1-(4-Chloro-2-fluoro-5-nitro­phen­yl)-4-difluoro­methyl-3-methyl-1H-1,2,4-triazol-5(4H)-one

Yang, L.; Liu, J.

doi:10.1107/S1600536812013013

organic compounds

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doi:10.1107/S1600536812013013

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1-(4-Chloro-2-fluoro-5-nitrophenyl)-4-difluoromethyl-3-methyl-1H-1,2,4-triazol-5(4H)-one

Li Yang ^a ^* and Jun Liu ^a

^aHenan Medical College for Staff and Workers, Zhengzhou 451191, People's Republic of China
^*Correspondence e-mail: yang_l2012@163.com

(Received 19 March 2012; accepted 25 March 2012; online 13 April 2012)

In the title compound, C₁₀H₆ClF₃N₄O₃, the dihedral angle between the benzene ring and the triazolone ring is 59.9 (1)°, while the nitro substituent subtends an angle of 39.5 (1)° to the benzene ring plane. In the crystal, pairs of molecules form inversion dimers via C—H⋯O hydrogen bonds.

Related literature

For background to applications of this class of compound, see: Ager & Polsz (1996 ). For the synthesis and the use of the title compound in the production of herbicides, see: Goudar (1998 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₆ClF₃N₄O₃
M_r = 322.64
Monoclinic, P 2₁ /c
a = 12.556 (3) Å
b = 14.800 (3) Å
c = 6.8760 (14) Å
β = 103.32 (3)°
V = 1243.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.899, T_max = 0.965
4877 measured reflections
2293 independent reflections
1589 reflections with I > 2σ(I)
R_int = 0.073
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.185
S = 1.01
2293 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1ⁱ	0.98	2.32	3.190 (6)	148
Symmetry code: (i) -x+2, -y+1, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812013013/sj5217sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013013/sj5217Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013013/sj5217Isup3.cml

checkCIF report

Comment top

The title compound is an important intermediate used to synthesize the herbicide Carfentrazone-ethyl. It can also be used to synthesize other herbicides (Goudar, 1998), which are of wide interest for application to the control of broadleaf weeds and sedges (Ager & Polsz, 1996). We report here the crystal structure of the title compound, (I), which is of interest to us in this field.

The molecular structure of (I) is shown in Fig. 1. Bond distances in the molecule are normal (Allen et al., 1987). The dihedral angle between the C1—C6 and N1/N3/C8/N2/C7 rings is 59.9 (1)° and the nitro substituent subtends an angle of 39.5 (1)° to the benzene ring plane.. In the crystal structure, molecules form inversion dimers via intermolecular C10—H10A···O1 hydrogen bonds (Table 1, Fig 2) .

Related literature top

For background to applications of this class of compound, see: Ager & Polsz (1996). For the synthesis and the use of the title compound in the production of herbicides, see: Goudar (1998). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Goudar, 1998). Crystals were obtained by dissolving (I) (0.2 g) in acetone (50 ml) and evaporating the solvent slowly at room temperature over 10 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I) with hydrogen bonds drawn as dashed lines.

1-(4-Chloro-2-fluoro-5-nitrophenyl)-4-difluoromethyl-3-methyl-1H- 1,2,4-triazol-5(4H)-one top

Crystal data top

C₁₀H₆ClF₃N₄O₃	F(000) = 648
M_r = 322.64	D_x = 1.724 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.556 (3) Å	θ = 9–13°
b = 14.800 (3) Å	µ = 0.36 mm⁻¹
c = 6.8760 (14) Å	T = 293 K
β = 103.32 (3)°	Block, colourless
V = 1243.4 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1589 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.073
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
ω/2θ scans	h = −15→14
Absorption correction: ψ scan (North et al., 1968)	k = −17→17
T_min = 0.899, T_max = 0.965	l = 0→8
4877 measured reflections	3 standard reflections every 200 reflections
2293 independent reflections	intensity decay: 1%

