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ISSN: 2056-9890

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

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[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.]); Macchiarulo et al. (2002[Macchiarulo, A., Costantino, G., Fringuelli, D., Vecchiarelli, A., Schiaffella, F. & Fringueui, R. (2002). Bioorg. Med. Chem. 10, 3415-3423.]). For a related structure, see: Pang et al. (2006[Pang, H.-L., Yang, H., Yin, D.-L. & Mao, C.-H. (2006). Acta Cryst. E62, o5165-o5166.]).

[Scheme 1]

Experimental

Crystal data
  • C8H6ClNO2

  • Mr = 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[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.878, Tmax = 0.973

  • 3857 measured reflections

  • 1314 independent reflections

  • 1143 reflections with I > 2σ(I)

  • Rint = 0.047

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.088

  • S = 1.07

  • 1314 reflections

  • 109 parameters

  • H-atom parameters constrained

  • Δρmax = 0.16 e Å−3

  • Δρmin = −0.21 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 500 Friedel pairs

  • Flack parameter: 0.06 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 CH2Cl2 solution at room temperature for 4 d.

Refinement top

All H atoms were positioned geometrically (N - H = 0.86 Å, aromatic C - H = 0.93 Å, methylene C - H = 0.97 Å) and refined using a riding model; Uiso(H) = 1.2 Ueq(C, N).

