2-Methyl-7-nitro-2,3-dihydro-1-benzofuran

Feng, M.-L.; Li, Y.-F.; Liu, S.; Yang, H.-Y.; Zhu, H.-J.

doi:10.1107/S1600536808017728

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1281

doi:10.1107/S1600536808017728

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2-Methyl-7-nitro-2,3-dihydro-1-benzofuran

Mei-Li Feng,^a Yu-Feng Li,^a Shan Liu,^a Hai-Yu Yang ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 4 June 2008; accepted 11 June 2008; online 19 June 2008)

The dihydrofuran ring of the title compound, C₉H₉NO₃, adopts an envelope conformation. The nitro group is twisted slightly away from the attached benzene ring [dihedral angle = 21.9 (1)°].

Related literature

For bond-length data, see: Allen et al. (1987 ). For details of the synthesis, see: Majumdar et al. (2008 ).

Experimental

Crystal data

C₉H₉NO₃
M_r = 179.17
Orthorhombic, P b c a
a = 8.4250 (17) Å
b = 7.2260 (14) Å
c = 28.295 (6) Å
V = 1722.6 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.969, T_max = 0.979
2977 measured reflections
1551 independent reflections
829 reflections with I > 2σ(I)
R_int = 0.048
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.182
S = 1.01
1551 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017728/ci2613sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017728/ci2613Isup2.hkl

checkCIF report

Comment top

The tittle compound, 2-methyl-7-nitro-2,3-dihydrobenzofuran, is an important intermediate for the synthesis of 2-methyl-2,3-dihydrobenzofuran-7-amine. we report here the crystal structure of the title compound.

The molecular structure of the compound is shown in Fig. 1. Bond lengths and angles are within normal ranges (Allen et al., 1987), except the C1—C2 bond length of 1.420 (6) Å. The dihydrofuran ring is in an envelope conformation with C2 as flap atom. The nitro group is slightly twisted away from the attached benzene ring [O2—N—C8—C9 = 5.3 (5)° and O3—N—C8—C7 = 5.9 (5)°]. No hydrogen bonding interactions are observed in the crystal structure (Fig.2).

Related literature top

For bond-length data, see: Allen et al. (1987). For details of the synthesis, see: Majumdar et al. (2008).

Experimental top

The title compound was synthesized according to the literature method (Majumdar et al., 2008). Single crystals were obtained by slow evaporation of a methanol (25 ml) solution of the compound (0.30 g, 1.6 mmol) at room temperature for about 4 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A view of the molecular packing in the title compound.

2-Methyl-7-nitro-2,3-dihydro-1-benzofuran top

Crystal data top

C₉H₉NO₃	F(000) = 752
M_r = 179.17	D_x = 1.382 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 8.4250 (17) Å	θ = 10–13°
b = 7.2260 (14) Å	µ = 0.11 mm⁻¹
c = 28.295 (6) Å	T = 298 K
V = 1722.6 (6) Å³	Block, colourless
Z = 8	0.30 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	829 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 25.2°, θ_min = 1.4°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.969, T_max = 0.979	l = 0→33
2977 measured reflections	3 standard reflections every 200 reflections
1551 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.06P)² + 1.5P] where P = (F_o² + 2F_c²)/3
1551 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₉H₉NO₃	V = 1722.6 (6) Å³
M_r = 179.17	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.4250 (17) Å	µ = 0.11 mm⁻¹
b = 7.2260 (14) Å	T = 298 K
c = 28.295 (6) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	829 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.048
T_min = 0.969, T_max = 0.979	3 standard reflections every 200 reflections
2977 measured reflections	intensity decay: none
1551 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.01	Δρ_max = 0.32 e Å⁻³
1551 reflections	Δρ_min = −0.26 e Å⁻³
118 parameters

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
N	0.5181 (3)	0.0623 (5)	0.39917 (10)	0.0581 (8)
O1	0.2624 (3)	0.0149 (4)	0.32787 (7)	0.0601 (8)
C1	0.1077 (6)	0.0403 (8)	0.25775 (16)	0.0970 (16)
H1A	0.1909	−0.0204	0.2405	0.146*
H1B	0.1258	0.1715	0.2576	0.146*
H1C	0.0074	0.0140	0.2431	0.146*
O2	0.5612 (3)	0.0409 (5)	0.35839 (9)	0.0867 (10)
C2	0.1064 (4)	−0.0249 (8)	0.30507 (14)	0.0812 (14)
H2A	0.0947	−0.1598	0.3038	0.097*
O3	0.6098 (3)	0.0689 (6)	0.43222 (10)	0.0992 (12)
C3	−0.0172 (4)	0.0473 (6)	0.33963 (14)	0.0706 (11)
H3A	−0.0614	0.1638	0.3289	0.085*
H3B	−0.1025	−0.0413	0.3438	0.085*
C4	0.0753 (4)	0.0725 (5)	0.38480 (12)	0.0532 (9)
C5	0.0285 (4)	0.1112 (5)	0.42971 (13)	0.0634 (10)
H5A	−0.0788	0.1240	0.4368	0.076*
C6	0.1416 (5)	0.1314 (6)	0.46479 (13)	0.0624 (10)
H6A	0.1093	0.1557	0.4956	0.075*
C7	0.3000 (4)	0.1164 (5)	0.45498 (12)	0.0560 (9)
H7A	0.3747	0.1319	0.4789	0.067*
C8	0.3491 (4)	0.0774 (5)	0.40863 (11)	0.0460 (8)
C9	0.2360 (4)	0.0537 (4)	0.37377 (11)	0.0459 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0376 (15)	0.085 (2)	0.0513 (17)	−0.0068 (16)	−0.0090 (16)	0.0044 (16)
O1	0.0358 (11)	0.104 (2)	0.0411 (12)	0.0006 (13)	−0.0058 (12)	−0.0061 (12)
C1	0.066 (3)	0.151 (5)	0.074 (3)	−0.004 (3)	−0.022 (3)	0.017 (3)
O2	0.0389 (13)	0.168 (3)	0.0530 (16)	0.0016 (17)	0.0045 (13)	−0.0016 (17)
C2	0.047 (2)	0.134 (4)	0.063 (2)	−0.004 (2)	−0.014 (2)	−0.002 (3)
O3	0.0446 (15)	0.176 (3)	0.0773 (19)	−0.0046 (19)	−0.0248 (16)	−0.009 (2)
C3	0.0399 (19)	0.098 (3)	0.074 (3)	−0.003 (2)	−0.009 (2)	−0.002 (2)
C4	0.0313 (16)	0.070 (2)	0.058 (2)	0.0012 (16)	0.0062 (16)	0.0053 (18)
C5	0.044 (2)	0.069 (3)	0.077 (3)	0.0068 (18)	0.009 (2)	0.004 (2)
C6	0.069 (2)	0.073 (2)	0.0458 (19)	0.006 (2)	0.011 (2)	−0.0021 (18)
C7	0.060 (2)	0.061 (2)	0.047 (2)	−0.0053 (19)	−0.0032 (18)	0.0004 (17)
C8	0.0352 (17)	0.060 (2)	0.0426 (18)	−0.0023 (15)	−0.0007 (15)	0.0044 (16)
C9	0.0375 (16)	0.0554 (19)	0.0447 (17)	−0.0043 (15)	−0.0028 (16)	0.0030 (16)