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.330P] where P = (F_o² + 2F_c²)/3
2293 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.78 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₀H₆ClF₃N₄O₃	V = 1243.4 (4) Å³
M_r = 322.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.556 (3) Å	µ = 0.36 mm⁻¹
b = 14.800 (3) Å	T = 293 K
c = 6.8760 (14) Å	0.30 × 0.20 × 0.10 mm
β = 103.32 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1589 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.073
T_min = 0.899, T_max = 0.965	3 standard reflections every 200 reflections
4877 measured reflections	intensity decay: 1%
2293 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.01	Δρ_max = 0.78 e Å⁻³
2293 reflections	Δρ_min = −0.34 e Å⁻³
190 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
Cl	0.47555 (10)	0.11625 (7)	0.08507 (17)	0.0670 (4)
F1	0.84029 (19)	0.26681 (16)	0.2492 (4)	0.0710 (7)
C1	0.5785 (3)	0.3747 (2)	0.1483 (5)	0.0470 (9)
H1A	0.5481	0.4322	0.1386	0.056*
N1	0.7581 (2)	0.43972 (19)	0.2491 (4)	0.0444 (7)
O1	0.8646 (3)	0.4432 (2)	0.0175 (5)	0.0709 (9)
O2	0.3580 (3)	0.3887 (3)	0.0249 (5)	0.0798 (10)
C2	0.5118 (3)	0.2996 (3)	0.1173 (7)	0.0580 (10)
F2	0.9214 (3)	0.6832 (2)	0.1945 (7)	0.1216 (14)
N2	0.7474 (2)	0.4912 (2)	0.4138 (5)	0.0481 (8)
N3	0.8789 (2)	0.5451 (2)	0.2821 (5)	0.0469 (8)
C3	0.5549 (3)	0.2129 (2)	0.1239 (6)	0.0521 (9)
F3	1.0420 (2)	0.6114 (2)	0.4004 (5)	0.0862 (9)
C4	0.6663 (3)	0.2027 (2)	0.1651 (5)	0.0414 (8)
H4A	0.6970	0.1454	0.1694	0.050*
N4	0.3939 (4)	0.3183 (3)	0.0870 (10)	0.113 (2)
C5	0.7323 (3)	0.2774 (2)	0.2001 (5)	0.0408 (8)
C6	0.6898 (3)	0.3641 (2)	0.1934 (5)	0.0379 (8)
C7	0.8207 (3)	0.5538 (2)	0.4266 (6)	0.0476 (9)
C8	0.8380 (3)	0.4709 (2)	0.1627 (5)	0.0471 (9)
C9	0.8423 (4)	0.6223 (3)	0.5868 (8)	0.0770 (14)
H9A	0.7916	0.6145	0.6708	0.116*
H9B	0.8337	0.6816	0.5287	0.116*
H9C	0.9157	0.6153	0.6653	0.116*
C10	0.9601 (3)	0.6014 (3)	0.2389 (7)	0.0626 (12)
H10A	0.9878	0.5764	0.1281	0.075*
O3	0.3405 (3)	0.2597 (4)	0.1869 (10)	0.143 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0777 (8)	0.0436 (6)	0.0810 (8)	−0.0207 (5)	0.0213 (6)	−0.0081 (5)
F1	0.0482 (13)	0.0551 (15)	0.109 (2)	0.0087 (11)	0.0167 (13)	−0.0066 (14)
C1	0.054 (2)	0.0352 (19)	0.053 (2)	0.0013 (16)	0.0148 (18)	0.0006 (15)
N1	0.0564 (18)	0.0368 (16)	0.0461 (16)	−0.0068 (14)	0.0245 (14)	−0.0097 (13)
O1	0.083 (2)	0.071 (2)	0.0702 (18)	−0.0221 (17)	0.0428 (17)	−0.0113 (16)
O2	0.062 (2)	0.077 (2)	0.097 (2)	0.0182 (17)	0.0115 (18)	0.0012 (19)
C2	0.045 (2)	0.042 (2)	0.081 (3)	−0.0005 (17)	0.003 (2)	−0.0040 (19)
F2	0.078 (2)	0.0610 (19)	0.216 (4)	−0.0003 (15)	0.015 (2)	0.064 (2)
N2	0.0489 (18)	0.0391 (17)	0.0596 (19)	−0.0017 (14)	0.0191 (15)	−0.0098 (14)
N3	0.0440 (17)	0.0391 (17)	0.0594 (18)	−0.0089 (13)	0.0157 (15)	−0.0011 (14)
C3	0.060 (2)	0.036 (2)	0.057 (2)	−0.0128 (18)	0.0075 (18)	−0.0031 (16)
F3	0.0552 (16)	0.085 (2)	0.107 (2)	−0.0209 (14)	−0.0060 (15)	0.0192 (16)
C4	0.064 (2)	0.0314 (17)	0.0366 (17)	0.0015 (16)	0.0283 (16)	−0.0008 (14)
N4	0.047 (2)	0.061 (3)	0.221 (6)	−0.007 (2)	0.011 (3)	−0.023 (4)
C5	0.046 (2)	0.047 (2)	0.0308 (16)	0.0043 (16)	0.0127 (14)	0.0011 (14)
C6	0.056 (2)	0.0337 (18)	0.0290 (16)	−0.0064 (15)	0.0188 (15)	−0.0035 (12)
C7	0.046 (2)	0.0327 (18)	0.060 (2)	0.0052 (16)	0.0041 (18)	−0.0031 (16)
C8	0.059 (2)	0.042 (2)	0.0453 (19)	−0.0057 (17)	0.0238 (18)	0.0005 (16)
C9	0.066 (3)	0.056 (3)	0.110 (4)	−0.002 (2)	0.021 (3)	−0.031 (3)
C10	0.059 (3)	0.040 (2)	0.089 (3)	−0.0079 (19)	0.017 (2)	0.023 (2)
O3	0.066 (2)	0.120 (4)	0.248 (7)	−0.023 (3)	0.044 (3)	−0.065 (4)

