1-(6-Bromo-3,4-dihydro-2H-1,4-benz­oxazin-4-yl)-2,2-dichloro­ethanone

Ye, F.; Li, Y.; Fu, Y.; Zhao, L.-X.; Gao, S.

doi:10.1107/S1600536812032011

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2509

https://doi.org/10.1107/S1600536812032011

Open

access

1-(6-Bromo-3,4-dihydro-2H-1,4-benzoxazin-4-yl)-2,2-dichloroethanone

Fei Ye,^a Ying Li,^a Ying Fu,^a ^* Li-Xia Zhao ^a and Shuang Gao ^a

^aCollege of Science, Northeast Agricultural University, Harbin 150030, People's Republic of China
^*Correspondence e-mail: fuying@neau.edu.cn

(Received 19 April 2012; accepted 13 July 2012; online 21 July 2012)

The title compound, C₁₀H₈BrCl₂NO₂, is a target molecule in our research on herbicide safeners. The oxazine ring has an envelope conformation, with puckering parameters close to ideal values [Q = 0.498 (3) Å, θ = 53.7 (3)° and φ = 253.4 (4)°]. The crystal structure is stabilized by C—H⋯O, C—H⋯Cl and C—H⋯Br interactions.

Related literature

For general background on 1,4-benzoxazine, see: Mizar & Myrboh (2006 ); Macias et al. (2006 ); Tang et al. (2011 ). For the herbicide safener activity of N-dichloroacetyl benzoxazine derivatives, see: Burton et al. (1994 ); Hatzios & Burgos (2004 ); Loniovereror (1993 ); Scarponi & Buono (2005 ). For the synthetic procedure, see: Fu et al. (2011 ).

Experimental

Crystal data

C₁₀H₈BrCl₂NO₂
M_r = 324.97
Monoclinic, P 2₁ /n
a = 6.8220 (8) Å
b = 23.567 (3) Å
c = 7.3746 (9) Å
β = 93.545 (1)°
V = 1183.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.91 mm⁻¹
T = 298 K
0.40 × 0.38 × 0.28 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.228, T_max = 0.335
11742 measured reflections
2924 independent reflections
2924 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.102
S = 1.09
2924 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.98	2.20	3.101 (3)	153
C12—H12B⋯Cl2ⁱ	0.97	2.88	3.664 (3)	139
C11—H11B⋯Br1ⁱⁱ	0.97	2.99	3.853 (3)	148
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x-1, y, z-1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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: https://doi.org/10.1107/S1600536812032011/fy2057sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032011/fy2057Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032011/fy2057Isup3.cml

checkCIF report

Comment top

Substituted benzoxazine derivatives have attracted attention because of their widespread application as fungicides and insecticides (Mizar & Myrboh, 2006; Macias et al., 2006; Tang et al., 2011). N-dichloroacetyl benzoxazines have been used as herbicide safeners, which protect the crop from injury by herbicides (Burton et al., 1994; Hatzios & Burgos, 2004; Loniovereror, 1993; Scarponi & Buono, 2005). As a part of our ongoing investigations of different herbicide safeners, we prepared the title compound (Fu et al., 2011).

The molecular structure of the title compound is shown in Fig. 1. In the crystal, molecules are linked by weak intermolecular C—H···O, C—H···Cl, and C—H···Br interactions to form one-dimensional chains (Fig. 2, Table 1).

Related literature top

For general background on 1,4-benzoxazine, see: Mizar & Myrboh (2006); Macias et al. (2006); Tang et al. (2011). For the herbicide safener activity of N-dichloroacetyl benzoxazine derivatives, see: Burton et al. (1994); Hatzios & Burgos (2004); Loniovereror (1993); Scarponi & Buono (2005). For the synthetic procedure, see: Fu et al. (2011).

Experimental top

The title compound was prepared according to the literature procedure (Fu et al., 2011).

The single crystal suitable for X-ray structural analysis was obtained by slow evaporation of a solution of the title compound in petroleum ether and ethyl acetate (v/v = 5:1) at room temperature.

