3-Methyl-4-nitro­phenol

Dong, S.-L.; Cheng, X.

doi:10.1107/S160053681200253X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o518

doi:10.1107/S160053681200253X

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3-Methyl-4-nitrophenol

Su-Lan Dong ^a ^* and Xiaochun Cheng ^a

^aCollege of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, Jiangsu, People's Republic of China
^*Correspondence e-mail: dsl710221@163.com

(Received 13 January 2012; accepted 20 January 2012; online 25 January 2012)

In the title molecule, C₇H₇NO₃, the nitro group is oriented at 14.4 (3)° with respect to the plane of the benzene ring. The crystal structure is stabilized by O—H⋯O hydrogen bonds and further consolidated by C—H⋯O interactions.

Related literature

For applications of the title compound in organophosphorus pesticides and for the synthetic procedure, see: Yin & Shi (2005 ). For a related structure, see: Barve & Pant (1971 ).

Experimental

Crystal data

C₇H₇NO₃
M_r = 153.14
Monoclinic, P 2₁ /c
a = 7.2993 (14) Å
b = 13.023 (3) Å
c = 7.4445 (16) Å
β = 91.217 (4)°
V = 707.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.978, T_max = 0.983
3860 measured reflections
1293 independent reflections
1071 reflections with I > 2σ
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.148
S = 1.00
1293 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	2.00	2.811 (2)	169
C5—H5⋯O3ⁱⁱ	0.93	2.58	3.437 (2)	154
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z.

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/S160053681200253X/pv2508sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200253X/pv2508Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200253X/pv2508Isup3.cml

checkCIF report

Comment top

The tittle compound is an important intermediate which can be used in many fields such as organophosphorus pesticides (Yin & Shi, 2005).

In the title molecule (Fig. 1), the nitro group (N1/O1/O2) and the benzene ring (C2—C7) are oriented at 14.4 (3) ° with respect to each other. The molecular structure is stabilized by O3—H3···O2 intermolecular hydrogen bonds and further consolidated by C5—H5···O3 type intermolecular hydrogen bonding interactions (Tab. 2 and Fig. 2). The bond lengths and angles in the title compound are in agreement with the corresponding bond legths and angles reported for a closely related compound (Barve & Pant, 1971).

Related literature top

For applications of the title compound in organophosphorus pesticides and for the synthetic procedure, see: Yin & Shi (2005). For a related structure, see: Barve & Pant (1971).

Experimental top

The title compound was prepared by a method reported in the literature (Yin & Shi, 2005). A solution of sodium nitrite (5.11 g, 74 mmol) and nitric acid (13 g, 208 mmol) in dichloromethane (50 ml) was added slowly to a solution of m-cresol (5 g, 46.2 mmol). After stirring for 5 h at a tempeature of 323 K, the solvent was evaporated on a rotary evaporator to obtain the title compound. The crystals were grown from an ethanol solution by slow evaporaton of the solvent at room temperature in about 7 days.

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 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the O—-H···O and C—H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound.

3-Methyl-4-nitrophenol top

Crystal data top

C₇H₇NO₃	F(000) = 320
M_r = 153.14	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2201 reflections
a = 7.2993 (14) Å	θ = 2.8–29.8°
b = 13.023 (3) Å	µ = 0.11 mm⁻¹
c = 7.4445 (16) Å	T = 296 K
β = 91.217 (4)°	Block, colorless
V = 707.5 (2) Å³	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1071 reflections with I > 2σ
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.5°, θ_min = 2.8°
ω/2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = −15→15
T_min = 0.978, T_max = 0.983	l = −9→6
3860 measured reflections	3 standard reflections every 200 reflections
1293 independent reflections	intensity decay: 1%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0847P)² + 0.266P] where P = (F_o² + 2F_c²)/3
1293 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₇H₇NO₃	V = 707.5 (2) Å³
M_r = 153.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2993 (14) Å	µ = 0.11 mm⁻¹
b = 13.023 (3) Å	T = 296 K
c = 7.4445 (16) Å	0.20 × 0.18 × 0.15 mm
β = 91.217 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1071 reflections with I > 2σ
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.023
T_min = 0.978, T_max = 0.983	3 standard reflections every 200 reflections
3860 measured reflections	intensity decay: 1%
1293 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
1293 reflections	Δρ_min = −0.21 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
O3	1.09340 (18)	0.37232 (10)	0.0133 (2)	0.0532 (4)
H3	1.1635	0.3301	−0.0293	0.080*
C7	0.9309 (2)	0.21737 (13)	0.0839 (2)	0.0388 (5)
H7	1.0295	0.1779	0.0476	0.047*
C3	0.6322 (2)	0.23242 (13)	0.1996 (2)	0.0370 (4)
C5	0.8008 (3)	0.38512 (14)	0.1339 (2)	0.0417 (5)
H5	0.8101	0.4563	0.1303	0.050*
C4	0.6461 (2)	0.33913 (14)	0.1958 (2)	0.0402 (5)
H4	0.5497	0.3792	0.2356	0.048*
C1	0.7737 (3)	0.05198 (14)	0.1483 (3)	0.0542 (6)
H1A	0.7391	0.0288	0.2652	0.081*
H1B	0.8940	0.0268	0.1226	0.081*
H1C	0.6877	0.0266	0.0597	0.081*
C2	0.7745 (2)	0.16801 (13)	0.1442 (2)	0.0366 (4)
C6	0.9445 (2)	0.32372 (14)	0.0763 (2)	0.0378 (4)
N1	0.4618 (2)	0.19093 (13)	0.2651 (2)	0.0467 (4)
O2	0.3574 (2)	0.24929 (12)	0.3445 (2)	0.0635 (5)
O1	0.4233 (2)	0.10112 (12)	0.2411 (3)	0.0868 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0443 (8)	0.0454 (8)	0.0708 (10)	−0.0081 (6)	0.0235 (7)	−0.0031 (7)
C7	0.0350 (10)	0.0421 (11)	0.0396 (9)	0.0033 (7)	0.0062 (7)	−0.0029 (7)
C3	0.0335 (10)	0.0432 (10)	0.0344 (9)	−0.0041 (7)	0.0044 (7)	0.0012 (7)
C5	0.0458 (10)	0.0327 (9)	0.0470 (10)	−0.0005 (7)	0.0102 (8)	0.0002 (7)
C4	0.0369 (9)	0.0416 (10)	0.0423 (10)	0.0039 (7)	0.0085 (7)	−0.0010 (7)
C1	0.0606 (13)	0.0382 (11)	0.0643 (13)	−0.0016 (9)	0.0113 (10)	0.0002 (9)
C2	0.0409 (9)	0.0348 (9)	0.0340 (8)	−0.0015 (7)	0.0012 (7)	−0.0006 (7)
C6	0.0367 (9)	0.0396 (10)	0.0373 (9)	−0.0061 (7)	0.0069 (7)	−0.0009 (7)
N1	0.0381 (9)	0.0517 (10)	0.0507 (9)	−0.0072 (7)	0.0075 (7)	0.0021 (7)
O2	0.0437 (8)	0.0656 (10)	0.0823 (11)	0.0005 (7)	0.0253 (8)	0.0006 (8)
O1	0.0719 (12)	0.0569 (10)	0.1333 (17)	−0.0280 (9)	0.0428 (11)	−0.0163 (10)

