Methyl 4-nitro­benzoate

Wu, H.; Xie, M.-H.; Zou, P.; Liu, Y.-L.; He, Y.-J.

doi:10.1107/S160053680904745X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3096

doi:10.1107/S160053680904745X

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Methyl 4-nitrobenzoate

Hao Wu,^a ^* Min-Hao Xie,^a Pei Zou,^a Ya-Ling Liu ^a and Yong-Jun He ^a

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: haijiaoyiya@sina.com

(Received 4 November 2009; accepted 10 November 2009; online 14 November 2009)

In the molecule of the title compound, C₈H₇NO₄, the nitro group is approximately coplanar with the benzene ring [dihedral angle = 0.6 (1)°], while the dihedral angle between the methoxycarbonyl group and the benzene ring is 8.8 (1)°. In the crystal structure, weak intermolecular aromatic C—H⋯O_carboxyl and C—H⋯O_nitro hydrogen-bonding interactions are present.

Related literature

For related literature on benzoates, see: Zhang (1992 ); Zhang et al. (1990 ); Zhang et al. (1995 ).

Experimental

Crystal data

C₈H₇NO₄
M_r = 181.15
Monoclinic, P 2₁ /c
a = 7.109 (3) Å
b = 17.092 (6) Å
c = 7.193 (3) Å
β = 116.292 (4)°
V = 783.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 93 K
0.43 × 0.40 × 0.10 mm

Data collection

Rigaku SPIDER CCD-detector diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.948, T_max = 0.988
6176 measured reflections
1787 independent reflections
1445 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.080
S = 1.00
1787 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.95	2.59	3.384 (2)	141
C5—H5⋯O4ⁱⁱ	0.95	2.58	3.378 (2)	142
Symmetry codes: (i) x, y, z-1; (ii) x, y, z+1.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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/S160053680904745X/zs2018sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680904745X/zs2018Isup2.hkl

checkCIF report

Comment top

Benzoates are important intermediates in the chemistry of pigments and pharmaceuticals, which are used worldwide (Zhang, 1992; Zhang et al., 1990; Zhang et al., 1995). We report here the crystal structure of methyl 4-nitrobenzoate, C₈H₇NO₄ (I). In the structure of the title compound (Fig. 1) the bond lengths and angles are within expected ranges. The nitro substituent group is nearly coplanar with the benzene ring [dihedral angle, 0.6 (1)°], while the methoxycarbonyl group forms a dihedral angle of 8.8 (1)° with the benzene ring. In the crystal structure, adjacent molecules are linked by weak intermolecular aromatic C—H···O_carboxyl and O_nitro hydrogen bonds (Table 1).

Related literature top

For related literature on benzoates, see: Zhang (1992); Zhang et al. (1990); Zhang et al. (1995).

Experimental top

4-Nitrobenzoic acid (5.0 g, 30 mmol) was dissolved in hot methanol (10 ml), then six drops of concentrated sulfuric acid were added. The mixture was stirred at 353 K for 4 h, poured into ice water and stirred for 3 min. After filtering, washing with water and drying in vacuum, a white powder was then obtained (yield: 73%). The crude product was purified by recrystallization from methanol (yield: 51%). Colourless plate-shaped crystals [m.p. 369 (2) K] were obtained after several days, by slow evaporation of a 1:1 (v/v) methanol-water solution. .

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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. Atom numbering scheme for the title compound (I) with the displacement ellipsoids drawn at the 30% probability level.

Methyl 4-nitrobenzoate top

Crystal data top

C₈H₇NO₄	F(000) = 376
M_r = 181.15	D_x = 1.536 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 369(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.109 (3) Å	Cell parameters from 2257 reflections
b = 17.092 (6) Å	θ = 3.2–27.4°
c = 7.193 (3) Å	µ = 0.13 mm⁻¹
β = 116.292 (4)°	T = 93 K
V = 783.6 (5) Å³	Plate, colorless
Z = 4	0.43 × 0.40 × 0.10 mm

