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

Ren, D.; Wang, Y.

doi:10.1107/S1600536812009452

organic compounds

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Volume 68| Part 4| April 2012| Page o1048

doi:10.1107/S1600536812009452

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

Dong-mei Ren ^a ^* and Yong-yi Wang ^a

^aSecurity and Environment Engineering College, Capital University of Economics and Business, Beijing 10070, People's Republic of China
^*Correspondence e-mail: nanoren@126.com

(Received 25 February 2012; accepted 4 March 2012; online 14 March 2012)

In the crystal structure of the title compound, C₁₀H₇ClF₃N₃O, pairs of molecules are connected into dimers via pairs of C—H⋯O hydrogen bonds. The dihedral angle between the benzene ring and attached triazolone ring is 53.2 (1)°.

Related literature

For background to this class of compound, see: Ager & Polz (1996 ); Li & Han (2010 ). For the synthesis of the title compound, see: Jaidev & Plainsboro (1998 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₇ClF₃N₃O
M_r = 277.64
Monoclinic, C 2/c
a = 15.286 (3) Å
b = 13.610 (3) Å
c = 11.231 (2) Å
β = 100.91 (3)°
V = 2294.3 (8) Å³
Z = 8
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
4290 measured reflections
2115 independent reflections
1273 reflections with I > 2σ(I)
R_int = 0.036
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.143
S = 1.00
2115 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.23 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⋯Oⁱ	0.98	2.41	3.259 (4)	144
Symmetry code: (i) $[-x+1, y, -z-{\script{1\over 2}}]$ .

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/S1600536812009452/bq2341sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009452/bq2341Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009452/bq2341Isup3.cml

checkCIF report

Comment top

The title compound is an important intermediate used to synthesize the Carfentrazone-ethyl, which can be utilized to synthesize herbicides (Jaidev & Plainsboro, 1998), which are of wide interest for applications in control of broadleaf weeds and sedges (Ager & Polz, 1996). They are widely used in protection of wheat, barley, oats, rice, corn, etc (Li & Han, 2010). We report here the crystal structure of the title compound, (I), which is of interest to us in the field.

The molecular structure of (I) is shown in Figure 1. In the structure, the molecules were connected together via C—H···O intermolecular hydrogen bonds (Table 1 and Figure 2.) to form dimers. The dihedral angle of the rings A(C1—C6), B(N1/N3/C8/N2/C7) is: A/B = 53.2 (1)°.

Related literature top

The title compound is an intermediate in organic synthesis. For background to this class of compound, see: Ager & Polz (1996); Li & Han (2010). For the synthesis of the title compound, see: Jaidev & Plainsboro (1998). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Jaidev & Plainsboro, 1998). The crystals were obtained by dissolving (I) (0.2 g) in acetone (50 ml) and evaporating the solvent slowly at room temperature for about 10 d.

Structure description top

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 of (I) showing the dimers formed by C—H···O H-bonds.

