organic compounds
3-Difluoromethyl-5-[4-(trifluoromethyl)phenyl]isoxazole
aAnhui Engineering Technology Research Center for Extraction and Isolation of Active Components, Anhui Academy of Applied Technology, Hefei, 230031, People's Republic of China
*Correspondence e-mail: zh1986@iccas.ac.cn
The title molecule, C11H6F5NO, lies on a mirror plane in the orthorhombic with only two F atoms each of the difluoro and trifluoromethyl substituents lying out of the plane. In the crystal, molecules are linked by C—H⋯O, C—H⋯N and C—H⋯F hydrogen bonds, forming a layer structure parallel to the (001) plane. Weak π–π interactions promote the formation of a three-dimensional network.
CCDC reference: 1577897
Structure description
Nitrogen heterocycles are important scaffolds in bioactive natural and synthesized compounds (Fried et al., 2001; Baraldi et al., 2008; Vitaku et al., 2014). Moreover, organic molecules with fluoroalkyl substituents often impart desirable physical and biological properties (Wang et al., 2014).
The title compound crystallizes in the orthorhombic Pbcm with most atoms of the molecule in the mirror plane (Fig. 1). Only the F1 and F3 atoms of the difluoro and trifluoromethyl substituents lie out of this plane. In the crystal, molecules are linked by a combination of C—H⋯O, C—H⋯N and C—H⋯F hydrogen bonds (Table 1) together with a weak π–π stacking interaction between C5–C10 rings [centroid–centroid separation = 3.904 (2) Å] (Fig. 2). In more detail, a chain running along the [010] direction forms through C3—H3⋯O1 and C3—H3⋯N1 hydrogen bonds, Table 1. These [010] chains are joined by the C1—H1⋯F2 hydrogen bonds, forming a layer structure parallel to the (001) plane. Finally, molecules in these (001) layers are linked by the weak π–π stacking interactions to generate a three-dimensional network.
Synthesis and crystallization
The title compound was synthesized by a one-pot `click synthesis' of fluoroalkylated isoxazoles from commercially avalilable 1-ethynyl-4-(trifluoromethyl)benzene and 2,2-difluoroethanamine, and the isolation and characterization have been reported previously (Zhang et al., 2018). Crystals for X-ray data collection were obtained by slow evaporation of a petroleum ether/ethylacetate (v:v = 100:1) solution.
Refinement
Crystal data, data collection, and structure .
details are summarized in Table 2Structural data
CCDC reference: 1577897
https://doi.org/10.1107/S2414314618004455/sj4168sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004455/sj4168Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618004455/sj4168Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314618004455/sj4168Isup4.cml
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al. 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al. 2009).C11H6F5NO | Dx = 1.666 Mg m−3 |
Mr = 263.17 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcm | Cell parameters from 1887 reflections |
a = 13.1081 (13) Å | θ = 3.7–26.4° |
b = 11.1491 (13) Å | µ = 0.17 mm−1 |
c = 7.1798 (11) Å | T = 293 K |