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
[Figure 1] 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
C8H6ClNO2Dx = 1.641 Mg m3
Mr = 183.59Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 1287 reflections
a = 4.5359 (6) Åθ = 3.3–24.4°
b = 7.700 (1) ŵ = 0.46 mm1
c = 21.281 (3) ÅT = 273 K
V = 743.28 (17) Å3Plate, colourless
Z = 40.12 × 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 tube1143 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ϕ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 54
Tmin = 0.878, Tmax = 0.973k = 89
3857 measured reflectionsl = 2523
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0401P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1314 reflectionsΔρmax = 0.16 e Å3
109 parametersΔρmin = 0.21 e Å3
0 restraintsAbsolute structure: Flack (1983), 500 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.06 (11)
Crystal data top
C8H6ClNO2V = 743.28 (17) Å3
Mr = 183.59Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 4.5359 (6) ŵ = 0.46 mm1
b = 7.700 (1) ÅT = 273 K
c = 21.281 (3) Å0.12 × 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)
Tmin = 0.878, Tmax = 0.973Rint = 0.047
3857 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.088Δρmax = 0.16 e Å3
S = 1.07Δρmin = 0.21 e Å3
1314 reflectionsAbsolute structure: Flack (1983), 500 Friedel pairs
109 parametersAbsolute 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
xyzUiso*/Ueq
Cl10.59509 (18)0.16633 (10)0.92672 (4)0.0538 (3)
O11.5486 (5)0.7552 (2)0.74891 (10)0.0488 (6)
O21.1177 (4)0.8424 (2)0.88354 (9)0.0466 (6)
N11.2830 (5)0.5732 (3)0.80882 (10)0.0347 (6)
H11.36510.48420.79180.042*
C11.3640 (6)0.7302 (3)0.79030 (14)0.0350 (7)
C21.2111 (7)0.8777 (3)0.82142 (15)0.0448 (8)
H2A1.34300.97680.82220.054*
H2B1.04040.90940.79650.054*
C30.9870 (6)0.6859 (3)0.89160 (13)0.0346 (7)
C41.0683 (6)0.5467 (3)0.85521 (12)0.0295 (6)
C50.9496 (6)0.3866 (3)0.86535 (13)0.0339 (6)
H51.00430.29240.84060.041*
C60.7466 (6)0.3675 (3)0.91299 (13)0.0369 (7)
C70.6661 (6)0.5045 (4)0.94990 (13)0.0408 (7)
H70.53170.48890.98240.049*
C80.7839 (6)0.6642 (4)0.93876 (13)0.0402 (7)
H80.72670.75860.96310.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0588 (5)0.0489 (4)0.0537 (5)0.0086 (4)0.0042 (4)0.0129 (4)
O10.0582 (14)0.0464 (11)0.0420 (13)0.0049 (10)0.0170 (12)0.0038 (9)
O20.0600 (14)0.0389 (10)0.0410 (13)0.0064 (12)0.0119 (11)0.0098 (9)
N10.0375 (13)0.0348 (12)0.0319 (14)0.0014 (11)0.0068 (11)0.0017 (10)
C10.0401 (17)0.0378 (14)0.0272 (16)0.0022 (13)0.0029 (14)0.0005 (12)
C20.0532 (19)0.0390 (15)0.0423 (19)0.0032 (14)0.0061 (16)0.0019 (14)
C30.0362 (16)0.0372 (14)0.0305 (16)0.0012 (13)0.0001 (12)0.0028 (12)
C40.0291 (14)0.0372 (14)0.0221 (14)0.0016 (13)0.0002 (13)0.0008 (11)
C50.0370 (15)0.0365 (14)0.0282 (15)0.0021 (13)0.0049 (13)0.0006 (11)
C60.0357 (15)0.0424 (15)0.0327 (17)0.0011 (13)0.0026 (13)0.0083 (13)
C70.0392 (18)0.0534 (17)0.0297 (17)0.0007 (15)0.0057 (13)0.0011 (15)
C80.0425 (16)0.0464 (15)0.0315 (17)0.0058 (16)0.0041 (13)0.0052 (14)
Geometric parameters (Å, º) top
Cl1—C61.720 (3)C3—C81.373 (4)
O1—C11.231 (3)C3—C41.373 (4)
O2—C31.354 (3)C4—C51.362 (4)
O2—C21.414 (4)C5—C61.377 (4)
N1—C11.324 (3)C5—H50.9300
N1—C41.402 (3)C6—C71.365 (4)
N1—H10.8600C7—C81.362 (4)
C1—C21.486 (4)C7—H70.9300
C2—H2A0.9700C8—H80.9300
C2—H2B0.9700
C3—O2—C2114.9 (2)C5—C4—C3120.7 (3)
C1—N1—C4122.4 (2)C5—C4—N1121.2 (2)
C1—N1—H1118.8C3—C4—N1118.0 (2)
C4—N1—H1118.8C4—C5—C6118.5 (3)
O1—C1—N1123.0 (3)C4—C5—H5120.7
O1—C1—C2121.1 (2)C6—C5—H5120.7
N1—C1—C2115.8 (3)C7—C6—C5121.3 (3)
O2—C2—C1114.2 (2)C7—C6—Cl1119.4 (2)
O2—C2—H2A108.7C5—C6—Cl1119.2 (2)
C1—C2—H2A108.7C8—C7—C6119.5 (3)
O2—C2—H2B108.7C8—C7—H7120.2
C1—C2—H2B108.7C6—C7—H7120.2
H2A—C2—H2B107.6C7—C8—C3120.1 (3)
O2—C3—C8119.7 (2)C7—C8—H8120.0
O2—C3—C4120.4 (2)C3—C8—H8120.0
C8—C3—C4119.8 (3)
C4—N1—C1—O1178.8 (2)C1—N1—C4—C5167.7 (3)
C4—N1—C1—C20.5 (4)C1—N1—C4—C314.2 (4)
C3—O2—C2—C144.4 (3)C3—C4—C5—C60.1 (4)
O1—C1—C2—O2152.3 (3)N1—C4—C5—C6177.9 (2)
N1—C1—C2—O229.4 (4)C4—C5—C6—C70.5 (4)
C2—O2—C3—C8152.6 (3)C4—C5—C6—Cl1179.8 (2)
C2—O2—C3—C431.1 (3)C5—C6—C7—C81.3 (4)
O2—C3—C4—C5176.3 (3)Cl1—C6—C7—C8179.4 (2)
C8—C3—C4—C50.0 (4)C6—C7—C8—C31.4 (4)
O2—C3—C4—N11.7 (4)O2—C3—C8—C7175.6 (2)
C8—C3—C4—N1178.1 (2)C4—C3—C8—C70.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.002.844 (3)166
Symmetry code: (i) x+3, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC8H6ClNO2
Mr183.59
Crystal system, space groupOrthorhombic, P212121
Temperature (K)273
a, b, c (Å)4.5359 (6), 7.700 (1), 21.281 (3)
V3)743.28 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.46
Crystal size (mm)0.12 × 0.10 × 0.06
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.878, 0.973
No. of measured, independent and
observed [I > 2σ(I)] reflections
3857, 1314, 1143
Rint0.047
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.088, 1.07
No. of reflections1314
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.21
Absolute structureFlack (1983), 500 Friedel pairs
Absolute structure parameter0.06 (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···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.002.844 (3)166
Symmetry code: (i) x+3, y1/2, z+3/2.
 

References

First citationBruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHuang, 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
First citationMacchiarulo, 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
First citationPang, 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
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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