Geometric parameters (Å, º) top

O3—C6	1.351 (2)	C5—C6	1.393 (3)
O3—H3	0.8200	C5—H5	0.9300
C7—C6	1.390 (3)	C4—H4	0.9300
C7—C2	1.393 (2)	C1—C2	1.511 (3)
C7—H7	0.9300	C1—H1A	0.9600
C3—C4	1.394 (3)	C1—H1B	0.9600
C3—C2	1.404 (2)	C1—H1C	0.9600
C3—N1	1.450 (2)	N1—O1	1.215 (2)
C5—C4	1.367 (2)	N1—O2	1.236 (2)

C6—O3—H3	109.5	C2—C1—H1B	109.5
C6—C7—C2	122.19 (15)	H1A—C1—H1B	109.5
C6—C7—H7	118.9	C2—C1—H1C	109.5
C2—C7—H7	118.9	H1A—C1—H1C	109.5
C4—C3—C2	122.34 (15)	H1B—C1—H1C	109.5
C4—C3—N1	116.23 (15)	C7—C2—C3	115.82 (15)
C2—C3—N1	121.42 (16)	C7—C2—C1	118.12 (16)
C4—C5—C6	118.99 (16)	C3—C2—C1	126.04 (16)
C4—C5—H5	120.5	O3—C6—C7	122.66 (15)
C6—C5—H5	120.5	O3—C6—C5	117.02 (16)
C5—C4—C3	120.33 (16)	C7—C6—C5	120.31 (15)
C5—C4—H4	119.8	O1—N1—O2	121.27 (16)
C3—C4—H4	119.8	O1—N1—C3	120.45 (16)
C2—C1—H1A	109.5	O2—N1—C3	118.28 (16)

C6—C5—C4—C3	−0.6 (3)	C2—C7—C6—O3	−178.06 (16)
C2—C3—C4—C5	1.1 (3)	C2—C7—C6—C5	1.6 (3)
N1—C3—C4—C5	−179.15 (15)	C4—C5—C6—O3	178.90 (16)
C6—C7—C2—C3	−1.0 (2)	C4—C5—C6—C7	−0.8 (3)
C6—C7—C2—C1	−179.66 (16)	C4—C3—N1—O1	165.72 (19)
C4—C3—C2—C7	−0.4 (2)	C2—C3—N1—O1	−14.6 (3)
N1—C3—C2—C7	179.95 (15)	C4—C3—N1—O2	−13.9 (2)
C4—C3—C2—C1	178.20 (17)	C2—C3—N1—O2	165.86 (17)
N1—C3—C2—C1	−1.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	2.00	2.811 (2)	169
C4—H4···O2	0.93	2.35	2.671 (2)	100
C5—H5···O3ⁱⁱ	0.93	2.58	3.437 (2)	154

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

Experimental details

Crystal data
Chemical formula	C₇H₇NO₃
M_r	153.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.2993 (14), 13.023 (3), 7.4445 (16)
β (°)	91.217 (4)
V (Å³)	707.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.978, 0.983
No. of measured, independent and observed (I > 2σ) reflections	3860, 1293, 1071
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.148, 1.00
No. of reflections	1293
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	2.00	2.811 (2)	169
C5—H5···O3ⁱⁱ	0.93	2.58	3.437 (2)	154

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection. We also thank the Contract grant sponsor, the Natural Science Foundation of Jiangsu Province of China (BK2008195), and the Science Research Foundation of Huaiyin Institute of Technology (2517045) for help.

References

Barve, J. V. & Pant, L. M. (1971). Acta Cryst. B27, 1158–1162. CSD CrossRef CAS IUCr Journals 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
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
Yin, W. P. & Shi, M. (2005). Tetrahedron, 61, 10861–10867. Web of Science CSD CrossRef CAS Google Scholar