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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1019.
Published online 2009 April 10. doi:  10.1107/S1600536809012586
PMCID: PMC2977705

4-Benzyl-7-chloro-2H-1,4-benz­oxazin-3(4H)-one

Abstract

In the title compound, C15H12ClNO2, the two benzene rings are nearly perpendicular to each other [dihedral angle = 89.99 (13)°]. The O atom of the six-membered heterocyclic ring is disordered over two sites in a ratio of 0.46 (4):0.54 (4) and is displaced from the mean plane formed by other five atoms, resulting an envelope conformation of the six-membered hetercycle ring.

Related literature

For the biological activity of benzo[b][1,4]oxazin-3(4H)-ones, see: Frechette & Weidner-Wells (1997 [triangle]); Maag et al. (2004 [triangle]). For the synthesis of benzo[b][1,4]oxazin-3(4H)-ones, see: Zuo et al. (2008 [triangle]). For a related structure, see: Cao et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1019-scheme1.jpg

Experimental

Crystal data

  • C15H12ClNO2
  • M r = 273.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1019-efi1.jpg
  • a = 5.0894 (11) Å
  • b = 12.630 (3) Å
  • c = 20.070 (4) Å
  • β = 91.833 (4)°
  • V = 1289.4 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 298 K
  • 0.16 × 0.14 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.955, T max = 0.971
  • 6606 measured reflections
  • 2268 independent reflections
  • 1402 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.121
  • S = 1.02
  • 2268 reflections
  • 182 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker 2005 [triangle]); cell refinement: SAINT (Bruker 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809012586/xu2496sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012586/xu2496Isup2.hkl

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

Acknowledgments

This study was supported by the Key Program Projects of the Municipal Natural Science Foundation of Chongqing, China (grant No. CSTC,2007AC1042).

supplementary crystallographic information

Comment

Benzo[b][1,4]oxazin-3(4H)-ones are an important class of heteroaromatic ring systems that have shown to exhibit a wide range of biological activities such as antimicrobial (Frechette & Weidner-Wells, 1997) and selective 5-HT6 antagonistic activities (Maag et al., 2004). Due to its extensive biological application, the efficient synthesis of benzo[b][1,4]oxazin-3(4H)-ones has recently received much attention (Zuo et al., 2008). We report here the crystal structure of the title compound (Fig. 1). All bond lengths and angles are normal. The dihedral angle between the two benzene rings is 89.99 (13)°. The crystal packing is mainly stabilized by van der Waals interactions. In the title compound the six-membered heterocyclic ring is envelope conformation while in the related compound (Cao et al., 2004) it adopts a screw-boat conformation.

Experimental

To the solution of N-benzyl-2-(2,4-dichlorophenoxy)acetamide (0.620 g, 2.0 mmol) in DMF (20 ml), caesium carbonate (0.787 g, 2.4 mmol) was added. The mixture was refluxed for 2 h. After completion of the reaction (by TLC monitoring), the DMF was removed under vacuum. Water (20 ml) was added into the residue to obtain a turbid solution and it was extracted by ethyl acetate (20 ml x 4). The combined organic layer was washed by 1 mol/L of hydrochloric acid (10 ml x 3) and saturated sodium chloride solution (10 ml x 3), dried over MgSO4. And then the mixture was filtered and the filtrate was concentrated under reduced pressure to obtain the corresponding crude product. The product was purified by column chromatography on silica gel using ethyl acetate/hexane = 1/5 as eluent (yield 70%). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid dissolved in ethyl acetate/hexane at room temperature for 10 days.

Refinement

H atoms were positioned geometrically with C—H = 0.93–0.97 Å and refined in the riding-model approximation with Uiso(H) = 1.2Ueq(C). The O2 atom is disordered over two sites with a ratio of 0.46 (4):0.54 (4).

