24.2°
4771 measured reflectionsh = 2525
4280 independent reflectionsk = 110
3640 reflections with refl observed if I > 1.75σ(I)l = 015
Refinement top
Refinement on FH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.073w = 1/[σ2(Fo2) + 0.03Fo2]
wR(F2) = 0.083(Δ/σ)max = 0.004
S = 1.58Δρmax = 0.21 e Å3
3640 reflectionsΔρmin = 0.33 e Å3
352 parameters
Crystal data top
C33H38N4O2V = 2867.8 (4) Å3
Mr = 522.69Z = 4
Monoclinic, P21/cMo Kα radiation
a = 22.9235 (7) ŵ = 0.08 mm1
b = 9.9309 (5) ÅT = 298 K
c = 12.8363 (7) Å0.30 × 0.25 × 0.10 mm
β = 101.078 (3)°
Data collection top
KappaCCD
diffractometer
3640 reflections with refl observed if I > 1.75σ(I)
4771 measured reflectionsRint = 0.071
4280 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.073352 parameters
wR(F2) = 0.083H-atom parameters not refined
S = 1.58Δρmax = 0.21 e Å3
3640 reflectionsΔρmin = 0.33 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.17658 (4)0.1811 (1)0.81897 (6)0.0481 (5)
O110.31419 (4)0.0716 (1)0.72296 (8)0.0609 (5)
N40.16773 (4)0.2042 (1)0.64187 (8)0.0421 (5)
C910.16641 (5)0.1016 (1)0.72308 (9)0.0431 (6)
N210.36212 (5)0.0935 (1)0.8087 (1)0.0580 (6)
C50.18798 (6)0.1722 (2)0.5448 (1)0.0511 (7)
N20.17360 (5)0.3240 (1)0.79071 (9)0.0496 (6)
N70.28569 (5)0.1557 (1)0.67058 (9)0.0567 (6)
C110.11917 (6)0.4771 (2)0.5471 (1)0.0522 (7)
C430.43471 (6)0.0847 (2)1.0309 (1)0.0543 (7)
C100.16936 (5)0.4524 (1)0.6276 (1)0.0459 (6)
C310.35796 (5)0.0115 (2)0.8837 (1)0.0486 (7)
C200.10415 (5)0.0395 (2)0.7055 (1)0.0480 (7)
C80.27863 (6)0.0489 (2)0.7437 (1)0.0475 (7)
C90.21548 (6)0.0032 (2)0.7280 (1)0.0473 (6)
C470.39271 (6)0.1363 (2)1.0527 (1)0.0598 (8)
C30.17134 (5)0.3269 (1)0.6900 (1)0.0421 (6)
C410.30602 (5)0.0815 (2)0.8591 (1)0.0488 (7)
C150.21680 (6)0.5434 (2)0.6449 (1)0.0549 (7)
C420.39734 (5)0.0217 (2)0.9897 (1)0.0501 (7)
C130.16629 (8)0.6781 (2)0.4956 (1)0.0637 (9)
C450.45790 (7)0.0273 (2)1.2010 (1)0.068 (1)
C120.11922 (7)0.5886 (2)0.4828 (1)0.0619 (8)
C160.06649 (7)0.3850 (2)0.5300 (1)0.0692 (9)
C210.08979 (7)0.0783 (2)0.6507 (2)0.074 (1)
C440.46501 (6)0.0779 (2)1.1350 (1)0.0632 (8)
C480.44429 (7)0.2029 (2)0.9636 (1)0.0662 (9)
C140.21390 (7)0.6554 (2)0.5777 (1)0.0663 (9)
C500.35824 (8)0.2580 (2)1.0101 (2)0.081 (1)
C60.25360 (7)0.1340 (2)0.5618 (1)0.0664 (9)
C460.42256 (7)0.1352 (2)1.1580 (1)0.069 (1)
C180.27030 (7)0.5229 (2)0.7302 (2)0.075 (1)
C250.05881 (7)0.1095 (2)0.7393 (2)0.0722 (9)
C230.01282 (8)0.0525 (3)0.6606 (2)0.089 (1)
C170.1661 (1)0.7961 (2)0.4220 (2)0.084 (1)
C190.34725 (8)0.1940 (3)0.6727 (2)0.087 (1)
C240.00100 (7)0.0632 (3)0.7169 (2)0.087 (1)
C220.0315 (1)0.1238 (3)0.6279 (2)0.103 (1)