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

Crystal data top

C₁₀H₇ClF₃N₃O	F(000) = 1120
M_r = 277.64	D_x = 1.608 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 15.286 (3) Å	θ = 10–13°
b = 13.610 (3) Å	µ = 0.36 mm⁻¹
c = 11.231 (2) Å	T = 293 K
β = 100.91 (3)°	Block, colorless
V = 2294.3 (8) Å³	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1273 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.4°, θ_min = 2.0°
ω/2θ scans	h = 0→18
Absorption correction: ψ scan (North et al., 1968)	k = −16→16
T_min = 0.899, T_max = 0.965	l = −13→13
4290 measured reflections	3 standard reflections every 200 reflections
2115 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.073P)²] where P = (F_o² + 2F_c²)/3
2115 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₀H₇ClF₃N₃O	V = 2294.3 (8) Å³
M_r = 277.64	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.286 (3) Å	µ = 0.36 mm⁻¹
b = 13.610 (3) Å	T = 293 K
c = 11.231 (2) Å	0.30 × 0.20 × 0.10 mm
β = 100.91 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1273 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.036
T_min = 0.899, T_max = 0.965	3 standard reflections every 200 reflections
4290 measured reflections	intensity decay: 1%
2115 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
2115 reflections	Δρ_min = −0.34 e Å⁻³
164 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	0.07385 (7)	0.56530 (8)	0.15418 (11)	0.1001 (5)
O	0.44175 (13)	0.54039 (17)	−0.12275 (18)	0.0621 (6)
F1	0.26705 (12)	0.64405 (16)	−0.14770 (16)	0.0796 (6)
N1	0.42189 (15)	0.65403 (18)	0.0253 (2)	0.0529 (6)
C1	0.3335 (2)	0.6085 (2)	0.1748 (3)	0.0637 (9)
H1A	0.3846	0.6094	0.2348	0.076*
N2	0.54325 (16)	0.66315 (18)	−0.0433 (2)	0.0541 (6)
F2	0.62510 (18)	0.72262 (17)	−0.1740 (2)	0.1082 (8)
C2	0.2523 (3)	0.5883 (3)	0.2052 (3)	0.0716 (10)
H2A	0.2483	0.5761	0.2855	0.086*
F3	0.68716 (13)	0.62152 (16)	−0.0370 (2)	0.0902 (7)
N3	0.47231 (18)	0.72846 (19)	0.0904 (2)	0.0598 (7)
C3	0.1768 (2)	0.5862 (2)	0.1157 (3)	0.0650 (9)
C4	0.1812 (2)	0.6026 (2)	−0.0036 (3)	0.0643 (9)
H4A	0.1304	0.5994	−0.0639	0.077*
C5	0.2627 (2)	0.6237 (2)	−0.0314 (3)	0.0547 (8)
C6	0.3396 (2)	0.6273 (2)	0.0557 (3)	0.0519 (7)
C7	0.4651 (2)	0.6095 (2)	−0.0559 (3)	0.0519 (7)
C8	0.5439 (2)	0.7331 (2)	0.0472 (3)	0.0576 (8)
C9	0.6171 (3)	0.8030 (3)	0.0887 (4)	0.0860 (11)
H9A	0.6034	0.8418	0.1541	0.129*
H9B	0.6242	0.8454	0.0228	0.129*
H9C	0.6714	0.7674	0.1160	0.129*
C10	0.6099 (2)	0.6433 (3)	−0.1112 (3)	0.0653 (9)
H10A	0.5914	0.5883	−0.1667	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0851 (7)	0.0982 (8)	0.1308 (10)	−0.0103 (6)	0.0553 (7)	−0.0134 (7)
O	0.0627 (13)	0.0687 (14)	0.0523 (12)	−0.0061 (11)	0.0041 (10)	−0.0161 (11)
F1	0.0680 (12)	0.1151 (16)	0.0514 (11)	0.0087 (11)	0.0005 (9)	0.0147 (10)
N1	0.0493 (14)	0.0558 (15)	0.0515 (14)	−0.0005 (12)	0.0043 (11)	−0.0083 (12)
C1	0.072 (2)	0.067 (2)	0.0484 (19)	0.0064 (17)	0.0025 (16)	−0.0009 (15)
N2	0.0524 (15)	0.0542 (15)	0.0540 (15)	−0.0009 (12)	0.0059 (12)	−0.0041 (12)
F2	0.133 (2)	0.0924 (17)	0.1152 (18)	0.0002 (15)	0.0645 (16)	0.0242 (14)
C2	0.090 (3)	0.068 (2)	0.061 (2)	0.006 (2)	0.026 (2)	0.0009 (17)
F3	0.0532 (12)	0.1008 (17)	0.1121 (17)	0.0055 (11)	0.0040 (11)	−0.0142 (13)
N3	0.0555 (16)	0.0563 (17)	0.0631 (17)	0.0009 (13)	0.0000 (13)	−0.0123 (12)
C3	0.068 (2)	0.0554 (19)	0.078 (2)	0.0011 (16)	0.0301 (19)	−0.0070 (17)
C4	0.051 (2)	0.065 (2)	0.074 (2)	0.0058 (16)	0.0060 (17)	−0.0029 (17)
C5	0.0574 (19)	0.0596 (19)	0.0447 (18)	0.0100 (15)	0.0033 (14)	0.0038 (14)
C6	0.0565 (19)	0.0483 (17)	0.0492 (18)	0.0060 (14)	0.0054 (14)	−0.0016 (13)
C7	0.0523 (18)	0.0570 (19)	0.0428 (17)	0.0052 (15)	0.0000 (14)	0.0011 (15)
C8	0.0539 (19)	0.0500 (18)	0.065 (2)	0.0000 (15)	0.0003 (16)	−0.0046 (15)
C9	0.081 (3)	0.068 (2)	0.105 (3)	−0.012 (2)	0.007 (2)	−0.020 (2)
C10	0.062 (2)	0.067 (2)	0.069 (2)	−0.0001 (17)	0.0165 (18)	0.0006 (17)

Geometric parameters (Å, º) top

Cl—C3	1.733 (3)	C2—C3	1.380 (5)
O—C7	1.214 (3)	C2—H2A	0.9300
F1—C5	1.349 (3)	F3—C10	1.344 (4)
N1—C7	1.365 (4)	N3—C8	1.280 (4)
N1—N3	1.393 (3)	C3—C4	1.373 (4)
N1—C6	1.412 (4)	C4—C5	1.371 (4)
C1—C2	1.375 (5)	C4—H4A	0.9300
C1—C6	1.383 (4)	C5—C6	1.380 (4)
C1—H1A	0.9300	C8—C9	1.476 (5)
N2—C7	1.385 (4)	C9—H9A	0.9600
N2—C8	1.391 (4)	C9—H9B	0.9600
N2—C10	1.409 (4)	C9—H9C	0.9600
F2—C10	1.334 (4)	C10—H10A	0.9800