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Crystal data

C15H12ClNO2F(000) = 568
Mr = 273.71Dx = 1.410 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1156 reflections
a = 5.0894 (11) Åθ = 2.6–20.8°
b = 12.630 (3) ŵ = 0.29 mm1
c = 20.070 (4) ÅT = 298 K
β = 91.833 (4)°Block, colorless
V = 1289.4 (5) Å30.16 × 0.14 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2268 independent reflections
Radiation source: fine-focus sealed tube1402 reflections with I > 2σ(I)
graphiteRint = 0.031
[var phi] and ω scansθmax = 25.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −6→6
Tmin = 0.955, Tmax = 0.971k = −15→10
6606 measured reflectionsl = −23→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1942P] where P = (Fo2 + 2Fc2)/3
2268 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
Cl11.04449 (14)0.70775 (6)0.03801 (4)0.0845 (3)
O1−0.0247 (4)0.38796 (16)0.23334 (10)0.0903 (6)
O20.459 (4)0.4090 (11)0.1102 (14)0.079 (4)0.46 (4)
O2'0.358 (5)0.4386 (16)0.0928 (5)0.085 (4)0.54 (4)
N10.2417 (4)0.52888 (17)0.21372 (9)0.0620 (5)
C10.8090 (5)0.6568 (2)0.09015 (12)0.0620 (7)
C20.6971 (5)0.5605 (2)0.07550 (13)0.0723 (7)
H20.74540.52330.03780.087*
C30.5134 (5)0.5196 (2)0.11685 (13)0.0679 (7)
C40.4348 (5)0.57338 (19)0.17315 (11)0.0567 (6)
C50.5528 (6)0.6694 (2)0.18658 (13)0.0715 (8)
H50.50580.70700.22420.086*
C60.7390 (6)0.7116 (2)0.14561 (14)0.0765 (8)
H60.81610.77670.15560.092*
C70.2299 (8)0.3790 (2)0.13820 (16)0.0967 (10)
H7A0.24460.30400.14810.116*0.46 (4)
H7B0.09130.38650.10420.116*0.46 (4)
H7'A0.32530.31620.15280.116*0.54 (4)
H7'B0.07570.35440.11310.116*0.54 (4)
C80.1376 (6)0.4322 (2)0.19949 (14)0.0713 (7)
C90.1563 (5)0.5849 (2)0.27351 (12)0.0673 (7)
H9A−0.01180.55640.28620.081*
H9B0.13060.65910.26260.081*
C100.3484 (4)0.57652 (19)0.33223 (11)0.0534 (6)
C110.5208 (5)0.4939 (2)0.34046 (13)0.0684 (7)
H110.52480.44070.30850.082*
C120.6897 (6)0.4889 (2)0.39610 (16)0.0849 (9)
H120.80710.43280.40100.102*
C130.6842 (6)0.5657 (3)0.44339 (14)0.0797 (8)
H130.79620.56160.48080.096*
C140.5167 (6)0.6478 (3)0.43615 (14)0.0819 (9)
H140.51420.70070.46830.098*
C150.3484 (5)0.6531 (2)0.38073 (14)0.0748 (8)
H150.23270.70980.37630.090*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0817 (5)0.0935 (6)0.0780 (5)−0.0153 (4)0.0008 (4)0.0149 (4)
O10.0999 (15)0.0831 (13)0.0889 (14)−0.0188 (12)0.0197 (12)0.0042 (11)
O20.081 (6)0.055 (5)0.103 (8)−0.012 (4)0.024 (6)−0.024 (5)
O2'0.111 (9)0.085 (6)0.062 (3)−0.030 (6)0.014 (4)−0.019 (3)
N10.0640 (13)0.0662 (13)0.0556 (12)−0.0020 (11)−0.0015 (10)−0.0049 (10)
C10.0630 (16)0.0635 (16)0.0585 (15)−0.0031 (13)−0.0109 (13)0.0075 (13)
C20.0794 (18)0.0759 (19)0.0618 (16)−0.0103 (15)0.0068 (14)−0.0117 (14)
C30.0764 (18)0.0629 (16)0.0642 (16)−0.0124 (14)−0.0004 (14)−0.0120 (14)
C40.0628 (15)0.0569 (15)0.0497 (14)−0.0002 (13)−0.0074 (12)0.0003 (12)
C50.098 (2)0.0594 (16)0.0570 (15)−0.0021 (15)0.0018 (15)−0.0067 (13)
C60.099 (2)0.0597 (16)0.0709 (18)−0.0122 (16)−0.0035 (16)0.0018 (15)
C70.135 (3)0.0709 (19)0.085 (2)−0.024 (2)0.028 (2)−0.0136 (18)
C80.0770 (19)0.0689 (18)0.0678 (17)−0.0049 (16)−0.0007 (15)0.0044 (15)
C90.0586 (15)0.0778 (18)0.0653 (16)0.0050 (13)0.0013 (13)−0.0107 (14)
C100.0501 (14)0.0603 (15)0.0501 (13)0.0006 (12)0.0070 (11)0.0018 (12)
C110.0787 (18)0.0624 (16)0.0640 (17)0.0060 (14)0.0017 (14)0.0003 (13)
C120.094 (2)0.075 (2)0.085 (2)0.0196 (16)−0.0067 (18)0.0158 (17)
C130.086 (2)0.094 (2)0.0594 (17)−0.0009 (18)−0.0062 (14)0.0101 (17)
C140.083 (2)0.097 (2)0.0655 (18)−0.0023 (18)−0.0002 (16)−0.0212 (17)
C150.0673 (17)0.0811 (19)0.0758 (18)0.0175 (14)0.0001 (15)−0.0147 (16)

