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

Abstract

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,

• a = 15.286 (3) Å

• b = 13.610 (3) Å

• c = 11.231 (2) Å

• β = 100.91 (3)°

• V = 2294.3 (8) ų

• 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[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812009452/bq2341Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

All H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.93 Å for aromatic H and 0.96 Å for alkyl H. The U_iso(H) = xU_eq(C), where x = 1.2 for aromatic H, and x = 1.5 for alkyl H.

Figures

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.

Crystal data

C10H7ClF3N3O	F(000) = 1120
Mr = 277.64	Dx = 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

Enraf–Nonius CAD-4 diffractometer	1273 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 25.4°, θmin = 2.0°
ω/2θ scans	h = 0→18
Absorption correction: ψ scan (North et al., 1968)	k = −16→16
Tmin = 0.899, Tmax = 0.965	l = −13→13
4290 measured reflections	3 standard reflections every 200 reflections
2115 independent reflections	intensity decay: 1%

Refinement

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(Fo2) + (0.073P)2] where P = (Fo2 + 2Fc2)/3
2115 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.34 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
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 (Ų)

	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)

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)

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.