6-Chloro-2H-1,4-benzoxazin-3(4H)-one

Zhuang, W.-C.; Xie, Y.-S.

doi:10.1107/S1600536808035599

organic compounds

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Volume 64| Part 12| December 2008| Page o2369

doi:10.1107/S1600536808035599

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6-Chloro-2H-1,4-benzoxazin-3(4H)-one

Wen-Chang Zhuang ^a and Yong-Sheng Xie ^b ^*

^aSchool of Chemistry and Chemical Engineering, Xuzhou Institute of Technology, Xuzhou, Jiangsu 221006, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: yshxl@yahoo.com.cn

(Received 5 October 2008; accepted 30 October 2008; online 20 November 2008)

In the title compound, C₈H₆ClNO₂, the conformation of the six-membered heterocyclic ring is close to screw boat and the molecules are linked via intermolecular N—H⋯O hydrogen bonds along the b axis.

Related literature

For biological activities of 1,4-benzoxazin-3(4H)-one derivatives, see: Huang et al. (2005 ); Macchiarulo et al. (2002 ). For a related structure, see: Pang et al. (2006 ).

Experimental

Crystal data

C₈H₆ClNO₂
M_r = 183.59
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.5359 (6) Å
b = 7.700 (1) Å
c = 21.281 (3) Å
V = 743.28 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 273 (2) K
0.12 × 0.10 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.878, T_max = 0.973
3857 measured reflections
1314 independent reflections
1143 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.088
S = 1.07
1314 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 500 Friedel pairs
Flack parameter: 0.06 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.00	2.844 (3)	166
Symmetry code: (i) $[-x+3, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker 2002); cell refinement: SAINT (Bruker 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035599/wn2285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035599/wn2285Isup2.hkl

checkCIF report

Comment top

Benzo[1,4]oxazin-3(4H)-one derivatives are one of the important classes of heterocyclic compounds and have been shown to exhibit a wide range of biological activities such as herbicidal (Huang et al., 2005) and antifungal (Macchiarulo et al., 2002). We report here the crystal structure of 6-chloro-2H-benzo[b][1,4]oxazin-3(4H)-one.

The molecular structure is illustrated in Fig. 1. The conformation of the six-membered heterocyclic ring is close to screw boat, with atoms C1 and C2 out of the plane of the remaining four atoms by 0.301 (5) and 0.635 (5) Å, respectively. In a related compound containing the benzo[1,4]oxazin-3(4H)-one system (Pang et al., 2006), the heterocyclic ring also adopts a screw boat conformation. The molecules are connected via N - H ··· O hydrogen bonding into chains along the b axis.

Related literature top

For biological activities of benzo[1,4]oxazin-3(4H)-one derivatives, see: Huang et al. (2005); Macchiarulo et al. (2002). For a related compound, see: Pang et al. (2006).

Experimental top

To a 25 ml round-bottomed flask equipped with a reflux condenser were added 2-chloro-N-(5-chloro-2-hydroxyphenyl)acetamide (2.19 g, 10 mmol), potassium carbonate (2.76 g, 20 mmol) and anhydrous DMF (20 ml). The resulting mixture was heated under reflux for 90 min. After this time, the reaction mixture was poured into 80 g of water, and stirred for 15 min. The mixture was extracted with ethyl acetate (2 x 20 ml). The ethyl acetate extract was washed with saturated brine (10 ml). After drying over Na₂SO₄, the solvent was removed under vacuum and a colourless solid was obtained in 80% yield (1.46 g). Suitable crystals were grown by evaporation of a CH₂Cl₂solution at room temperature for 4 d.

Computing details top

Data collection: SMART (Bruker 2002); cell refinement: SAINT (Bruker 2002); data reduction: SAINT (Bruker 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

6-Chloro-2H-1,4-benzoxazin-3(4H)-one top

Crystal data top

C₈H₆ClNO₂	D_x = 1.641 Mg m⁻³
M_r = 183.59	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1287 reflections
a = 4.5359 (6) Å	θ = 3.3–24.4°
b = 7.700 (1) Å	µ = 0.46 mm⁻¹
c = 21.281 (3) Å	T = 273 K
V = 743.28 (17) Å³	Plate, colourless
Z = 4	0.12 × 0.10 × 0.06 mm
F(000) = 376

