Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002203/cf6029sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002203/cf6029Isup2.hkl |
CCDC reference: 159842
A 0,005 M de β-uréidoxyalcool dans 100 ml de benzène anhydre, on ajoute 0,005 M de benzaldéhyde en présence d'acide para-toluène sulfonique. On chauffe à reflux sous agitation, pendant 2 h. Le mélange réactionnel est laissé à température ambiante pendant une nuit. Le précipité formé est filtré et recristallisé dans l'éthanol anhydre.
Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: DENZO and SCALEPACK (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); molecular graphics: ORTEP (Johnson, 1976); software used to prepare material for publication: maXus (Mackay et al., 1999).
Fig. 1. Perspective view of the molecule showing the labelling of the atoms with displacement ellipsoids at the 50% probability level. [Please supply French version of this caption] |
C12H16N2O3 | Z = 2 |
Mr = 236.26 | F(000) = 248 |
Triclinic, P1 | Dx = 1.265 Mg m−3 |
a = 5.4856 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.906 (1) Å | Cell parameters from 4318 reflections |
c = 12.227 (1) Å | θ = 1–25.5° |
α = 73.429 (4)° | µ = 0.09 mm−1 |
β = 77.443 (7)° | T = 298 K |
γ = 78.576 (7)° | Needle, colourless |
V = 615.0 (1) Å3 | 0.35 × 0.15 × 0.10 mm |
KappaCCD diffractometer | Rint = 0.029 |
Radiation source: fine-focus sealed tube | θmax = 25.6° |
ϕ scans | h = 0→6 |
4318 measured reflections | k = −11→12 |
2218 independent reflections | l = −14→15 |
1827 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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.064 | Weighting scheme based on measured s.u.'s w = 1/(σ2(Fo2) + 0.03Fo2) |
S = 1.04 | (Δ/σ)max = 0.006 |
1827 reflections | Δρmax = 0.26 e Å−3 |
154 parameters | Δρmin = −0.20 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C12H16N2O3 | γ = 78.576 (7)° |
Mr = 236.26 | V = 615.0 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.4856 (4) Å | Mo Kα radiation |
b = 9.906 (1) Å | µ = 0.09 mm−1 |
c = 12.227 (1) Å | T = 298 K |
α = 73.429 (4)° | 0.35 × 0.15 × 0.10 mm |
β = 77.443 (7)° |
KappaCCD diffractometer | 1827 reflections with I > 3σ(I) |
4318 measured reflections | Rint = 0.029 |
2218 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 154 parameters |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.26 e Å−3 |
1827 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 | ||
O1 | 0.53152 (7) | 0.23889 (4) | 0.22372 (4) | 0.0393 (2) | |
O4 | 0.94699 (7) | 0.37529 (4) | 0.19767 (3) | 0.0354 (2) | |
O8 | 1.10390 (8) | 0.06410 (5) | 0.10771 (4) | 0.0454 (2) | |
N2 | 0.77961 (9) | 0.16291 (5) | 0.22503 (4) | 0.0345 (2) | |
N9 | 0.70377 (10) | 0.08574 (6) | 0.07517 (5) | 0.0477 (3) | |
C3 | 0.93914 (11) | 0.23168 (6) | 0.26545 (5) | 0.0335 (3) | |
C5 | 0.69906 (11) | 0.45726 (6) | 0.19626 (5) | 0.0368 (3) | |
