(E)-3-[1-(2,4-Difluoro-phen-yl)eth-yl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine.

The 1,3,5-oxadiazinane ring in the title compound, C(12)H(14)F(2)N(4)O(3), has a conformation inter-mediate between half-chair and screw-boat. The crystal structure is stabilized by weak inter-molecular C-H⋯O hydrogen bonds. Weak π-π inter-actions are indicated by the relatively long centroid-centroid distance of 3.9199 (12) Å and inter-planar distance of 3.803 Å between symmetry-related benzene rings from neighbouring mol-ecules.

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 = 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

Δρmax = 0.31 e Å−3

Δρmin = −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 ▶).

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

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

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

C12H14F2N4O3	F(000) = 624
Mr = 300.27	Dx = 1.494 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybc	Cell parameters from 1502 reflections
a = 13.385 (3) Å	θ = 27.7–72.0°
b = 6.7470 (13) Å	µ = 1.11 mm−1
c = 15.073 (3) Å	T = 113 K
β = 101.25 (3)°	Prism, colorless
V = 1335.0 (5) Å3	0.26 × 0.24 × 0.22 mm
Z = 4

Rigaku Saturn diffractometer	2567 independent reflections
Radiation source: fine-focus sealed tube	2168 reflections with I > 2σ(I)
graphite	Rint = 0.061
Detector resolution: 14.63 pixels mm-1	θmax = 72.3°, θmin = 3.4°
ω scans	h = −16→15
Absorption correction: numerical (CrystalClear; Rigaku, 2005)	k = −7→7
Tmin = 0.762, Tmax = 0.793	l = −17→18
13266 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.106	w = 1/[σ2(Fo2) + (0.0692P)2 + 0.0616P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
2567 reflections	Δρmax = 0.31 e Å−3
193 parameters	Δρmin = −0.30 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0131 (11)

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.

	x	y	z	Uiso*/Ueq
F1	0.40932 (6)	0.24125 (13)	0.33990 (6)	0.0436 (3)
F2	0.67967 (7)	0.68795 (18)	0.36250 (8)	0.0676 (4)
O1	0.23598 (6)	0.67016 (13)	0.16461 (6)	0.0279 (2)
O2	0.04094 (7)	0.32758 (14)	0.35714 (7)	0.0374 (3)
O3	0.09896 (7)	0.03447 (15)	0.39933 (6)	0.0365 (3)
N1	0.13558 (7)	0.38098 (16)	0.16500 (6)	0.0230 (2)
N2	0.21022 (7)	0.52761 (15)	0.29879 (6)	0.0235 (2)
N3	0.16278 (8)	0.18616 (15)	0.29436 (7)	0.0272 (3)
N4	0.09994 (7)	0.18567 (15)	0.35200 (7)	0.0246 (3)
C1	0.16316 (9)	0.5470 (2)	0.11134 (8)	0.0274 (3)
H1A	0.1910	0.4946	0.0598	0.033*
H1B	0.1015	0.6254	0.0866	0.033*
C2	0.16748 (8)	0.36822 (18)	0.25358 (8)	0.0220 (3)
C3	0.20435 (10)	0.71093 (19)	0.24732 (8)	0.0261 (3)
H3A	0.1336	0.7618	0.2352	0.031*
H3B	0.2492	0.8126	0.2820	0.031*
C4	0.07765 (10)	0.2205 (2)	0.11312 (9)	0.0302 (3)
H4A	0.1237	0.1110	0.1065	0.045*
H4B	0.0455	0.2697	0.0532	0.045*
H4C	0.0250	0.1736	0.1450	0.045*
C5	0.27466 (9)	0.51446 (19)	0.39058 (7)	0.0240 (3)
H5	0.2741	0.3734	0.4108	0.029*
C6	0.22926 (10)	0.6404 (2)	0.45658 (8)	0.0330 (3)
H6A	0.2235	0.7781	0.4355	0.050*
H6B	0.2735	0.6344	0.5165	0.050*
H6C	0.1615	0.5897	0.4602	0.050*
C7	0.38383 (9)	0.5676 (2)	0.38557 (8)	0.0265 (3)
C8	0.44655 (10)	0.4260 (2)	0.35833 (8)	0.0299 (3)
C9	0.54602 (10)	0.4619 (3)	0.34965 (9)	0.0401 (4)
H9	0.5870	0.3615	0.3307	0.048*
C10	0.58224 (10)	0.6488 (3)	0.36972 (11)	0.0442 (4)
C11	0.52547 (12)	0.7976 (3)	0.39754 (12)	0.0480 (4)
H11	0.5533	0.9261	0.4112	0.058*
C12	0.42598 (11)	0.7545 (2)	0.40513 (10)	0.0380 (3)
H12	0.3856	0.8557	0.4242	0.046*

