2-Methyl-4-nitro­phenol

Bi, S.; Wu, Y.-Z.; Zhou, Y.-X.; Tang, J.-G.; Guo, C.

doi:10.1107/S1600536809018716

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1378

doi:10.1107/S1600536809018716

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2-Methyl-4-nitrophenol

Sheng Bi,^a Yong-Zhong Wu,^b Yi-Xin Zhou,^a Jian-Guo Tang ^a and Cheng Guo ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Geguan Road No. 625 Dachang District Nanjing, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 14 May 2009; accepted 18 May 2009; online 23 May 2009)

The molecule of the title compound, C₇H₇NO₃, is nearly planar [maximum deviation 0.112 (3) Å for one of the notro O atoms]. In the crystal structure, intermolecular O—H⋯O and C—H⋯O interactions link the molecules into a three-dimensional network.

Related literature

For a related structure, see: Ahmed & Ashwini (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₇NO₃
M_r = 153.14
Monoclinic, P 2₁ /n
a = 5.6210 (11) Å
b = 8.7420 (17) Å>
c = 14.300 (3) Å
β = 100.71 (3)°
V = 690.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 294 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 = 0.966, T_max = 0.988
1378 measured reflections
1245 independent reflections
870 reflections with I > 2σ(I)
R_int = 0.027
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.181
S = 1.01
1245 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.82	2.10	2.770 (4)	138
C7—H7C⋯O1ⁱⁱ	0.96	2.57	3.505 (5)	165
Symmetry codes: (i) x, y-1, z; (ii) -x-1, -y+1, -z+2.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); 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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018716/hk2688sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018716/hk2688Isup2.hkl

checkCIF report

Comment top

Some derivatives of benzoic acids are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar. Atoms O1, O2, O3, N and C7 are 0.112 (3), 0.023 (3), 0.049 (3), 0.026 (4) and -0.042 (3) Å away from the ring plane, respectively. So, the molecule is nearly planar.

In the crystal structure, intermolecular O-H···O and C-H···O interactions (Table 1) link the molecules into a network, in which they may be effective in the stabilization of the structure.

Related literature top

For a related structure, see: Ahmed & Ashwini (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, ethyl acetate (150 ml), 2-methyl-phenol (5.9 g) and zinc chloride (7.4 g) are placed in an ultrasonic cleaning bath equipped with a round botton flask, and then nitric acid (5.9 g) was added dropwise in 3 min. After the reaction was completed, water (200 ml) was added. After evaporation of the organic layer, the obtained product (Ahmed & Ashwini, 2004) was crystallized by slow evaporation of a methanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

2-Methyl-4-nitrophenol top

Crystal data top

C₇H₇NO₃	F(000) = 320
M_r = 153.14	D_x = 1.473 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 5.6210 (11) Å	θ = 9–13°
b = 8.7420 (17) Å	µ = 0.12 mm⁻¹
c = 14.300 (3) Å	T = 294 K
β = 100.71 (3)°	Block, colorless
V = 690.4 (2) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	870 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 25.3°, θ_min = 2.7°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.966, T_max = 0.988	l = −17→16
1378 measured reflections	3 standard reflections every 120 min
1245 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)] = 0.054	H-atom parameters constrained
wR(F²) = 0.181	w = 1/[σ²(F_o²) + (0.08P)² + 0.74P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1245 reflections	Δρ_max = 0.25 e Å⁻³
102 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (4)