C490.4882 (1)0.0276 (3)1.3161 (2)0.101 (1)
H5A0.164080.098820.511930.05000*
H5B0.180980.250220.499930.05000*
H41A0.277220.065070.902960.05000*
H41B0.317720.174370.864660.05000*
H120.085020.603530.427940.05000*
H16A0.073590.312960.580830.05000*0.50
H16B0.031790.434360.539230.05000*0.50
H16C0.060290.348360.459530.05000*0.50
H210.120590.129180.627810.05000*
H440.491510.150571.160800.05000*
H48A0.420590.193670.893630.05000*0.50
H48B0.433290.283870.995830.05000*0.50
H48C0.485590.207170.959030.05000*0.50
H140.246700.717280.590270.05000*
H50A0.340440.243080.937040.05000*0.50
H50B0.384340.334381.015540.05000*0.50
H50C0.327640.274681.050140.05000*0.50
H6A0.255500.040510.543890.05000*
H6B0.271300.187110.513690.05000*
H460.418060.211841.201430.05000*
H18A0.265900.442630.769600.05000*
H18B0.304700.514830.698300.05000*
H18C0.274900.599030.777100.05000*
H250.068310.190880.779300.05000*
H230.053020.084760.643230.05000*
H17A0.129800.796170.370200.05000*0.50
H17B0.169000.878070.462200.05000*0.50
H17C0.199300.789370.386700.05000*0.50
H19A0.367250.207570.744760.05000*
H19B0.366750.123370.641260.05000*
H19C0.348450.275670.633160.05000*
H240.029400.113670.741510.05000*
H220.022820.206440.589140.05000*
H49A0.510790.053701.332720.05000*
H49B0.458790.033801.359920.05000*
H49C0.514290.103901.329120.05000*
H50D0.376540.305580.955740.05000*0.50
H48D0.477590.257871.000930.05000*0.50
H50E0.319840.208880.986940.05000*0.50
H16D0.074490.287160.511030.05000*0.50
H17D0.131700.859470.425600.05000*0.50
H48E0.44960.1450.8990.050*0.50
H16E0.032290.411660.469230.05000*0.50
H17E0.156700.752270.355100.05000*0.50
H50F0.353240.336581.052640.05000*0.50
H17F0.205700.841870.437100.05000*0.50
H48F0.406690.254770.960830.05000*0.50
H16F0.051090.379460.597630.05000*0.50
H9A0.207280.055620.659290.05000*
H9B0.213080.065720.789090.05000*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0658 (6)0.0498 (6)0.0274 (4)0.0023 (4)0.0106 (3)0.0036 (4)
O110.0679 (6)0.0630 (7)0.0495 (6)0.0118 (5)0.0113 (4)0.0148 (5)
N40.0586 (6)0.0390 (7)0.0279 (5)0.0048 (5)0.0122 (4)0.0019 (4)
C910.0584 (7)0.0419 (8)0.0277 (6)0.0044 (6)0.0107 (5)0.0020 (5)
N210.0576 (7)0.0593 (9)0.0557 (8)0.0100 (5)0.0155 (5)0.0041 (6)
C50.0790 (9)0.0466 (8)0.0263 (6)0.0023 (7)0.0133 (6)0.0025 (6)
N20.0631 (7)0.0467 (7)0.0376 (7)0.0034 (5)0.0119 (5)0.0064 (5)
N70.0544 (7)0.0640 (9)0.0512 (7)0.0067 (5)0.0187 (5)0.0065 (6)
C110.0620 (8)0.0425 (9)0.0489 (8)0.0006 (6)0.0058 (6)0.0059 (6)
C430.0484 (7)0.056 (1)0.0571 (9)0.0074 (6)0.0132 (6)0.0033 (7)
C100.0582 (8)0.0380 (8)0.0401 (7)0.0016 (6)0.0116 (5)0.0066 (6)
C310.0514 (7)0.0463 (8)0.0476 (8)0.0008 (6)0.0170 (5)0.0006 (7)