	U11	U22	U33	U12	U13	U23
F1	0.0385 (5)	0.0347 (5)	0.0584 (6)	0.0058 (4)	0.0117 (4)	−0.0135 (4)
F2	0.0272 (5)	0.0938 (9)	0.0812 (8)	−0.0096 (5)	0.0090 (4)	0.0320 (6)
O1	0.0302 (5)	0.0302 (5)	0.0240 (4)	−0.0087 (4)	0.0076 (3)	0.0012 (3)
O2	0.0327 (5)	0.0287 (6)	0.0561 (6)	0.0059 (4)	0.0219 (4)	0.0054 (4)
O3	0.0432 (6)	0.0312 (6)	0.0361 (5)	−0.0011 (4)	0.0104 (4)	0.0155 (4)
N1	0.0241 (5)	0.0235 (6)	0.0218 (5)	−0.0033 (4)	0.0051 (4)	−0.0011 (4)
N2	0.0298 (5)	0.0210 (6)	0.0193 (5)	−0.0006 (4)	0.0041 (4)	0.0004 (4)
N3	0.0332 (6)	0.0203 (6)	0.0312 (6)	0.0007 (4)	0.0139 (4)	0.0022 (4)
N4	0.0255 (5)	0.0232 (6)	0.0249 (5)	−0.0001 (4)	0.0043 (4)	0.0041 (4)
C1	0.0324 (6)	0.0294 (7)	0.0201 (6)	−0.0057 (5)	0.0048 (4)	0.0016 (5)
C2	0.0220 (5)	0.0225 (6)	0.0229 (6)	0.0016 (4)	0.0082 (4)	0.0000 (4)
C3	0.0327 (6)	0.0222 (7)	0.0228 (6)	−0.0016 (5)	0.0038 (5)	0.0012 (4)
C4	0.0280 (6)	0.0294 (7)	0.0317 (6)	−0.0035 (5)	0.0022 (5)	−0.0082 (5)
C5	0.0274 (6)	0.0251 (7)	0.0193 (6)	0.0029 (5)	0.0038 (4)	0.0007 (4)
C6	0.0339 (7)	0.0420 (8)	0.0227 (6)	0.0089 (6)	0.0043 (5)	−0.0043 (5)
C7	0.0283 (6)	0.0286 (7)	0.0218 (6)	0.0020 (5)	0.0030 (4)	0.0023 (5)
C8	0.0297 (6)	0.0325 (8)	0.0271 (6)	0.0030 (5)	0.0041 (5)	0.0006 (5)
C9	0.0291 (7)	0.0560 (10)	0.0356 (7)	0.0096 (7)	0.0074 (5)	0.0064 (7)
C10	0.0239 (7)	0.0612 (11)	0.0458 (8)	−0.0045 (7)	0.0026 (6)	0.0193 (7)
C11	0.0405 (8)	0.0409 (10)	0.0587 (10)	−0.0124 (7)	−0.0004 (7)	0.0099 (7)
C12	0.0372 (7)	0.0305 (8)	0.0447 (8)	−0.0009 (6)	0.0039 (6)	−0.0008 (6)

