Isopropyl 4-chloro-3,5-dinitro­benzoate

Tai, X.-X.; Sun, J.

doi:10.1107/S160053681004359X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2986

https://doi.org/10.1107/S160053681004359X

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Isopropyl 4-chloro-3,5-dinitrobenzoate

Xiao-Xi Tai ^a and Jing Sun ^a ^*

^aGuangdong Food and Drug Vocational College, Guangzhou 510520, People's Republic of China
^*Correspondence e-mail: gzsunjing@163.com

(Received 25 October 2010; accepted 26 October 2010; online 30 October 2010)

In the title compound, C₁₀H₉ClN₂O₆, the two nitro groups and the ester group are oriented with respect to the benzene ring at dihedral angles of 49.42 (13)/87.61 (13) and 9.10 (10)°, respectively. In the crystal structure, a weak C—H⋯O interaction is present. A short Cl⋯O contact of 2.972 (2) Å is also observed in the crystal structure.

Related literature

For the application of the title compound as a herbicide and fungicide, see: Akira et al. (1978 ); Ferenc et al. (1984 ).

Experimental

Crystal data

C₁₀H₉ClN₂O₆
M_r = 288.64
Triclinic, $[P \overline 1]$
a = 4.703 (2) Å
b = 10.783 (5) Å
c = 12.734 (5) Å
α = 69.483 (12)°
β = 87.75 (2)°
γ = 89.61 (2)°
V = 604.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 103 K
0.57 × 0.22 × 0.10 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.830, T_max = 0.967
5643 measured reflections
2689 independent reflections
1756 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.114
S = 1.00
2689 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2ⁱ	0.95	2.35	3.178 (3)	146
Symmetry code: (i) -x+1, -y+1, -z+2.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681004359X/xu5065sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004359X/xu5065Isup2.hkl

checkCIF report

Comment top

Isopropyl 4-chloro-3,5-dinitrobenzoate (Fig. 1) is a useful herbicide and fungicide (Akira et al., 1978; Ferenc et al., 1984). It was used as the acid compounds to combat fungal diseases and weeds. We report here the crystal structure of the title compound. Two nitro groups (O3/ N1/O4 and O5/N2/O6) attached at C2 and C4, the ester group (O1/C7/O2) attached at C6 form dihedral angles of 49.4 (1)°, 87.6 (1)° and 9.1 (1)° with the mean plane of the C1-benzene ring, respectively. In the crystal structure, adjacent molecules are linked together by the weak C—H···O hydrogen bonds (Table 1).

Related literature top

For the application of the title compound as a herbicide and fungicide, see: Akira et al. (1978); Ferenc et al. (1984).

Experimental top

Commercial isopropyl 4-chloro-3,5-dinitrobenzoate was recrystallized by slow evaporation of methanol solution. Colourless single crystals were formed after several weeks.

Structure description top

For the application of the title compound as a herbicide and fungicide, see: Akira et al. (1978); Ferenc et al. (1984).

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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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-chloro-3,5-dinitrobenzoate top

Crystal data top

C₁₀H₉ClN₂O₆	Z = 2
M_r = 288.64	F(000) = 296
Triclinic, P1	D_x = 1.586 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.703 (2) Å	Cell parameters from 1327 reflections
b = 10.783 (5) Å	θ = 3.1–27.5°
c = 12.734 (5) Å	µ = 0.34 mm⁻¹
α = 69.483 (12)°	T = 103 K
β = 87.75 (2)°	Prism, colourless
γ = 89.61 (2)°	0.57 × 0.22 × 0.10 mm
V = 604.3 (5) Å³

Data collection top

Rigaku SPIDER diffractometer	2689 independent reflections
Radiation source: Rotating Anode	1756 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 3.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
T_min = 0.830, T_max = 0.967	k = −14→13
5643 measured reflections	l = −16→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0496P)² + 0.219P] where P = (F_o² + 2F_c²)/3
2689 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₀H₉ClN₂O₆	γ = 89.61 (2)°
M_r = 288.64	V = 604.3 (5) Å³
Triclinic, P1	Z = 2
a = 4.703 (2) Å	Mo Kα radiation
b = 10.783 (5) Å	µ = 0.34 mm⁻¹
c = 12.734 (5) Å	T = 103 K
α = 69.483 (12)°	0.57 × 0.22 × 0.10 mm
β = 87.75 (2)°