C200.0540 (8)0.0514 (9)0.0371 (7)0.0059 (6)0.0088 (5)0.0058 (6)
C80.0553 (7)0.0460 (8)0.0407 (7)0.0019 (6)0.0152 (5)0.0037 (6)
C90.0572 (8)0.0435 (8)0.0396 (7)0.0051 (6)0.0098 (5)0.0005 (6)
C470.0537 (8)0.059 (1)0.066 (1)0.0070 (7)0.0163 (7)0.0097 (8)
C30.0448 (7)0.0436 (8)0.0360 (7)0.0032 (5)0.0072 (5)0.0063 (6)
C410.0513 (7)0.0500 (9)0.0437 (7)0.0022 (6)0.0107 (5)0.0048 (6)
C150.0677 (9)0.0432 (9)0.0517 (8)0.0082 (6)0.0130 (6)0.0111 (7)
C420.0448 (7)0.0533 (9)0.0516 (8)0.0072 (6)0.0148 (5)0.0010 (7)
C130.095 (1)0.0346 (8)0.060 (1)0.0046 (8)0.0206 (8)0.0019 (7)
C450.070 (1)0.074 (1)0.056 (1)0.0263 (9)0.0000 (7)0.0007 (9)
C120.084 (1)0.0430 (9)0.0541 (9)0.0092 (7)0.0037 (7)0.0023 (7)
C160.0616 (9)0.062 (1)0.076 (1)0.0038 (7)0.0121 (7)0.0109 (9)
C210.0637 (9)0.071 (1)0.085 (1)0.0165 (8)0.0161 (8)0.017 (1)
C440.0584 (9)0.063 (1)0.064 (1)0.0117 (7)0.0022 (7)0.0105 (8)
C480.0681 (9)0.062 (1)0.066 (1)0.0124 (7)0.0106 (7)0.0077 (8)
C140.084 (1)0.0388 (9)0.075 (1)0.0151 (7)0.0241 (8)0.0113 (8)
C500.084 (1)0.070 (1)0.088 (1)0.0111 (9)0.0215 (9)0.019 (1)
C60.084 (1)0.077 (1)0.0399 (8)0.0026 (8)0.0301 (7)0.0026 (7)
C460.071 (1)0.071 (1)0.063 (1)0.0209 (8)0.0160 (8)0.0204 (9)
C180.071 (1)0.068 (1)0.081 (1)0.0219 (8)0.0037 (8)0.0056 (9)
C250.061 (1)0.076 (1)0.078 (1)0.0078 (8)0.0212 (8)0.0094 (9)
C230.059 (1)0.095 (2)0.107 (2)0.022 (1)0.0020 (9)0.017 (1)
C170.127 (2)0.046 (1)0.077 (1)0.0002 (9)0.022 (1)0.0041 (9)
C190.065 (1)0.100 (2)0.097 (1)0.0102 (9)0.0283 (9)0.029 (1)
C240.057 (1)0.101 (2)0.101 (1)0.003 (1)0.0251 (8)0.007 (1)
C220.083 (1)0.087 (2)0.130 (2)0.035 (1)0.000 (1)0.024 (1)
C490.121 (2)0.102 (2)0.071 (1)0.034 (1)0.011 (1)0.002 (1)
Geometric parameters (Å, º) top
O1—C911.443 (2)C10—C151.399 (2)
O1—N21.463 (2)C31—C411.492 (2)
O11—N211.414 (2)C31—C421.485 (2)
O11—C81.501 (2)C20—C211.372 (3)
N4—C911.461 (2)C20—C251.387 (3)
N4—C51.446 (2)C8—C91.514 (2)
N4—C31.362 (2)C8—C411.527 (2)
C91—C201.531 (2)C47—C421.412 (3)
C91—C91.525 (2)C47—C501.489 (3)
N21—C311.279 (2)C47—C461.393 (3)
C5—C61.526 (3)C15—C141.402 (3)
N2—C31.284 (2)C15—C181.493 (3)
N7—C81.446 (2)C13—C121.383 (3)
N7—C61.464 (2)C13—C141.382 (3)
N7—C191.457 (3)C13—C171.505 (3)
C11—C101.412 (2)C45—C441.374 (3)
C11—C121.382 (3)C45—C461.392 (3)
C11—C161.497 (3)C45—C491.507 (3)
C43—C421.398 (3)C21—C221.387 (3)
C43—C441.385 (3)C25—C241.380 (3)
C43—C481.498 (3)C23—C241.361 (4)
C10—C31.477 (2)C23—C221.370 (4)
C91—O1—N2109.1 (1)O11—C8—C41101.8 (2)
N21—O11—C8110.6 (2)N7—C8—C9112.8 (2)
C91—N4—C5121.1 (2)N7—C8—C41113.5 (2)
C91—N4—C3107.9 (1)C9—C8—C41114.0 (2)
C5—N4—C3125.8 (2)C91—C9—C8116.8 (2)
O1—C91—N4101.8 (2)C42—C47—C50122.5 (2)
O1—C91—C20109.9 (1)C42—C47—C46118.2 (2)
