Isopropyl 4-nitro­benzoate

Zou, P.; Xie, M.-H.; Wu, H.; Liu, Y.-L.; Chen, Z.-P.

doi:10.1107/S1600536811039407

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2806

https://doi.org/10.1107/S1600536811039407

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Isopropyl 4-nitrobenzoate

Pei Zou,^a Min-Hao Xie,^a Hao Wu,^a Ya-Ling Liu ^a and Zheng-Ping Chen ^a ^*

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: wxzoupei@126.com

(Received 22 September 2011; accepted 26 September 2011; online 30 September 2011)

In the molecule of the title compound, C₁₀H₁₁NO₄, the nitro group is approximately coplanar with the benzene ring [dihedral angle = 4.57 (10)°], while the carboxylate group is slightly twisted, making an angle of 12.16 (8)°. In the crystal, weak intermolecular C—H⋯O hydrogen bonding and π–π stacking interactions [centroid–centroid distances = 3.670 (2) and 3.665 (2) Å] are observed.

Related literature

For applications of benzoates in the chemistry of pigments and pharmaceuticals, see: Zhang et al. (1990 , 1995 ). For a related structure, see: Wu et al. (2009 ).

Experimental

Crystal data

C₁₀H₁₁NO₄
M_r = 209.20
Triclinic, $[P \overline 1]$
a = 6.729 (4) Å
b = 7.192 (4) Å
c = 10.388 (6) Å
α = 94.751 (9)°
β = 92.503 (7)°
γ = 95.901 (10)°
V = 497.6 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 153 K
0.37 × 0.33 × 0.10 mm

Data collection

Rigaku SPIDER diffractometer
6626 measured reflections
2862 independent reflections
1947 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.150
S = 1.00
2862 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O4ⁱ	0.95	2.46	3.311 (3)	149
C4—H4⋯O2ⁱⁱ	0.95	2.46	3.294 (3)	147
Symmetry codes: (i) x, y-1, z; (ii) x, y+1, z.

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: https://doi.org/10.1107/S1600536811039407/xu5329sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811039407/xu5329Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811039407/xu5329Isup3.cml

checkCIF report

Comment top

Benzoates are important intermediates in the chemistry of pigments and pharmaceuticals, which are widely used all over the world (Zhang et al., 1995; Zhang et al., 1990). The crystal structure of methyl 4-nitrobenzoate has been reported (Wu et al., 2009). As an extension of our study, we report here the crystal structure of the title compound.

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, 4.57 (10)°), while the ester group forms a dihedral angle of 12.16 (8)° with the benzene ring. In the crystal structure, adjacent molecules are linked together by weak C—H···O hydrogen bonds (Table 1). π-π stacking is observed between parallel benzene rings, centroids distances being 3.670 (2) [symmetry code -x,1-y,1-z] and 3.665 (2) Å [symmetry code 1-x,1-y,1-z].

Related literature top

For applications of benzoates in the chemistry of pigments and pharmaceuticals, see: Zhang et al. (1990, 1995). For a related structure, see: Wu et al. (2009).

Experimental top

A sample of commercial isopropyl 4-nitrobenzoate was crystallized by slow evaporation of a solution in methanol, colorless platelet-shaped crystals were formed after several days.

Structure description top

For applications of benzoates in the chemistry of pigments and pharmaceuticals, see: Zhang et al. (1990, 1995). For a related structure, see: Wu et al. (2009).

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. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.

Isopropyl 4-nitrobenzoate top

Crystal data top

C₁₀H₁₁NO₄	Z = 2
M_r = 209.20	F(000) = 220
Triclinic, P1	D_x = 1.396 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.729 (4) Å	Cell parameters from 1490 reflections
b = 7.192 (4) Å	θ = 2.9–30.0°
c = 10.388 (6) Å	µ = 0.11 mm⁻¹
α = 94.751 (9)°	T = 153 K
β = 92.503 (7)°	Platelet, colorless
γ = 95.901 (10)°	0.37 × 0.33 × 0.10 mm
V = 497.6 (5) Å³

Data collection top

Rigaku SPIDER diffractometer	1947 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.023
Graphite monochromator	θ_max = 30.0°, θ_min = 2.0°
ω scans	h = −9→9
6626 measured reflections	k = −10→9
2862 independent reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.071P)² + 0.196P] where P = (F_o² + 2F_c²)/3
2862 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₁₁NO₄	γ = 95.901 (10)°
M_r = 209.20	V = 497.6 (5) Å³
Triclinic, P1	Z = 2
a = 6.729 (4) Å	Mo Kα radiation
b = 7.192 (4) Å	µ = 0.11 mm⁻¹
c = 10.388 (6) Å	T = 153 K
α = 94.751 (9)°	0.37 × 0.33 × 0.10 mm
β = 92.503 (7)°