Geometric parameters (Å, °)

Cl1—C11.739 (3)C7—H7A0.9700
O1—C81.222 (3)C7—H7B0.9700
O2—C71.363 (11)C7—H7'A0.9700
O2—C31.429 (11)C7—H7'B0.9700
O2'—C71.363 (9)C9—C101.511 (3)
O2'—C31.372 (9)C9—H9A0.9700
N1—C81.357 (3)C9—H9B0.9700
N1—C41.413 (3)C10—C111.370 (3)
N1—C91.471 (3)C10—C151.372 (3)
C1—C61.368 (4)C11—C121.389 (4)
C1—C21.370 (3)C11—H110.9300
C2—C31.371 (3)C12—C131.357 (4)
C2—H20.9300C12—H120.9300
C3—C41.388 (3)C13—C141.348 (4)
C4—C51.376 (3)C13—H130.9300
C5—C61.381 (4)C14—C151.384 (4)
C5—H50.9300C14—H140.9300
C6—H60.9300C15—H150.9300
C7—C81.491 (4)
C7—O2—C3113.6 (7)O2'—C7—H7'A114.1
C7—O2'—C3117.4 (6)C8—C7—H7'A106.6
C8—N1—C4120.7 (2)H7B—C7—H7'A129.7
C8—N1—C9118.7 (2)O2—C7—H7'B124.2
C4—N1—C9120.5 (2)O2'—C7—H7'B103.0
C6—C1—C2120.4 (3)C8—C7—H7'B107.6
C6—C1—Cl1120.3 (2)H7A—C7—H7'B81.4
C2—C1—Cl1119.3 (2)H7'A—C7—H7'B106.6
C1—C2—C3119.4 (2)O1—C8—N1124.1 (3)
C1—C2—H2120.3O1—C8—C7119.3 (3)
C3—C2—H2120.3N1—C8—C7116.6 (3)
C2—C3—O2'117.7 (5)N1—C9—C10113.70 (19)
C2—C3—C4121.9 (2)N1—C9—H9A108.8
O2'—C3—C4118.2 (8)C10—C9—H9A108.8
C2—C3—O2116.5 (5)N1—C9—H9B108.8
C4—C3—O2119.5 (8)C10—C9—H9B108.8
C5—C4—C3117.1 (2)H9A—C9—H9B107.7
C5—C4—N1123.0 (2)C11—C10—C15117.8 (2)
C3—C4—N1119.9 (2)C11—C10—C9122.9 (2)
C4—C5—C6121.8 (3)C15—C10—C9119.3 (2)
C4—C5—H5119.1C10—C11—C12120.6 (3)
C6—C5—H5119.1C10—C11—H11119.7
C1—C6—C5119.4 (3)C12—C11—H11119.7
C1—C6—H6120.3C13—C12—C11120.2 (3)
C5—C6—H6120.3C13—C12—H12119.9
O2—C7—C8120.6 (7)C11—C12—H12119.9
O2'—C7—C8118.1 (8)C14—C13—C12120.1 (3)
O2—C7—H7A107.2C14—C13—H13120.0
O2'—C7—H7A129.9C12—C13—H13120.0
C8—C7—H7A107.2C13—C14—C15119.8 (3)
O2—C7—H7B107.2C13—C14—H14120.1
O2'—C7—H7B80.1C15—C14—H14120.1
C8—C7—H7B107.2C10—C15—C14121.5 (3)
H7A—C7—H7B106.8C10—C15—H15119.3