Crystal data top

C₇H₇NO₃	V = 690.4 (2) Å³
M_r = 153.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.6210 (11) Å	µ = 0.12 mm⁻¹
b = 8.7420 (17) Å	T = 294 K
c = 14.300 (3) Å	0.30 × 0.20 × 0.10 mm
β = 100.71 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	870 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.027
T_min = 0.966, T_max = 0.988	3 standard reflections every 120 min
1378 measured reflections	intensity decay: 1%
1245 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
1245 reflections	Δρ_min = −0.24 e Å⁻³
102 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
O1	−0.3440 (5)	0.6807 (3)	0.9304 (2)	0.0769 (9)
O2	−0.0576 (5)	0.7542 (3)	0.8605 (2)	0.0682 (8)
O3	0.0480 (4)	0.0536 (3)	0.81980 (17)	0.0567 (7)
H3A	−0.0372	−0.0079	0.8417	0.085*
N	−0.1770 (5)	0.6536 (3)	0.8896 (2)	0.0490 (8)
C1	0.0652 (6)	0.4640 (4)	0.8248 (2)	0.0478 (9)
H1A	0.1525	0.5429	0.8034	0.057*
C2	0.1146 (6)	0.3143 (4)	0.8076 (2)	0.0487 (9)
H2A	0.2352	0.2908	0.7734	0.058*
C3	−0.0137 (6)	0.1979 (4)	0.8410 (2)	0.0417 (8)
C4	−0.1941 (5)	0.2284 (3)	0.8932 (2)	0.0410 (8)
C5	−0.2457 (6)	0.3796 (4)	0.9085 (2)	0.0415 (8)
H5A	−0.3678	0.4038	0.9418	0.050*
C6	−0.1175 (5)	0.4950 (4)	0.8747 (2)	0.0413 (8)
C7	−0.3278 (6)	0.1019 (4)	0.9313 (3)	0.0531 (9)
H7A	−0.2143	0.0360	0.9707	0.080*
H7B	−0.4172	0.0441	0.8793	0.080*
H7C	−0.4375	0.1443	0.9684	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.093 (2)	0.0485 (16)	0.104 (2)	0.0137 (14)	0.0576 (18)	−0.0051 (15)
O2	0.0861 (19)	0.0303 (13)	0.097 (2)	−0.0030 (12)	0.0392 (16)	0.0063 (13)
O3	0.0661 (15)	0.0341 (13)	0.0802 (17)	0.0000 (11)	0.0405 (13)	−0.0053 (11)
N	0.0594 (18)	0.0337 (15)	0.0567 (17)	0.0039 (13)	0.0180 (14)	0.0005 (13)
C1	0.0539 (19)	0.0371 (17)	0.059 (2)	−0.0036 (14)	0.0281 (17)	0.0044 (15)
C2	0.0496 (19)	0.0413 (18)	0.063 (2)	−0.0036 (15)	0.0302 (17)	−0.0024 (16)
C3	0.0438 (17)	0.0339 (15)	0.0503 (18)	−0.0019 (14)	0.0168 (14)	−0.0029 (14)
C4	0.0389 (16)	0.0397 (17)	0.0473 (18)	−0.0032 (13)	0.0156 (14)	−0.0012 (14)
C5	0.0403 (16)	0.0407 (17)	0.0469 (17)	0.0021 (14)	0.0171 (14)	0.0005 (14)
C6	0.0461 (17)	0.0312 (16)	0.0500 (18)	0.0009 (13)	0.0177 (14)	−0.0006 (13)
C7	0.054 (2)	0.045 (2)	0.068 (2)	−0.0034 (15)	0.0285 (17)	0.0007 (16)

Geometric parameters (Å, º) top

O3—C3	1.357 (4)	C2—H2A	0.9300
O3—H3A	0.8200	C3—C4	1.393 (4)
N—O1	1.217 (3)	C4—C5	1.379 (4)
N—O2	1.225 (4)	C4—C7	1.496 (4)
N—C6	1.451 (4)	C5—C6	1.379 (4)
C1—C2	1.370 (5)	C5—H5A	0.9300
C1—C6	1.382 (4)	C7—H7A	0.9600
C1—H1A	0.9300	C7—H7B	0.9600
C2—C3	1.382 (4)	C7—H7C	0.9600

C3—O3—H3A	109.5	C5—C4—C7	121.1 (3)
O1—N—O2	122.9 (3)	C3—C4—C7	121.2 (3)
O1—N—C6	118.4 (3)	C6—C5—C4	120.5 (3)
O2—N—C6	118.7 (3)	C6—C5—H5A	119.8
C2—C1—C6	118.4 (3)	C4—C5—H5A	119.8
C2—C1—H1A	120.8	C5—C6—C1	121.6 (3)
C6—C1—H1A	120.8	C5—C6—N	119.9 (3)
C1—C2—C3	120.4 (3)	C1—C6—N	118.5 (3)
C1—C2—H2A	119.8	C4—C7—H7A	109.5
C3—C2—H2A	119.8	C4—C7—H7B	109.5
O3—C3—C2	115.9 (3)	H7A—C7—H7B	109.5
O3—C3—C4	122.7 (3)	C4—C7—H7C	109.5
C2—C3—C4	121.5 (3)	H7A—C7—H7C	109.5
C5—C4—C3	117.7 (3)	H7B—C7—H7C	109.5

O1—N—C6—C5	−1.5 (5)	O3—C3—C4—C5	−178.4 (3)
O2—N—C6—C5	178.6 (3)	C2—C3—C4—C5	1.8 (5)
O1—N—C6—C1	177.3 (3)	O3—C3—C4—C7	1.4 (5)
O2—N—C6—C1	−2.6 (5)	C2—C3—C4—C7	−178.3 (3)
C6—C1—C2—C3	−1.0 (5)	C3—C4—C5—C6	−1.5 (5)
C2—C1—C6—C5	1.2 (5)	C7—C4—C5—C6	178.6 (3)
C2—C1—C6—N	−177.5 (3)	C4—C5—C6—C1	0.0 (5)
C1—C2—C3—O3	179.7 (3)	C4—C5—C6—N	178.8 (3)
C1—C2—C3—C4	−0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.82	2.10	2.770 (4)	138
C7—H7C···O1ⁱⁱ	0.96	2.57	3.505 (5)	165

Symmetry codes: (i) x, y−1, z; (ii) −x−1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₇H₇NO₃
M_r	153.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	5.6210 (11), 8.7420 (17), 14.300 (3)
β (°)	100.71 (3)
V (Å³)	690.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.966, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	1378, 1245, 870
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.181, 1.01
No. of reflections	1245
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.82	2.10	2.770 (4)	138.00
C7—H7C···O1ⁱⁱ	0.96	2.57	3.505 (5)	165.00

Symmetry codes: (i) x, y−1, z; (ii) −x−1, −y+1, −z+2.

Acknowledgements

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

References

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