Geometric parameters (Å, º) top

N—O3	1.214 (4)	C3—H3A	0.97
N—O2	1.219 (3)	C3—H3B	0.97
N—C8	1.453 (4)	C4—C5	1.360 (5)
O1—C9	1.347 (4)	C4—C9	1.396 (4)
O1—C2	1.492 (4)	C5—C6	1.384 (5)
C1—C2	1.420 (6)	C5—H5A	0.93
C1—H1A	0.96	C6—C7	1.367 (5)
C1—H1B	0.96	C6—H6A	0.93
C1—H1C	0.96	C7—C8	1.404 (4)
C2—C3	1.520 (6)	C7—H7A	0.93
C2—H2A	0.98	C8—C9	1.382 (4)
C3—C4	1.508 (5)

O3—N—O2	123.0 (3)	C2—C3—H3B	111.1
O3—N—C8	118.6 (3)	H3A—C3—H3B	109.0
O2—N—C8	118.4 (3)	C5—C4—C9	120.7 (3)
C9—O1—C2	108.2 (3)	C5—C4—C3	131.8 (3)
C2—C1—H1A	109.5	C9—C4—C3	107.5 (3)
C2—C1—H1B	109.5	C4—C5—C6	119.5 (3)
H1A—C1—H1B	109.5	C4—C5—H5A	120.3
C2—C1—H1C	109.5	C6—C5—H5A	120.3
H1A—C1—H1C	109.5	C7—C6—C5	121.2 (3)
H1B—C1—H1C	109.5	C7—C6—H6A	119.4
C1—C2—O1	109.7 (4)	C5—C6—H6A	119.4
C1—C2—C3	119.9 (4)	C6—C7—C8	119.6 (3)
O1—C2—C3	105.0 (3)	C6—C7—H7A	120.2
C1—C2—H2A	107.2	C8—C7—H7A	120.2
O1—C2—H2A	107.2	C9—C8—C7	119.2 (3)
C3—C2—H2A	107.2	C9—C8—N	122.3 (3)
C4—C3—C2	103.5 (3)	C7—C8—N	118.4 (3)
C4—C3—H3A	111.1	O1—C9—C8	126.9 (3)
C2—C3—H3A	111.1	O1—C9—C4	113.3 (3)
C4—C3—H3B	111.1	C8—C9—C4	119.8 (3)

C9—O1—C2—C1	145.4 (4)	O2—N—C8—C9	5.3 (5)
C9—O1—C2—C3	15.4 (4)	O3—N—C8—C7	5.9 (5)
C1—C2—C3—C4	−139.3 (4)	O2—N—C8—C7	−175.1 (3)
O1—C2—C3—C4	−15.5 (5)	C2—O1—C9—C8	172.0 (4)
C2—C3—C4—C5	−170.7 (4)	C2—O1—C9—C4	−8.9 (4)
C2—C3—C4—C9	10.9 (5)	C7—C8—C9—O1	−179.7 (3)
C9—C4—C5—C6	−0.2 (6)	N—C8—C9—O1	0.0 (6)
C3—C4—C5—C6	−178.4 (4)	C7—C8—C9—C4	1.3 (5)
C4—C5—C6—C7	1.2 (6)	N—C8—C9—C4	−179.1 (3)
C5—C6—C7—C8	−0.8 (6)	C5—C4—C9—O1	179.8 (3)
C6—C7—C8—C9	−0.4 (5)	C3—C4—C9—O1	−1.6 (4)
C6—C7—C8—N	180.0 (3)	C5—C4—C9—C8	−1.0 (6)
O3—N—C8—C9	−173.7 (3)	C3—C4—C9—C8	177.6 (3)

Experimental details

Crystal data
Chemical formula	C₉H₉NO₃
M_r	179.17
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	8.4250 (17), 7.2260 (14), 28.295 (6)
V (Å³)	1722.6 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.969, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	2977, 1551, 829
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.182, 1.01
No. of reflections	1551
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Center for Testing and Analysis, Nanjing University, for support.

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–S19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Majumdar, K. C., Alam, S. & Chattopadhyay, B. (2008). Tetrahedron, 64, 597–643. Web of Science CrossRef 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