Bifenox: methyl 5-(2,4-di-chloro-phen-oxy)-2-nitro-benzoate.

In the title compound, the herbicide bifenox, C14H9Cl2NO5, the dihedral angle between the dichlorobenzene and nitro-benzene rings is 78.79 (14)°. In the crystal, C-H⋯O hydrogen bonds give rise to a three-dimensional network structure in which there are both a π-π inter-action [ring centroid separation = 3.6212 (16) Å] and a C-Cl⋯π inter-action [Cl⋯ring centroid = 3.4754 (8) Å]. In addition, short Cl⋯Cl contacts [3.3767 (11) and 3.3946 (11) Å] are present.

Related literature

For information on the insecticidal activity of the title compound, see: Jinno et al. (1999 ▶); O’Neil (2001 ▶). For a related crystal structure, see: Smith et al. (1981 ▶).

Experimental

Crystal data

C14H9Cl2NO5

M = 342.12

Triclinic,

a = 8.4945 (7) Å

b = 9.9610 (8) Å

c = 10.3969 (8) Å

α = 64.601 (1)°

β = 68.720 (1)°

γ = 70.421 (1)°

V = 723.48 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.47 mm−1

T = 173 K

0.20 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.912, T max = 0.954

5707 measured reflections

2830 independent reflections

2217 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.098

S = 1.06

2830 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813018266/zs2269sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018266/zs2269Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813018266/zs2269Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H9Cl2NO5	Z = 2
Mr = 342.12	F(000) = 348
Triclinic, P1	Dx = 1.570 Mg m−3
Hall symbol: -P 1	Melting point = 357–359 K
a = 8.4945 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9610 (8) Å	Cell parameters from 2834 reflections
c = 10.3969 (8) Å	θ = 2.3–27.4°
α = 64.601 (1)°	µ = 0.47 mm−1
β = 68.720 (1)°	T = 173 K
γ = 70.421 (1)°	Block, colourless
V = 723.48 (10) Å3	0.20 × 0.10 × 0.10 mm

Bruker APEXII CCD-detector diffractometer	2830 independent reflections
Radiation source: fine-focus sealed tube	2217 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→10
Tmin = 0.912, Tmax = 0.954	k = −12→12
5707 measured reflections	l = −12→12

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0274P)2 + 0.5552P] where P = (Fo2 + 2Fc2)/3
2830 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	1.32195 (8)	0.11710 (8)	0.94482 (7)	0.03459 (19)
Cl2	1.02470 (9)	−0.03963 (9)	0.66832 (8)	0.0410 (2)
O1	0.7224 (2)	0.2017 (2)	0.74018 (19)	0.0329 (5)
O2	0.2690 (2)	0.3461 (3)	0.4414 (2)	0.0493 (6)
O3	0.4770 (2)	0.2201 (2)	0.3023 (2)	0.0379 (5)
O4	0.5339 (3)	0.5178 (3)	0.1364 (2)	0.0515 (6)
O5	0.8081 (2)	0.5119 (2)	0.0585 (2)	0.0371 (5)
N1	0.6782 (3)	0.4819 (2)	0.1575 (2)	0.0301 (5)
C1	1.1456 (3)	0.1440 (3)	0.8819 (3)	0.0256 (6)
C2	1.1569 (3)	0.0548 (3)	0.8061 (3)	0.0266 (6)
H2	1.2589	−0.0193	0.7880	0.032*
C3	1.0159 (3)	0.0761 (3)	0.7571 (3)	0.0256 (6)
C4	0.8694 (3)	0.1865 (3)	0.7802 (3)	0.0267 (6)
C5	0.8603 (3)	0.2739 (3)	0.8570 (3)	0.0285 (6)
H5	0.7588	0.3487	0.8742	0.034*
C6	0.9992 (3)	0.2526 (3)	0.9092 (3)	0.0281 (6)
H6	0.9935	0.3117	0.9627	0.034*
C7	0.7221 (3)	0.2709 (3)	0.5937 (3)	0.0264 (6)
C8	0.8489 (3)	0.3448 (3)	0.4844 (3)	0.0272 (6)
H8	0.9450	0.3493	0.5076	0.033*
C9	0.8337 (3)	0.4121 (3)	0.3410 (3)	0.0267 (6)
H9	0.9191	0.4638	0.2648	0.032*
C10	0.6932 (3)	0.4035 (3)	0.3092 (3)	0.0244 (5)
C11	0.5659 (3)	0.3277 (3)	0.4177 (3)	0.0254 (6)
C12	0.5811 (3)	0.2624 (3)	0.5610 (3)	0.0260 (6)
H12	0.4951	0.2116	0.6375	0.031*
C13	0.4188 (3)	0.3035 (3)	0.3881 (3)	0.0273 (6)
C14	0.3450 (4)	0.1934 (4)	0.2634 (4)	0.0501 (9)
H14A	0.2658	0.1409	0.3533	0.075*
H14B	0.3999	0.1304	0.2013	0.075*
H14C	0.2802	0.2909	0.2093	0.075*

