organic compounds
6-[4-Chloro-2-(trifluoromethyl)phenyl]-3-fluoro-2-methylpyridine
aDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India, bDepartment of Studies and Research in Chemistry, U.C.S, Tumkur University, Tumkur, Karnataka 572 103, India, cDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, and dCentre of Advanced Study in Crystallography and Biophysics, University of Madras Guindy Campus, Chennai 600 025, India
*Correspondence e-mail: drsreenivasa@yahoo.co.in
In the title compound, C13H8ClF4N, the dihedral angle between the benzene and pyridine rings is 59.8 (3)°. In the crystal, molecules are stacked in columns along the b axis through weak C—H⋯π interactions.
Related literature
For the biological activity of pyridine derivatives, see: Patrick & Kinsmar (1996); Hishmat et al. (1990); Doshi et al. (1999); Bhatt et al. (2001).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812046211/is5209sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046211/is5209Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812046211/is5209Isup3.cml
2-Methyl-3-fluoropiridine-6-boromic acid (8.4 mmol) was taken in a mixture of dioxane (20 ml) and water (5 ml) at RT undernitrogen atmosphere. The reaction mixture was degassed with argon for 10 min, and K2CO3 (23.1 mmol) and dichlorobis(triphenylphosphene)-palladium(II) (0.231 mmol) were added and again degassed for 10 min. 2-Bromo-5-chlorobenzotrifluoride (7.7 mmol) was added and then reaction mixture was heated to 100 °C for 1 h (reaction was monitored by TLC), and the reaction mass was cooled to RT, diluted with ethyl acetate, filtered over celite, and washed with ethyl acetate. The filtrate was washed with water and brine, and the ethyl acetate layer was dried with anhydrous Na2SO4 and concentrated. The crude product was purified by tritulating with petroleum ether. Single crystals of the title compound used for X-ray diffraction studies were obtained from slow evaporation of the solution of the compound in petroleum ether-ethyl acetate mixture (1:1).
The H atoms were positioned with idealized geometry (C—H = 0.93–0.96 Å) using a riding model with Uiso(H) = 1.2 or 1.5Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell
SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C13H8ClF4N | Prism |
Mr = 289.65 | Dx = 1.559 Mg m−3 |
Monoclinic, P21/n | Melting point: 408 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 13.1813 (7) Å | Cell parameters from 2116 reflections |
b = 4.5837 (3) Å | θ = 1.8–26.8° |
c = 20.4448 (11) Å | µ = 0.34 mm−1 |
β = 92.441 (3)° | T = 293 K |
V = 1234.14 (12) Å3 | Prism, colourless |
Z = 4 | 0.2 × 0.18 × 0.16 mm |
F(000) = 584 |
Bruker APEXII CCD area-detector diffractometer | 2116 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 28.3°, θmin = 1.8° |
Detector resolution: 1.20 pixels mm-1 | h = −17→17 |
multi–scan | k = −5→6 |
11077 measured reflections | l = −27→27 |
3033 independent 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.4806P] where P = (Fo2 + 2Fc2)/3 |
3033 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
0 constraints |
C13H8ClF4N | V = 1234.14 (12) Å3 |
Mr = 289.65 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.1813 (7) Å | µ = 0.34 mm−1 |
b = 4.5837 (3) Å | T = 293 K |
c = 20.4448 (11) Å | 0.2 × 0.18 × 0.16 mm |
β = 92.441 (3)° |
Bruker APEXII CCD area-detector diffractometer | 2116 reflections with I > 2σ(I) |
11077 measured reflections | Rint = 0.031 |