Data collection top

Rigaku SPIDER diffractometer	2689 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1756 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.967	R_int = 0.030
5643 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.00	Δρ_max = 0.38 e Å⁻³
2689 reflections	Δρ_min = −0.27 e Å⁻³
174 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
Cl1	1.35262 (13)	0.43193 (6)	0.65836 (5)	0.02487 (18)
O1	0.4518 (3)	0.85871 (15)	0.76139 (13)	0.0185 (4)
O2	0.3137 (3)	0.67501 (15)	0.90566 (13)	0.0208 (4)
O3	1.2776 (4)	0.83028 (19)	0.51714 (14)	0.0338 (5)
O4	1.1930 (4)	0.66488 (19)	0.46231 (15)	0.0359 (5)
O5	1.2157 (4)	0.31097 (18)	0.93908 (16)	0.0343 (5)
O6	0.8756 (4)	0.24121 (18)	0.86381 (17)	0.0364 (5)
N1	1.1805 (4)	0.7201 (2)	0.53094 (17)	0.0240 (5)
N2	1.0218 (4)	0.3277 (2)	0.87522 (18)	0.0226 (5)
C1	0.8350 (5)	0.7223 (2)	0.67783 (18)	0.0170 (5)
H1	0.7969	0.8119	0.6342	0.020*
C2	1.0341 (5)	0.6512 (2)	0.64011 (18)	0.0182 (5)
C3	1.1009 (5)	0.5203 (2)	0.7020 (2)	0.0187 (5)
C4	0.9569 (5)	0.4649 (2)	0.80468 (19)	0.0170 (5)
C5	0.7538 (5)	0.5317 (2)	0.8453 (2)	0.0177 (5)
H5	0.6590	0.4898	0.9161	0.021*
C6	0.6914 (5)	0.6612 (2)	0.78022 (19)	0.0165 (5)
C7	0.4638 (5)	0.7312 (2)	0.82410 (19)	0.0160 (5)
C8	0.2407 (5)	0.9393 (2)	0.7970 (2)	0.0188 (5)
H8	0.0665	0.8848	0.8302	0.023*
C9	0.3717 (6)	0.9834 (3)	0.8837 (2)	0.0288 (6)
H9A	0.4320	0.9057	0.9461	0.043*
H9B	0.2316	1.0332	0.9117	0.043*
H9C	0.5372	1.0401	0.8500	0.043*
C10	0.1679 (6)	1.0513 (2)	0.6922 (2)	0.0290 (6)
H10A	0.3399	1.1034	0.6591	0.043*
H10B	0.0261	1.1082	0.7108	0.043*
H10C	0.0902	1.0155	0.6383	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0219 (3)	0.0263 (3)	0.0289 (3)	0.0080 (2)	−0.0003 (2)	−0.0129 (3)
O1	0.0203 (9)	0.0125 (8)	0.0194 (8)	0.0043 (6)	0.0027 (7)	−0.0019 (7)
O2	0.0215 (9)	0.0166 (8)	0.0197 (9)	0.0035 (7)	0.0035 (7)	−0.0011 (7)
O3	0.0334 (11)	0.0378 (12)	0.0238 (10)	−0.0102 (9)	0.0041 (8)	−0.0030 (9)
O4	0.0432 (12)	0.0413 (12)	0.0239 (10)	0.0147 (9)	0.0041 (9)	−0.0130 (9)
O5	0.0284 (11)	0.0266 (10)	0.0409 (11)	0.0075 (8)	−0.0108 (9)	−0.0020 (9)
O6	0.0382 (12)	0.0172 (9)	0.0545 (13)	−0.0016 (8)	−0.0044 (10)	−0.0131 (9)
N1	0.0205 (11)	0.0307 (12)	0.0175 (10)	0.0076 (9)	−0.0001 (8)	−0.0049 (9)
N2	0.0201 (11)	0.0172 (11)	0.0291 (11)	0.0044 (8)	0.0030 (9)	−0.0068 (9)
C1	0.0176 (12)	0.0161 (12)	0.0170 (12)	0.0022 (9)	−0.0039 (9)	−0.0050 (10)
C2	0.0174 (12)	0.0212 (12)	0.0155 (12)	0.0012 (9)	−0.0005 (9)	−0.0057 (10)
C3	0.0149 (11)	0.0200 (12)	0.0248 (13)	0.0037 (9)	−0.0022 (10)	−0.0122 (10)
C4	0.0172 (12)	0.0125 (11)	0.0210 (12)	0.0014 (9)	−0.0049 (9)	−0.0049 (9)
C5	0.0182 (12)	0.0155 (12)	0.0193 (12)	0.0002 (9)	0.0000 (9)	−0.0059 (10)
C6	0.0155 (11)	0.0169 (11)	0.0184 (12)	−0.0007 (9)	−0.0007 (9)	−0.0078 (10)
C7	0.0183 (12)	0.0128 (11)	0.0162 (11)	0.0021 (9)	−0.0039 (9)	−0.0041 (9)
C8	0.0190 (12)	0.0140 (11)	0.0243 (13)	0.0043 (9)	0.0013 (10)	−0.0081 (10)
C9	0.0336 (15)	0.0229 (14)	0.0324 (14)	0.0073 (11)	−0.0029 (12)	−0.0128 (12)
C10	0.0358 (16)	0.0197 (13)	0.0272 (14)	0.0096 (11)	−0.0017 (12)	−0.0029 (11)

