organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

5-Nitro-1-benzo­furan-2(3H)-one

aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and bCollege of Food Science and Light Industry, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 23 March 2012; accepted 1 June 2012; online 13 June 2012)

In the crystal structure of the title compound, C8H5NO4, essentially planar mol­ecules [largest deviation from the least-squares plane = 0.030 (2) Å] form stacks along the a-axis direction. Intercentroid separations between overlapping benzene rings within the stack are 3.6594 (12) Å and 3.8131 (12) Å. Mol­ecules from neighboring stacks are linked by weak C—H⋯O hydrogen bonds into inversion dimers.

Related literature

The title compound is an inter­mediate in the synthesis of the drug dronedarone [systematic (name: N-(2-butyl-3-(p-(3-(di­butyl­amino)­prop­oxy)benzo­yl)-5-benzofuran­yl)methane­sulf­on­amide, which has been used in the treatment of atrial fibrillation and atrial flutter. For applications of the title compound in drug discovery, see: Katritzky et al. (1992[Katritzky, A. R., Ji, F.-B., Fan, W.-Q. & Beretta, P. (1992). J. Heterocycl. Chem. 29, 1519-1523.]). For the synthetic procedure, see: Munoz-Muniz & Juaristi (2003[Munoz-Muniz, O. & Juaristi, E. (2003). Tetrahedron, 59, 4223-4229.]). For standard bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C8H5NO4

  • Mr = 179.13

  • Monoclinic, P 21 /c

  • a = 7.4510 (15) Å

  • b = 8.9150 (18) Å

  • c = 11.249 (2) Å

  • β = 93.45 (3)°

  • V = 745.9 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.13 mm−1

  • T = 293 K

  • 0.30 × 0.20 × 0.10 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.962, Tmax = 0.987

  • 2234 measured reflections

  • 1362 independent reflections

  • 1063 reflections with I > 2σ(I)

  • Rint = 0.039

  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.146

  • S = 1.00

  • 1362 reflections

  • 119 parameters

  • H-atom parameters constrained

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3A⋯O2i 0.97 2.56 3.334 (3) 137
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1993[Enraf-Nonius (1993). CAD-4 EXPRESS. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996[Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

The title compound, C8H5NO4 (Fig. 1), is an important pharmaceutical intermediate (Munoz-Muniz & Juaristi, 2003). We report here its crystal structure. All bond lengths and angles lie within the expected ranges (Allen et al., 1987). In the crystal structure, the molecules are joined by π-π interactions and weak C-H···O hydrogen bonds (Fig. 2).

Related literature top

The title compound is an intermediate in the synthesis of dronedarone [systematic (name: N-(2-butyl-3-(p-(3-(dibutylamino)propoxy)benzoyl)-5-benzofuranyl)methanesulfonamide, a drug recommended for the treatment of atrial fibrillation and atrial flutter. For applications of the title compound in drug discovery, see: Katritzky et al. (1992). For the synthetic procedure, see: Munoz-Muniz & Juaristi (2003). For standard bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, 5-nitro-1-benzofuran-2(3H)-one, was prepared by the literature method (Munoz-Muniz & Juaristi, 2003). To a 100 mL flask provided with Dean–Stark tramp and magnetic stirrer was added 2-hydroxyphenyl- acetic acid (4.4 g, 29 mmol) in 60 mL of toluene and catalytic amounts of p-TsOH. The mixture was refluxed for 4 h with removal of water and then the residual solvent was removed at reduced pressure to give 3H-benzofuran-2-one in quantitative yield (3.9 g), mp 325K. Then, a mixture of 65% nitric acid (4 ml) and glacial acetic acid (4 ml) was added dropwise to a solution of 3H-benzofuran-2-one (3.9 g) in acetic anhydride (25 ml) while the temperature was maintained below 293K. The mixture was stirred and refluxed for 1 hour and decomposed with ice and sulfuric acid. The precipitate was filtered off. Pure 5-nitro-1-benzofuran-2(3H)-one was obtained by recrystallisation from ethyl acetate, yield 70%. Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement top

All H atoms were positioned geometrically, with C—H = 0.93, 0.98 and 0.96 Å for aromatic, methine and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Structure description top

The title compound, C8H5NO4 (Fig. 1), is an important pharmaceutical intermediate (Munoz-Muniz & Juaristi, 2003). We report here its crystal structure. All bond lengths and angles lie within the expected ranges (Allen et al., 1987). In the crystal structure, the molecules are joined by π-π interactions and weak C-H···O hydrogen bonds (Fig. 2).

