1-(6-Bromo-3,4-dihydro-2H-1,4-benz-oxazin-4-yl)-2,2-dichloro-ethanone.

The title compound, C(10)H(8)BrCl(2)NO(2), is a target mol-ecule 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 inter-actions.

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 = 324.97

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.102

S = 1.09

2924 reflections

145 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.92 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032011/fy2057sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032011/fy2057Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812032011/fy2057Isup3.cml

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

C10H8BrCl2NO2	F(000) = 640.0
Mr = 324.97	Dx = 1.824 Mg m−3Dm = 1.824 Mg m−3Dm 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

Bruker SMART APEX CCD area-detector diffractometer	2924 independent reflections
Radiation source: fine-focus sealed tube	2924 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 28.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→9
Tmin = 0.228, Tmax = 0.335	k = −31→30
11742 measured reflections	l = −9→9

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(Fo2) + (0.0487P)2 + 0.7003P] where P = (Fo2 + 2Fc2)/3
2924 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.92 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) .