Geometric parameters (Å, º) top

Cl1—C3	1.709 (2)	C3—C4	1.384 (3)
O1—C7	1.328 (3)	C4—C5	1.382 (3)
O1—C8	1.475 (3)	C5—C6	1.388 (3)
O2—C7	1.205 (3)	C5—H5	0.9500
O3—N1	1.227 (3)	C6—C7	1.505 (3)
O4—N1	1.217 (3)	C8—C9	1.500 (3)
O5—N2	1.216 (3)	C8—C10	1.503 (3)
O6—N2	1.215 (3)	C8—H8	1.0000
N1—C2	1.472 (3)	C9—H9A	0.9800
N2—C4	1.474 (3)	C9—H9B	0.9800
C1—C2	1.382 (3)	C9—H9C	0.9800
C1—C6	1.388 (3)	C10—H10A	0.9800
C1—H1	0.9500	C10—H10B	0.9800
C2—C3	1.395 (3)	C10—H10C	0.9800

C7—O1—C8	116.83 (18)	C1—C6—C7	121.8 (2)
O4—N1—O3	125.7 (2)	C5—C6—C7	117.9 (2)
O4—N1—C2	118.2 (2)	O2—C7—O1	125.9 (2)
O3—N1—C2	116.1 (2)	O2—C7—C6	122.6 (2)
O6—N2—O5	125.8 (2)	O1—C7—C6	111.5 (2)
O6—N2—C4	116.5 (2)	O1—C8—C9	107.98 (19)
O5—N2—C4	117.61 (19)	O1—C8—C10	105.83 (19)
C2—C1—C6	119.1 (2)	C9—C8—C10	113.8 (2)
C2—C1—H1	120.4	O1—C8—H8	109.7
C6—C1—H1	120.4	C9—C8—H8	109.7
C1—C2—C3	122.5 (2)	C10—C8—H8	109.7
C1—C2—N1	117.2 (2)	C8—C9—H9A	109.5
C3—C2—N1	120.3 (2)	C8—C9—H9B	109.5
C4—C3—C2	116.1 (2)	H9A—C9—H9B	109.5
C4—C3—Cl1	120.62 (18)	C8—C9—H9C	109.5
C2—C3—Cl1	123.26 (19)	H9A—C9—H9C	109.5
C5—C4—C3	123.4 (2)	H9B—C9—H9C	109.5
C5—C4—N2	117.8 (2)	C8—C10—H10A	109.5
C3—C4—N2	118.8 (2)	C8—C10—H10B	109.5
C4—C5—C6	118.5 (2)	H10A—C10—H10B	109.5
C4—C5—H5	120.7	C8—C10—H10C	109.5
C6—C5—H5	120.7	H10A—C10—H10C	109.5
C1—C6—C5	120.3 (2)	H10B—C10—H10C	109.5

C6—C1—C2—C3	−1.1 (3)	O6—N2—C4—C3	−92.1 (3)
C6—C1—C2—N1	179.8 (2)	O5—N2—C4—C3	87.7 (3)
O4—N1—C2—C1	−131.1 (2)	C3—C4—C5—C6	−0.3 (3)
O3—N1—C2—C1	48.2 (3)	N2—C4—C5—C6	179.6 (2)
O4—N1—C2—C3	49.9 (3)	C2—C1—C6—C5	2.0 (3)
O3—N1—C2—C3	−130.8 (2)	C2—C1—C6—C7	−177.5 (2)
C1—C2—C3—C4	−0.4 (3)	C4—C5—C6—C1	−1.3 (3)
N1—C2—C3—C4	178.6 (2)	C4—C5—C6—C7	178.3 (2)
C1—C2—C3—Cl1	−178.36 (18)	C8—O1—C7—O2	1.9 (3)
N1—C2—C3—Cl1	0.6 (3)	C8—O1—C7—C6	−178.73 (17)
C2—C3—C4—C5	1.2 (3)	C1—C6—C7—O2	170.8 (2)
Cl1—C3—C4—C5	179.18 (18)	C5—C6—C7—O2	−8.8 (3)
C2—C3—C4—N2	−178.78 (19)	C1—C6—C7—O1	−8.7 (3)
Cl1—C3—C4—N2	−0.8 (3)	C5—C6—C7—O1	171.78 (19)
O6—N2—C4—C5	87.9 (3)	C7—O1—C8—C9	84.7 (2)
O5—N2—C4—C5	−92.3 (3)	C7—O1—C8—C10	−153.16 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.95	2.35	3.178 (3)	146

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₀H₉ClN₂O₆
M_r	288.64
Crystal system, space group	Triclinic, P1
Temperature (K)	103
a, b, c (Å)	4.703 (2), 10.783 (5), 12.734 (5)
α, β, γ (°)	69.483 (12), 87.75 (2), 89.61 (2)
V (Å³)	604.3 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.57 × 0.22 × 0.10

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.830, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	5643, 2689, 1756
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.114, 1.00
No. of reflections	2689
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.27

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.95	2.35	3.178 (3)	146

Symmetry code: (i) −x+1, −y+1, −z+2.

Acknowledgements

The authors acknowledge financial support from Guangdong Food and Drug Vocational College, China.

References

Akira, S., Shoji, K. & Kenichi, S. (1978). Jpn. Patent No. 53101528. Google Scholar
Ferenc, B., Gyoery, K. & Mihaly, N. (1984). Ger. Patent No. 3410566. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar