6-[4-Chloro-2-(trifluoro­meth­yl)phen­yl]-3-fluoro-2-methyl­pyridine

Sreenivasa, S.; Manojkumar, K.E.; Suchetan, P.A.; Mohan, N.R.; Palakshamurthy, B.S.; Srinivasan, T.; Velmurgan, D.

doi:10.1107/S1600536812046211

organic compounds

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Volume 68| Part 12| December 2012| Page o3370

doi:10.1107/S1600536812046211

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6-[4-Chloro-2-(trifluoromethyl)phenyl]-3-fluoro-2-methylpyridine

S. Sreenivasa,^a ^* K. E. Manojkumar,^a P. A. Suchetan,^b N. R. Mohan,^a B. S. Palakshamurthy,^c T. Srinivasan ^d and D. Velmurgan ^d

^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

(Received 14 October 2012; accepted 8 November 2012; online 17 November 2012)

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

C₁₃H₈ClF₄N
M_r = 289.65
Monoclinic, P 2₁ /n
a = 13.1813 (7) Å
b = 4.5837 (3) Å
c = 20.4448 (11) Å
β = 92.441 (3)°
V = 1234.14 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.2 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
11077 measured reflections
3033 independent reflections
2116 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.129
S = 1.01
3033 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812046211/is5209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046211/is5209Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046211/is5209Isup3.cml

checkCIF report

Comment top

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).

Related literature top

For the biological activity of pyridine derivatives, see: Patrick & Kinsmar (1996); Hishmat et al. (1990); Doshi et al. (1999); Bhatt et al. (2001).

Experimental top

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).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound, showing C—H··· π interactions (dotted lines).

6-[4-Chloro-2-(trifluoromethyl)phenyl]-3-fluoro-2-methylpyridine top

Crystal data top

C₁₃H₈ClF₄N	Prism
M_r = 289.65	D_x = 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

Data collection top

Bruker APEXII CCD area-detector diffractometer	2116 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 28.3°, θ_min = 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 top

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(F_o²) + (0.0549P)² + 0.4806P] where P = (F_o² + 2F_c²)/3
3033 reflections	(Δ/σ)_max = 0.001
173 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³
0 constraints

Crystal data top

C₁₃H₈ClF₄N	V = 1234.14 (12) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2116 reflections with I > 2σ(I)
11077 measured reflections	R_int = 0.031
3033 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.01	Δρ_max = 0.23 e Å⁻³
3033 reflections	Δρ_min = −0.30 e Å⁻³
173 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

Bhatt, A. H., Parekh, M. H., Parikh, K. A. & Parikh, A. R. (2001). J. Indian Chem. Soc. 40, 57–21. Google Scholar
Bruker (2004). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Doshi, R., Kagthara, P. & Parekh, H. (1999). Indian J. Chem. 38, 348–352. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hishmat, O. H., Abdel Galil, F. M. & Farrag, D. S. (1990). Pharmazie, 45, 793–795. CAS PubMed Web of Science Google Scholar
Patrick, G. L. & Kinsmar, O. S. (1996). Eur. J. Med. Chem. 31, 615–624. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3370

doi:10.1107/S1600536812046211

Open

access