5-Nitro-1-benzofuran-2(3H)-one

Han, X.-Y.; Shi, Y.-B.; Shen, H.; Bai, S.-Y.; Wang, H.-B.

doi:10.1107/S1600536812025093

organic compounds

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Volume 68| Part 7| July 2012| Page o2029

https://doi.org/10.1107/S1600536812025093

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5-Nitro-1-benzofuran-2(3H)-one

Xin-Yi Han,^a,^b Ya-Bin Shi,^a,^b Hong Shen,^a,^b Shu-Yuan Bai ^a,^b and Hai-Bo Wang ^b ^*

^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 ). For the synthetic procedure, see: Munoz-Muniz & Juaristi (2003 ). For standard bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₅NO₄
M_r = 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 ) T_min = 0.962, T_max = 0.987
2234 measured reflections
1362 independent reflections
1063 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: CAD-4 EXPRESS; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812025093/yk2051sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025093/yk2051Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025093/yk2051Isup3.cml

checkCIF report

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.

Structure description top

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

	Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	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

C₈H₅NO₄	F(000) = 368
M_r = 179.13	D_x = 1.595 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 453 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4510 (15) Å	Cell parameters from 25 reflections
b = 8.9150 (18) Å	θ = 10–14°
c = 11.249 (2) Å	µ = 0.13 mm⁻¹
β = 93.45 (3)°	T = 293 K
V = 745.9 (3) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1063 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
Graphite monochromator	θ_max = 25.4°, θ_min = 2.7°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −4→10
T_min = 0.962, T_max = 0.987	l = −13→13
2234 measured reflections	3 standard reflections every 200 reflections
1362 independent reflections	intensity decay: 1%

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.1P)² + 0.045P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1362 reflections	Δρ_max = 0.22 e Å⁻³
119 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (7)

Crystal data top

C₈H₅NO₄	V = 745.9 (3) Å³
M_r = 179.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4510 (15) Å	µ = 0.13 mm⁻¹
b = 8.9150 (18) Å	T = 293 K
c = 11.249 (2) Å	0.30 × 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)	R_int = 0.039
T_min = 0.962, T_max = 0.987	3 standard reflections every 200 reflections
2234 measured reflections	intensity decay: 1%
1362 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
1362 reflections	Δρ_min = −0.20 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N	0.8821 (2)	0.70812 (19)	1.15062 (16)	0.0546 (5)
O2	0.6163 (2)	0.01034 (17)	0.87673 (13)	0.0722 (5)
C2	0.6559 (3)	0.1292 (2)	0.91761 (18)	0.0539 (5)
O1	0.62020 (18)	0.25817 (15)	0.85172 (12)	0.0545 (4)
C8	0.6802 (2)	0.3797 (2)	0.91898 (15)	0.0433 (5)
O3	0.9499 (2)	0.67114 (19)	1.24720 (15)	0.0811 (6)
C9	0.7562 (2)	0.33732 (19)	1.02933 (14)	0.0404 (5)
O4	0.8753 (3)	0.83771 (18)	1.11869 (17)	0.1003 (7)
C3	0.7447 (3)	0.1713 (2)	1.03692 (16)	0.0535 (5)
H3A	0.6724	0.1404	1.1015	0.064*
H3B	0.8632	0.1266	1.0482	0.064*
C7	0.6656 (3)	0.5261 (2)	0.88133 (16)	0.0510 (5)
H7A	0.6133	0.5509	0.8068	0.061*
C6	0.7322 (2)	0.6344 (2)	0.95957 (16)	0.0499 (5)
H6A	0.7259	0.7352	0.9385	0.060*
C5	0.8087 (2)	0.59213 (19)	1.06991 (15)	0.0426 (5)
C4	0.8230 (2)	0.4451 (2)	1.10729 (15)	0.0417 (5)
H4A	0.8755	0.4201	1.1818	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0607 (10)	0.0423 (10)	0.0606 (11)	−0.0029 (7)	0.0005 (8)	−0.0091 (8)
O2	0.0933 (12)	0.0518 (10)	0.0695 (9)	−0.0181 (8)	−0.0122 (8)	−0.0149 (8)
C2	0.0595 (11)	0.0472 (11)	0.0541 (11)	−0.0113 (9)	−0.0035 (9)	−0.0039 (9)
O1	0.0621 (8)	0.0549 (9)	0.0445 (8)	−0.0074 (6)	−0.0134 (6)	−0.0041 (6)
C8	0.0433 (9)	0.0457 (11)	0.0401 (9)	−0.0042 (8)	−0.0045 (7)	−0.0030 (7)
O3	0.1034 (13)	0.0622 (10)	0.0728 (10)	−0.0035 (9)	−0.0338 (9)	−0.0167 (8)
C9	0.0400 (9)	0.0397 (9)	0.0405 (9)	−0.0032 (7)	−0.0051 (7)	0.0012 (7)
O4	0.170 (2)	0.0362 (9)	0.0916 (13)	−0.0105 (10)	−0.0194 (12)	−0.0042 (9)
C3	0.0669 (12)	0.0421 (10)	0.0495 (10)	−0.0091 (9)	−0.0121 (9)	0.0013 (8)
C7	0.0555 (11)	0.0544 (12)	0.0418 (9)	0.0021 (9)	−0.0089 (8)	0.0076 (8)
C6	0.0540 (11)	0.0416 (10)	0.0540 (11)	0.0044 (8)	0.0021 (8)	0.0069 (8)
C5	0.0394 (9)	0.0399 (10)	0.0483 (10)	0.0002 (7)	−0.0004 (7)	−0.0032 (8)
C4	0.0419 (9)	0.0421 (10)	0.0402 (9)	−0.0017 (7)	−0.0060 (7)	0.0005 (7)