Data collection top

Rigaku SPIDER CCD-detector diffractometer	1787 independent reflections
Radiation source: rotating anode	1445 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: ψ scan (North et al., 1968)	h = −9→9
T_min = 0.948, T_max = 0.988	k = −20→22
6176 measured reflections	l = −9→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0303P)² + 0.336P] where P = (F_o² + 2F_c²)/3
1787 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₈H₇NO₄	V = 783.6 (5) Å³
M_r = 181.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.109 (3) Å	µ = 0.13 mm⁻¹
b = 17.092 (6) Å	T = 93 K
c = 7.193 (3) Å	0.43 × 0.40 × 0.10 mm
β = 116.292 (4)°

Data collection top

Rigaku SPIDER CCD-detector diffractometer	1787 independent reflections
Absorption correction: ψ scan (North et al., 1968)	1445 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.988	R_int = 0.023
6176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.00	Δρ_max = 0.31 e Å⁻³
1787 reflections	Δρ_min = −0.18 e Å⁻³
119 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	0.35100 (15)	0.66883 (5)	0.67509 (14)	0.0205 (2)
O2	0.30933 (15)	0.59510 (5)	0.91414 (14)	0.0216 (2)
O3	0.14128 (16)	0.28185 (5)	0.23700 (16)	0.0265 (2)
O4	0.14076 (17)	0.36321 (6)	0.00524 (15)	0.0275 (2)
N1	0.15702 (17)	0.34819 (6)	0.17881 (17)	0.0185 (2)
C1	0.25319 (19)	0.54972 (7)	0.39808 (19)	0.0155 (3)
H1	0.2638	0.6016	0.3563	0.019*
C2	0.21513 (19)	0.48826 (7)	0.2601 (2)	0.0160 (3)
H2	0.2007	0.4971	0.1240	0.019*
C3	0.19872 (19)	0.41347 (7)	0.3264 (2)	0.0155 (3)
C4	0.21927 (19)	0.39748 (7)	0.5240 (2)	0.0167 (3)
H4	0.2065	0.3456	0.5643	0.020*
C5	0.25907 (19)	0.45958 (7)	0.6606 (2)	0.0160 (3)
H5	0.2749	0.4503	0.7970	0.019*
C6	0.27592 (18)	0.53560 (7)	0.59852 (19)	0.0149 (3)
C7	0.31372 (19)	0.60132 (7)	0.7484 (2)	0.0162 (3)
C8	0.3760 (2)	0.73724 (8)	0.8036 (2)	0.0239 (3)
H8A	0.2532	0.7425	0.8310	0.029*
H8B	0.3890	0.7840	0.7313	0.029*
H8C	0.5025	0.7314	0.9351	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0302 (5)	0.0155 (5)	0.0190 (5)	−0.0039 (4)	0.0139 (4)	−0.0029 (4)
O2	0.0259 (5)	0.0241 (5)	0.0167 (5)	−0.0026 (4)	0.0111 (4)	−0.0005 (4)
O3	0.0390 (6)	0.0150 (5)	0.0290 (6)	−0.0025 (4)	0.0182 (5)	0.0006 (4)
O4	0.0437 (6)	0.0225 (5)	0.0202 (5)	−0.0009 (5)	0.0177 (5)	−0.0016 (4)
N1	0.0196 (5)	0.0163 (5)	0.0211 (6)	0.0005 (4)	0.0102 (5)	0.0002 (4)
C1	0.0151 (6)	0.0144 (6)	0.0172 (7)	−0.0002 (5)	0.0075 (5)	0.0022 (5)
C2	0.0152 (6)	0.0189 (6)	0.0142 (6)	0.0007 (5)	0.0067 (5)	0.0024 (5)
C3	0.0132 (6)	0.0160 (6)	0.0172 (6)	0.0011 (5)	0.0066 (5)	−0.0008 (5)
C4	0.0152 (6)	0.0153 (6)	0.0204 (7)	0.0008 (5)	0.0088 (5)	0.0033 (5)
C5	0.0143 (6)	0.0196 (6)	0.0150 (6)	0.0012 (5)	0.0071 (5)	0.0036 (5)
C6	0.0115 (5)	0.0175 (6)	0.0152 (6)	0.0003 (5)	0.0055 (5)	−0.0002 (5)
C7	0.0134 (6)	0.0181 (6)	0.0162 (6)	0.0005 (5)	0.0059 (5)	0.0017 (5)
C8	0.0339 (8)	0.0176 (6)	0.0243 (7)	−0.0055 (6)	0.0167 (6)	−0.0060 (5)