V = 1049.3 (2) Å3 | Block, colourless |
Z = 4 | 0.24 × 0.22 × 0.20 mm |
F(000) = 528 |
Rigaku Oxford Diffraction SuperNova, Dual, Cu at zero, Atlas diffractometer | 1066 independent reflections |
Radiation source: fine-focus sealed tube | 707 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 8.0353 pixels mm-1 | θmax = 25.5°, θmin = 3.6° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −13→12 |
Tmin = 0.961, Tmax = 0.967 | l = −7→8 |
5659 measured reflections |
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)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.292 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1997P)2 + 0.0686P] where P = (Fo2 + 2Fc2)/3 |
1066 reflections | (Δ/σ)max < 0.001 |
103 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
N1 | 0.5503 (3) | 0.1715 (3) | 0.2500 | 0.0724 (13) | |
O1 | 0.4442 (3) | 0.1696 (2) | 0.2500 | 0.0689 (11) | |
F1 | 0.7082 (2) | 0.3834 (2) | 0.3982 (4) | 0.1078 (12) | |
C4 | 0.4094 (4) | 0.2842 (3) | 0.2500 | 0.0544 (12) | |
C5 | 0.2998 (4) | 0.3006 (4) | 0.2500 | 0.0542 (12) | |
C3 | 0.4895 (4) | 0.3580 (4) | 0.2500 | 0.0650 (14) | |
H3 | 0.4882 | 0.4414 | 0.2500 | 0.078* | |
C9 | 0.1574 (4) | 0.4343 (5) | 0.2500 | 0.0844 (17) | |
H9 | 0.1312 | 0.5118 | 0.2500 | 0.101* | |
C8 | 0.0914 (4) | 0.3356 (4) | 0.2500 | 0.0794 (16) | |
C6 | 0.2315 (4) | 0.2038 (4) | 0.2500 | 0.0683 (14) | |
H6 | 0.2568 | 0.1259 | 0.2500 | 0.082* | |
C10 | 0.2593 (4) | 0.4164 (4) | 0.2500 | 0.0704 (15) | |
H10 | 0.3031 | 0.4821 | 0.2500 | 0.084* | |
C11 | −0.0320 (6) | 0.3614 (6) | 0.2500 | 0.0780 (19) | |
C7 | 0.1293 (5) | 0.2218 (4) | 0.2500 | 0.0797 (17) | |
H7 | 0.0851 | 0.1565 | 0.2500 | 0.096* | |
C1 | 0.6860 (4) | 0.3158 (5) | 0.2500 | 0.0734 (15) | |
H1 | 0.7276 | 0.2428 | 0.2500 | 0.088* | |
C2 | 0.5753 (4) | 0.2845 (4) | 0.2500 | 0.0607 (13) | |
F2 | −0.0709 (6) | 0.2549 (10) | 0.2500 | 0.327 (7) | |
F3 | −0.0478 (5) | 0.3962 (6) | 0.3638 (11) | 0.260 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.066 (3) | 0.053 (3) | 0.098 (3) | 0.0016 (18) | 0.000 | 0.000 |
O1 | 0.064 (2) | 0.0454 (19) | 0.097 (3) | −0.0009 (14) | 0.000 | 0.000 |
F1 | 0.0887 (19) | 0.124 (2) | 0.111 (2) | −0.0307 (14) | −0.0063 (14) | −0.0265 (15) |
C4 | 0.073 (3) | 0.043 (2) | 0.047 (2) | −0.0011 (19) | 0.000 | 0.000 |
C5 | 0.064 (3) | 0.048 (2) | 0.050 (2) | 0.003 (2) | 0.000 | 0.000 |
C3 | 0.074 (3) | 0.041 (2) | 0.080 (3) | −0.004 (2) | 0.000 | 0.000 |
C9 | 0.079 (4) | 0.055 (3) | 0.118 (5) | 0.005 (2) | 0.000 | 0.000 |
C8 | 0.066 (3) | 0.072 (4) | 0.100 (4) | 0.009 (3) | 0.000 | 0.000 |
C6 | 0.078 (4) | 0.047 (3) | 0.080 (3) | −0.009 (2) | 0.000 | 0.000 |
C10 | 0.066 (3) | 0.053 (3) | 0.092 (4) | −0.001 (2) | 0.000 | 0.000 |
C11 | 0.058 (4) | 0.060 (3) | 0.115 (6) | −0.021 (3) | 0.000 | 0.000 |
C7 | 0.074 (4) | 0.062 (3) | 0.103 (4) | −0.014 (3) | 0.000 | 0.000 |
C1 | 0.070 (3) | 0.063 (3) | 0.088 (4) | −0.015 (3) | 0.000 | 0.000 |
C2 | 0.069 (3) | 0.051 (3) | 0.062 (3) | −0.005 (2) | 0.000 | 0.000 |
