5-(2,3-Dichloro­phen­yl)-2-fluoro­pyridine

Elahi, F.; Adeel, M.; Tahir, M.N.

doi:10.1107/S1600536812027833

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2180

https://doi.org/10.1107/S1600536812027833

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5-(2,3-Dichlorophenyl)-2-fluoropyridine

Fazal Elahi,^a Muhammad Adeel ^a and M. Nawaz Tahir ^b ^*

^aDepartment of Chemistry, Gomal University, Dera Ismail Khan, K.P.K., Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 17 June 2012; accepted 19 June 2012; online 23 June 2012)

In the title compound, C₁₁H₆Cl₂FN, the dichlorobenzene and the 2-fluoropyridine rings are oriented at a dihedral angle of 47.73 (3)°. In the crystal, pairs of C—H⋯N interactions link the molecules into dimers with R₂²(12) motifs. Molecules are arranged in stacks extending along [100] via π–π interactions with a centroid–centroid distance of 3.8889 (3) Å.

Related literature

For related structures, see: Adeel et al. (2012 ); Elahi, Adeel & Tahir (2012 ); Elahi, Adeel, Tahir et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₆Cl₂FN
M_r = 242.07
Triclinic, $[P \overline 1]$
a = 3.8889 (3) Å
b = 11.1006 (11) Å
c = 12.0542 (11) Å
α = 101.526 (5)°
β = 94.930 (4)°
γ = 92.057 (5)°
V = 507.24 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 296 K
0.34 × 0.18 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.874, T_max = 0.898
6978 measured reflections
1874 independent reflections
1625 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.075
S = 1.04
1874 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.18 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
C6—H6⋯N1ⁱ	0.93	2.63	3.557 (2)	178
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027833/gk2505sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027833/gk2505Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027833/gk2505Isup3.cml

checkCIF report

Comment top

We have reported the crystal structure of 5-(4-chlorophenyl)-2-fluoropyridine (Adeel et al., 2012), 4-(2-fluoropyridin-5-yl)phenol (Elahi, Adeel & Tahir, 2012) and 5-(4-fluorophenyl)-2-fluoropyridine (Elahi, Adeel, Tahir et al., 2012)which have common moiety of 2-fluoropyridine as in (I).

In (I) the dichlorobenzene A (C1–C6/CL1/CL2) and the 2-fluoropyridine B (C7—C11/N1/F1) are planar with r.m.s. deviations of 0.0189 Å and 0.0042 Å, respectively. The dihedral angle between A/B is 47.73 (3)°. The molecules are stabilized in the form of dimers with R₂²(12) ring motif (Bernstein et al., 1995) due to hydrogen bonding of C—H···N type between dichlorophenyl and pyridine groups (Table 1, Fig. 2).

Related literature top

For related structures, see: Adeel et al. (2012); Elahi, Adeel & Tahir (2012); Elahi, Adeel, Tahir et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

To a 6 ml solution of 5-bromo-2-fluoropyridine (0.2 g, 1.136 mmol), 2,3-dichlorophynyl boronic acid (0.260 g, 1.36 mmol) in dioxane and K₃PO₄ (0.361 g, 1.5 mmol, in 1 ml H₂O) was added Pd(PPh₃)₄ (1.5 mole %) at 373 K under N₂ atmosphere. The reaction mixture was refluxed for 8 h. Then 20 ml of distilled water was added. The aqueous layer was extracted three times with ethyl acetate (3 × 15 ml). The organic layer was evaporated in vacuo and the crude product was obtained. Colorless needles of (I) were obtained by the recrystalization of crude product in a saturated CHCl₃/CH₃OH (m.p. 350-352 K).

Structure description top

For related structures, see: Adeel et al. (2012); Elahi, Adeel & Tahir (2012); Elahi, Adeel, Tahir et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Dispalcement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form dimers via R₂²(12) motif.