The title compound is an intermediate in the synthesis of dronedarone [systematic (name: N-(2-butyl-3-(p-(3-(dibutylamino)propoxy)benzoyl)-5-benzofuranyl)methanesulfonamide, a drug recommended for the treatment of atrial fibrillation and atrial flutter. For applications of the title compound in drug discovery, see: Katritzky et al. (1992). For the synthetic procedure, see: Munoz-Muniz & Juaristi (2003). For standard bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1993); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1993); data reduction: XCAD4 (Harms & Wocadlo, 1996); 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: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
5-Nitro-1-benzofuran-2(3H)-one top
Crystal data top
C8H5NO4F(000) = 368
Mr = 179.13Dx = 1.595 Mg m3
Monoclinic, P21/cMelting point: 453 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.4510 (15) ÅCell parameters from 25 reflections
b = 8.9150 (18) Åθ = 10–14°
c = 11.249 (2) ŵ = 0.13 mm1
β = 93.45 (3)°T = 293 K
V = 745.9 (3) Å3Block, yellow
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1063 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
Graphite monochromatorθmax = 25.4°, θmin = 2.7°
ω/2θ scansh = 08
Absorption correction: ψ scan
(North et al., 1968)
k = 410
Tmin = 0.962, Tmax = 0.987l = 1313
2234 measured reflections3 standard reflections every 200 reflections
1362 independent reflections intensity decay: 1%
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)] = 0.046H-atom parameters constrained
wR(F2) = 0.146 w = 1/[σ2(Fo2) + (0.1P)2 + 0.045P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1362 reflectionsΔρmax = 0.22 e Å3
119 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.032 (7)
Crystal data top
C8H5NO4V = 745.9 (3) Å3
Mr = 179.13Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.4510 (15) ŵ = 0.13 mm1
b = 8.9150 (18) ÅT = 293 K
c = 11.249 (2) Å0.30 × 0.20 × 0.10 mm
β = 93.45 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1063 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.039
Tmin = 0.962, Tmax = 0.9873 standard reflections every 200 reflections
2234 measured reflections intensity decay: 1%
1362 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 1.00Δρmax = 0.22 e Å3
1362 reflectionsΔρmin = 0.20 e Å3
119 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
xyzUiso*/Ueq
N0.8821 (2)0.70812 (19)1.15062 (16)0.0546 (5)
O20.6163 (2)0.01034 (17)0.87673 (13)0.0722 (5)
C20.6559 (3)0.1292 (2)0.91761 (18)0.0539 (5)
O10.62020 (18)0.25817 (15)0.85172 (12)0.0545 (4)
C80.6802 (2)0.3797 (2)0.91898 (15)0.0433 (5)
O30.9499 (2)0.67114 (19)1.24720 (15)0.0811 (6)
C90.7562 (2)0.33732 (19)1.02933 (14)0.0404 (5)
O40.8753 (3)0.83771 (18)1.11869 (17)0.1003 (7)
C30.7447 (3)0.1713 (2)1.03692 (16)0.0535 (5)
H3A0.67240.14041.10150.064*
H3B0.86320.12661.04820.064*
C70.6656 (3)0.5261 (2)0.88133 (16)0.0510 (5)
H7A0.61330.55090.80680.061*
C60.7322 (2)0.6344 (2)0.95957 (16)0.0499 (5)
H6A0.72590.73520.93850.060*
C50.8087 (2)0.59213 (19)1.06991 (15)0.0426 (5)
C40.8230 (2)0.4451 (2)1.10729 (15)0.0417 (5)
H4A0.87550.42011.18180.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N0.0607 (10)0.0423 (10)0.0606 (11)0.0029 (7)0.0005 (8)0.0091 (8)
O20.0933 (12)0.0518 (10)0.0695 (9)0.0181 (8)0.0122 (8)0.0149 (8)
C20.0595 (11)0.0472 (11)0.0541 (11)0.0113 (9)0.0035 (9)0.0039 (9)