Geometric parameters (Å, º) top

Cl—C3	1.729 (4)	N3—C7	1.368 (5)
F1—C5	1.329 (4)	N3—C8	1.397 (5)
C1—C6	1.368 (5)	N3—C10	1.401 (5)
C1—C2	1.379 (5)	C3—C4	1.370 (5)
C1—H1A	0.9300	F3—C10	1.336 (5)
N1—C8	1.359 (5)	C4—C5	1.369 (5)
N1—N2	1.397 (4)	C4—H4A	0.9300
N1—C6	1.408 (4)	N4—O3	1.373 (8)
O1—C8	1.196 (4)	C5—C6	1.387 (5)
O2—N4	1.176 (6)	C7—C9	1.475 (6)
C2—C3	1.389 (5)	C9—H9A	0.9600
C2—N4	1.473 (6)	C9—H9B	0.9600
F2—C10	1.315 (5)	C9—H9C	0.9600
N2—C7	1.294 (5)	C10—H10A	0.9800

C6—C1—C2	119.7 (3)	F1—C5—C6	118.7 (3)
C6—C1—H1A	120.1	C4—C5—C6	121.9 (3)
C2—C1—H1A	120.1	C1—C6—C5	118.6 (3)
C8—N1—N2	112.8 (3)	C1—C6—N1	119.8 (3)
C8—N1—C6	128.0 (3)	C5—C6—N1	121.3 (3)
N2—N1—C6	119.2 (3)	N2—C7—N3	111.9 (3)
C1—C2—C3	121.4 (4)	N2—C7—C9	123.3 (4)
C1—C2—N4	115.2 (4)	N3—C7—C9	124.7 (4)
C3—C2—N4	123.3 (4)	O1—C8—N1	128.7 (4)
C7—N2—N1	104.3 (3)	O1—C8—N3	128.7 (3)
C7—N3—C8	108.4 (3)	N1—C8—N3	102.6 (3)
C7—N3—C10	129.4 (3)	C7—C9—H9A	109.5
C8—N3—C10	122.0 (3)	C7—C9—H9B	109.5
C4—C3—C2	118.7 (3)	H9A—C9—H9B	109.5
C4—C3—Cl	117.7 (3)	C7—C9—H9C	109.5
C2—C3—Cl	123.5 (3)	H9A—C9—H9C	109.5
C5—C4—C3	119.7 (3)	H9B—C9—H9C	109.5
C5—C4—H4A	120.2	F2—C10—F3	105.3 (4)
C3—C4—H4A	120.2	F2—C10—N3	110.4 (4)
O2—N4—O3	123.4 (5)	F3—C10—N3	110.4 (3)
O2—N4—C2	120.4 (5)	F2—C10—H10A	110.2
O3—N4—C2	113.7 (5)	F3—C10—H10A	110.2
F1—C5—C4	119.4 (3)	N3—C10—H10A	110.2