Geometric parameters (Å, º) top

N—O4	1.210 (2)	C9—C3	1.485 (2)
N—O3	1.216 (2)	C3—H3A	0.9700
N—C5	1.460 (2)	C3—H3B	0.9700
O2—C2	1.185 (2)	C7—C6	1.379 (3)
C2—O1	1.385 (2)	C7—H7A	0.9300
C2—C3	1.508 (3)	C6—C5	1.387 (2)
O1—C8	1.380 (2)	C6—H6A	0.9300
C8—C7	1.374 (2)	C5—C4	1.378 (3)
C8—C9	1.385 (2)	C4—H4A	0.9300
C9—C4	1.374 (2)

O4—N—O3	122.14 (18)	C9—C3—H3B	111.2
O4—N—C5	118.95 (17)	C2—C3—H3B	111.2
O3—N—C5	118.91 (17)	H3A—C3—H3B	109.1
O2—C2—O1	119.93 (17)	C8—C7—C6	116.70 (17)
O2—C2—C3	130.8 (2)	C8—C7—H7A	121.6
O1—C2—C3	109.23 (15)	C6—C7—H7A	121.6
C8—O1—C2	108.23 (13)	C7—C6—C5	119.61 (17)
C7—C8—O1	124.00 (15)	C7—C6—H6A	120.2
C7—C8—C9	123.75 (17)	C5—C6—H6A	120.2
O1—C8—C9	112.24 (15)	C4—C5—C6	123.47 (16)
C4—C9—C8	119.60 (16)	C4—C5—N	117.66 (16)
C4—C9—C3	132.86 (15)	C6—C5—N	118.85 (16)
C8—C9—C3	107.55 (15)	C9—C4—C5	116.86 (16)
C9—C3—C2	102.75 (15)	C9—C4—H4A	121.6
C9—C3—H3A	111.2	C5—C4—H4A	121.6
C2—C3—H3A	111.2

O2—C2—O1—C8	−179.61 (18)	C9—C8—C7—C6	0.3 (3)
C3—C2—O1—C8	0.4 (2)	C8—C7—C6—C5	−0.1 (3)
C2—O1—C8—C7	−179.64 (16)	C7—C6—C5—C4	0.1 (3)
C2—O1—C8—C9	0.0 (2)	C7—C6—C5—N	178.69 (16)
C7—C8—C9—C4	−0.5 (3)	O4—N—C5—C4	178.15 (17)
O1—C8—C9—C4	179.89 (14)	O3—N—C5—C4	−1.0 (2)
C7—C8—C9—C3	179.23 (17)	O4—N—C5—C6	−0.5 (3)
O1—C8—C9—C3	−0.40 (19)	O3—N—C5—C6	−179.70 (17)
C4—C9—C3—C2	−179.74 (18)	C8—C9—C4—C5	0.4 (2)
C8—C9—C3—C2	0.61 (18)	C3—C9—C4—C5	−179.21 (17)
O2—C2—C3—C9	179.4 (2)	C6—C5—C4—C9	−0.2 (3)
O1—C2—C3—C9	−0.6 (2)	N—C5—C4—C9	−178.85 (14)
O1—C8—C7—C6	179.91 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱ	0.97	2.56	3.334 (3)	137

Symmetry code: (i) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₈H₅NO₄
M_r	179.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4510 (15), 8.9150 (18), 11.249 (2)
β (°)	93.45 (3)
V (Å³)	745.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.962, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	2234, 1362, 1063
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.146, 1.00
No. of reflections	1362
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱ	0.9700	2.5600	3.334 (3)	137.00

Symmetry code: (i) −x+1, −y, −z+2.

References

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. CSD CrossRef Web of Science Google Scholar
Enraf–Nonius (1993). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany. Google Scholar
Katritzky, A. R., Ji, F.-B., Fan, W.-Q. & Beretta, P. (1992). J. Heterocycl. Chem. 29, 1519–1523. CrossRef CAS Google Scholar
Munoz-Muniz, O. & Juaristi, E. (2003). Tetrahedron, 59, 4223–4229. CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2029

https://doi.org/10.1107/S1600536812025093

Open

access