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

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.104
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     --  N4      ..       5.24 su
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         57
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....         11
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         53

Alert level G
PLAT793_ALERT_4_G The Model has Chirality at C5      (Verify) ....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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)°; φ = 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).

Related literature

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

S2. 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.

S3. 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 U_iso(H) = 1.2U_eq(C).

Computing details

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

Figures

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

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

Crystal data

C12H15ClN4O3	F(000) = 624
Mr = 298.73	Dx = 1.450 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybc	Cell parameters from 1058 reflections
a = 17.259 (4) Å	θ = 27.5–71.9°
b = 6.9157 (14) Å	µ = 2.61 mm^−1
c = 12.169 (2) Å	T = 113 K
β = 109.63 (3)°	Block, colorless
V = 1368.0 (5) Å^3	0.26 × 0.22 × 0.18 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	2590 independent reflections
Radiation source: fine-focus sealed tube	2562 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 14.63 pixels mm^-1	θmax = 72.1°, θmin = 2.7°
ω scans	h = −20→21
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
Tmin = 0.550, Tmax = 0.651	l = −13→14
12087 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 0.6637P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2590 reflections	Δρmax = 0.26 e Å^−3
184 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction 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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.36163 (2)	0.37729 (6)	−0.00540 (3)	0.02744 (17)
N1	0.09670 (7)	0.33360 (16)	−0.04098 (10)	0.0152 (3)
N2	0.21260 (7)	0.48468 (16)	0.08081 (10)	0.0146 (3)
N3	0.19653 (7)	0.15435 (16)	0.10592 (10)	0.0165 (3)
N4	0.15382 (7)	0.09523 (17)	0.17188 (10)	0.0172 (3)
O1	0.09734 (6)	0.67120 (14)	−0.01841 (9)	0.0180 (2)
O2	0.09602 (7)	0.19372 (16)	0.18398 (9)	0.0247 (3)
O3	0.17457 (7)	−0.06237 (15)	0.22426 (9)	0.0238 (3)
C1	0.06227 (8)	0.5189 (2)	−0.09525 (12)	0.0171 (3)