Data collection top

Bruker SMART CCD area-detector diffractometer	1314 independent reflections
Radiation source: fine-focus sealed tube	1143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −5→4
T_min = 0.878, T_max = 0.973	k = −8→9
3857 measured reflections	l = −25→23

Refinement top

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0401P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1314 reflections	Δρ_max = 0.16 e Å⁻³
109 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 500 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (11)

Crystal data top

C₈H₆ClNO₂	V = 743.28 (17) Å³
M_r = 183.59	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.5359 (6) Å	µ = 0.46 mm⁻¹
b = 7.700 (1) Å	T = 273 K
c = 21.281 (3) Å	0.12 × 0.10 × 0.06 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1314 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1143 reflections with I > 2σ(I)
T_min = 0.878, T_max = 0.973	R_int = 0.047
3857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.088	Δρ_max = 0.16 e Å⁻³
S = 1.07	Δρ_min = −0.21 e Å⁻³
1314 reflections	Absolute structure: Flack (1983), 500 Friedel pairs
109 parameters	Absolute structure parameter: 0.06 (11)
0 restraints

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
Cl1	0.59509 (18)	0.16633 (10)	0.92672 (4)	0.0538 (3)
O1	1.5486 (5)	0.7552 (2)	0.74891 (10)	0.0488 (6)
O2	1.1177 (4)	0.8424 (2)	0.88354 (9)	0.0466 (6)
N1	1.2830 (5)	0.5732 (3)	0.80882 (10)	0.0347 (6)
H1	1.3651	0.4842	0.7918	0.042*
C1	1.3640 (6)	0.7302 (3)	0.79030 (14)	0.0350 (7)
C2	1.2111 (7)	0.8777 (3)	0.82142 (15)	0.0448 (8)
H2A	1.3430	0.9768	0.8222	0.054*
H2B	1.0404	0.9094	0.7965	0.054*
C3	0.9870 (6)	0.6859 (3)	0.89160 (13)	0.0346 (7)
C4	1.0683 (6)	0.5467 (3)	0.85521 (12)	0.0295 (6)
C5	0.9496 (6)	0.3866 (3)	0.86535 (13)	0.0339 (6)
H5	1.0043	0.2924	0.8406	0.041*
C6	0.7466 (6)	0.3675 (3)	0.91299 (13)	0.0369 (7)
C7	0.6661 (6)	0.5045 (4)	0.94990 (13)	0.0408 (7)
H7	0.5317	0.4889	0.9824	0.049*
C8	0.7839 (6)	0.6642 (4)	0.93876 (13)	0.0402 (7)
H8	0.7267	0.7586	0.9631	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0588 (5)	0.0489 (4)	0.0537 (5)	−0.0086 (4)	0.0042 (4)	0.0129 (4)
O1	0.0582 (14)	0.0464 (11)	0.0420 (13)	−0.0049 (10)	0.0170 (12)	0.0038 (9)
O2	0.0600 (14)	0.0389 (10)	0.0410 (13)	−0.0064 (12)	0.0119 (11)	−0.0098 (9)
N1	0.0375 (13)	0.0348 (12)	0.0319 (14)	0.0014 (11)	0.0068 (11)	−0.0017 (10)
C1	0.0401 (17)	0.0378 (14)	0.0272 (16)	−0.0022 (13)	−0.0029 (14)	−0.0005 (12)
C2	0.0532 (19)	0.0390 (15)	0.0423 (19)	−0.0032 (14)	0.0061 (16)	0.0019 (14)
C3	0.0362 (16)	0.0372 (14)	0.0305 (16)	−0.0012 (13)	−0.0001 (12)	−0.0028 (12)
C4	0.0291 (14)	0.0372 (14)	0.0221 (14)	0.0016 (13)	0.0002 (13)	−0.0008 (11)
C5	0.0370 (15)	0.0365 (14)	0.0282 (15)	0.0021 (13)	−0.0049 (13)	−0.0006 (11)
C6	0.0357 (15)	0.0424 (15)	0.0327 (17)	−0.0011 (13)	−0.0026 (13)	0.0083 (13)
C7	0.0392 (18)	0.0534 (17)	0.0297 (17)	−0.0007 (15)	0.0057 (13)	0.0011 (15)
C8	0.0425 (16)	0.0464 (15)	0.0315 (17)	0.0058 (16)	0.0041 (13)	−0.0052 (14)

