(E)-3-[1-(2,4-Difluoro­phen­yl)eth­yl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine

Yuan-yuan Zhong; Cong-cong Li; Liang-zhong Xu

doi:10.1107/S1600536810026425

. 2010 Jul 10;66(Pt 8):o1981. doi: 10.1107/S1600536810026425

(E)-3-[1-(2,4-Difluorophenyl)ethyl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine

Yuan-yuan Zhong ^a, Cong-cong Li ^a, Liang-zhong Xu ^a,^*

PMCID: PMC3007461 PMID: 21588297

Abstract

The 1,3,5-oxadiazinane ring in the title compound, C₁₂H₁₄F₂N₄O₃, has a conformation intermediate between half-chair and screw-boat. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds. Weak π–π interactions are indicated by the relatively long centroid–centroid distance of 3.9199 (12) Å and interplanar distance of 3.803 Å between symmetry-related benzene rings from neighbouring molecules.

Related literature

An important type of insecticide, oxadiazine compounds are highly efficient and of low toxicity, see: Gsell et al.(1998 ▶). The title compound has been used to synthesize many similar insecticides, see: Maienfisch et al. (1994 ▶). For the preparation of the title compound, see: Gottfied et al.(2001 ▶). For the related structures, see: Chopra et al., (2004 ▶); Kang et al. (2008 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₂H₁₄F₂N₄O₃
M _r = 300.27
Monoclinic,
a = 13.385 (3) Å
b = 6.7470 (13) Å
c = 15.073 (3) Å
β = 101.25 (3)°
V = 1335.0 (5) Å³
Z = 4
Cu Kα radiation
μ = 1.11 mm⁻¹
T = 113 K
0.26 × 0.24 × 0.22 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: numerical (CrystalClear; Rigaku, 2005 ▶) T _min = 0.762, T _max = 0.793
13266 measured reflections
2567 independent reflections
2168 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.106
S = 1.09
2567 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026425/dn2586sup1.cif

e-66-o1981-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026425/dn2586Isup2.hkl

e-66-o1981-Isup2.hkl^{(126.1KB, 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
C1—H1A⋯O3ⁱ	0.99	2.50	3.1908 (16)	127
C3—H3A⋯O2ⁱⁱ	0.99	2.51	3.4439 (18)	156
C4—H4C⋯O2ⁱⁱⁱ	0.98	2.49	3.1665 (17)	126
C6—H6A⋯O3^iv	0.98	2.39	3.2046 (18)	140

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

As an important type of insecticides, oxadiazine compounds are highly efficient and of low toxicity (Gsell, et al., 1998). Lots of similar insecticides compounds were synthesized with the title compounds (I) (Maienfisch, et al., 1994). We report the synthesis and crystal structure of the title compound, (I).

The conformation of the 1,3,5-oxadiazinane ring in(I)is intermediate between half-chair and screw-boat with puckering parameters (Cremer & Pople, 1975): Q= 0.5303 (12)Å; θ= 59.14 (13)°; φ= 329,54 (15)°. The benzene ring forms dihedral angles of 74.84 (3)° and 87.30 (2)° with the mean plane of the oxadiazine ring. The bond lengths and angles of the oxadiazine rings are in a good agreement with those reported previously (Chopra, et al., 2004). The N=C bond length [N3=C2 = 1.3804 (2) Å] are close to the value reported in the literature (Kang,et al.,2008).

The structure is stabilized by hydrogen bonds of C-H···O type. And with a π-π stacking between symmetry related phenyl rings with a centroid-to-centroid distance of 3.9199 (12)Å and interplanar distance of 3.803Å resulting in a 0.951Å slippage.

Experimental

1-(1-bromoethyl)-2,4-difluorobenzene 4.5 g (20.0 mmol),(Z)-3-methyl-N– nitro-1,3,5-oxadiazinan-4-imine 3.2 g (20.0 mmol), potassium carbonate 2.8 g (20.0 mmol) and acetonitril 20 g were charged in a flask equipped with stirrer, water separator and reflux condenser. The mixture was heated to reflux for 4 h. Upon cooling at room temperature. The reaction mixture was filtered, and the solution was concentrated under reduced pressure to give the title compound (I) 4.5 g (76% yield). (Gottfied, et al., 2001). Single crystals suitable for X-ray measurement were grown by slow evaporation of an ethanol solution of (I).