3033 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.23 e Å−3 |
3033 reflections | Δρmin = −0.30 e Å−3 |
173 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 | ||
Cl1 | 0.83131 (5) | 0.3848 (2) | 0.03175 (3) | 0.0883 (3) | |
F1 | 1.12038 (13) | 1.0835 (4) | 0.09837 (7) | 0.0978 (6) | |
F2 | 1.18924 (9) | 0.8102 (3) | 0.17220 (10) | 0.0964 (5) | |
F3 | 1.11540 (11) | 1.2001 (3) | 0.19839 (7) | 0.0781 (4) | |
F4 | 1.09214 (11) | 1.1818 (4) | 0.46328 (6) | 0.0853 (5) | |
N1 | 0.93981 (11) | 1.0496 (3) | 0.31763 (7) | 0.0451 (3) | |
C1 | 0.87112 (13) | 0.6135 (5) | 0.21835 (9) | 0.0528 (5) | |
H1 | 0.8368 | 0.5883 | 0.2568 | 0.063* | |
C2 | 0.83018 (14) | 0.4976 (5) | 0.16091 (9) | 0.0589 (5) | |
H2 | 0.7693 | 0.395 | 0.1605 | 0.071* | |
C3 | 0.88083 (15) | 0.5361 (5) | 0.10418 (9) | 0.0565 (5) | |
C4 | 0.96922 (14) | 0.6939 (5) | 0.10389 (9) | 0.0552 (5) | |
H4 | 1.0015 | 0.7239 | 0.0649 | 0.066* | |
C5 | 1.01029 (13) | 0.8085 (4) | 0.16185 (9) | 0.0472 (4) | |
C6 | 0.96206 (12) | 0.7668 (4) | 0.22062 (9) | 0.0445 (4) | |
C7 | 1.10812 (16) | 0.9742 (5) | 0.15823 (11) | 0.0609 (5) | |
C8 | 1.00181 (13) | 0.8725 (4) | 0.28603 (9) | 0.0453 (4) | |
C9 | 1.09464 (14) | 0.7800 (5) | 0.31331 (11) | 0.0587 (5) | |
H9 | 1.1349 | 0.6502 | 0.291 | 0.07* | |
C10 | 1.12574 (16) | 0.8841 (5) | 0.37399 (11) | 0.0638 (6) | |
H10 | 1.1876 | 0.8282 | 0.3937 | 0.077* | |
C11 | 1.06333 (16) | 1.0706 (5) | 0.40409 (10) | 0.0571 (5) | |
C12 | 0.96959 (14) | 1.1523 (4) | 0.37664 (9) | 0.0485 (4) | |
C13 | 0.90004 (18) | 1.3525 (5) | 0.41073 (10) | 0.0642 (6) | |
H13A | 0.8421 | 1.3959 | 0.3823 | 0.096* | |
H13B | 0.9352 | 1.5301 | 0.422 | 0.096* | |
H13C | 0.8779 | 1.2605 | 0.4498 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0773 (4) | 0.1319 (7) | 0.0551 (3) | −0.0171 (4) | −0.0033 (3) | −0.0247 (4) |
F1 | 0.1080 (12) | 0.1124 (13) | 0.0752 (9) | −0.0472 (10) | 0.0308 (8) | 0.0014 (9) |
F2 | 0.0459 (7) | 0.0725 (10) | 0.1719 (16) | −0.0025 (6) | 0.0166 (8) | −0.0082 (10) |
F3 | 0.0911 (9) | 0.0542 (8) | 0.0897 (10) | −0.0197 (7) | 0.0125 (7) | −0.0126 (7) |
F4 | 0.0926 (10) | 0.0965 (11) | 0.0645 (8) | 0.0001 (8) | −0.0251 (7) | −0.0226 (8) |
N1 | 0.0467 (8) | 0.0453 (8) | 0.0433 (7) | 0.0016 (6) | 0.0034 (6) | 0.0002 (6) |
C1 | 0.0444 (9) | 0.0704 (13) | 0.0438 (9) | −0.0028 (9) | 0.0057 (7) | 0.0011 (9) |
C2 | 0.0436 (9) | 0.0797 (15) | 0.0535 (11) | −0.0116 (10) | 0.0012 (8) | −0.0005 (10) |
C3 | 0.0505 (10) | 0.0717 (14) | 0.0471 (10) | 0.0010 (10) | 0.0000 (8) | −0.0079 (10) |
C4 | 0.0539 (10) | 0.0649 (13) | 0.0477 (10) | 0.0011 (9) | 0.0122 (8) | −0.0030 (9) |
C5 | 0.0432 (9) | 0.0463 (10) | 0.0526 (10) | 0.0013 (8) | 0.0078 (7) | −0.0038 (8) |
C6 | 0.0410 (8) | 0.0463 (10) | 0.0464 (9) | 0.0061 (7) | 0.0032 (7) | −0.0021 (8) |
C7 | 0.0592 (12) | 0.0535 (12) | 0.0710 (13) | −0.0077 (10) | 0.0164 (10) | −0.0069 (11) |
C8 | 0.0431 (9) | 0.0460 (10) | 0.0470 (9) | 0.0014 (7) | 0.0024 (7) | −0.0006 (8) |
C9 | 0.0483 (10) | 0.0615 (13) | 0.0656 (12) | 0.0120 (9) | −0.0042 (9) | −0.0081 (10) |
C10 | 0.0507 (11) | 0.0709 (15) | 0.0684 (13) | 0.0043 (10) | −0.0145 (9) | −0.0026 (11) |
C11 | 0.0626 (12) | 0.0567 (12) | 0.0508 (10) | −0.0059 (10) | −0.0099 (9) | −0.0062 (9) |
C12 | 0.0557 (10) | 0.0437 (10) | 0.0460 (9) | −0.0040 (8) | 0.0030 (8) | 0.0001 (8) |
C13 | 0.0785 (14) | 0.0619 (14) | 0.0526 (11) | 0.0043 (11) | 0.0078 (10) | −0.0098 (10) |
Cl1—C3 | 1.737 (2) | C5—C7 | 1.501 (3) |
F1—C7 | 1.339 (3) | C6—C1 | 1.388 (3) |