C6 | 0.54479 (11) | 0.38205 (7) | 0.15118 (5) | 0.0414 (3) | |
C7 | 0.87501 (12) | 0.10272 (6) | 0.13120 (5) | 0.0346 (3) | |
C10 | 0.86905 (12) | 0.22307 (6) | 0.39386 (5) | 0.0378 (3) | |
C11 | 0.98720 (19) | 0.29907 (11) | 0.43876 (7) | 0.0908 (6) | |
C12 | 0.9425 (2) | 0.28934 (12) | 0.55535 (8) | 0.1101 (8) | |
C13 | 0.78309 (18) | 0.20232 (9) | 0.62992 (6) | 0.0735 (5) | |
C14 | 0.6669 (2) | 0.12700 (10) | 0.58675 (7) | 0.0853 (6) | |
C15 | 0.70959 (18) | 0.13705 (9) | 0.46902 (6) | 0.0751 (5) | |
C16 | 0.72913 (13) | 0.60545 (7) | 0.12261 (6) | 0.0480 (4) | |
C17 | 0.87203 (15) | 0.68325 (7) | 0.17302 (7) | 0.0621 (4) | |
H3 | 1.10482 | 0.17854 | 0.25490 | 0.05230* | |
H5 | 0.62206 | 0.46075 | 0.27409 | 0.05532* | |
H11 | 1.09903 | 0.36161 | 0.38726 | 0.11030* | |
H12 | 1.02954 | 0.34290 | 0.58429 | 0.12968* | |
H13 | 0.75027 | 0.19423 | 0.71174 | 0.09045* | |
H14 | 0.55059 | 0.06661 | 0.63841 | 0.10213* | |
H15 | 0.62564 | 0.08226 | 0.43923 | 0.09357* | |
H6A | 0.37667 | 0.43398 | 0.15066 | 0.05976* | |
H6B | 0.62246 | 0.37832 | 0.07362 | 0.05976* | |
H9A | 0.75506 | 0.03264 | 0.01827 | 0.06721* | |
H9B | 0.52796 | 0.10504 | 0.10327 | 0.06721* | |
H16A | 0.81916 | 0.59960 | 0.04718 | 0.06583* | |
H16B | 0.56423 | 0.65995 | 0.11564 | 0.06583* | |
H17A | 0.88627 | 0.77682 | 0.12352 | 0.07991* | |
H17B | 1.03606 | 0.63031 | 0.17981 | 0.07991* | |
H17C | 0.78111 | 0.69066 | 0.24826 | 0.07991* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0242 (2) | 0.0440 (3) | 0.0456 (3) | −0.00725 (18) | −0.00231 (18) | −0.0186 (2) |
O4 | 0.0277 (2) | 0.0384 (2) | 0.0352 (2) | −0.00807 (17) | −0.00497 (17) | −0.00854 (19) |
O8 | 0.0363 (3) | 0.0525 (3) | 0.0423 (3) | 0.0015 (2) | −0.00585 (19) | −0.0239 (2) |
N2 | 0.0254 (3) | 0.0399 (3) | 0.0348 (3) | −0.0038 (2) | −0.0039 (2) | −0.0169 (2) |
N9 | 0.0376 (3) | 0.0568 (3) | 0.0473 (3) | −0.0053 (2) | −0.0092 (2) | −0.0312 (3) |
C3 | 0.0280 (3) | 0.0374 (3) | 0.0316 (3) | −0.0058 (2) | −0.0062 (2) | −0.0114 (3) |
C5 | 0.0297 (4) | 0.0403 (4) | 0.0360 (3) | −0.0032 (2) | −0.0058 (2) | −0.0142 (3) |
C6 | 0.0297 (4) | 0.0439 (4) | 0.0457 (4) | −0.0019 (3) | −0.0104 (3) | −0.0150 (3) |
C7 | 0.0353 (4) | 0.0334 (3) | 0.0309 (3) | −0.0053 (3) | −0.0042 (3) | −0.0112 (3) |
C10 | 0.0379 (4) | 0.0396 (3) | 0.0316 (3) | −0.0040 (3) | −0.0079 (3) | −0.0118 (3) |
C11 | 0.1077 (8) | 0.1215 (8) | 0.0418 (4) | −0.0676 (6) | −0.0064 (5) | −0.0277 (5) |
C12 | 0.1409 (10) | 0.1414 (10) | 0.0467 (5) | −0.0723 (8) | −0.0126 (6) | −0.0372 (6) |
C13 | 0.0922 (7) | 0.0853 (6) | 0.0338 (4) | −0.0091 (5) | −0.0128 (4) | −0.0194 (4) |
C14 | 0.1139 (8) | 0.0955 (7) | 0.0370 (4) | −0.0532 (6) | 0.0044 (4) | −0.0105 (4) |
C15 | 0.1010 (7) | 0.0836 (6) | 0.0361 (4) | −0.0546 (5) | 0.0005 (4) | −0.0154 (4) |
C16 | 0.0525 (5) | 0.0410 (4) | 0.0439 (4) | −0.0060 (3) | −0.0116 (3) | −0.0097 (3) |
C17 | 0.0722 (6) | 0.0416 (4) | 0.0660 (5) | −0.0160 (4) | −0.0148 (4) | −0.0135 (4) |
