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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2456.
Published online 2010 August 28. doi:  10.1107/S1600536810034343
PMCID: PMC3008131

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

Abstract

In the title compound, C12H15ClN4O3, which has potential insecticidal activity, the oxadiazine ring and the benzene ring make a dihedral angle of 84.63 (2)° to one another. The crystal packing involves weak inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the biological activity of oxadiazine derivatives, see: Maienfisch & Huerlimann (1994 [triangle]); Gsell & Maienfisch (1998 [triangle]). For the synthesis, see: Gottfied et al. (2001 [triangle]). For related structures, see: Chopra et al. (2004 [triangle]); Kang et al. (2008 [triangle]); Zhong et al. (2010 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-66-o2456-scheme1.jpg

Experimental

Crystal data

  • C12H15ClN4O3
  • M r = 298.73
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2456-efi1.jpg
  • a = 17.259 (4) Å
  • b = 6.9157 (14) Å
  • c = 12.169 (2) Å
  • β = 109.63 (3)°
  • V = 1368.0 (5) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 2.61 mm−1
  • T = 113 K
  • 0.26 × 0.22 × 0.18 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.550, T max = 0.651
  • 12087 measured reflections
  • 2590 independent reflections
  • 2562 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.104
  • S = 1.08
  • 2590 reflections
  • 184 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034343/zs2061sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034343/zs2061Isup2.hkl

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

supplementary crystallographic information

Comment

Currently, studies on oxadiazine derivatives have mainly concentrated on compounds with oxadiazine as the only active group (Gsell, et al., 1998) and a number of highly insecticidal compounds of this type have been synthesized (Maienfisch et al., 1994). We report here the synthesis and crystal structure of the title compound C12H15Cl1N4O3 (I).

In (I) (Fig. 1) the bond lengths and angles of the oxadiazine rings are in agreement with those in previous reported structures (Chopra et al., 2004). The 1,3,5-oxadiazinane ring is in a half-chair conformation and the ring-puckering parameters (Cremer & Pople, 1975;) were calculated as Q = 0.05126 (12) Å; θ = 121.33 (13)°; [var phi] = 166.3676 (15)°. The N3═O bondlength [1.3904 (17) Å] is close to the value reported in the literature (Zhong et al., 2010). The oxadiazine ring and the benzene ring make a dihedral angle of 84.63 (2)°. Weak intermolecular C—H···O hydrogen bonds give a three-dimensional network (Table 1).

Experimental

A solution of 1-(1-bromoethyl)-2-chlorobenzene (4.3 g, 20 mmol), N-nitro-1,3,5-oxadiazinan-4-imine (3.2 g, 20 mmol) and potassium carbonate (2.8 g, 20 mmol) in 20 g of acetonitrile was heated under reflux for 4 h. Upon cooling to room temperature the solution was filtered and then concentrated under reduced pressure to give the title compound (I) (7.89 g, 90% yield) (Gottfried, et al., 2001). Single crystals suitable for X-ray measurement were obtained by recrystallization from ethanol at room temperature.

Refinement

All C-bound H atoms were placed in calculated positions, with C—H = 0.95-0.97 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
Molecular configuration and atom numbering scheme for the title compound (I), with displacement ellipsoids drawn at the 50% probability level.

Crystal data

C12H15ClN4O3F(000) = 624
Mr = 298.73Dx = 1.450 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybcCell parameters from 1058 reflections
a = 17.259 (4) Åθ = 27.5–71.9°
b = 6.9157 (14) ŵ = 2.61 mm1
c = 12.169 (2) ÅT = 113 K
β = 109.63 (3)°Block, colorless
V = 1368.0 (5) Å30.26 × 0.22 × 0.18 mm
Z = 4