O10.0621 (8)0.0549 (9)0.0445 (8)0.0074 (6)0.0134 (6)0.0041 (6)
C80.0433 (9)0.0457 (11)0.0401 (9)0.0042 (8)0.0045 (7)0.0030 (7)
O30.1034 (13)0.0622 (10)0.0728 (10)0.0035 (9)0.0338 (9)0.0167 (8)
C90.0400 (9)0.0397 (9)0.0405 (9)0.0032 (7)0.0051 (7)0.0012 (7)
O40.170 (2)0.0362 (9)0.0916 (13)0.0105 (10)0.0194 (12)0.0042 (9)
C30.0669 (12)0.0421 (10)0.0495 (10)0.0091 (9)0.0121 (9)0.0013 (8)
C70.0555 (11)0.0544 (12)0.0418 (9)0.0021 (9)0.0089 (8)0.0076 (8)
C60.0540 (11)0.0416 (10)0.0540 (11)0.0044 (8)0.0021 (8)0.0069 (8)
C50.0394 (9)0.0399 (10)0.0483 (10)0.0002 (7)0.0004 (7)0.0032 (8)
C40.0419 (9)0.0421 (10)0.0402 (9)0.0017 (7)0.0060 (7)0.0005 (7)
Geometric parameters (Å, º) top
N—O41.210 (2)C9—C31.485 (2)
N—O31.216 (2)C3—H3A0.9700
N—C51.460 (2)C3—H3B0.9700
O2—C21.185 (2)C7—C61.379 (3)
C2—O11.385 (2)C7—H7A0.9300
C2—C31.508 (3)C6—C51.387 (2)
O1—C81.380 (2)C6—H6A0.9300
C8—C71.374 (2)C5—C41.378 (3)
C8—C91.385 (2)C4—H4A0.9300
C9—C41.374 (2)
O4—N—O3122.14 (18)C9—C3—H3B111.2
O4—N—C5118.95 (17)C2—C3—H3B111.2
O3—N—C5118.91 (17)H3A—C3—H3B109.1
O2—C2—O1119.93 (17)C8—C7—C6116.70 (17)
O2—C2—C3130.8 (2)C8—C7—H7A121.6
O1—C2—C3109.23 (15)C6—C7—H7A121.6
C8—O1—C2108.23 (13)C7—C6—C5119.61 (17)
C7—C8—O1124.00 (15)C7—C6—H6A120.2
C7—C8—C9123.75 (17)C5—C6—H6A120.2
O1—C8—C9112.24 (15)C4—C5—C6123.47 (16)
C4—C9—C8119.60 (16)C4—C5—N117.66 (16)
C4—C9—C3132.86 (15)C6—C5—N118.85 (16)
C8—C9—C3107.55 (15)C9—C4—C5116.86 (16)
C9—C3—C2102.75 (15)C9—C4—H4A121.6
C9—C3—H3A111.2C5—C4—H4A121.6
C2—C3—H3A111.2
O2—C2—O1—C8179.61 (18)C9—C8—C7—C60.3 (3)
C3—C2—O1—C80.4 (2)C8—C7—C6—C50.1 (3)
C2—O1—C8—C7179.64 (16)C7—C6—C5—C40.1 (3)
C2—O1—C8—C90.0 (2)C7—C6—C5—N178.69 (16)
C7—C8—C9—C40.5 (3)O4—N—C5—C4178.15 (17)
O1—C8—C9—C4179.89 (14)O3—N—C5—C41.0 (2)
C7—C8—C9—C3179.23 (17)O4—N—C5—C60.5 (3)
O1—C8—C9—C30.40 (19)O3—N—C5—C6179.70 (17)
C4—C9—C3—C2179.74 (18)C8—C9—C4—C50.4 (2)
C8—C9—C3—C20.61 (18)C3—C9—C4—C5179.21 (17)
O2—C2—C3—C9179.4 (2)C6—C5—C4—C90.2 (3)
O1—C2—C3—C90.6 (2)N—C5—C4—C9178.85 (14)
O1—C8—C7—C6179.91 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O2i0.972.563.334 (3)137
Symmetry code: (i) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC8H5NO4
Mr179.13
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)7.4510 (15), 8.9150 (18), 11.249 (2)
β (°) 93.45 (3)
V3)745.9 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.962, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
2234, 1362, 1063
Rint0.039
(sin θ/λ)max1)0.603
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.146, 1.00
No. of reflections1362
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.20

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1993), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O2i0.97002.56003.334 (3)137.00
Symmetry code: (i) x+1, y, z+2.
 

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CSD CrossRef Web of Science Google Scholar
First citationEnraf–Nonius (1993). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany.  Google Scholar
First citationKatritzky, A. R., Ji, F.-B., Fan, W.-Q. & Beretta, P. (1992). J. Heterocycl. Chem. 29, 1519–1523.  CrossRef CAS Google Scholar
First citationMunoz-Muniz, O. & Juaristi, E. (2003). Tetrahedron, 59, 4223–4229.  CAS Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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