2-(3-Methyl-2-nitro­phen­yl)-4,5-dihydro-1,3-oxazole

Lei, D.; Yang, H.; Li, B.; Kang, Z.

doi:10.1107/S1600536808040920

organic compounds

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Volume 65| Part 1| January 2009| Page o54

doi:10.1107/S1600536808040920

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2-(3-Methyl-2-nitrophenyl)-4,5-dihydro-1,3-oxazole

Dongwei Lei,^a Huibin Yang,^b Bin Li ^b and Zhuo Kang ^b ^*

^aShenyang Institute of Chemical Technology, Shenyang 110142, People's Republic of China, and ^bAgrochemicals Division, Shenyang Research Institute of Chemical Industry, Shenyang 110021, People's Republic of China
^*Correspondence e-mail: kangzhuo@sinochem.com

(Received 27 November 2008; accepted 4 December 2008; online 10 December 2008)

In the title compound, C₁₀H₁₀N₂O₃, an intermediate in the synthesis of anthranilamide insecticides, all the non-H atoms except the nitro-group O atom lie on a crystallographic mirror plane. The H atoms of the methyl group are disordered over two sets of sites with equal occupancies. In the crystal structure, C—H⋯N links lead to chains of molecules propagating in [100].

Related literature

For background to anthranilamide compounds, a new class of inseticides, see: Lahm et al. (2003 , 2005 ).

Experimental

Crystal data

C₁₀H₁₀N₂O₃
M_r = 206.20
Monoclinic, P 2₁ /m
a = 7.7767 (10) Å
b = 7.3370 (10) Å
c = 8.6468 (12) Å
β = 99.414 (2)°
V = 486.72 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 (2) K
0.24 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.834, T_max = 1.000 (expected range = 0.818–0.981)
2462 measured reflections
937 independent reflections
842 reflections with I > 2σ(I)
R_int = 0.011

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.110
S = 1.07
937 reflections
90 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N1ⁱ	0.93	2.60	3.508 (3)	167
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040920/hb2868sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040920/hb2868Isup2.hkl

checkCIF report

Comment top

Anthranilamide compounds as a new class of inseticides are characterized by their high levels of insecticidal activity, no-cross resistance to existing insecticides, safety to off-target animal and low toxicity to mammals (Lahm et al. 2003, 2005)

The title compound (I) as an intermediate for preparing Chlorantraniliprole analogs plays an important role in identifying the configuration of two possible products.

In the molecular structure of (I), (Fig. 1) all the non-hydrogen atoms except the nitro-group O atom lie on a crystallographic mirror plane. In the crystal, C—H···N links lead to chains of molecules propagating in [100].

Related literature top

For background to anthranilamide compounds, a new class of inseticides, see: Lahm et al. (2003, 2005).

Experimental top

2-Bromoethanamine hydrobromide (10.25 g, 50 mmol) and 3-methyl-2-nitrobenzoyl chloride (9.98 g, 50 mmol) were added into dichloromethane (200 ml), then triethylamine (16.70 g, 165 mmol) was added. The mixture was heated to reflux for 14 h and cooled down to room temperature, washed with water and brine, dried by anhydrous sulfate magnesium, then evaporated to give the title compound as a white solid. The product was dissolved in dichloromethane and left to stand at room temperature and colourless blocks of (I) were obtained.

Anal. Calcd for C₁₀H₁₀N₂O₃: C, 58.25; H, 4.89; N, 13.59; O, 23.28. Found: C, 58.20; H, 4.90; N, 13.61; O, 23.25 ¹H NMR(CDCl₃): 2.35 (s, 3H, CH₃), 4.06 (t, J=9.8 Hz, 2H, CH₂), 4.40 (t, J=9.6 Hz, 2H, CH₂), 7.41–7.43(m, 2H), 7.78–7.81 (m, 1H).

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for the non-hydrogen atoms. Symmetry code: A x, 1/2–y, z.

2-(3-Methyl-2-nitrophenyl)-4,5-dihydro-1,3-oxazole top

Crystal data top

C₁₀H₁₀N₂O₃	F(000) = 216
M_r = 206.20	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
a = 7.7767 (10) Å	Cell parameters from 1713 reflections
b = 7.337 (1) Å	θ = 2.7–27.9°
c = 8.6468 (12) Å	µ = 0.11 mm⁻¹
β = 99.414 (2)°	T = 296 K
V = 486.72 (11) Å³	BLOCK, colourless
Z = 2	0.24 × 0.22 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	937 independent reflections
Radiation source: fine-focus sealed tube	842 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.834, T_max = 1.000	k = −6→8
2462 measured reflections	l = −10→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0583P)² + 0.1052P] where P = (F_o² + 2F_c²)/3
937 reflections	(Δ/σ)_max < 0.001
90 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₀H₁₀N₂O₃	V = 486.72 (11) Å³
M_r = 206.20	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.7767 (10) Å	µ = 0.11 mm⁻¹
b = 7.337 (1) Å	T = 296 K
c = 8.6468 (12) Å	0.24 × 0.22 × 0.18 mm
β = 99.414 (2)°