5-(2,3-Dichlorophenyl)-2-fluoropyridine top

Crystal data top

C₁₁H₆Cl₂FN	Z = 2
M_r = 242.07	F(000) = 244
Triclinic, P1	D_x = 1.585 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8889 (3) Å	Cell parameters from 869 reflections
b = 11.1006 (11) Å	θ = 1.7–25.5°
c = 12.0542 (11) Å	µ = 0.61 mm⁻¹
α = 101.526 (5)°	T = 296 K
β = 94.930 (4)°	Needle, colorless
γ = 92.057 (5)°	0.34 × 0.18 × 0.16 mm
V = 507.24 (8) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	1874 independent reflections
Radiation source: fine-focus sealed tube	1625 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.5°, θ_min = 1.7°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
T_min = 0.874, T_max = 0.898	l = −14→14
6978 measured 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0353P)² + 0.1351P] where P = (F_o² + 2F_c²)/3
1874 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₁H₆Cl₂FN	γ = 92.057 (5)°
M_r = 242.07	V = 507.24 (8) Å³
Triclinic, P1	Z = 2
a = 3.8889 (3) Å	Mo Kα radiation
b = 11.1006 (11) Å	µ = 0.61 mm⁻¹
c = 12.0542 (11) Å	T = 296 K
α = 101.526 (5)°	0.34 × 0.18 × 0.16 mm
β = 94.930 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1874 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1625 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.898	R_int = 0.023
6978 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
1874 reflections	Δρ_min = −0.22 e Å⁻³
136 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.89637 (11)	0.34986 (4)	0.42850 (3)	0.0469 (2)
Cl2	0.69950 (16)	0.07317 (5)	0.40724 (5)	0.0705 (2)
F1	0.8508 (4)	0.81300 (10)	0.19925 (12)	0.0787 (5)
N1	0.8522 (4)	0.61337 (13)	0.12178 (12)	0.0454 (5)
C1	0.5754 (4)	0.32731 (14)	0.21540 (13)	0.0333 (5)
C2	0.6680 (4)	0.26882 (14)	0.30479 (13)	0.0355 (5)
C3	0.5869 (4)	0.14425 (15)	0.29533 (15)	0.0441 (6)
C4	0.4176 (5)	0.07576 (17)	0.19693 (18)	0.0535 (6)
C5	0.3322 (5)	0.13175 (16)	0.10746 (17)	0.0518 (6)
C6	0.4073 (4)	0.25512 (15)	0.11605 (14)	0.0421 (5)
C7	0.6503 (4)	0.46004 (14)	0.21958 (12)	0.0329 (5)
C8	0.5751 (4)	0.55329 (15)	0.30850 (13)	0.0393 (5)
C9	0.6419 (5)	0.67424 (16)	0.30366 (15)	0.0469 (6)
C10	0.7801 (5)	0.69556 (15)	0.20828 (16)	0.0475 (6)
C11	0.7863 (4)	0.49632 (15)	0.12855 (13)	0.0383 (5)
H4	0.36156	−0.00758	0.19106	0.0642*
H5	0.22187	0.08546	0.04010	0.0621*
H6	0.34500	0.29133	0.05456	0.0505*
H8	0.47957	0.53360	0.37117	0.0472*
H9	0.59579	0.73832	0.36209	0.0562*
H11	0.83512	0.43519	0.06797	0.0460*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0512 (3)	0.0576 (3)	0.0312 (2)	0.0030 (2)	−0.0007 (2)	0.0092 (2)
Cl2	0.0884 (4)	0.0636 (3)	0.0719 (4)	0.0107 (3)	0.0127 (3)	0.0404 (3)
F1	0.1164 (11)	0.0382 (6)	0.0853 (9)	−0.0001 (6)	0.0163 (8)	0.0196 (6)
N1	0.0540 (9)	0.0448 (8)	0.0408 (8)	0.0054 (7)	0.0071 (7)	0.0155 (6)
C1	0.0300 (8)	0.0385 (8)	0.0319 (8)	0.0047 (6)	0.0071 (6)	0.0060 (6)
C2	0.0325 (8)	0.0425 (9)	0.0322 (8)	0.0039 (6)	0.0076 (6)	0.0068 (6)
C3	0.0422 (10)	0.0445 (9)	0.0512 (10)	0.0069 (7)	0.0130 (8)	0.0185 (8)
C4	0.0530 (11)	0.0382 (9)	0.0687 (13)	−0.0011 (8)	0.0091 (9)	0.0089 (9)
C5	0.0497 (11)	0.0452 (10)	0.0524 (11)	−0.0033 (8)	−0.0035 (8)	−0.0045 (8)
C6	0.0422 (9)	0.0444 (9)	0.0383 (9)	0.0049 (7)	0.0011 (7)	0.0058 (7)
C7	0.0309 (8)	0.0383 (8)	0.0294 (8)	0.0051 (6)	0.0019 (6)	0.0064 (6)
C8	0.0409 (9)	0.0446 (9)	0.0323 (8)	0.0049 (7)	0.0062 (7)	0.0062 (7)
C9	0.0555 (11)	0.0409 (9)	0.0407 (10)	0.0093 (8)	0.0031 (8)	−0.0007 (7)
C10	0.0558 (11)	0.0360 (9)	0.0519 (10)	0.0019 (8)	−0.0005 (8)	0.0141 (8)
C11	0.0428 (9)	0.0407 (9)	0.0323 (8)	0.0073 (7)	0.0051 (7)	0.0079 (7)

