organic compounds
5-(2,3-Dichlorophenyl)-2-fluoropyridine
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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
https://doi.org/10.1107/S1600536812027833/gk2505sup1.cif
contains datablocks global, I. DOI: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
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).
The H atoms were positioned geometrically (C–H = 0.93 Å) and refined as riding with Uiso(H) = xUeq(C), where x = 1.2 for aryl H atoms.
We have reported the
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).
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).
Data collection: APEX2 (Bruker, 2007); cell
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).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 |
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 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 |
C11H6Cl2FN | γ = 92.057 (5)° |
Mr = 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)° |
Bruker Kappa APEXII CCD diffractometer | 1874 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1625 reflections with I > 2σ(I) |
Tmin = 0.874, Tmax = 0.898 | Rint = 0.023 |
6978 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.18 e Å−3 |
1874 reflections | Δρmin = −0.22 e Å−3 |
136 parameters |
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. |
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.874, 0.898 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6978, 1874, 1625 |
Rint | 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 |
Δρmax, Δρmin (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).
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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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).