Data collection top

Bruker SMART CCD diffractometer	937 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	842 reflections with I > 2σ(I)
T_min = 0.834, T_max = 1.000	R_int = 0.011
2462 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.07	Δρ_max = 0.17 e Å⁻³
937 reflections	Δρ_min = −0.15 e Å⁻³
90 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.2190 (2)	0.2500	1.12373 (17)	0.0794 (6)
O2	0.33918 (12)	0.10351 (17)	0.61731 (13)	0.0628 (4)
N1	0.4057 (2)	0.2500	0.95534 (19)	0.0617 (6)
N2	0.27535 (19)	0.2500	0.64083 (17)	0.0428 (4)
C1	−0.0249 (3)	0.2500	0.4054 (2)	0.0520 (5)
H1A	0.0705	0.3268	0.3893	0.078*	0.50
H1B	−0.1309	0.2952	0.3449	0.078*	0.50
H1C	−0.0041	0.1280	0.3728	0.078*	0.50
C2	−0.0410 (2)	0.2500	0.5759 (2)	0.0430 (5)
C3	−0.2030 (3)	0.2500	0.6245 (3)	0.0533 (5)
H3	−0.3034	0.2500	0.5495	0.064*
C4	−0.2181 (3)	0.2500	0.7801 (3)	0.0630 (6)
H4	−0.3281	0.2500	0.8092	0.076*
C5	−0.0709 (3)	0.2500	0.8946 (3)	0.0589 (6)
H5	−0.0828	0.2500	0.9998	0.071*
C6	0.0946 (2)	0.2500	0.8531 (2)	0.0434 (5)
C7	0.1040 (2)	0.2500	0.6938 (2)	0.0381 (4)
C8	0.2508 (2)	0.2500	0.9762 (2)	0.0428 (5)
C9	0.3878 (3)	0.2500	1.2242 (3)	0.0671 (7)
H9	0.4021	0.1424	1.2902	0.081*
C10	0.5156 (3)	0.2500	1.1111 (2)	0.0580 (6)
H10	0.5890	0.3576	1.1251	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0487 (9)	0.1510 (17)	0.0384 (8)	0.000	0.0066 (7)	0.000
O2	0.0475 (6)	0.0714 (8)	0.0701 (8)	0.0137 (5)	0.0117 (5)	−0.0128 (5)
N1	0.0353 (9)	0.1100 (16)	0.0376 (9)	0.000	−0.0005 (7)	0.000
N2	0.0323 (8)	0.0582 (10)	0.0363 (8)	0.000	0.0013 (6)	0.000
C1	0.0451 (11)	0.0637 (13)	0.0437 (11)	0.000	−0.0033 (8)	0.000
C2	0.0358 (10)	0.0443 (10)	0.0463 (10)	0.000	−0.0010 (8)	0.000
C3	0.0316 (9)	0.0658 (13)	0.0594 (13)	0.000	−0.0020 (8)	0.000
C4	0.0322 (10)	0.0932 (17)	0.0649 (14)	0.000	0.0114 (9)	0.000
C5	0.0397 (11)	0.0885 (16)	0.0505 (12)	0.000	0.0130 (9)	0.000
C6	0.0347 (10)	0.0516 (11)	0.0434 (10)	0.000	0.0046 (8)	0.000
C7	0.0290 (8)	0.0422 (10)	0.0428 (10)	0.000	0.0047 (7)	0.000
C8	0.0408 (10)	0.0521 (11)	0.0352 (9)	0.000	0.0057 (7)	0.000
C9	0.0550 (13)	0.1013 (19)	0.0413 (11)	0.000	−0.0030 (10)	0.000
C10	0.0445 (11)	0.0834 (16)	0.0418 (11)	0.000	−0.0058 (8)	0.000