O1—N2 | 1.4198 (6) | C5—C6 | 1.5040 (8) |
O1—C6 | 1.4486 (7) | C5—C16 | 1.5068 (8) |
O4—C3 | 1.4313 (7) | C10—C11 | 1.3682 (9) |
O4—C5 | 1.4402 (7) | C10—C15 | 1.3546 (9) |
O8—C7 | 1.2334 (7) | C11—C12 | 1.3713 (11) |
N2—C3 | 1.4459 (7) | C12—C13 | 1.3576 (12) |
N2—C7 | 1.3968 (7) | C13—C14 | 1.3419 (11) |
N9—C7 | 1.3373 (7) | C14—C15 | 1.3849 (10) |
C3—C10 | 1.5147 (8) | C16—C17 | 1.5194 (9) |
N2—O1—C6 | 109.20 (4) | O8—C7—N2 | 119.75 (5) |
C3—O4—C5 | 112.25 (4) | O8—C7—N9 | 124.28 (5) |
O1—N2—C3 | 112.51 (4) | N2—C7—N9 | 115.90 (5) |
O1—N2—C7 | 114.09 (4) | C3—C10—C11 | 118.20 (6) |
C3—N2—C7 | 120.23 (5) | C3—C10—C15 | 124.17 (6) |
O4—C3—N2 | 110.84 (4) | C11—C10—C15 | 117.47 (6) |
O4—C3—C10 | 111.86 (4) | C10—C11—C12 | 120.94 (8) |
N2—C3—C10 | 113.26 (5) | C11—C12—C13 | 121.07 (8) |
O4—C5—C6 | 107.81 (4) | C12—C13—C14 | 118.42 (7) |
O4—C5—C16 | 107.82 (5) | C13—C14—C15 | 120.85 (8) |
C6—C5—C16 | 113.42 (5) | C10—C15—C14 | 121.24 (7) |
O1—C6—C5 | 110.35 (5) | C5—C16—C17 | 112.80 (5) |
Experimental details
Crystal data | |
Chemical formula | C12H16N2O3 |
Mr | 236.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 5.4856 (4), 9.906 (1), 12.227 (1) |
α, β, γ (°) | 73.429 (4), 77.443 (7), 78.576 (7) |
V (Å3) | 615.0 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.15 × 0.10 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 3σ(I)] reflections | 4318, 2218, 1827 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.607 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.064, 1.04 |
No. of reflections | 1827 |
No. of parameters | 154 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.20 |
Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), maXus (Mackay et al., 1999), ORTEP (Johnson, 1976).
Les hétérocycles saturés à six chaînons, possédant trois hétéroatomes, telle que la 1,4,2-dioxazine, ont été peu décrits dans la littérature (El Meslouhi & Petrus, 1982; Riddell et al., 1978; El Meslouhi et al., 2000; Richard et al., 1973, 1974; Fruchier et al., 1983). Leurs études structurales et conformationnelles suscitent un intérêt certain à cause de l'inversion de l'azote et du cycle à six éléments. Afin de contribuer à l'étude structurale de ce type de composés, nous avons réalisé une analyse cristallographique de la 2-carbamoyl-6-éthyl-3-phényl-2,3,5,6 - tétrahydro-1,4,2-dioxazine, (I), obtenue par action du benzaldéhyde sur le β-uréidoxyalcool, en présence de l'acide para-toluène sulfonique.
Le cycle dioxazine présente une conformation chaise classique: les atomes O1/C3/O4/C6 formant un plan (déviation r.c.m. 0.0156 Å), N2 est situé à -0.6292 (5) Å e t C5 à 0.6764 (6) Å de ce plan. Le cycle phényl C10–C15 est plan (déviation r.c.m. 0.0028 Å) et fait un angle de 62.6 (3)° avec le plan du cycle dioxazine. Le groupement carbamoyl établit une liaison hydrogène inter-moléculaire entre l'atome d'azote N9 et l'oxygène O8: distance 2.9264 (7) Å.