(Z)-1-(2,4-Difluoro­phen­yl)-2-(1H-1,2,4-triazol-1-yl)ethanone oxime

Yu, G.; Li, C.; Xiao, T.; Li, S.; Tian, X.

doi:10.1107/S1600536811050008

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3468

https://doi.org/10.1107/S1600536811050008

Open

access

(Z)-1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone oxime

Guang-yan Yu,^a Chen Li,^a Tao Xiao,^a ^* Song Li ^a and Xin Tian ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: taoxiao@njut.edu.cn

(Received 8 November 2011; accepted 22 November 2011; online 30 November 2011)

In the title compound, C₁₀H₈F₂N₄O, the dihedral angle between the rings is 65.4 (1)°. In the crystal, intermolecular O—H⋯N and C—H⋯F hydrogen bonds link the molecules in a stacked arrangement along the a and c axes, respectively.

Related literature

For applications of related compounds, see: Foroumadi et al. (2003 ); Mixich & Thiele (1979 ); Wolfgang et al. (1981 ). For a related structure, see: Tao et al. (2007 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₈F₂N₄O
M_r = 238.20
Monoclinic, P 2₁ /n
a = 8.6320 (17) Å
b = 12.433 (3) Å
c = 10.417 (2) Å
β = 104.85 (3)°
V = 1080.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 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 = 0.964, T_max = 0.988
3127 measured reflections
1987 independent reflections
1217 reflections with I > 2σ(I)
R_int = 0.042
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.171
S = 1.01
1987 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N4ⁱ	0.82	1.94	2.764 (3)	176
C10—H10⋯F1ⁱⁱ	0.93	2.47	3.289 (4)	148
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811050008/zq2136sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050008/zq2136Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811050008/zq2136Isup3.cml

checkCIF report

Comment top

The title compound, C₁₀H₈O₁N₄F₂, is the key intermediate in the synthesis of a new kind of antifungal drug (Tao et al., 2007; Foroumadi et al., 2003; Wolfgang et al., 1981) and exhibits a chemical structure similar to oxiconazole (Mixich & Thiele, 1979). We designed and synthesized the title compound, and we herein report its crystal structure (Fig. 1).

The bond lengths are within normal ranges (Allen et al., 1987). The dihedral angle between rings A (N2-N4/C9/C10) and B (C1-C6) is 65.4 (1) °. In the crystal structure, intermolecular intermolecular O–H···N and C-H···F hydrogen bonds (Table 2) link the molecules in a stacked arrangement along along the a and c axes, respectively (Fig. 2).

Related literature top

For applications of related compounds, see: Foroumadi et al. (2003); Mixich & Thiele (1979); Wolfgang et al. (1981). For a related structure, see: Tao et al. (2007). For standard bond lengths, see: Allen et al. (1987).

Experimental top

Hydroxylammonium chloride (3 g, 43.2 mmol) dissolved in ethanol (20 ml) was dropwise added to a solution of 1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone (5 g,22.4 mmol) in ethanol (50 ml) which contained CH₃COONa (4 g, 48.8 mmol) under reflux conditions for 4 h. The mixture was placed in ice-water (100 ml), and the crystalline product was isolated by filtration, washed with water (100 ml). The crystals were obtained by dissolving the product in ethanol (20 ml) and evaporating acetone slowly at room temperature for about 7 d.

Structure description top

For applications of related compounds, see: Foroumadi et al. (2003); Mixich & Thiele (1979); Wolfgang et al. (1981). For a related structure, see: Tao et al. (2007). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

(Z)-1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone oxime top

Crystal data top

C₁₀H₈F₂N₄O	F(000) = 488
M_r = 238.20	D_x = 1.464 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 400 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.6320 (17) Å	Cell parameters from 25 reflections
b = 12.433 (3) Å	θ = 9–13°
c = 10.417 (2) Å	µ = 0.12 mm⁻¹
β = 104.85 (3)°	T = 293 K
V = 1080.6 (4) Å³	Black, white
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1217 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 25.4°, θ_min = 2.6°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −5→14
T_min = 0.964, T_max = 0.988	l = −12→12
3127 measured reflections	3 standard reflections every 200 reflections
1987 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.090P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1987 reflections	Δρ_max = 0.53 e Å⁻³
154 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (5)