F2—C7 | 1.328 (3) | C6—C5 | 1.396 (2) |
F3—C7 | 1.322 (2) | C8—C9 | 1.389 (2) |
F4—C11 | 1.353 (2) | C8—C6 | 1.496 (2) |
N1—C8 | 1.338 (2) | C9—C10 | 1.375 (3) |
N1—C12 | 1.338 (2) | C9—H9 | 0.93 |
C1—C2 | 1.378 (3) | C10—H10 | 0.93 |
C1—H1 | 0.93 | C11—C10 | 1.352 (3) |
C2—H2 | 0.93 | C11—C12 | 1.387 (3) |
C3—C2 | 1.374 (3) | C12—C13 | 1.491 (3) |
C4—C3 | 1.372 (3) | C13—H13A | 0.96 |
C4—H4 | 0.93 | C13—H13B | 0.96 |
C5—C4 | 1.385 (3) | C13—H13C | 0.96 |
C8—N1—C12 | 119.16 (15) | F2—C7—C5 | 112.85 (18) |
C2—C1—C6 | 121.99 (17) | F1—C7—C5 | 111.83 (18) |
C2—C1—H1 | 119 | N1—C8—C9 | 122.48 (17) |
C6—C1—H1 | 119 | N1—C8—C6 | 115.49 (15) |
C3—C2—C1 | 118.89 (18) | C9—C8—C6 | 121.94 (17) |
C3—C2—H2 | 120.6 | C10—C9—C8 | 118.67 (19) |
C1—C2—H2 | 120.6 | C10—C9—H9 | 120.7 |
C4—C3—C2 | 120.98 (18) | C8—C9—H9 | 120.7 |
C4—C3—Cl1 | 119.69 (15) | C11—C10—C9 | 117.78 (18) |
C2—C3—Cl1 | 119.33 (16) | C11—C10—H10 | 121.1 |
C3—C4—C5 | 119.83 (17) | C9—C10—H10 | 121.1 |
C3—C4—H4 | 120.1 | F4—C11—C10 | 119.50 (18) |
C5—C4—H4 | 120.1 | F4—C11—C12 | 118.13 (19) |
C4—C5—C6 | 120.57 (17) | C10—C11—C12 | 122.36 (18) |
C4—C5—C7 | 117.07 (17) | N1—C12—C11 | 119.46 (18) |
C6—C5—C7 | 122.37 (17) | N1—C12—C13 | 118.39 (17) |
C1—C6—C5 | 117.69 (17) | C11—C12—C13 | 122.15 (18) |
C1—C6—C8 | 117.57 (16) | C12—C13—H13A | 109.5 |
C5—C6—C8 | 124.74 (16) | C12—C13—H13B | 109.5 |
F3—C7—F2 | 105.85 (18) | H13A—C13—H13B | 109.5 |
F3—C7—F1 | 105.45 (18) | C12—C13—H13C | 109.5 |
F2—C7—F1 | 106.32 (18) | H13A—C13—H13C | 109.5 |
F3—C7—C5 | 113.91 (17) | H13B—C13—H13C | 109.5 |
Cg1 is the centroid of the N1/C8–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13B···Cg1i | 0.96 | 2.83 | 3.606 (2) | 138 |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C13H8ClF4N |
Mr | 289.65 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.1813 (7), 4.5837 (3), 20.4448 (11) |
β (°) | 92.441 (3) |
V (Å3) | 1234.14 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.2 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11077, 3033, 2116 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.129, 1.01 |
No. of reflections | 3033 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.30 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).
Cg1 is the centroid of the N1/C8–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13B···Cg1i | 0.96 | 2.83 | 3.606 (2) | 138 |
Symmetry code: (i) x, y+1, z. |
Acknowledgements
Authors thank Dr. S. C. Sharma, Vice Chancellor, Tumkur University, Tumkur for his constant encouragement and G·B. Sadananda, Department of Studies and Research in Physics, U.C.S. Tumkur University, Tumkur, for his help and valuable suggestions. BSP thanks Dr. H. C. Devaraje Gowda, Department of Physics, Yuvarajas College (constituent), University of Mysore for his guidance.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Pyridine derivatives of different heterocyclic nucleus have shown potent pharmacological properties like antifungal (Patrick & Kinsmar, 1996), antitubercular (Hishmat et al., 1990) and antibacterial (Doshi et al., 1999; Bhatt et al., 2001). Keeping in view of the biological importance of this class of compound, we synthesized the title compound to study its X-ray crystal structure.
In the title compound, the dihedral angle between the least square planes through the benzene ring and the pyridine ring is 59.8 (3)°. In the absence of hydrogen bonds, the structure is stabilized by a weak intermolecular C—H···π interaction (Table 1).