Isopropyl 4-chloro-3,5-dinitro­benzoate

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.

Key indicators

• Single-crystal X-ray study
• T = 103 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.114
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O4      ..       2.98 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         30
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         37

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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

S3. Refinement

H atoms were placed in calculated positions and were allowed to ride on the parent C atoms with C—H distances of 0.95 (aromatic), 0.98 (methyl) and 1.00 Å (methine); U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others.

Computing details

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

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

Crystal data

C10H9ClN2O6	Z = 2
Mr = 288.64	F(000) = 296
Triclinic, P1	Dx = 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) Å^3

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 0.219P] where P = (Fo^2 + 2Fc^2)/3
2689 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2^i	0.95	2.35	3.178 (3)	146

Symmetry code: (i) −x+1, −y+1, −z+2.