	U11	U22	U33	U12	U13	U23
Cl1	0.0281 (3)	0.0478 (4)	0.0343 (4)	−0.0092 (3)	−0.0157 (3)	−0.0130 (3)
Cl2	0.0433 (4)	0.0470 (5)	0.0498 (5)	−0.0054 (3)	−0.0189 (3)	−0.0297 (4)
O1	0.0243 (9)	0.0494 (12)	0.0270 (10)	−0.0116 (9)	−0.0117 (8)	−0.0081 (9)
O2	0.0217 (10)	0.0761 (16)	0.0698 (15)	−0.0060 (10)	−0.0101 (10)	−0.0478 (13)
O3	0.0288 (10)	0.0505 (13)	0.0516 (13)	−0.0017 (9)	−0.0186 (9)	−0.0315 (11)
O4	0.0353 (12)	0.0652 (15)	0.0457 (13)	−0.0094 (11)	−0.0264 (10)	0.0000 (11)
O5	0.0334 (11)	0.0450 (12)	0.0299 (10)	−0.0096 (9)	−0.0056 (9)	−0.0117 (9)
N1	0.0298 (12)	0.0278 (12)	0.0343 (13)	−0.0021 (10)	−0.0161 (10)	−0.0090 (10)
C1	0.0240 (13)	0.0306 (14)	0.0216 (13)	−0.0088 (11)	−0.0088 (10)	−0.0040 (11)
C2	0.0234 (13)	0.0279 (14)	0.0264 (14)	−0.0032 (11)	−0.0087 (11)	−0.0073 (11)
C3	0.0269 (13)	0.0272 (14)	0.0245 (13)	−0.0073 (11)	−0.0082 (11)	−0.0083 (11)
C4	0.0234 (13)	0.0334 (15)	0.0247 (13)	−0.0110 (11)	−0.0108 (10)	−0.0040 (11)
C5	0.0256 (13)	0.0281 (14)	0.0316 (14)	−0.0012 (11)	−0.0099 (11)	−0.0115 (12)
C6	0.0324 (14)	0.0276 (14)	0.0273 (14)	−0.0085 (11)	−0.0081 (11)	−0.0106 (12)
C7	0.0226 (13)	0.0278 (14)	0.0295 (14)	−0.0024 (11)	−0.0123 (11)	−0.0083 (12)
C8	0.0231 (13)	0.0272 (14)	0.0355 (15)	−0.0045 (11)	−0.0151 (11)	−0.0093 (12)
C9	0.0246 (13)	0.0230 (13)	0.0310 (15)	−0.0057 (11)	−0.0106 (11)	−0.0046 (11)
C10	0.0240 (13)	0.0201 (13)	0.0287 (14)	−0.0009 (10)	−0.0115 (11)	−0.0074 (11)
C11	0.0194 (12)	0.0238 (13)	0.0351 (15)	−0.0006 (10)	−0.0104 (11)	−0.0126 (12)
C12	0.0215 (12)	0.0315 (14)	0.0267 (14)	−0.0052 (11)	−0.0083 (11)	−0.0103 (12)
C13	0.0233 (14)	0.0287 (14)	0.0304 (14)	−0.0042 (11)	−0.0098 (11)	−0.0096 (12)
C14	0.0442 (18)	0.063 (2)	0.067 (2)	−0.0051 (16)	−0.0316 (17)	−0.0349 (19)

