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

Abstract

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 R ₂ ²(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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812027833/gk2505Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

The H atoms were positioned geometrically (C–H = 0.93 Å) and refined as riding with U_iso(H) = xU_eq(C), where x = 1.2 for aryl H atoms.

Figures

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.

Crystal data

C11H6Cl2FN	Z = 2
Mr = 242.07	F(000) = 244
Triclinic, P1	Dx = 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

Bruker Kappa APEXII CCD diffractometer	1874 independent reflections
Radiation source: fine-focus sealed tube	1625 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.10 pixels mm-1	θmax = 25.5°, θmin = 1.7°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
Tmin = 0.874, Tmax = 0.898	l = −14→14
6978 measured reflections

Refinement

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(Fo2) + (0.0353P)2 + 0.1351P] where P = (Fo2 + 2Fc2)/3
1874 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.