Geometric parameters (Å, º) top

Cl1—C6	1.720 (3)	C3—C8	1.373 (4)
O1—C1	1.231 (3)	C3—C4	1.373 (4)
O2—C3	1.354 (3)	C4—C5	1.362 (4)
O2—C2	1.414 (4)	C5—C6	1.377 (4)
N1—C1	1.324 (3)	C5—H5	0.9300
N1—C4	1.402 (3)	C6—C7	1.365 (4)
N1—H1	0.8600	C7—C8	1.362 (4)
C1—C2	1.486 (4)	C7—H7	0.9300
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700

C3—O2—C2	114.9 (2)	C5—C4—C3	120.7 (3)
C1—N1—C4	122.4 (2)	C5—C4—N1	121.2 (2)
C1—N1—H1	118.8	C3—C4—N1	118.0 (2)
C4—N1—H1	118.8	C4—C5—C6	118.5 (3)
O1—C1—N1	123.0 (3)	C4—C5—H5	120.7
O1—C1—C2	121.1 (2)	C6—C5—H5	120.7
N1—C1—C2	115.8 (3)	C7—C6—C5	121.3 (3)
O2—C2—C1	114.2 (2)	C7—C6—Cl1	119.4 (2)
O2—C2—H2A	108.7	C5—C6—Cl1	119.2 (2)
C1—C2—H2A	108.7	C8—C7—C6	119.5 (3)
O2—C2—H2B	108.7	C8—C7—H7	120.2
C1—C2—H2B	108.7	C6—C7—H7	120.2
H2A—C2—H2B	107.6	C7—C8—C3	120.1 (3)
O2—C3—C8	119.7 (2)	C7—C8—H8	120.0
O2—C3—C4	120.4 (2)	C3—C8—H8	120.0
C8—C3—C4	119.8 (3)

C4—N1—C1—O1	−178.8 (2)	C1—N1—C4—C5	167.7 (3)
C4—N1—C1—C2	−0.5 (4)	C1—N1—C4—C3	−14.2 (4)
C3—O2—C2—C1	−44.4 (3)	C3—C4—C5—C6	−0.1 (4)
O1—C1—C2—O2	−152.3 (3)	N1—C4—C5—C6	177.9 (2)
N1—C1—C2—O2	29.4 (4)	C4—C5—C6—C7	−0.5 (4)
C2—O2—C3—C8	−152.6 (3)	C4—C5—C6—Cl1	−179.8 (2)
C2—O2—C3—C4	31.1 (3)	C5—C6—C7—C8	1.3 (4)
O2—C3—C4—C5	176.3 (3)	Cl1—C6—C7—C8	−179.4 (2)
C8—C3—C4—C5	0.0 (4)	C6—C7—C8—C3	−1.4 (4)
O2—C3—C4—N1	−1.7 (4)	O2—C3—C8—C7	−175.6 (2)
C8—C3—C4—N1	−178.1 (2)	C4—C3—C8—C7	0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.00	2.844 (3)	166

Symmetry code: (i) −x+3, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₆ClNO₂
M_r	183.59
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	273
a, b, c (Å)	4.5359 (6), 7.700 (1), 21.281 (3)
V (Å³)	743.28 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.12 × 0.10 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.878, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	3857, 1314, 1143
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.088, 1.07
No. of reflections	1314
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21
Absolute structure	Flack (1983), 500 Friedel pairs
Absolute structure parameter	0.06 (11)

Computer programs: SMART (Bruker 2002), SAINT (Bruker 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.00	2.844 (3)	166

Symmetry code: (i) −x+3, y−1/2, −z+3/2.

References

Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Huang, M. Z., Huang, K. L., Ren, Y. G., Lei, M. X., Huang, L., Hou, Z. K., Liu, A. P. & Ou, X. M. (2005). J. Agric. Food Chem. 53, 7908–7914. Web of Science CrossRef PubMed CAS Google Scholar
Macchiarulo, A., Costantino, G., Fringuelli, D., Vecchiarelli, A., Schiaffella, F. & Fringueui, R. (2002). Bioorg. Med. Chem. 10, 3415–3423. Web of Science CrossRef PubMed CAS Google Scholar
Pang, H.-L., Yang, H., Yin, D.-L. & Mao, C.-H. (2006). Acta Cryst. E62, o5165–o5166. Web of Science CSD CrossRef IUCr Journals 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 64| Part 12| December 2008| Page o2369

doi:10.1107/S1600536808035599

Open

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