Structure description top

For general background on 1,4-benzoxazine, see: Mizar & Myrboh (2006); Macias et al. (2006); Tang et al. (2011). For the herbicide safener activity of N-dichloroacetyl benzoxazine derivatives, see: Burton et al. (1994); Hatzios & Burgos (2004); Loniovereror (1993); Scarponi & Buono (2005). For the synthetic procedure, see: Fu et al. (2011).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. Molecular structure of the title compound with the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram for the title compound, showing the intramolecular C–H···Br interaction as dashed lines.

1-(6-Bromo-3,4-dihydro-2H-1,4-benzoxazin-4-yl)-2,2-dichloroethanone top

Crystal data top

C₁₀H₈BrCl₂NO₂	F(000) = 640.0
M_r = 324.97	D_x = 1.824 Mg m⁻³ D_m = 1.824 Mg m⁻³ D_m measured by not measured
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4705 reflections
a = 6.8220 (8) Å	θ = 2.8–25.8°
b = 23.567 (3) Å	µ = 3.91 mm⁻¹
c = 7.3746 (9) Å	T = 298 K
β = 93.545 (1)°	Block, colourless
V = 1183.4 (3) Å³	0.40 × 0.38 × 0.28 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2924 independent reflections
Radiation source: fine-focus sealed tube	2924 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→9
T_min = 0.228, T_max = 0.335	k = −31→30
11742 measured reflections	l = −9→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0487P)² + 0.7003P] where P = (F_o² + 2F_c²)/3
2924 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.92 e Å⁻³