F1—C8	1.3508 (17)	C4—H4A	0.9800
F2—C10	1.3555 (16)	C4—H4B	0.9800
O1—C1	1.4071 (15)	C4—H4C	0.9800
O1—C3	1.4195 (15)	C5—C7	1.5207 (16)
O2—N4	1.2531 (14)	C5—C6	1.5220 (16)
O3—N4	1.2463 (13)	C5—H5	1.0000
N1—C2	1.3229 (15)	C6—H6A	0.9800
N1—C4	1.4656 (16)	C6—H6B	0.9800
N1—C1	1.4703 (15)	C6—H6C	0.9800
N2—C2	1.3402 (16)	C7—C8	1.3859 (18)
N2—C3	1.4540 (16)	C7—C12	1.389 (2)
N2—C5	1.4834 (15)	C8—C9	1.3843 (18)
N3—N4	1.3219 (14)	C9—C10	1.364 (2)
N3—C2	1.3804 (16)	C9—H9	0.9500
C1—H1A	0.9900	C10—C11	1.373 (3)
C1—H1B	0.9900	C11—C12	1.389 (2)
C3—H3A	0.9900	C11—H11	0.9500
C3—H3B	0.9900	C12—H12	0.9500
C1—O1—C3	108.88 (9)	H4B—C4—H4C	109.5
C2—N1—C4	121.56 (10)	N2—C5—C7	109.21 (9)
C2—N1—C1	122.59 (10)	N2—C5—C6	110.04 (10)
C4—N1—C1	115.64 (10)	C7—C5—C6	114.27 (11)
C2—N2—C3	115.97 (10)	N2—C5—H5	107.7
C2—N2—C5	122.63 (10)	C7—C5—H5	107.7
C3—N2—C5	120.64 (10)	C6—C5—H5	107.7
N4—N3—C2	112.64 (10)	C5—C6—H6A	109.5
O3—N4—O2	120.86 (10)	C5—C6—H6B	109.5
O3—N4—N3	117.21 (10)	H6A—C6—H6B	109.5
O2—N4—N3	121.88 (10)	C5—C6—H6C	109.5
O1—C1—N1	110.87 (9)	H6A—C6—H6C	109.5
O1—C1—H1A	109.5	H6B—C6—H6C	109.5
N1—C1—H1A	109.5	C8—C7—C12	116.37 (12)
O1—C1—H1B	109.5	C8—C7—C5	119.71 (12)
N1—C1—H1B	109.5	C12—C7—C5	123.90 (12)
H1A—C1—H1B	108.1	F1—C8—C9	117.73 (12)
N1—C2—N2	118.86 (11)	F1—C8—C7	118.46 (11)
N1—C2—N3	118.27 (11)	C9—C8—C7	123.80 (14)
N2—C2—N3	122.66 (11)	C10—C9—C8	116.62 (14)
O1—C3—N2	108.03 (10)	C10—C9—H9	121.7
O1—C3—H3A	110.1	C8—C9—H9	121.7
N2—C3—H3A	110.1	F2—C10—C9	117.92 (15)
O1—C3—H3B	110.1	F2—C10—C11	118.73 (15)
N2—C3—H3B	110.1	C9—C10—C11	123.35 (13)
H3A—C3—H3B	108.4	C10—C11—C12	117.93 (15)
N1—C4—H4A	109.5	C10—C11—H11	121.0
N1—C4—H4B	109.5	C12—C11—H11	121.0
H4A—C4—H4B	109.5	C7—C12—C11	121.92 (15)
N1—C4—H4C	109.5	C7—C12—H12	119.0
H4A—C4—H4C	109.5	C11—C12—H12	119.0
C2—N3—N4—O3	−172.41 (10)	C2—N2—C5—C6	−121.23 (12)
C2—N3—N4—O2	10.03 (16)	C3—N2—C5—C6	69.16 (14)
C3—O1—C1—N1	−47.20 (13)	N2—C5—C7—C8	−81.41 (14)
C2—N1—C1—O1	7.42 (16)	C6—C5—C7—C8	154.88 (11)
C4—N1—C1—O1	−167.37 (10)	N2—C5—C7—C12	97.20 (13)
C4—N1—C2—N2	−172.76 (10)	C6—C5—C7—C12	−26.51 (17)
C1—N1—C2—N2	12.76 (16)	C12—C7—C8—F1	179.02 (11)
C4—N1—C2—N3	12.45 (16)	C5—C7—C8—F1	−2.26 (17)
C1—N1—C2—N3	−162.04 (10)	C12—C7—C8—C9	−0.32 (19)
C3—N2—C2—N1	8.56 (15)	C5—C7—C8—C9	178.39 (11)
C5—N2—C2—N1	−161.50 (10)	F1—C8—C9—C10	−179.21 (12)
C3—N2—C2—N3	−176.88 (10)	C7—C8—C9—C10	0.1 (2)
C5—N2—C2—N3	13.05 (16)	C8—C9—C10—F2	179.50 (12)
N4—N3—C2—N1	−116.27 (12)	C8—C9—C10—C11	0.2 (2)
N4—N3—C2—N2	69.15 (14)	F2—C10—C11—C12	−179.59 (13)
C1—O1—C3—N2	67.89 (12)	C9—C10—C11—C12	−0.2 (2)
C2—N2—C3—O1	−48.47 (13)	C8—C7—C12—C11	0.2 (2)
C5—N2—C3—O1	121.80 (11)	C5—C7—C12—C11	−178.43 (13)
C2—N2—C5—C7	112.59 (12)	C10—C11—C12—C7	0.0 (2)
C3—N2—C5—C7	−57.02 (14)

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···O3iv	0.98	2.39	3.2046 (18)	140

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⋯O3iv	0.98	2.39	3.2046 (18)	140

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