Crystal data top

C₁₀H₈F₂N₄O	V = 1080.6 (4) Å³
M_r = 238.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.6320 (17) Å	µ = 0.12 mm⁻¹
b = 12.433 (3) Å	T = 293 K
c = 10.417 (2) Å	0.30 × 0.20 × 0.10 mm
β = 104.85 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1217 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.964, T_max = 0.988	3 standard reflections every 200 reflections
3127 measured reflections	intensity decay: 1%
1987 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.01	Δρ_max = 0.53 e Å⁻³
1987 reflections	Δρ_min = −0.22 e Å⁻³
154 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
O1	−0.0689 (3)	0.1304 (2)	0.0266 (2)	0.0885 (7)
H1A	−0.1670	0.1325	0.0102	0.133*
F1	0.0628 (2)	0.39466 (19)	−0.12253 (18)	0.1082 (8)
N1	−0.0109 (3)	0.2303 (3)	0.0363 (2)	0.0787 (8)
C1	0.3526 (3)	0.3487 (3)	0.1896 (3)	0.0689 (8)
H1	0.3862	0.2944	0.2520	0.083*
N2	0.3725 (2)	0.13025 (17)	0.0097 (2)	0.0535 (6)
C2	0.4296 (4)	0.4452 (3)	0.2083 (3)	0.0880 (11)
H2	0.5142	0.4572	0.2826	0.106*
F2	0.4618 (4)	0.61943 (18)	0.1316 (3)	0.1508 (12)
N3	0.3361 (2)	0.1384 (2)	−0.1226 (2)	0.0654 (7)
C3	0.3801 (5)	0.5240 (3)	0.1156 (4)	0.0917 (10)
N4	0.6005 (2)	0.1436 (2)	−0.0387 (2)	0.0679 (7)
C4	0.2564 (4)	0.5106 (3)	0.0065 (3)	0.0944 (11)
H4	0.2229	0.5659	−0.0545	0.113*
C5	0.1822 (3)	0.4114 (3)	−0.0101 (3)	0.0707 (9)
C6	0.2250 (3)	0.3288 (2)	0.0798 (2)	0.0538 (7)
C7	0.1461 (3)	0.2225 (3)	0.0625 (2)	0.0619 (8)
C8	0.2467 (3)	0.1224 (2)	0.0803 (3)	0.0605 (8)
H8A	0.2951	0.1110	0.1741	0.073*
H8B	0.1789	0.0609	0.0471	0.073*
C9	0.4781 (3)	0.1454 (2)	−0.1470 (3)	0.0663 (8)
H9	0.4918	0.1511	−0.2324	0.080*
C10	0.5286 (3)	0.1362 (2)	0.0578 (3)	0.0597 (7)
H10	0.5810	0.1353	0.1477	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0712 (14)	0.0982 (19)	0.0951 (17)	0.0097 (14)	0.0198 (12)	−0.0037 (14)
F1	0.0744 (12)	0.160 (2)	0.0717 (12)	−0.0057 (12)	−0.0146 (10)	0.0297 (11)
N1	0.0610 (14)	0.115 (3)	0.0608 (15)	−0.0278 (15)	0.0177 (11)	−0.0027 (15)
C1	0.0595 (16)	0.078 (2)	0.0599 (16)	0.0107 (16)	−0.0024 (13)	−0.0075 (15)
N2	0.0337 (10)	0.0662 (15)	0.0611 (13)	−0.0045 (10)	0.0133 (9)	0.0006 (11)
C2	0.095 (2)	0.087 (3)	0.0639 (19)	0.012 (2)	−0.0120 (18)	−0.0177 (19)
F2	0.183 (3)	0.0744 (16)	0.161 (2)	−0.0211 (16)	−0.017 (2)	−0.0079 (15)
N3	0.0441 (11)	0.093 (2)	0.0577 (13)	−0.0116 (12)	0.0107 (10)	−0.0005 (12)
C3	0.106 (3)	0.067 (2)	0.091 (2)	0.002 (2)	0.004 (2)	−0.014 (2)
N4	0.0449 (12)	0.0795 (18)	0.0822 (16)	−0.0011 (11)	0.0216 (12)	−0.0008 (13)
C4	0.108 (3)	0.078 (3)	0.085 (2)	0.016 (2)	0.002 (2)	0.014 (2)
C5	0.0594 (16)	0.100 (3)	0.0456 (15)	0.0192 (18)	0.0007 (13)	0.0074 (16)
C6	0.0283 (11)	0.084 (2)	0.0503 (14)	0.0060 (12)	0.0120 (10)	−0.0023 (14)
C7	0.0463 (13)	0.096 (2)	0.0464 (14)	0.0039 (15)	0.0175 (11)	0.0027 (14)
C8	0.0363 (12)	0.080 (2)	0.0674 (17)	−0.0076 (13)	0.0175 (12)	0.0078 (15)
C9	0.0470 (14)	0.089 (2)	0.0659 (17)	−0.0109 (15)	0.0205 (13)	−0.0046 (16)
C10	0.0297 (11)	0.075 (2)	0.0724 (17)	0.0046 (12)	0.0091 (11)	0.0088 (14)