Crystal data top

C₁₀H₈BrCl₂NO₂	V = 1183.4 (3) Å³
M_r = 324.97	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8220 (8) Å	µ = 3.91 mm⁻¹
b = 23.567 (3) Å	T = 298 K
c = 7.3746 (9) Å	0.40 × 0.38 × 0.28 mm
β = 93.545 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2924 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	2924 reflections with I > 2σ(I)
T_min = 0.228, T_max = 0.335	R_int = 0.020
11742 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.09	Δρ_max = 0.44 e Å⁻³
2924 reflections	Δρ_min = −0.92 e Å⁻³
145 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C11	0.5861 (5)	0.13121 (15)	0.7608 (5)	0.0693 (9)
H11A	0.5504	0.1652	0.8251	0.083*
H11B	0.4856	0.1243	0.6644	0.083*
C12	0.7804 (5)	0.14020 (15)	0.6796 (4)	0.0640 (9)
H12A	0.8180	0.1062	0.6160	0.077*
H12B	0.7708	0.1713	0.5933	0.077*
C13	0.9285 (5)	0.02632 (13)	1.2299 (4)	0.0535 (7)
H13	0.9280	−0.0021	1.3173	0.064*
C1	0.7665 (5)	0.03564 (13)	1.1156 (4)	0.0561 (7)
H1	0.6559	0.0130	1.1240	0.067*
C2	0.7655 (4)	0.07871 (12)	0.9869 (4)	0.0484 (6)
C3	1.0255 (4)	0.23991 (11)	0.6714 (3)	0.0464 (6)
H3	0.8872	0.2438	0.6289	0.056*
O1	0.5943 (3)	0.08487 (10)	0.8818 (3)	0.0658 (6)
C5	1.0986 (4)	0.10184 (10)	1.0846 (3)	0.0414 (5)
H5	1.2119	0.1232	1.0742	0.050*
C6	1.0390 (4)	0.20127 (11)	0.8395 (3)	0.0436 (6)
C7	0.9324 (4)	0.11209 (10)	0.9693 (3)	0.0403 (5)
C8	1.0934 (4)	0.05971 (11)	1.2139 (4)	0.0440 (6)
O2	1.1457 (3)	0.21396 (9)	0.9706 (3)	0.0601 (6)
N1	0.9288 (3)	0.15339 (9)	0.8282 (3)	0.0477 (5)
Br1	1.31802 (5)	0.046715 (14)	1.37285 (4)	0.06190 (14)
Cl2	1.12004 (16)	0.30735 (4)	0.72659 (12)	0.0759 (3)
Cl3	1.15557 (16)	0.20811 (5)	0.49693 (13)	0.0834 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.0554 (18)	0.069 (2)	0.079 (2)	−0.0032 (15)	−0.0341 (16)	−0.0157 (17)
C12	0.072 (2)	0.0626 (18)	0.0528 (16)	−0.0159 (15)	−0.0313 (15)	−0.0025 (14)
C13	0.0639 (18)	0.0466 (14)	0.0513 (15)	−0.0081 (13)	0.0138 (13)	0.0011 (12)
C1	0.0510 (16)	0.0524 (16)	0.0665 (18)	−0.0156 (13)	0.0155 (14)	−0.0071 (13)
C2	0.0414 (13)	0.0462 (14)	0.0570 (15)	−0.0054 (11)	−0.0018 (11)	−0.0139 (12)
C3	0.0450 (13)	0.0492 (14)	0.0436 (13)	0.0012 (11)	−0.0083 (11)	0.0065 (11)
O1	0.0448 (11)	0.0669 (14)	0.0835 (15)	−0.0111 (10)	−0.0128 (10)	−0.0057 (12)
C5	0.0423 (13)	0.0382 (12)	0.0434 (12)	−0.0042 (10)	−0.0004 (10)	0.0012 (10)
C6	0.0411 (12)	0.0449 (13)	0.0430 (13)	−0.0011 (10)	−0.0121 (10)	0.0052 (10)
C7	0.0420 (13)	0.0356 (12)	0.0428 (12)	−0.0021 (10)	−0.0022 (10)	−0.0046 (10)
C8	0.0512 (14)	0.0406 (13)	0.0405 (12)	0.0024 (11)	0.0043 (11)	0.0002 (10)
O2	0.0667 (13)	0.0535 (11)	0.0559 (11)	−0.0221 (10)	−0.0302 (10)	0.0168 (9)
N1	0.0520 (13)	0.0427 (11)	0.0455 (11)	−0.0083 (10)	−0.0194 (10)	0.0016 (9)
Br1	0.0668 (2)	0.0634 (2)	0.05402 (19)	0.00348 (14)	−0.00809 (14)	0.01693 (13)
Cl2	0.1089 (7)	0.0562 (5)	0.0599 (5)	−0.0264 (4)	−0.0170 (4)	0.0171 (4)
Cl3	0.0936 (7)	0.0934 (7)	0.0651 (5)	0.0173 (5)	0.0213 (5)	0.0018 (5)

Geometric parameters (Å, º) top

C11—O1	1.409 (4)	C2—C7	1.397 (4)
C11—C12	1.503 (5)	C3—C6	1.536 (3)
C11—H11A	0.9700	C3—Cl2	1.754 (3)
C11—H11B	0.9700	C3—Cl3	1.774 (3)
C12—N1	1.479 (3)	C3—H3	0.9800
C12—H12A	0.9700	C5—C8	1.379 (4)
C12—H12B	0.9700	C5—C7	1.396 (3)
C13—C1	1.365 (5)	C5—H5	0.9300
C13—C8	1.384 (4)	C6—O2	1.211 (3)
C13—H13	0.9300	C6—N1	1.356 (3)
C1—C2	1.390 (4)	C7—N1	1.424 (3)
C1—H1	0.9300	C8—Br1	1.895 (3)
C2—O1	1.369 (3)