H1A	0.0740	0.5363	−0.1689	0.021*
H1B	0.0018	0.5188	−0.1139	0.021*
C2	0.16607 (8)	0.32676 (19)	0.04897 (12)	0.0138 (3)
C3	0.18404 (8)	0.66306 (19)	0.01450 (13)	0.0172 (3)
H3A	0.2089	0.7767	0.0630	0.021*
H3B	0.2007	0.6644	−0.0558	0.021*
C4	0.04698 (9)	0.1625 (2)	−0.08861 (13)	0.0196 (3)
H4A	0.0801	0.0459	−0.0611	0.029*
H4B	0.0285	0.1670	−0.1740	0.029*
H4C	−0.0010	0.1599	−0.0626	0.029*
C5	0.28920 (8)	0.48416 (19)	0.18389 (12)	0.0171 (3)
H5	0.3141	0.3524	0.1894	0.020*
C6	0.26984 (10)	0.5185 (2)	0.29596 (12)	0.0225 (3)
H6A	0.3212	0.5198	0.3627	0.034*
H6B	0.2342	0.4147	0.3061	0.034*
H6C	0.2418	0.6430	0.2910	0.034*
C7	0.34952 (8)	0.6269 (2)	0.16156 (13)	0.0184 (3)
C8	0.38573 (9)	0.5900 (2)	0.07689 (13)	0.0209 (3)
C9	0.44068 (9)	0.7161 (2)	0.05401 (14)	0.0257 (4)
H9	0.4640	0.6869	−0.0045	0.031*
C10	0.46123 (10)	0.8863 (2)	0.11817 (16)	0.0305 (4)
H10	0.4997	0.9733	0.1048	0.037*
C11	0.42544 (10)	0.9287 (2)	0.20160 (15)	0.0308 (4)
H11	0.4389	1.0459	0.2445	0.037*
C12	0.37004 (9)	0.8007 (2)	0.22283 (13)	0.0247 (3)
H12	0.3457	0.8320	0.2800	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0282 (2)	0.0206 (2)	0.0376 (3)	−0.00083 (13)	0.01641 (18)	−0.00617 (14)
N1	0.0166 (6)	0.0106 (5)	0.0167 (6)	−0.0008 (4)	0.0035 (4)	−0.0001 (4)
N2	0.0146 (5)	0.0095 (5)	0.0179 (6)	0.0011 (4)	0.0029 (4)	0.0012 (4)
N3	0.0171 (6)	0.0104 (5)	0.0226 (6)	0.0015 (4)	0.0075 (5)	0.0038 (4)
N4	0.0216 (6)	0.0110 (5)	0.0182 (6)	0.0015 (5)	0.0058 (5)	0.0019 (4)
O1	0.0167 (5)	0.0119 (5)	0.0225 (5)	0.0038 (4)	0.0030 (4)	−0.0010 (4)
O2	0.0286 (6)	0.0209 (6)	0.0301 (6)	0.0107 (4)	0.0170 (5)	0.0072 (4)
O3	0.0338 (6)	0.0117 (5)	0.0275 (6)	0.0059 (4)	0.0123 (4)	0.0083 (4)
C1	0.0168 (6)	0.0134 (6)	0.0183 (7)	0.0022 (5)	0.0021 (5)	0.0009 (5)
C2	0.0156 (6)	0.0100 (6)	0.0173 (6)	0.0016 (5)	0.0077 (5)	−0.0003 (5)
C3	0.0165 (7)	0.0099 (6)	0.0226 (7)	0.0010 (5)	0.0032 (5)	0.0035 (5)
C4	0.0204 (7)	0.0144 (6)	0.0222 (7)	−0.0049 (5)	0.0048 (6)	−0.0024 (5)
C5	0.0163 (6)	0.0123 (6)	0.0190 (7)	0.0019 (5)	0.0011 (5)	0.0014 (5)
C6	0.0274 (7)	0.0183 (7)	0.0192 (7)	0.0004 (6)	0.0042 (6)	0.0019 (5)
C7	0.0149 (6)	0.0136 (7)	0.0216 (7)	0.0010 (5)	−0.0006 (5)	0.0026 (5)
C8	0.0157 (6)	0.0157 (7)	0.0270 (8)	0.0018 (5)	0.0015 (6)	0.0030 (6)
C9	0.0182 (7)	0.0267 (8)	0.0298 (8)	0.0013 (6)	0.0047 (6)	0.0093 (6)
C10	0.0211 (8)	0.0248 (8)	0.0372 (9)	−0.0083 (6)	−0.0013 (7)	0.0108 (7)
C11	0.0302 (8)	0.0187 (7)	0.0325 (9)	−0.0086 (7)	−0.0042 (7)	0.0003 (6)
C12	0.0249 (7)	0.0185 (7)	0.0242 (7)	−0.0029 (6)	−0.0004 (6)	−0.0013 (6)