F2 | 0.127 (6) | 0.223 (8) | 0.63 (2) | 0.010 (7) | 0.000 | 0.000 |
F3 | 0.101 (3) | 0.264 (6) | 0.414 (15) | −0.013 (4) | −0.016 (5) | −0.005 (5) |
N1—C2 | 1.302 (5) | C8—C7 | 1.363 (7) |
N1—O1 | 1.392 (6) | C8—C11 | 1.643 (10) |
O1—C4 | 1.356 (5) | C6—C7 | 1.354 (8) |
F1—C1 | 1.336 (3) | C6—H6 | 0.9300 |
C4—C3 | 1.334 (7) | C10—H10 | 0.9300 |
C4—C5 | 1.449 (7) | C11—F3i | 0.928 (8) |
C5—C10 | 1.395 (6) | C11—F3 | 0.928 (8) |
C5—C6 | 1.402 (7) | C11—F2 | 1.293 (13) |
C3—C2 | 1.393 (7) | C7—H7 | 0.9300 |
C3—H3 | 0.9300 | C1—F1i | 1.336 (3) |
C9—C10 | 1.351 (7) | C1—C2 | 1.492 (7) |
C9—C8 | 1.400 (7) | C1—H1 | 0.9800 |
C9—H9 | 0.9300 | F3—F3i | 1.634 (16) |
C2—N1—O1 | 105.4 (3) | C9—C10—H10 | 119.6 |
C4—O1—N1 | 108.8 (3) | C5—C10—H10 | 119.6 |
C3—C4—O1 | 108.5 (5) | F3i—C11—F3 | 123.3 (15) |
C3—C4—C5 | 134.6 (4) | F3i—C11—F2 | 107.2 (7) |
O1—C4—C5 | 116.9 (4) | F3—C11—F2 | 107.2 (7) |
C10—C5—C6 | 118.0 (5) | F3i—C11—C8 | 107.1 (8) |
C10—C5—C4 | 119.6 (4) | F3—C11—C8 | 107.1 (8) |
C6—C5—C4 | 122.4 (4) | F2—C11—C8 | 103.1 (6) |
C4—C3—C2 | 105.8 (4) | C6—C7—C8 | 119.9 (5) |
C4—C3—H3 | 127.1 | C6—C7—H7 | 120.1 |
C2—C3—H3 | 127.1 | C8—C7—H7 | 120.1 |
C10—C9—C8 | 119.7 (5) | F1—C1—F1i | 105.6 (4) |
C10—C9—H9 | 120.2 | F1—C1—C2 | 110.1 (3) |
C8—C9—H9 | 120.2 | F1i—C1—C2 | 110.1 (3) |
C7—C8—C9 | 120.5 (5) | F1—C1—H1 | 110.3 |
C7—C8—C11 | 121.5 (5) | F1i—C1—H1 | 110.3 |
C9—C8—C11 | 118.1 (4) | C2—C1—H1 | 110.3 |
C7—C6—C5 | 121.2 (5) | N1—C2—C3 | 111.5 (5) |
C7—C6—H6 | 119.4 | N1—C2—C1 | 118.1 (4) |
C5—C6—H6 | 119.4 | C3—C2—C1 | 130.4 (4) |
C9—C10—C5 | 120.8 (5) | C11—F3—F3i | 28.3 (7) |
C2—N1—O1—C4 | 0.0 | C7—C8—C11—F3 | 112.9 (8) |
N1—O1—C4—C3 | 0.0 | C9—C8—C11—F3 | −67.1 (8) |
N1—O1—C4—C5 | 180.0 | C7—C8—C11—F2 | 0.0 |
C3—C4—C5—C10 | 0.0 | C9—C8—C11—F2 | 180.0 |
O1—C4—C5—C10 | 180.0 | C5—C6—C7—C8 | 0.0 |
C3—C4—C5—C6 | 180.0 | C9—C8—C7—C6 | 0.0 |
O1—C4—C5—C6 | 0.0 | C11—C8—C7—C6 | 180.0 |
O1—C4—C3—C2 | 0.0 | O1—N1—C2—C3 | 0.0 |
C5—C4—C3—C2 | 180.0 | O1—N1—C2—C1 | 180.0 |
C10—C9—C8—C7 | 0.0 | C4—C3—C2—N1 | 0.0 |
C10—C9—C8—C11 | 180.0 | C4—C3—C2—C1 | 180.0 |
C10—C5—C6—C7 | 0.0 | F1—C1—C2—N1 | −122.0 (3) |
C4—C5—C6—C7 | 180.0 | F1i—C1—C2—N1 | 122.0 (3) |
C8—C9—C10—C5 | 0.0 | F1—C1—C2—C3 | 58.0 (3) |
C6—C5—C10—C9 | 0.0 | F1i—C1—C2—C3 | −58.0 (3) |
C4—C5—C10—C9 | 180.0 | F2—C11—F3—F3i | −125.1 (18) |
C7—C8—C11—F3i | −112.9 (8) | C8—C11—F3—F3i | 124.8 (15) |
C9—C8—C11—F3i | 67.1 (8) |
Symmetry code: (i) x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1ii | 0.93 | 2.69 | 3.581 (7) | 160 |
C3—H3···N1ii | 0.93 | 2.62 | 3.534 (6) | 170 |
C1—H1···F2iii | 0.98 | 2.65 | 3.258 (6) | 121 |
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x+1, y, z. |
Funding information
Funding for this research was provided by: National Natural Science Foundation of China (award No. 21502076); Natural Science Foundation of Jiangxi Province (award No. 20161BAB213068); Hundred–Talent Program (Hefei); Outstanding Young Talent Program of Jiangxi Province (award No. 2017BCB23039).
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