O2—C7—H7'A85.8C14—C15—H15119.3
C6—C1—C2—C30.2 (4)C4—C5—C6—C10.0 (4)
Cl1—C1—C2—C3179.3 (2)C3—O2—C7—O2'60.5 (13)
C1—C2—C3—O2'163.7 (15)C3—O2—C7—C8−34 (3)
C1—C2—C3—C40.6 (4)C3—O2'—C7—O2−69.5 (14)
C1—C2—C3—O2−163.1 (15)C3—O2'—C7—C834 (3)
C7—O2'—C3—C2162.2 (16)C4—N1—C8—O1178.0 (2)
C7—O2'—C3—C4−34 (3)C9—N1—C8—O10.1 (4)
C7—O2'—C3—O266.7 (14)C4—N1—C8—C7−2.3 (4)
C7—O2—C3—C2−162.9 (15)C9—N1—C8—C7179.8 (2)
C7—O2—C3—O2'−62.9 (13)O2—C7—C8—O1−160.9 (16)
C7—O2—C3—C433 (3)O2'—C7—C8—O1164.1 (14)
C2—C3—C4—C5−1.1 (4)O2—C7—C8—N119.4 (17)
O2'—C3—C4—C5−164.0 (13)O2'—C7—C8—N1−15.6 (15)
O2—C3—C4—C5162.1 (14)C8—N1—C9—C10100.5 (3)
C2—C3—C4—N1179.0 (2)C4—N1—C9—C10−77.4 (3)
O2'—C3—C4—N116.0 (14)N1—C9—C10—C11−25.9 (3)
O2—C3—C4—N1−17.9 (14)N1—C9—C10—C15155.7 (2)
C8—N1—C4—C5−177.8 (2)C15—C10—C11—C12−0.3 (4)
C9—N1—C4—C50.1 (3)C9—C10—C11—C12−178.7 (3)
C8—N1—C4—C32.1 (3)C10—C11—C12—C130.6 (4)
C9—N1—C4—C3−180.0 (2)C11—C12—C13—C14−0.8 (5)
C3—C4—C5—C60.8 (4)C12—C13—C14—C150.7 (5)
N1—C4—C5—C6−179.3 (2)C11—C10—C15—C140.2 (4)
C2—C1—C6—C5−0.5 (4)C9—C10—C15—C14178.6 (2)
Cl1—C1—C6—C5−179.6 (2)C13—C14—C15—C10−0.4 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2496).

References

  • Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cao, D.-Y., Chen, L.-G., Song, J., Feng, R.-X. & Lou, K.-X. (2004). Acta Cryst. E60, o1788–o1789.
  • Frechette, R. & Weidner-Wells, M. A. (1997). WO Patent No. 9 717 333.
  • Maag, H., Sui, M. & Zhao, S. H. (2004). WO Patent No. 20 04 041 792.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zuo, H., Meng, L. J., Ghate, M., Hwang, K., Cho, Y. K., Chandrasekhar, S., Raji Reddy, Ch. & Shin, D. S. (2008). Tetrahedron Lett.49, 3827–3830.

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