organic compounds
(Z)-1-(2,4-Difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone oxime
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
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
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Refinement
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Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell 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
https://doi.org/10.1107/S1600536811050008/zq2136sup1.cif
contains datablocks I, global. DOI: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
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.
The H atom of the hydroxy group was located in a Fourier difference map but was constrained to ride on the parent atom with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). The other H atoms were positioned geometrically with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene) and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
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
(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
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).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).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
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).C10H8F2N4O | F(000) = 488 |
Mr = 238.20 | Dx = 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 |
Enraf–Nonius CAD-4 diffractometer | 1217 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 25.4°, θmin = 2.6° |
ω/2θ scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = −5→14 |
Tmin = 0.964, Tmax = 0.988 | l = −12→12 |
3127 measured reflections | 3 standard reflections every 200 reflections |
1987 independent reflections | intensity decay: 1% |
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(Fo2) + (0.090P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
1987 reflections | Δρmax = 0.53 e Å−3 |
154 parameters | Δρmin = −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) |
C10H8F2N4O | V = 1080.6 (4) Å3 |
Mr = 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)° |
Enraf–Nonius CAD-4 diffractometer | 1217 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.042 |
Tmin = 0.964, Tmax = 0.988 | 3 standard reflections every 200 reflections |
3127 measured reflections | intensity decay: 1% |
1987 independent reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.53 e Å−3 |
1987 reflections | Δρmin = −0.22 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.964, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3127, 1987, 1217 |
Rint | 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 |
Δρmax, Δρmin (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).
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
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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).