Data collection top

Rigaku SPIDER diffractometer	1947 reflections with I > 2σ(I)
6626 measured reflections	R_int = 0.023
2862 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.00	Δρ_max = 0.34 e Å⁻³
2862 reflections	Δρ_min = −0.29 e Å⁻³
138 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	0.24504 (18)	0.35230 (15)	0.12880 (10)	0.0258 (3)
O2	0.3016 (2)	0.12996 (17)	0.26213 (12)	0.0375 (3)
O3	0.2023 (2)	0.79014 (18)	0.77175 (11)	0.0381 (3)
O4	0.2382 (3)	1.00939 (19)	0.64283 (13)	0.0513 (4)
N1	0.2278 (2)	0.8444 (2)	0.66434 (13)	0.0288 (3)
C1	0.2535 (2)	0.3845 (2)	0.47750 (14)	0.0226 (3)
H1	0.2540	0.2559	0.4922	0.027*
C2	0.2421 (2)	0.5176 (2)	0.58075 (14)	0.0233 (3)
H2	0.2325	0.4818	0.6665	0.028*
C3	0.2450 (2)	0.7032 (2)	0.55569 (14)	0.0221 (3)
C4	0.2586 (2)	0.7627 (2)	0.43241 (14)	0.0234 (3)
H4	0.2618	0.8919	0.4186	0.028*
C5	0.2672 (2)	0.6275 (2)	0.32976 (14)	0.0223 (3)
H5	0.2752	0.6638	0.2441	0.027*
C6	0.2642 (2)	0.4393 (2)	0.35198 (14)	0.0207 (3)
C7	0.2732 (2)	0.2890 (2)	0.24432 (14)	0.0225 (3)
C8	0.2391 (2)	0.2167 (2)	0.01385 (15)	0.0252 (3)
H8	0.2027	0.0870	0.0392	0.030*
C9	0.4432 (3)	0.2293 (3)	−0.04028 (18)	0.0374 (4)
H9A	0.4766	0.3551	−0.0682	0.056*
H9B	0.4435	0.1358	−0.1145	0.056*
H9C	0.5424	0.2052	0.0265	0.056*
C10	0.0769 (3)	0.2689 (3)	−0.07652 (17)	0.0376 (4)
H10A	−0.0497	0.2638	−0.0331	0.056*
H10B	0.0624	0.1806	−0.1543	0.056*
H10C	0.1125	0.3963	−0.1010	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0401 (7)	0.0214 (5)	0.0164 (5)	0.0043 (4)	0.0039 (4)	0.0014 (4)
O2	0.0614 (9)	0.0256 (6)	0.0276 (6)	0.0129 (6)	0.0017 (6)	0.0047 (5)
O3	0.0533 (8)	0.0423 (7)	0.0184 (6)	0.0022 (6)	0.0076 (5)	0.0014 (5)
O4	0.0989 (13)	0.0302 (7)	0.0272 (7)	0.0169 (7)	0.0103 (7)	0.0003 (5)
N1	0.0359 (8)	0.0324 (7)	0.0185 (6)	0.0060 (6)	0.0028 (5)	0.0004 (5)
C1	0.0229 (7)	0.0240 (7)	0.0218 (7)	0.0027 (6)	0.0012 (5)	0.0071 (5)
C2	0.0234 (7)	0.0296 (8)	0.0174 (6)	0.0024 (6)	0.0014 (5)	0.0061 (5)
C3	0.0223 (7)	0.0275 (7)	0.0165 (6)	0.0035 (6)	0.0021 (5)	0.0006 (5)
C4	0.0290 (8)	0.0229 (7)	0.0191 (7)	0.0046 (6)	0.0025 (6)	0.0035 (5)
C5	0.0265 (8)	0.0257 (7)	0.0158 (6)	0.0043 (6)	0.0036 (5)	0.0047 (5)
C6	0.0197 (7)	0.0245 (7)	0.0183 (6)	0.0030 (5)	0.0021 (5)	0.0034 (5)
C7	0.0245 (7)	0.0234 (7)	0.0201 (7)	0.0030 (6)	0.0030 (5)	0.0041 (5)
C8	0.0341 (9)	0.0198 (7)	0.0209 (7)	0.0016 (6)	0.0039 (6)	−0.0021 (5)
C9	0.0406 (10)	0.0350 (9)	0.0352 (9)	0.0023 (7)	0.0103 (8)	−0.0087 (7)
C10	0.0462 (11)	0.0389 (10)	0.0276 (8)	0.0134 (8)	−0.0034 (7)	−0.0064 (7)