O1—C11—C12	111.1 (3)	C6—C3—Cl3	109.09 (19)
O1—C11—H11A	109.4	Cl2—C3—Cl3	110.98 (16)
C12—C11—H11A	109.4	C6—C3—H3	108.8
O1—C11—H11B	109.4	Cl2—C3—H3	108.8
C12—C11—H11B	109.4	Cl3—C3—H3	108.8
H11A—C11—H11B	108.0	C2—O1—C11	116.1 (2)
N1—C12—C11	108.3 (3)	C8—C5—C7	119.5 (2)
N1—C12—H12A	110.0	C8—C5—H5	120.3
C11—C12—H12A	110.0	C7—C5—H5	120.3
N1—C12—H12B	110.0	O2—C6—N1	123.9 (2)
C11—C12—H12B	110.0	O2—C6—C3	120.1 (2)
H12A—C12—H12B	108.4	N1—C6—C3	116.0 (2)
C1—C13—C8	119.2 (3)	C5—C7—C2	118.8 (2)
C1—C13—H13	120.4	C5—C7—N1	122.7 (2)
C8—C13—H13	120.4	C2—C7—N1	118.4 (2)
C13—C1—C2	120.6 (3)	C5—C8—C13	121.6 (3)
C13—C1—H1	119.7	C5—C8—Br1	119.3 (2)
C2—C1—H1	119.7	C13—C8—Br1	119.1 (2)
O1—C2—C1	115.6 (3)	C6—N1—C7	122.7 (2)
O1—C2—C7	124.0 (3)	C6—N1—C12	124.9 (2)
C1—C2—C7	120.4 (3)	C7—N1—C12	112.2 (2)
C6—C3—Cl2	110.32 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.98	2.20	3.101 (3)	153
C12—H12B···Cl2ⁱ	0.97	2.88	3.664 (3)	139
C11—H11B···Br1ⁱⁱ	0.97	2.99	3.853 (3)	148

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈BrCl₂NO₂
M_r	324.97
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.8220 (8), 23.567 (3), 7.3746 (9)
β (°)	93.545 (1)
V (Å³)	1183.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.91
Crystal size (mm)	0.40 × 0.38 × 0.28

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.228, 0.335
No. of measured, independent and observed [I > 2σ(I)] reflections	11742, 2924, 2924
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.09
No. of reflections	2924
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.92

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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
C3—H3···O2ⁱ	0.98	2.20	3.101 (3)	152.6
C12—H12B···Cl2ⁱ	0.97	2.88	3.664 (3)	138.9
C11—H11B···Br1ⁱⁱ	0.97	2.99	3.853 (3)	148.2

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

Acknowledgements

The authors thank the National Nature Science Foundation of China (grant No. 31101473), the Science and Technology Research Project of Heilongjiang Education Department (grant No. 12521002), the Research Science Foundation in Technology Innovation of Harbin (grant No. 2012RFXXN002) and the Northeast Agricultural University Doctoral Foundation for generously supporting this study.

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burton, J. D., Maness, E. P., Monks, D. W. & Robinson, D. K. (1994). Pestic. Biochem. Physiol. 48, 163–172. CrossRef Web of Science Google Scholar
Fu, Y., Zhang, S. S. & Ye, F. (2011). Indian J. Heterocycl. Chem. 20, 405–406. CAS Google Scholar
Hatzios, K. K. & Burgos, N. (2004). Weed Sci. 52, 454–457. Web of Science CrossRef CAS Google Scholar
Loniovereror, G. L. (1993). Weed Res. 33, 311–318. Google Scholar
Macias, F. A., Marin, D., Oliveros-Bastidas, A., Chinchilla, D., Simonet, A. M. & Molinillo, J. M. G. (2006). J. Agric. Food Chem. 54, 991–1000. Web of Science PubMed CAS Google Scholar
Mizar, P. & Myrboh, B. (2006). Tetrahedron Lett. 47, 7823–7826. Web of Science CrossRef CAS Google Scholar
Scarponi, L. & Buono, D. D. (2005). J. Agric. Food Chem. 53, 2483–2488. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, Z. L., Chen, W. W., Zhu, Z. H. & Liu, H. W. (2011). J. Heterocycl. Chem. 48, 255–260. Web of Science CSD CrossRef CAS Google Scholar