O1—C91—C9110.0 (1)C50—C47—C46119.3 (2)
N4—C91—C20108.8 (1)N4—C3—N2115.1 (2)
N4—C91—C9112.9 (1)N4—C3—C10121.1 (2)
C20—C91—C9113.0 (2)N2—C3—C10123.8 (2)
O11—N21—C31109.2 (2)C31—C41—C8103.7 (2)
N4—C5—C6113.7 (2)C10—C15—C14118.1 (2)
O1—N2—C3105.2 (2)C10—C15—C18122.2 (2)
C8—N7—C6114.4 (2)C14—C15—C18119.7 (2)
C8—N7—C19114.1 (2)C43—C42—C31121.0 (2)
C6—N7—C19111.3 (2)C43—C42—C47120.0 (2)
C10—C11—C12118.8 (2)C31—C42—C47118.7 (2)
C10—C11—C16121.5 (2)C12—C13—C14118.0 (2)
C12—C11—C16119.7 (2)C12—C13—C17121.2 (2)
C42—C43—C44119.0 (2)C14—C13—C17120.8 (2)
C42—C43—C48121.4 (2)C44—C45—C46118.0 (2)
C44—C43—C48119.5 (2)C44—C45—C49121.3 (2)
C11—C10—C3118.6 (2)C46—C45—C49120.7 (2)
C11—C10—C15120.2 (2)C11—C12—C13122.3 (2)
C3—C10—C15121.1 (2)C20—C21—C22120.8 (2)
N21—C31—C41114.0 (2)C43—C44—C45122.4 (2)
N21—C31—C42121.8 (2)C15—C14—C13122.4 (2)
C41—C31—C42123.8 (2)C5—C6—N7113.6 (2)
C91—C20—C21123.0 (2)C47—C46—C45122.0 (2)
C91—C20—C25119.0 (2)C20—C25—C24121.0 (2)
C21—C20—C25117.8 (2)C24—C23—C22119.2 (2)
O11—C8—N7109.7 (2)C25—C24—C23120.5 (2)
O11—C8—C9104.0 (2)C21—C22—C23120.5 (3)

Experimental details

Crystal data
Chemical formulaC33H38N4O2
Mr522.69
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)22.9235 (7), 9.9309 (5), 12.8363 (7)
β (°) 101.078 (3)
V3)2867.8 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.30 × 0.25 × 0.10
Data collection
DiffractometerKappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [refl observed if I > 1.75σ(I)] reflections
4771, 4280, 3640
Rint0.071
(sin θ/λ)max1)0.577
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.073, 0.083, 1.58
No. of reflections3640
No. of parameters352
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.21, 0.33

Computer programs: KappaCCD Reference Manual (Nonius, 1998), maXus (Mackay et al., 1998), maXus.

Selected geometric parameters (Å, º) top
O1—C911.443 (2)N21—C311.279 (2)
O1—N21.463 (2)C5—C61.526 (3)
O11—N211.414 (2)N2—C31.284 (2)
O11—C81.501 (2)N7—C81.446 (2)
N4—C911.461 (2)N7—C61.464 (2)
N4—C51.446 (2)C31—C411.492 (2)
N4—C31.362 (2)C8—C91.514 (2)
C91—C91.525 (2)C8—C411.527 (2)
C91—O1—N2109.1 (1)C6—N7—C19111.3 (2)
N21—O11—C8110.6 (2)C3—C10—C15121.1 (2)
C91—N4—C5121.1 (2)N21—C31—C41114.0 (2)
C91—N4—C3107.9 (1)O11—C8—N7109.7 (2)
C5—N4—C3125.8 (2)O11—C8—C9104.0 (2)
O1—C91—N4101.8 (2)O11—C8—C41101.8 (2)
O1—C91—C9110.0 (1)N7—C8—C9112.8 (2)
N4—C91—C20108.8 (1)N7—C8—C41113.5 (2)
N4—C91—C9112.9 (1)C9—C8—C41114.0 (2)
O11—N21—C31109.2 (2)C91—C9—C8116.8 (2)
N4—C5—C6113.7 (2)N4—C3—N2115.1 (2)
O1—N2—C3105.2 (2)C31—C41—C8103.7 (2)
C8—N7—C6114.4 (2)C5—C6—N7113.6 (2)
 

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