Geometric parameters (Å, º) top

O1—C7	1.3429 (15)	C2—H2	0.9500
O1—C8	1.4517 (15)	C3—C4	1.3901 (18)
O2—C7	1.2111 (16)	C4—C5	1.3880 (18)
O3—N1	1.2308 (14)	C4—H4	0.9500
O4—N1	1.2290 (15)	C5—C6	1.3962 (18)
N1—C3	1.4770 (16)	C5—H5	0.9500
C1—C2	1.3872 (18)	C6—C7	1.4965 (18)
C1—C6	1.3988 (18)	C8—H8A	0.9800
C1—H1	0.9500	C8—H8B	0.9800
C2—C3	1.3873 (17)	C8—H8C	0.9800

C7—O1—C8	115.59 (10)	C4—C5—C6	120.30 (12)
O4—N1—O3	123.79 (11)	C4—C5—H5	119.8
O4—N1—C3	118.11 (10)	C6—C5—H5	119.8
O3—N1—C3	118.10 (11)	C5—C6—C1	120.22 (12)
C2—C1—C6	120.25 (12)	C5—C6—C7	118.78 (11)
C2—C1—H1	119.9	C1—C6—C7	120.98 (11)
C6—C1—H1	119.9	O2—C7—O1	123.89 (12)
C1—C2—C3	118.10 (12)	O2—C7—C6	124.65 (11)
C1—C2—H2	121.0	O1—C7—C6	111.46 (11)
C3—C2—H2	121.0	O1—C8—H8A	109.5
C2—C3—C4	123.11 (12)	O1—C8—H8B	109.5
C2—C3—N1	118.00 (11)	H8A—C8—H8B	109.5
C4—C3—N1	118.89 (11)	O1—C8—H8C	109.5
C5—C4—C3	118.01 (12)	H8A—C8—H8C	109.5
C5—C4—H4	121.0	H8B—C8—H8C	109.5
C3—C4—H4	121.0

C6—C1—C2—C3	0.59 (18)	C4—C5—C6—C1	−0.12 (18)
C1—C2—C3—C4	−0.22 (18)	C4—C5—C6—C7	178.53 (11)
C1—C2—C3—N1	179.66 (11)	C2—C1—C6—C5	−0.43 (18)
O4—N1—C3—C2	0.62 (17)	C2—C1—C6—C7	−179.05 (11)
O3—N1—C3—C2	−179.62 (11)	C8—O1—C7—O2	−3.17 (18)
O4—N1—C3—C4	−179.49 (12)	C8—O1—C7—C6	176.11 (10)
O3—N1—C3—C4	0.27 (17)	C5—C6—C7—O2	−8.15 (19)
C2—C3—C4—C5	−0.31 (18)	C1—C6—C7—O2	170.48 (12)
N1—C3—C4—C5	179.80 (11)	C5—C6—C7—O1	172.58 (11)
C3—C4—C5—C6	0.48 (18)	C1—C6—C7—O1	−8.78 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1	0.95	2.39	2.7149 (19)	100
C2—H2···O2ⁱ	0.95	2.59	3.384 (2)	141
C5—H5···O4ⁱⁱ	0.95	2.58	3.378 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₈H₇NO₄
M_r	181.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	7.109 (3), 17.092 (6), 7.193 (3)
β (°)	116.292 (4)
V (Å³)	783.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.43 × 0.40 × 0.10

Data collection
Diffractometer	Rigaku SPIDER CCD-detector diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.948, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6176, 1787, 1445
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.080, 1.00
No. of reflections	1787
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.18

Computer programs: RAPID-AUTO (Rigaku, 2004), 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
C2—H2···O2ⁱ	0.95	2.5900	3.384 (2)	141
C5—H5···O4ⁱⁱ	0.95	2.5800	3.378 (2)	142

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

Acknowledgements

The authors acknowledge financial support from Jiangsu Institute of Nuclear Medicine.

References

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