Geometric parameters (Å, º)

Cl1—C8	1.7492 (16)	C4—H4B	0.9800
N1—C2	1.324 (2)	C4—H4C	0.9800
N1—C4	1.4621 (17)	C5—C7	1.524 (2)
N1—C1	1.4721 (17)	C5—C6	1.528 (2)
N2—C2	1.3336 (18)	C5—H5	1.0000
N2—C3	1.4658 (16)	C6—H6A	0.9800
N2—C5	1.4856 (17)	C6—H6B	0.9800
N3—N4	1.3237 (17)	C6—H6C	0.9800
N3—C2	1.3904 (17)	C7—C12	1.396 (2)
N4—O3	1.2526 (15)	C7—C8	1.396 (2)
N4—O2	1.2567 (16)	C8—C9	1.384 (2)
O1—C1	1.4037 (17)	C9—C10	1.391 (2)
O1—C3	1.4143 (18)	C9—H9	0.9500
C1—H1A	0.9900	C10—C11	1.386 (3)
C1—H1B	0.9900	C10—H10	0.9500
C3—H3A	0.9900	C11—C12	1.389 (2)
C3—H3B	0.9900	C11—H11	0.9500
C4—H4A	0.9800	C12—H12	0.9500
C2—N1—C4	123.09 (11)	H4B—C4—H4C	109.5
C2—N1—C1	121.23 (11)	N2—C5—C7	108.38 (11)
C4—N1—C1	115.58 (11)	N2—C5—C6	110.73 (11)
C2—N2—C3	118.10 (11)	C7—C5—C6	115.21 (12)
C2—N2—C5	121.43 (11)	N2—C5—H5	107.4
C3—N2—C5	120.40 (11)	C7—C5—H5	107.4
N4—N3—C2	111.90 (11)	C6—C5—H5	107.4
O3—N4—O2	120.96 (12)	C5—C6—H6A	109.5
O3—N4—N3	117.07 (11)	C5—C6—H6B	109.5
O2—N4—N3	121.95 (11)	H6A—C6—H6B	109.5
C1—O1—C3	109.70 (10)	C5—C6—H6C	109.5
O1—C1—N1	109.62 (11)	H6A—C6—H6C	109.5
O1—C1—H1A	109.7	H6B—C6—H6C	109.5
N1—C1—H1A	109.7	C12—C7—C8	117.08 (14)
O1—C1—H1B	109.7	C12—C7—C5	121.90 (14)
N1—C1—H1B	109.7	C8—C7—C5	121.02 (13)
H1A—C1—H1B	108.2	C9—C8—C7	122.70 (14)
N1—C2—N2	119.99 (12)	C9—C8—Cl1	117.52 (13)
N1—C2—N3	121.87 (12)	C7—C8—Cl1	119.78 (11)
N2—C2—N3	117.88 (12)	C8—C9—C10	118.89 (16)
O1—C3—N2	108.51 (11)	C8—C9—H9	120.6
O1—C3—H3A	110.0	C10—C9—H9	120.6
N2—C3—H3A	110.0	C11—C10—C9	119.87 (15)
O1—C3—H3B	110.0	C11—C10—H10	120.1
N2—C3—H3B	110.0	C9—C10—H10	120.1
H3A—C3—H3B	108.4	C10—C11—C12	120.38 (15)
N1—C4—H4A	109.5	C10—C11—H11	119.8
N1—C4—H4B	109.5	C12—C11—H11	119.8
H4A—C4—H4B	109.5	C11—C12—C7	121.07 (16)
N1—C4—H4C	109.5	C11—C12—H12	119.5
H4A—C4—H4C	109.5	C7—C12—H12	119.5
C2—N3—N4—O3	177.78 (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—N1	55.36 (14)	C3—N2—C5—C6	93.38 (14)
C2—N1—C1—O1	−18.08 (18)	N2—C5—C7—C12	110.06 (14)
C4—N1—C1—O1	158.55 (12)	C6—C5—C7—C12	−14.60 (19)
C4—N1—C2—N2	173.37 (12)	N2—C5—C7—C8	−68.88 (16)
C1—N1—C2—N2	−10.3 (2)	C6—C5—C7—C8	166.46 (13)
C4—N1—C2—N3	−0.6 (2)	C12—C7—C8—C9	0.9 (2)
C1—N1—C2—N3	175.73 (12)	C5—C7—C8—C9	179.93 (13)
C3—N2—C2—N1	0.66 (19)	C12—C7—C8—Cl1	−178.83 (10)
C5—N2—C2—N1	177.72 (12)	C5—C7—C8—Cl1	0.15 (18)
C3—N2—C2—N3	174.91 (11)	C7—C8—C9—C10	0.4 (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—N2	111.90 (14)	C9—C10—C11—C12	1.0 (2)
C1—O1—C3—N2	−64.67 (14)	C10—C11—C12—C7	0.4 (2)
C2—N2—C3—O1	36.13 (16)	C8—C7—C12—C11	−1.3 (2)
C5—N2—C3—O1	−140.96 (12)	C5—C7—C12—C11	179.72 (13)
C2—N2—C5—C7	149.11 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2^i	0.99	2.52	3.2817 (18)	134
C1—H1A···O3^i	0.99	2.50	3.396 (2)	150
C1—H1B···O2^ii	0.99	2.56	3.2555 (18)	127
C3—H3A···O3^iii	0.99	2.49	3.2294 (19)	131
C4—H4B···O2^i	0.98	2.57	3.3070 (19)	132
C4—H4C···O1^ii	0.98	2.49	3.377 (2)	150
C6—H6C···O3^iii	0.98	2.35	3.3020 (19)	164

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