Geometric parameters (Å, º) top

Cl1—C2	1.7323 (16)	C5—C6	1.372 (2)
Cl2—C3	1.7271 (18)	C7—C8	1.392 (2)
F1—C10	1.350 (2)	C7—C11	1.381 (2)
N1—C10	1.299 (2)	C8—C9	1.372 (2)
N1—C11	1.335 (2)	C9—C10	1.368 (3)
C1—C2	1.394 (2)	C4—H4	0.9300
C1—C6	1.396 (2)	C5—H5	0.9300
C1—C7	1.482 (2)	C6—H6	0.9300
C2—C3	1.387 (2)	C8—H8	0.9300
C3—C4	1.374 (3)	C9—H9	0.9300
C4—C5	1.371 (3)	C11—H11	0.9300

C10—N1—C11	115.72 (15)	C8—C9—C10	116.44 (16)
C2—C1—C6	117.42 (15)	F1—C10—N1	114.38 (16)
C2—C1—C7	123.81 (14)	F1—C10—C9	118.82 (16)
C6—C1—C7	118.76 (14)	N1—C10—C9	126.79 (17)
Cl1—C2—C1	120.44 (12)	N1—C11—C7	124.31 (15)
Cl1—C2—C3	118.82 (12)	C3—C4—H4	120.00
C1—C2—C3	120.72 (15)	C5—C4—H4	120.00
Cl2—C3—C2	120.27 (13)	C4—C5—H5	120.00
Cl2—C3—C4	119.16 (14)	C6—C5—H5	120.00
C2—C3—C4	120.57 (16)	C1—C6—H6	119.00
C3—C4—C5	119.21 (18)	C5—C6—H6	119.00
C4—C5—C6	120.85 (18)	C7—C8—H8	120.00
C1—C6—C5	121.20 (16)	C9—C8—H8	120.00
C1—C7—C8	123.79 (14)	C8—C9—H9	122.00
C1—C7—C11	119.39 (14)	C10—C9—H9	122.00
C8—C7—C11	116.74 (15)	N1—C11—H11	118.00
C7—C8—C9	119.99 (15)	C7—C11—H11	118.00

C11—N1—C10—F1	179.73 (16)	Cl1—C2—C3—C4	−177.52 (14)
C11—N1—C10—C9	−0.7 (3)	C1—C2—C3—Cl2	−179.38 (12)
C10—N1—C11—C7	0.0 (2)	C1—C2—C3—C4	0.9 (2)
C6—C1—C2—Cl1	176.78 (12)	Cl2—C3—C4—C5	−179.13 (15)
C6—C1—C2—C3	−1.6 (2)	C2—C3—C4—C5	0.6 (3)
C7—C1—C2—Cl1	−2.2 (2)	C3—C4—C5—C6	−1.4 (3)
C7—C1—C2—C3	179.45 (15)	C4—C5—C6—C1	0.6 (3)
C2—C1—C6—C5	0.9 (2)	C1—C7—C8—C9	−177.67 (16)
C7—C1—C6—C5	179.88 (16)	C11—C7—C8—C9	−1.0 (2)
C2—C1—C7—C8	−49.6 (2)	C1—C7—C11—N1	177.60 (15)
C2—C1—C7—C11	133.83 (17)	C8—C7—C11—N1	0.8 (2)
C6—C1—C7—C8	131.43 (17)	C7—C8—C9—C10	0.5 (3)
C6—C1—C7—C11	−45.1 (2)	C8—C9—C10—F1	−179.97 (19)
Cl1—C2—C3—Cl2	2.22 (19)	C8—C9—C10—N1	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.93	2.63	3.557 (2)	178

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₆Cl₂FN
M_r	242.07
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	3.8889 (3), 11.1006 (11), 12.0542 (11)
α, β, γ (°)	101.526 (5), 94.930 (4), 92.057 (5)
V (Å³)	507.24 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.34 × 0.18 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.874, 0.898
No. of measured, independent and observed [I > 2σ(I)] reflections	6978, 1874, 1625
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.075, 1.04
No. of reflections	1874
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.22

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.93	2.63	3.557 (2)	178

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. MA also acknowledges financial support from the World University Service, Germany, for an equipment grant and the Higher Education Commission, Pakistan, for a resource grant.

References

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