Bifenox: methyl 5-(2,4-di­chloro­phen­oxy)-2-nitro­benzoate

In the title compound, the herbicide bifenox, C₁₄H₉Cl₂NO₅, the dihedral angle between the dichlorobenzene and nitro­benzene 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 inter­action [ring centroid separation = 3.6212 (16) Å] and a C—Cl...π inter­action [Cl...ring centroid = 3.4754 (8) Å]. In addition, short Cl...Cl contacts [3.3767 (11) and 3.3946 (11) Å] are present.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.098
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      6.474
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         17

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ? Do !
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00100 Deg.
PLAT434_ALERT_2_G Short Inter HL..HL Contact  Cl1    ..  Cl1     .       3.38 Ang.
PLAT434_ALERT_2_G Short Inter HL..HL Contact  Cl2    ..  Cl2     .       3.39 Ang.
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         15
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          ! Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

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

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S1. Comment

The title compound bifenox, C₁₄H₉Cl₂NO₅, is commonly used as a photobleaching herbicide for the control of many types of weeds (Jinno et al., 1999; O'Neil, 2001) and its crystal structure is reported herein. In this compound (Fig. 1), the dihedral angle between the dichlorophenyl ring and the nitrobenzene ring is 78.79 (14)°. All bond lengths and bond angles are normal and comparable to those observed in a similar phenoxy herbicide structure, methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propionate (diclofop methyl) (Smith et al., 1981).

In the crystal structure (Fig. 2), intermolecular C—H···O hydrogen bonds are observed (Table 1), giving a three-dimensional network structure (Fig. 2). In this structure there are both a π–π interaction between the dichlorophenyl rings [ring centroid separation = 3.6212 (16) Å] and a C3—Cl2···π interaction with the nitrobenzene ring [Cl2···Cg^iv = 3.4754 (8) Å]. In addition, short Cl···Cl contacts [Cl1···Cl1^v, 3.3767 (11) Å and Cl2···Cl2^iv3.3946 (11) Å] are present [for symmetry codes: (iv), -x+2, -y, -z+1 and (v), -x+3, -y, -z+2].

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).

S2. Experimental

The title compound was purchased from Wako Pure Chemicals. Slow evaporation of a solution in CH₂Cl₂ gave single crystals suitable for X-ray analysis.

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.95 Å, U_iso = 1.2U_eq(C) for Csp²—H and d(C—H) = 0.98 Å, U_iso = 1.5U_eq(C) for CH₃ groups.

Computing details

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

	Fig. 1. The molecular structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Crystal packing of the title compound with weak intermolecular Cl···Cl interactions and C—H···O hydrogen bonds shown as dashed lines.

Methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate

Crystal data

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) Å^3	0.20 × 0.10 × 0.10 mm

Data collection

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

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0274P)^2 + 0.5552P] where P = (Fo^2 + 2Fc^2)/3
2830 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.33 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	1.32195 (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*

Atomic displacement parameters (Ų)

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

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4^i	0.95	2.41	3.290 (3)	153
C6—H6···O5^ii	0.95	2.43	3.243 (3)	143
C8—H8···O2^iii	0.95	2.58	3.435 (3)	151

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