Geometric parameters (Å, º) top

O1—C8	1.339 (2)	C3—C4	1.370 (3)
O1—C9	1.451 (3)	C3—H3	0.9300
O2—N2	1.2149 (13)	C4—C5	1.385 (3)
N1—C8	1.247 (2)	C4—H4	0.9300
N1—C10	1.472 (2)	C5—C6	1.391 (3)
N2—O2ⁱ	1.2149 (13)	C5—H5	0.9300
N2—C7	1.478 (2)	C6—C7	1.391 (3)
C1—C2	1.501 (3)	C6—C8	1.478 (3)
C1—H1A	0.9600	C9—C10	1.504 (3)
C1—H1B	0.9600	C9—H9	0.9700
C1—H1C	0.9600	C9—H9ⁱ	0.9700
C2—C7	1.391 (2)	C10—H10	0.9700
C2—C3	1.391 (3)	C10—H10ⁱ	0.9700

C8—O1—C9	106.31 (16)	C6—C5—H5	119.8
C8—N1—C10	107.34 (17)	C7—C6—C5	117.07 (18)
O2ⁱ—N2—O2	124.43 (16)	C7—C6—C8	122.89 (17)
O2ⁱ—N2—C7	117.75 (8)	C5—C6—C8	120.04 (18)
O2—N2—C7	117.75 (8)	C2—C7—C6	123.93 (17)
C2—C1—H1A	109.5	C2—C7—N2	115.90 (16)
C2—C1—H1B	109.5	C6—C7—N2	120.18 (15)
H1A—C1—H1B	109.5	N1—C8—O1	118.10 (17)
C2—C1—H1C	109.5	N1—C8—C6	126.55 (17)
H1A—C1—H1C	109.5	O1—C8—C6	115.35 (16)
H1B—C1—H1C	109.5	O1—C9—C10	103.87 (16)
C7—C2—C3	116.38 (18)	O1—C9—H9	111.0
C7—C2—C1	122.16 (17)	C10—C9—H9ⁱ	111.0
C3—C2—C1	121.46 (17)	O1—C9—H9ⁱ	111.0
C4—C3—C2	121.60 (18)	C10—C9—H9ⁱ	111.0
C4—C3—H3	119.2	H9—C9—H9ⁱ	109.0
C2—C3—H3	119.2	N1—C10—C9	104.38 (16)
C3—C4—C5	120.52 (19)	N1—C10—H10	110.9
C3—C4—H4	119.7	C9—C10—H10	110.9
C5—C4—H4	119.7	N1—C10—H10ⁱ	110.9
C4—C5—C6	120.5 (2)	C9—C10—H10ⁱ	110.9
C4—C5—H5	119.8	H10—C10—H10ⁱ	108.9

C7—C2—C3—C4	0.0	O2—N2—C7—C2	−88.46 (13)
C1—C2—C3—C4	180.0	O2ⁱ—N2—C7—C6	−91.54 (13)
C2—C3—C4—C5	0.0	O2—N2—C7—C6	91.54 (13)
C3—C4—C5—C6	0.0	C10—N1—C8—O1	0.0
C4—C5—C6—C7	0.0	C10—N1—C8—C6	180.0
C4—C5—C6—C8	180.0	C9—O1—C8—N1	0.0
C3—C2—C7—C6	0.0	C9—O1—C8—C6	180.0
C1—C2—C7—C6	180.0	C7—C6—C8—N1	0.0
C3—C2—C7—N2	180.0	C5—C6—C8—N1	180.0
C1—C2—C7—N2	0.0	C7—C6—C8—O1	180.0
C5—C6—C7—C2	0.0	C5—C6—C8—O1	0.0
C8—C6—C7—C2	180.0	C8—O1—C9—C10	0.0
C5—C6—C7—N2	180.0	C8—N1—C10—C9	0.0
C8—C6—C7—N2	0.0	O1—C9—C10—N1	0.0
O2ⁱ—N2—C7—C2	88.46 (13)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1ⁱⁱ	0.93	2.60	3.508 (3)	167

Symmetry code: (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂O₃
M_r	206.20
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	296
a, b, c (Å)	7.7767 (10), 7.337 (1), 8.6468 (12)
β (°)	99.414 (2)
V (Å³)	486.72 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.834, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2462, 937, 842
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.110, 1.07
No. of reflections	937
No. of parameters	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1ⁱ	0.93	2.60	3.508 (3)	167

Symmetry code: (i) x−1, y, z.

References

Bruker (2005). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lahm, G. P., Selby, T. P., Freudenberger, J. H., Stevenson, T. M., Myers, B. J., Seburyamo, G., Smith, B. K., Flexner, L., Clark, C. E. & Cordova, D. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906. Web of Science CrossRef PubMed CAS Google Scholar
Lahm, G. P., Selby, T. P. & Stevenson, T. M. (2003). International Patent WO 03/015 519. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o54

doi:10.1107/S1600536808040920

Open

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