Data collection

Rigaku Saturn diffractometer2590 independent reflections
Radiation source: fine-focus sealed tube2562 reflections with I > 2σ(I)
graphiteRint = 0.054
Detector resolution: 14.63 pixels mm-1θmax = 72.1°, θmin = 2.7°
ω scansh = −20→21
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.550, Tmax = 0.651l = −13→14
12087 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.104w = 1/[σ2(Fo2) + (0.058P)2 + 0.6637P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2590 reflectionsΔρmax = 0.26 e Å3
184 parametersΔρmin = −0.37 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0057 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.36163 (2)0.37729 (6)−0.00540 (3)0.02744 (17)
N10.09670 (7)0.33360 (16)−0.04098 (10)0.0152 (3)
N20.21260 (7)0.48468 (16)0.08081 (10)0.0146 (3)
N30.19653 (7)0.15435 (16)0.10592 (10)0.0165 (3)
N40.15382 (7)0.09523 (17)0.17188 (10)0.0172 (3)
O10.09734 (6)0.67120 (14)−0.01841 (9)0.0180 (2)
O20.09602 (7)0.19372 (16)0.18398 (9)0.0247 (3)
O30.17457 (7)−0.06237 (15)0.22426 (9)0.0238 (3)
C10.06227 (8)0.5189 (2)−0.09525 (12)0.0171 (3)
H1A0.07400.5363−0.16890.021*
H1B0.00180.5188−0.11390.021*
C20.16607 (8)0.32676 (19)0.04897 (12)0.0138 (3)
C30.18404 (8)0.66306 (19)0.01450 (13)0.0172 (3)
H3A0.20890.77670.06300.021*
H3B0.20070.6644−0.05580.021*
C40.04698 (9)0.1625 (2)−0.08861 (13)0.0196 (3)
H4A0.08010.0459−0.06110.029*
H4B0.02850.1670−0.17400.029*
H4C−0.00100.1599−0.06260.029*
C50.28920 (8)0.48416 (19)0.18389 (12)0.0171 (3)
H50.31410.35240.18940.020*
C60.26984 (10)0.5185 (2)0.29596 (12)0.0225 (3)
H6A0.32120.51980.36270.034*
H6B0.23420.41470.30610.034*
H6C0.24180.64300.29100.034*
C70.34952 (8)0.6269 (2)0.16156 (13)0.0184 (3)
C80.38573 (9)0.5900 (2)0.07689 (13)0.0209 (3)
C90.44068 (9)0.7161 (2)0.05401 (14)0.0257 (4)
H90.46400.6869−0.00450.031*
C100.46123 (10)0.8863 (2)0.11817 (16)0.0305 (4)
H100.49970.97330.10480.037*
C110.42544 (10)0.9287 (2)0.20160 (15)0.0308 (4)
H110.43891.04590.24450.037*
C120.37004 (9)0.8007 (2)0.22283 (13)0.0247 (3)
H120.34570.83200.28000.030*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0282 (2)0.0206 (2)0.0376 (3)−0.00083 (13)0.01641 (18)−0.00617 (14)
N10.0166 (6)0.0106 (5)0.0167 (6)−0.0008 (4)0.0035 (4)−0.0001 (4)
N20.0146 (5)0.0095 (5)0.0179 (6)0.0011 (4)0.0029 (4)0.0012 (4)
N30.0171 (6)0.0104 (5)0.0226 (6)0.0015 (4)0.0075 (5)0.0038 (4)
N40.0216 (6)0.0110 (5)0.0182 (6)0.0015 (5)0.0058 (5)0.0019 (4)
O10.0167 (5)0.0119 (5)0.0225 (5)0.0038 (4)0.0030 (4)−0.0010 (4)
O20.0286 (6)0.0209 (6)0.0301 (6)0.0107 (4)0.0170 (5)0.0072 (4)
O30.0338 (6)0.0117 (5)0.0275 (6)0.0059 (4)0.0123 (4)0.0083 (4)
C10.0168 (6)0.0134 (6)0.0183 (7)0.0022 (5)0.0021 (5)0.0009 (5)
C20.0156 (6)0.0100 (6)0.0173 (6)0.0016 (5)0.0077 (5)−0.0003 (5)
C30.0165 (7)0.0099 (6)0.0226 (7)0.0010 (5)0.0032 (5)0.0035 (5)
C40.0204 (7)0.0144 (6)0.0222 (7)−0.0049 (5)0.0048 (6)−0.0024 (5)
C50.0163 (6)0.0123 (6)0.0190 (7)0.0019 (5)0.0011 (5)0.0014 (5)
C60.0274 (7)0.0183 (7)0.0192 (7)0.0004 (6)0.0042 (6)0.0019 (5)
C70.0149 (6)0.0136 (7)0.0216 (7)0.0010 (5)−0.0006 (5)0.0026 (5)
C80.0157 (6)0.0157 (7)0.0270 (8)0.0018 (5)0.0015 (6)0.0030 (6)
C90.0182 (7)0.0267 (8)0.0298 (8)0.0013 (6)0.0047 (6)0.0093 (6)
C100.0211 (8)0.0248 (8)0.0372 (9)−0.0083 (6)−0.0013 (7)0.0108 (7)
C110.0302 (8)0.0187 (7)0.0325 (9)−0.0086 (7)−0.0042 (7)0.0003 (6)
C120.0249 (7)0.0185 (7)0.0242 (7)−0.0029 (6)−0.0004 (6)−0.0013 (6)

Geometric parameters (Å, °)