Geometric parameters (Å, º) top

O1—N1	1.334 (3)	N3—C9	1.317 (3)
O1—H1A	0.8200	C3—C4	1.356 (5)
F1—C5	1.364 (3)	N4—C10	1.313 (3)
N1—C7	1.315 (3)	N4—C9	1.333 (3)
C1—C2	1.362 (4)	C4—C5	1.380 (5)
C1—C6	1.392 (3)	C4—H4	0.9300
C1—H1	0.9300	C5—C6	1.375 (4)
N2—C10	1.314 (3)	C6—C7	1.477 (4)
N2—N3	1.337 (3)	C7—C8	1.502 (4)
N2—C8	1.463 (3)	C8—H8A	0.9700
C2—C3	1.365 (5)	C8—H8B	0.9700
C2—H2	0.9300	C9—H9	0.9300
F2—C3	1.368 (4)	C10—H10	0.9300

N1—O1—H1A	109.5	F1—C5—C4	117.9 (3)
C7—N1—O1	107.1 (3)	C6—C5—C4	123.2 (3)
C2—C1—C6	121.9 (3)	C5—C6—C1	116.4 (3)
C2—C1—H1	119.0	C5—C6—C7	123.4 (2)
C6—C1—H1	119.0	C1—C6—C7	120.1 (3)
C10—N2—N3	109.6 (2)	N1—C7—C6	112.2 (3)
C10—N2—C8	129.3 (2)	N1—C7—C8	128.2 (3)
N3—N2—C8	120.97 (18)	C6—C7—C8	119.5 (2)
C1—C2—C3	118.6 (3)	N2—C8—C7	111.3 (2)
C1—C2—H2	120.7	N2—C8—H8A	109.4
C3—C2—H2	120.7	C7—C8—H8A	109.4
C9—N3—N2	102.7 (2)	N2—C8—H8B	109.4
C4—C3—C2	122.8 (4)	C7—C8—H8B	109.4
C4—C3—F2	118.6 (4)	H8A—C8—H8B	108.0
C2—C3—F2	118.6 (3)	N3—C9—N4	114.2 (2)
C10—N4—C9	102.8 (2)	N3—C9—H9	122.9
C3—C4—C5	117.1 (3)	N4—C9—H9	122.9
C3—C4—H4	121.5	N4—C10—N2	110.6 (2)
C5—C4—H4	121.5	N4—C10—H10	124.7
F1—C5—C6	118.8 (3)	N2—C10—H10	124.7

C6—C1—C2—C3	−0.5 (5)	O1—N1—C7—C6	−178.2 (2)
C10—N2—N3—C9	2.1 (3)	O1—N1—C7—C8	−0.5 (4)
C8—N2—N3—C9	179.0 (2)	C5—C6—C7—N1	−50.9 (3)
C1—C2—C3—C4	0.7 (6)	C1—C6—C7—N1	130.8 (3)
C1—C2—C3—F2	−177.3 (3)	C5—C6—C7—C8	131.1 (3)
C2—C3—C4—C5	−1.5 (6)	C1—C6—C7—C8	−47.1 (3)
F2—C3—C4—C5	176.6 (3)	C10—N2—C8—C7	112.4 (3)
C3—C4—C5—F1	−176.8 (3)	N3—N2—C8—C7	−63.8 (3)
C3—C4—C5—C6	2.0 (5)	N1—C7—C8—N2	135.8 (3)
F1—C5—C6—C1	177.1 (2)	C6—C7—C8—N2	−46.7 (3)
C4—C5—C6—C1	−1.7 (4)	N2—N3—C9—N4	−0.9 (3)
F1—C5—C6—C7	−1.2 (4)	C10—N4—C9—N3	−0.7 (4)
C4—C5—C6—C7	180.0 (3)	C9—N4—C10—N2	2.0 (3)
C2—C1—C6—C5	0.9 (4)	N3—N2—C10—N4	−2.7 (3)
C2—C1—C6—C7	179.3 (3)	C8—N2—C10—N4	−179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N4ⁱ	0.82	1.94	2.764 (3)	176
C10—H10···F1ⁱⁱ	0.93	2.47	3.289 (4)	148

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈F₂N₄O
M_r	238.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.6320 (17), 12.433 (3), 10.417 (2)
β (°)	104.85 (3)
V (Å³)	1080.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
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	0.964, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	3127, 1987, 1217
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.171, 1.01
No. of reflections	1987
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.22

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N4ⁱ	0.82	1.94	2.764 (3)	176
C10—H10···F1ⁱⁱ	0.93	2.47	3.289 (4)	148

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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 (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Foroumadi, A., Soltani, F. & Asadipour, A. (2003). Boll. Chim. Farm. 142, 130–134. PubMed CAS Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Mixich, G. & Thiele, K. (1979). Arzneim. Forsch. 29, 1510–1513. CAS 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
Spek, A. L. (2009). Acta Cryst. D65, 148-155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tao, X., Yuan, L., Zhang, X.-Q., Jing, C. & Wang, J.-T. (2007). Acta Cryst. E63, o1330–o1331. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wolfgang, K., Karl, H. B., Helmut, T., Wilhelm, B. & Paul-Ernst, F. (1981). US Patent 4 264 772. Google Scholar