Cl1—C1	1.743 (2)	C5—C6	1.389 (3)
Cl2—C3	1.729 (3)	C5—H5	0.9500
O1—C7	1.377 (3)	C6—H6	0.9500
O1—C4	1.397 (3)	C7—C8	1.386 (3)
O2—C13	1.198 (3)	C7—C12	1.394 (3)
O3—C13	1.331 (3)	C8—C9	1.383 (3)
O3—C14	1.454 (3)	C8—H8	0.9500
O4—N1	1.230 (3)	C9—C10	1.386 (3)
O5—N1	1.224 (3)	C9—H9	0.9500
N1—C10	1.462 (3)	C10—C11	1.393 (3)
C1—C6	1.379 (4)	C11—C12	1.383 (3)
C1—C2	1.381 (4)	C11—C13	1.504 (3)
C2—C3	1.386 (3)	C12—H12	0.9500
C2—H2	0.9500	C14—H14A	0.9800
C3—C4	1.382 (4)	C14—H14B	0.9800
C4—C5	1.381 (4)	C14—H14C	0.9800
C7—O1—C4	118.65 (19)	C8—C7—C12	121.1 (2)
C13—O3—C14	115.5 (2)	C9—C8—C7	119.1 (2)
O5—N1—O4	123.3 (2)	C9—C8—H8	120.5
O5—N1—C10	118.8 (2)	C7—C8—H8	120.5
O4—N1—C10	117.9 (2)	C8—C9—C10	119.6 (2)
C6—C1—C2	121.9 (2)	C8—C9—H9	120.2
C6—C1—Cl1	119.5 (2)	C10—C9—H9	120.2
C2—C1—Cl1	118.61 (19)	C9—C10—C11	121.9 (2)
C1—C2—C3	118.4 (2)	C9—C10—N1	117.7 (2)
C1—C2—H2	120.8	C11—C10—N1	120.3 (2)
C3—C2—H2	120.8	C12—C11—C10	118.1 (2)
C4—C3—C2	120.7 (2)	C12—C11—C13	117.5 (2)
C4—C3—Cl2	120.33 (19)	C10—C11—C13	124.3 (2)
C2—C3—Cl2	118.96 (19)	C11—C12—C7	120.2 (2)
C5—C4—C3	120.0 (2)	C11—C12—H12	119.9
C5—C4—O1	118.7 (2)	C7—C12—H12	119.9
C3—C4—O1	121.0 (2)	O2—C13—O3	124.4 (2)
C4—C5—C6	120.1 (2)	O2—C13—C11	124.5 (2)
C4—C5—H5	119.9	O3—C13—C11	111.0 (2)
C6—C5—H5	119.9	O3—C14—H14A	109.5
C1—C6—C5	118.8 (2)	O3—C14—H14B	109.5
C1—C6—H6	120.6	H14A—C14—H14B	109.5
C5—C6—H6	120.6	O3—C14—H14C	109.5
O1—C7—C8	124.2 (2)	H14A—C14—H14C	109.5
O1—C7—C12	114.7 (2)	H14B—C14—H14C	109.5
C6—C1—C2—C3	−0.2 (4)	C8—C9—C10—C11	−0.5 (4)
Cl1—C1—C2—C3	179.62 (19)	C8—C9—C10—N1	177.3 (2)
C1—C2—C3—C4	1.6 (4)	O5—N1—C10—C9	21.5 (3)
C1—C2—C3—Cl2	−177.51 (19)	O4—N1—C10—C9	−156.8 (2)
C2—C3—C4—C5	−2.1 (4)	O5—N1—C10—C11	−160.7 (2)
Cl2—C3—C4—C5	177.1 (2)	O4—N1—C10—C11	21.0 (3)
C2—C3—C4—O1	−175.6 (2)	C9—C10—C11—C12	1.2 (4)
Cl2—C3—C4—O1	3.6 (3)	N1—C10—C11—C12	−176.5 (2)
C7—O1—C4—C5	109.5 (3)	C9—C10—C11—C13	−174.7 (2)
C7—O1—C4—C3	−77.0 (3)	N1—C10—C11—C13	7.6 (4)
C3—C4—C5—C6	1.0 (4)	C10—C11—C12—C7	−1.1 (4)
O1—C4—C5—C6	174.6 (2)	C13—C11—C12—C7	175.1 (2)
C2—C1—C6—C5	−0.9 (4)	O1—C7—C12—C11	180.0 (2)
Cl1—C1—C6—C5	179.32 (19)	C8—C7—C12—C11	0.3 (4)
C4—C5—C6—C1	0.5 (4)	C14—O3—C13—O2	5.6 (4)
C4—O1—C7—C8	−8.8 (4)	C14—O3—C13—C11	−178.4 (2)
C4—O1—C7—C12	171.5 (2)	C12—C11—C13—O2	61.9 (4)
O1—C7—C8—C9	−179.2 (2)	C10—C11—C13—O2	−122.1 (3)
C12—C7—C8—C9	0.5 (4)	C12—C11—C13—O3	−114.1 (3)
C7—C8—C9—C10	−0.4 (4)	C10—C11—C13—O3	61.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4i	0.95	2.41	3.290 (3)	153
C6—H6···O5ii	0.95	2.43	3.243 (3)	143
C8—H8···O2iii	0.95	2.58	3.435 (3)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O4i	0.95	2.41	3.290 (3)	153
C6—H6⋯O5ii	0.95	2.43	3.243 (3)	143
C8—H8⋯O2iii	0.95	2.58	3.435 (3)	151

Symmetry codes: (i) ; (ii) ; (iii) .