Cl1—C81.7492 (16)C4—H4B0.9800
N1—C21.324 (2)C4—H4C0.9800
N1—C41.4621 (17)C5—C71.524 (2)
N1—C11.4721 (17)C5—C61.528 (2)
N2—C21.3336 (18)C5—H51.0000
N2—C31.4658 (16)C6—H6A0.9800
N2—C51.4856 (17)C6—H6B0.9800
N3—N41.3237 (17)C6—H6C0.9800
N3—C21.3904 (17)C7—C121.396 (2)
N4—O31.2526 (15)C7—C81.396 (2)
N4—O21.2567 (16)C8—C91.384 (2)
O1—C11.4037 (17)C9—C101.391 (2)
O1—C31.4143 (18)C9—H90.9500
C1—H1A0.9900C10—C111.386 (3)
C1—H1B0.9900C10—H100.9500
C3—H3A0.9900C11—C121.389 (2)
C3—H3B0.9900C11—H110.9500
C4—H4A0.9800C12—H120.9500
C2—N1—C4123.09 (11)H4B—C4—H4C109.5
C2—N1—C1121.23 (11)N2—C5—C7108.38 (11)
C4—N1—C1115.58 (11)N2—C5—C6110.73 (11)
C2—N2—C3118.10 (11)C7—C5—C6115.21 (12)
C2—N2—C5121.43 (11)N2—C5—H5107.4
C3—N2—C5120.40 (11)C7—C5—H5107.4
N4—N3—C2111.90 (11)C6—C5—H5107.4
O3—N4—O2120.96 (12)C5—C6—H6A109.5
O3—N4—N3117.07 (11)C5—C6—H6B109.5
O2—N4—N3121.95 (11)H6A—C6—H6B109.5
C1—O1—C3109.70 (10)C5—C6—H6C109.5
O1—C1—N1109.62 (11)H6A—C6—H6C109.5
O1—C1—H1A109.7H6B—C6—H6C109.5
N1—C1—H1A109.7C12—C7—C8117.08 (14)
O1—C1—H1B109.7C12—C7—C5121.90 (14)
N1—C1—H1B109.7C8—C7—C5121.02 (13)
H1A—C1—H1B108.2C9—C8—C7122.70 (14)
N1—C2—N2119.99 (12)C9—C8—Cl1117.52 (13)
N1—C2—N3121.87 (12)C7—C8—Cl1119.78 (11)
N2—C2—N3117.88 (12)C8—C9—C10118.89 (16)
O1—C3—N2108.51 (11)C8—C9—H9120.6
O1—C3—H3A110.0C10—C9—H9120.6
N2—C3—H3A110.0C11—C10—C9119.87 (15)
O1—C3—H3B110.0C11—C10—H10120.1
N2—C3—H3B110.0C9—C10—H10120.1
H3A—C3—H3B108.4C10—C11—C12120.38 (15)
N1—C4—H4A109.5C10—C11—H11119.8
N1—C4—H4B109.5C12—C11—H11119.8
H4A—C4—H4B109.5C11—C12—C7121.07 (16)
N1—C4—H4C109.5C11—C12—H12119.5
H4A—C4—H4C109.5C7—C12—H12119.5
C2—N3—N4—O3177.78 (11)C3—N2—C5—C7−33.89 (16)
C2—N3—N4—O2−3.68 (18)C2—N2—C5—C6−83.61 (15)
C3—O1—C1—N155.36 (14)C3—N2—C5—C693.38 (14)
C2—N1—C1—O1−18.08 (18)N2—C5—C7—C12110.06 (14)
C4—N1—C1—O1158.55 (12)C6—C5—C7—C12−14.60 (19)
C4—N1—C2—N2173.37 (12)N2—C5—C7—C8−68.88 (16)
C1—N1—C2—N2−10.3 (2)C6—C5—C7—C8166.46 (13)
C4—N1—C2—N3−0.6 (2)C12—C7—C8—C90.9 (2)
C1—N1—C2—N3175.73 (12)C5—C7—C8—C9179.93 (13)
C3—N2—C2—N10.66 (19)C12—C7—C8—Cl1−178.83 (10)
C5—N2—C2—N1177.72 (12)C5—C7—C8—Cl10.15 (18)
C3—N2—C2—N3174.91 (11)C7—C8—C9—C100.4 (2)
C5—N2—C2—N3−8.03 (19)Cl1—C8—C9—C10−179.86 (11)
N4—N3—C2—N1−73.97 (16)C8—C9—C10—C11−1.3 (2)
N4—N3—C2—N2111.90 (14)C9—C10—C11—C121.0 (2)
C1—O1—C3—N2−64.67 (14)C10—C11—C12—C70.4 (2)
C2—N2—C3—O136.13 (16)C8—C7—C12—C11−1.3 (2)
C5—N2—C3—O1−140.96 (12)C5—C7—C12—C11179.72 (13)
C2—N2—C5—C7149.11 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1A···O2i0.992.523.2817 (18)134.
C1—H1A···O3i0.992.503.396 (2)150.
C1—H1B···O2ii0.992.563.2555 (18)127.
C3—H3A···O3iii0.992.493.2294 (19)131.
C4—H4B···O2i0.982.573.3070 (19)132.
C4—H4C···O1ii0.982.493.377 (2)150.
C6—H6C···O3iii0.982.353.3020 (19)164.

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y+1, −z; (iii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2061).

References

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  • Chopra, D., Mohan, T. P., Rao, K. S. & Guru Row, T. N. (2004). Acta Cryst. E60, o2413–o2414.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Gottfied, S., Thomas, R. & Verena, G. (2001). WO Patent 0100623.
  • Gsell, L. & Maienfisch, P. (1998). WO Patent 9806710.
  • Kang, T.-N., Zhang, L., Ling, Y. & Yang, X.-L. (2008). Acta Cryst. E64, o1154. [PMC free article] [PubMed]
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