4-Methyl-3-(2-phenoxy­acet­yl)-5-phenyl-1,3,4-oxadiazinan-2-one

Julio Zukerman-Schpector; Lucas Sousa Madureira; Alessandro Rodrigues; Elisângela Vinhato; Paulo R Olivato

doi:10.1107/S1600536809020285

. 2009 Jun 6;65(Pt 7):o1468. doi: 10.1107/S1600536809020285

4-Methyl-3-(2-phenoxyacetyl)-5-phenyl-1,3,4-oxadiazinan-2-one

Julio Zukerman-Schpector ^a,^*, Lucas Sousa Madureira ^a, Alessandro Rodrigues ^b, Elisângela Vinhato ^b, Paulo R Olivato ^b

PMCID: PMC2969466 PMID: 21582771

Abstract

The 1,3,4-oxadiazinane ring in the title compound, C₁₈H₁₈N₂O₄, is in a twisted boat conformation. The two carbonyl groups are orientated towards the same side of the molecule. The dihedral angle between the planes of the benzene rings is 76.6 (3)°. Molecules are sustained in the three-dimensional structure by a combination of C—H⋯O, C—H⋯π and π–π [shortest centroid–centroid distance = 3.672 (6) Å] interactions.

Related literature

For synthetic and structural studies of substituted heterocyclic rings, see: Rodrigues et al. (2006 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶); Iulek & Zukerman-Schpector (1997 ▶). For the synthesis, see: Rodrigues et al. (2005 ▶).

Experimental

Crystal data

C₁₈H₁₈N₂O₄
M _r = 326.34
Monoclinic,
a = 9.6024 (9) Å
b = 9.4203 (10) Å
c = 19.275 (3) Å
β = 114.206 (9)°
V = 1590.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 290 K
0.15 × 0.10 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2971 measured reflections
2793 independent reflections
1355 reflections with I > 2σ(I)
R _int = 0.030
3 standard reflections frequency: 60 min intensity decay: <1%

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.246
S = 1.12
2793 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST (Nardelli, 1995 ▶) and MarvinSketch (ChemAxon, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020285/tk2466sup1.cif

e-65-o1468-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020285/tk2466Isup2.hkl

e-65-o1468-Isup2.hkl^{(134.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O4ⁱ	0.93	2.53	3.394 (7)	154
C9—H9⋯O3ⁱⁱ	0.93	2.61	3.383 (8)	141
C13—H13⋯Cg2ⁱⁱⁱ	0.93	2.86	3.715 (6)	153
C18—H18B⋯Cg3ⁱ	0.96	2.74	3.672 (6)	165

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg2 is the centroid of the C6–C11 ring and Cg3 is the centroid of the C12–C17 ring.

Acknowledgments

We thank FAPESP (2008/02531–5 to JZ—S; 2003/05520–0 to AR), CNPq and CAPES for financial support.

supplementary crystallographic information

Comment

In continuation of synthetic and structural studies of substituted heterocyclic rings (Rodrigues et al., 2006), the title compound (I) was prepared. The 1,3,4-oxadiazinane ring in (I), Fig. 1, is in a distorted twist boat conformation with the distortion being towards a boat conformation. The ring-puckering parameters (Cremer & Pople, 1975; Iulek & Zukerman-Schpector, 1997) were calculated as q₂ = 0.119 (6) Å, q₃ = -0.496 (6) Å, Q = 0.510 (6) Å, and φ₂ = -108 (3)°. The ring- and side-chain-bound carbonyl groups lie to the same side of the molecule. The dihedral angle between the phenyl rings is of 76.6 (3)°. Molecules are sustained in the 3-D structure by a combination of C-H···O and π–π interactions, Table 1.

Experimental

The starting (R)-4-methyl-5-phenyl-1,3,4-oxadiazinan-2-one was synthesized by using a previously reported procedure (Rodrigues et al. 2005). The phenoxyacetyl-1,3,4-oxadiazinan-2-one derivative was prepared by an acylation reaction of 1,3,4-oxadiazinan-2-one (Rodrigues et al. 2005). To a mixture of 1,3,4-oxadiazinan-2-one (500 mg, 2.60 mmol), 4-dimethylaminopyridine (16 mg, 0.13 mmol) and 2-phenoxyacetic acid (435 mg, 2.86 mmol) in CH₂Cl₂ (4 ml) at 273 K, under a nitrogen atmosphere, N,N-Dicyclohexylcarbodiimide was added in one portion (590 mg, 2.86 mmol). The temperature of the resulting suspension was allowed to reach room temperature. Stirring was continued until no starting material was left, as confirmed by TLC (20 h). The dicyclohexylurea formed was filtered and the precipitate washed with CH₂Cl₂ (20 ml). The filtrate was washed with a saturated aqueous solution of NaHCO₃ (15 ml) and dried over Na₂SO₄. Filtration and evaporation yielded the crude solid, which was purified by flash chromatography on silica gel (hexane-EtOAc, 6:4). Colourless crystals of (I) were obtained by vapour diffusion from hexane/chloroform at 298 K.