C7—N1—N3	112.6 (2)	C5—C6—C1	118.3 (3)
C7—N1—C6	127.8 (3)	C5—C6—N1	121.1 (3)
N3—N1—C6	119.4 (2)	C1—C6—N1	120.5 (3)
C2—C1—C6	120.4 (3)	O—C7—N1	129.4 (3)
C2—C1—H1A	119.8	O—C7—N2	128.2 (3)
C6—C1—H1A	119.8	N1—C7—N2	102.4 (3)
C7—N2—C8	108.8 (3)	N3—C8—N2	110.8 (3)
C7—N2—C10	122.8 (3)	N3—C8—C9	124.3 (3)
C8—N2—C10	128.4 (3)	N2—C8—C9	124.9 (3)
C1—C2—C3	119.5 (3)	C8—C9—H9A	109.5
C1—C2—H2A	120.2	C8—C9—H9B	109.5
C3—C2—H2A	120.2	H9A—C9—H9B	109.5
C8—N3—N1	105.3 (2)	C8—C9—H9C	109.5
C4—C3—C2	121.3 (3)	H9A—C9—H9C	109.5
C4—C3—Cl	119.0 (3)	H9B—C9—H9C	109.5
C2—C3—Cl	119.7 (3)	F2—C10—F3	106.6 (3)
C5—C4—C3	118.1 (3)	F2—C10—N2	110.3 (3)
C5—C4—H4A	120.9	F3—C10—N2	110.3 (3)
C3—C4—H4A	120.9	F2—C10—H10A	109.9
F1—C5—C4	118.5 (3)	F3—C10—H10A	109.9
F1—C5—C6	119.2 (3)	N2—C10—H10A	109.9
C4—C5—C6	122.3 (3)

C6—C1—C2—C3	0.5 (5)	N3—N1—C7—O	176.9 (3)
C7—N1—N3—C8	2.6 (3)	C6—N1—C7—O	3.1 (5)
C6—N1—N3—C8	177.0 (2)	N3—N1—C7—N2	−3.1 (3)
C1—C2—C3—C4	0.9 (5)	C6—N1—C7—N2	−177.0 (2)
C1—C2—C3—Cl	−177.6 (3)	C8—N2—C7—O	−177.6 (3)
C2—C3—C4—C5	−1.7 (5)	C10—N2—C7—O	0.2 (5)
Cl—C3—C4—C5	176.9 (2)	C8—N2—C7—N1	2.5 (3)
C3—C4—C5—F1	−177.1 (3)	C10—N2—C7—N1	−179.8 (3)
C3—C4—C5—C6	1.0 (5)	N1—N3—C8—N2	−0.8 (3)
F1—C5—C6—C1	178.5 (3)	N1—N3—C8—C9	179.4 (3)
C4—C5—C6—C1	0.3 (5)	C7—N2—C8—N3	−1.1 (3)
F1—C5—C6—N1	1.4 (4)	C10—N2—C8—N3	−178.7 (3)
C4—C5—C6—N1	−176.8 (3)	C7—N2—C8—C9	178.7 (3)
C2—C1—C6—C5	−1.1 (5)	C10—N2—C8—C9	1.1 (5)
C2—C1—C6—N1	176.1 (3)	C7—N2—C10—F2	122.1 (3)
C7—N1—C6—C5	−58.7 (4)	C8—N2—C10—F2	−60.6 (4)
N3—N1—C6—C5	127.8 (3)	C7—N2—C10—F3	−120.5 (3)
C7—N1—C6—C1	124.2 (3)	C8—N2—C10—F3	56.8 (4)
N3—N1—C6—C1	−49.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···Oⁱ	0.98	2.41	3.259 (4)	144

Symmetry code: (i) −x+1, y, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₇ClF₃N₃O
M_r	277.64
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.286 (3), 13.610 (3), 11.231 (2)
β (°)	100.91 (3)
V (Å³)	2294.3 (8)
Z	8
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
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	4290, 2115, 1273
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.143, 1.00
No. of reflections	2115
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −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···Oⁱ	0.9800	2.4100	3.259 (4)	144.00

Symmetry code: (i) −x+1, y, −z−1/2.

Acknowledgements

This study was supported financially by the Capital University of Economics and Business (00891162721716) and the Scientific Research Level Project of Beijing Education Commission Foundation. The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

Ager, J. W. & Polz, 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. CSD CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Jaidev, S. G. & Plainsboro, N. J. (1998). US Patent No. 5756755. Google Scholar
Li, M. F. & Han, B. Y. (2010). Mod. Agrochem. 9, 28–33. 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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doi:10.1107/S1600536812009452

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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