Geometric parameters (Å, º) top

O1—C7	1.3309 (18)	C4—H4	0.9500
O1—C8	1.4741 (18)	C5—C6	1.390 (2)
O2—C7	1.2067 (19)	C5—H5	0.9500
O3—N1	1.2255 (18)	C6—C7	1.497 (2)
O4—N1	1.221 (2)	C8—C9	1.503 (2)
N1—C3	1.471 (2)	C8—C10	1.506 (2)
C1—C2	1.387 (2)	C8—H8	1.0000
C1—C6	1.396 (2)	C9—H9A	0.9800
C1—H1	0.9500	C9—H9B	0.9800
C2—C3	1.380 (2)	C9—H9C	0.9800
C2—H2	0.9500	C10—H10A	0.9800
C3—C4	1.387 (2)	C10—H10B	0.9800
C4—C5	1.390 (2)	C10—H10C	0.9800

C7—O1—C8	117.82 (12)	O2—C7—O1	124.91 (14)
O4—N1—O3	123.35 (14)	O2—C7—C6	123.18 (14)
O4—N1—C3	118.42 (13)	O1—C7—C6	111.91 (13)
O3—N1—C3	118.23 (14)	O1—C8—C9	108.43 (13)
C2—C1—C6	120.08 (14)	O1—C8—C10	105.50 (13)
C2—C1—H1	120.0	C9—C8—C10	114.14 (15)
C6—C1—H1	120.0	O1—C8—H8	109.5
C3—C2—C1	118.24 (14)	C9—C8—H8	109.5
C3—C2—H2	120.9	C10—C8—H8	109.5
C1—C2—H2	120.9	C8—C9—H9A	109.5
C2—C3—C4	123.15 (14)	C8—C9—H9B	109.5
C2—C3—N1	118.50 (13)	H9A—C9—H9B	109.5
C4—C3—N1	118.34 (14)	C8—C9—H9C	109.5
C3—C4—C5	117.92 (14)	H9A—C9—H9C	109.5
C3—C4—H4	121.0	H9B—C9—H9C	109.5
C5—C4—H4	121.0	C8—C10—H10A	109.5
C4—C5—C6	120.24 (13)	C8—C10—H10B	109.5
C4—C5—H5	119.9	H10A—C10—H10B	109.5
C6—C5—H5	119.9	C8—C10—H10C	109.5
C5—C6—C1	120.35 (13)	H10A—C10—H10C	109.5
C5—C6—C7	122.02 (13)	H10B—C10—H10C	109.5
C1—C6—C7	117.62 (14)

C6—C1—C2—C3	−1.0 (2)	C4—C5—C6—C7	179.97 (14)
C1—C2—C3—C4	0.1 (2)	C2—C1—C6—C5	1.2 (2)
C1—C2—C3—N1	178.46 (13)	C2—C1—C6—C7	−179.10 (14)
O4—N1—C3—C2	177.20 (16)	C8—O1—C7—O2	2.8 (2)
O3—N1—C3—C2	−3.3 (2)	C8—O1—C7—C6	−176.78 (12)
O4—N1—C3—C4	−4.3 (2)	C5—C6—C7—O2	168.27 (16)
O3—N1—C3—C4	175.17 (15)	C1—C6—C7—O2	−11.5 (2)
C2—C3—C4—C5	0.8 (2)	C5—C6—C7—O1	−12.1 (2)
N1—C3—C4—C5	−177.64 (14)	C1—C6—C7—O1	168.17 (13)
C3—C4—C5—C6	−0.6 (2)	C7—O1—C8—C9	−96.71 (16)
C4—C5—C6—C1	−0.3 (2)	C7—O1—C8—C10	140.63 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4ⁱ	0.95	2.46	3.311 (3)	149
C4—H4···O2ⁱⁱ	0.95	2.46	3.294 (3)	147

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₄
M_r	209.20
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	6.729 (4), 7.192 (4), 10.388 (6)
α, β, γ (°)	94.751 (9), 92.503 (7), 95.901 (10)
V (Å³)	497.6 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.37 × 0.33 × 0.10

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6626, 2862, 1947
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.150, 1.00
No. of reflections	2862
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.29

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
C1—H1···O4ⁱ	0.95	2.46	3.311 (3)	149
C4—H4···O2ⁱⁱ	0.95	2.46	3.294 (3)	147

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

Acknowledgements

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

References

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