3-[(E)-3,7-Dimethyl­octa-2,6-dien­yl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine

Tie-Niu Kang; Li Zhang; Yun Ling; Xin-Ling Yang

doi:10.1107/S160053680801492X

. 2008 May 24;64(Pt 6):o1154. doi: 10.1107/S160053680801492X

3-[(E)-3,7-Dimethylocta-2,6-dienyl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine

Tie-Niu Kang ^a, Li Zhang ^a, Yun Ling ^a, Xin-Ling Yang ^a,^*

PMCID: PMC2961447 PMID: 21202662

Abstract

The title compound, C₁₄H₂₄N₄O₃, was synthesized by the reaction of geranyl and 3-methyl-4-nitroimino-1,3,5-oxadiazinane. In the crystal structure, molecules are assembled by weak intermolecular C—H⋯O hydrogen bonds. The nitryl and the long carbon chain are located on the same side of the C=N bond due to the two weak intramolecular C—H⋯N hydrogen bonds; the configuration of the oxadiazinane is Z.

Related literature

For background literature, see: Bowers et al. (1972 ▶). For related literature, see: Yang et al. (2004 ▶); Van Oosten et al. (1990 ▶).

Experimental

Crystal data

C₁₄H₂₄N₄O₃
M _r = 296.37
Monoclinic,
a = 7.9318 (16) Å
b = 6.6423 (13) Å
c = 31.191 (7) Å
β = 99.55 (3)°
V = 1620.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.60 × 0.30 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.943, T _max = 0.993
7692 measured reflections
2825 independent reflections
1306 reflections with I > 2σ(I)
R _int = 0.0508

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.152
S = 0.84
2825 reflections
194 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2000 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2000 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801492X/rk2083sup1.cif

e-64-o1154-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801492X/rk2083Isup2.hkl

e-64-o1154-Isup2.hkl^{(138.7KB, 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
C2—H2B⋯O1ⁱ	0.97	2.48	3.257 (4)	136
C3—H3A⋯N2ⁱⁱ	0.97	2.43	3.336 (4)	155
C3—H3B⋯O1ⁱⁱⁱ	0.97	2.38	3.264 (4)	151
C5—H5B⋯N1	0.97	2.53	3.117 (4)	119
C5—H5B⋯N2	0.97	2.55	2.960 (4)	105
C13—H13C⋯O2^iv	0.96	2.59	3.425 (5)	145

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

Acknowledgments

This work was supported by the National Basic Research Program of China (grant No. 2003CB 114400), the National High Technology Research and Development Program of China (grant No. 2006 A A10A209) and the ‘11th Five-Year Plan’ Scientific and Technological Support Project on Pesticide Development Engineering (grant No. 2006BAE01A01). The authors acknowledge Shi-Wei Zhang for carrying out the X-ray diffraction at the College of Chemistry and Molecular Engineering, Peking University, Beijing, People’s Republic of China.

supplementary crystallographic information

Comment

E-b-farnesene (EBF), the primary component of aphides alarm pheromone, not only stimulate the movement of aphid (Bowers et al., 1972), but also possess the acute activity to many economically aphid species at a dose of 100 ng/aphid (Van Oosten et al., 1990). However, EBF is limited in field application due to its high volatility, readily air oxidation and degradation under field conditions. In order to improve its chemical stability and biological efficacy, the pharmacophore of neonicotinoids was introduced to substitute the conjugated double bond of EBF (Yang et al., 2004). The title compound (I), in which 3-methyl-5-(E)-3,7-dimethylocta-2,6-dienyl connect to N-nitro-1,3,5-oxadiazinan-4-imine instead of the conjugated double bond, was synthesized as EBF analogue with potent insecticidal activity. To study the further structure-activity relationship, we reported here its molecular and crystal structure. The molecular structure showed Z-isomer by the interaction forces of weak intramolecular C5–H5b···N1 and C5–H5b···N2 hydrogen bonds (Fig. 1). The compound was assembled by four weak intermolecular hydrogen bonds (Fig. 2 and Table 1).

Experimental

To a solution of 3-methyl-N-nitro-1,3,5-oxadiazinan-4-imine (1.60 g, 10.0 mmol) dissolved in anhydrous acetonitrile (15 ml), geranyl (1.89 g, 10.1 mmol) was added. Then the reaction solution was slowly heated to reflux for 7h. After removing the solvent, the residue was purified by column chromatography on silica gel (200-300 mesh) with petroleum ether/ethylacetate (2.5:1v/v) as eluent to obtain the title compound I. Then, 50 mg I was dissolved in 20 ml me thanol. The solution was kept at room temperature for 20 d by natural evaporation to give colorless single crystals of I, suitable for X-Ray analysis.

¹H NMR (CDCl₃, 300 MHz) 1.60 (s, 3H, CH₃–C═C), 1.68 [s, 6H, (CH₃)₂C═C], 2.07~2.10 (t, J = 5.27 Hz, 4H, -CH₂–CH₂-), 3.05 (s, 3H, N–CH₃), 4.11 (d, J = 7.26, 2H,-CH₂–N), 4.09 (s, 2H, N–CH₂–O), 4.12 (s, 2H, O–CH₂–N), 5.03~5.18 (m, 2H, 2CH═C); Calc. for C₁₄H₂₄N₄O₃: C 56.74, H 8.16, N 18.90; found C 56.69, H 8.19, N 18.80.