C6—C1—C2—C3	−2.3 (6)	C8—N1—C6—C1	−123.1 (4)
C6—C1—C2—N4	174.9 (4)	N2—N1—C6—C1	57.8 (4)
C8—N1—N2—C7	0.3 (4)	C8—N1—C6—C5	62.6 (5)
C6—N1—N2—C7	179.5 (3)	N2—N1—C6—C5	−116.5 (3)
C1—C2—C3—C4	1.0 (6)	N1—N2—C7—N3	−0.9 (4)
N4—C2—C3—C4	−176.0 (5)	N1—N2—C7—C9	−177.2 (4)
C1—C2—C3—Cl	−179.7 (3)	C8—N3—C7—N2	1.2 (4)
N4—C2—C3—Cl	3.4 (7)	C10—N3—C7—N2	176.2 (4)
C2—C3—C4—C5	0.5 (6)	C8—N3—C7—C9	177.5 (4)
Cl—C3—C4—C5	−178.9 (2)	C10—N3—C7—C9	−7.5 (6)
C1—C2—N4—O2	25.3 (8)	N2—N1—C8—O1	−177.8 (4)
C3—C2—N4—O2	−157.6 (5)	C6—N1—C8—O1	3.1 (7)
C1—C2—N4—O3	−137.4 (5)	N2—N1—C8—N3	0.4 (4)
C3—C2—N4—O3	39.7 (8)	C6—N1—C8—N3	−178.7 (3)
C3—C4—C5—F1	176.9 (3)	C7—N3—C8—O1	177.3 (4)
C3—C4—C5—C6	−0.6 (5)	C10—N3—C8—O1	1.9 (6)
C2—C1—C6—C5	2.1 (5)	C7—N3—C8—N1	−0.9 (4)
C2—C1—C6—N1	−172.3 (3)	C10—N3—C8—N1	−176.3 (3)
F1—C5—C6—C1	−178.2 (3)	C7—N3—C10—F2	−59.3 (6)
C4—C5—C6—C1	−0.7 (5)	C8—N3—C10—F2	115.1 (5)
F1—C5—C6—N1	−3.9 (4)	C7—N3—C10—F3	56.7 (5)
C4—C5—C6—N1	173.6 (3)	C8—N3—C10—F3	−128.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱ	0.98	2.32	3.190 (6)	148

Symmetry code: (i) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₆ClF₃N₄O₃
M_r	322.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.556 (3), 14.800 (3), 6.8760 (14)
β (°)	103.32 (3)
V (Å³)	1243.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.899, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	4877, 2293, 1589
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.185, 1.01
No. of reflections	2293
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.34

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱ	0.9800	2.3200	3.190 (6)	148.00

Symmetry code: (i) −x+2, −y+1, −z.

Acknowledgements

The authors thank the Center for Testing and Analysis, Nanjing University, for the data collection.

References

Ager, J. W. & Polsz, C. A. (1996). EP Patent No. 1273232. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Goudar, J. S. (1998). US Patent No. 5756755. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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1-(4-Chloro-2-fluoro-5-nitro­phen­yl)-4-di­fluoro­methyl-3-methyl-1H-1,2,4-triazol-5(4H)-one

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-(4-Chloro-2-fluoro-5-nitrophenyl)-4-difluoromethyl-3-methyl-1H-1,2,4-triazol-5(4H)-one