2-Amino-4-(4-fluoro­phen­yl)-6-(naphthalen-1-yl)pyridine-3-carbonitrile

Jian-Qiang Wang; Shi-Gui Tang; Cheng Guo

doi:10.1107/S1600536810050804

. 2010 Dec 8;67(Pt 1):o56. doi: 10.1107/S1600536810050804

2-Amino-4-(4-fluorophenyl)-6-(naphthalen-1-yl)pyridine-3-carbonitrile

Jian-Qiang Wang ^a, Shi-Gui Tang ^b, Cheng Guo ^a,^*

PMCID: PMC3050308 PMID: 21522766

Abstract

The title compound, C₂₂H₁₄FN₃, was prepared by a one-pot condensation using malononitrile, an aromatic aldehyde, a methyl ketone and ammonium acetate as reactants under microwave irradiation. The pyridine ring is twisted with respect to the benzene ring and the naphthalene ring system, making dihedral angles of 41.9 (1) and 45.2 (1)°, respectively. In the crystal, molecules are connected via intermolecular N—H⋯N and C—H⋯F hydrogen bonds, forming a three-dimensional network.

Related literature

For the use of 2-amino-3-cyanopyridines as intermediates in the preparation of heterocyclic compounds, see: Shishoo et al. (1983 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₂H₁₄FN₃
M _r = 339.36
Monoclinic,
a = 14.531 (3) Å
b = 8.0900 (16) Å
c = 15.516 (3) Å
β = 110.04 (3)°
V = 1713.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 292 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.974, T _max = 0.991
3274 measured reflections
3144 independent reflections
2046 reflections with I > 2σ(I)
R _int = 0.056
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.177
S = 1.00
3144 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810050804/vm2063sup1.cif

e-67-00o56-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050804/vm2063Isup2.hkl

e-67-00o56-Isup2.hkl^{(154.3KB, hkl)}

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
N2—H2A⋯N1ⁱ	0.86	2.33	3.149 (3)	158
C20—H20A⋯Fⁱⁱ	0.93	2.50	3.284 (4)	142

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We gratefully acknowledge the financial support from the Youth Foundation of Nanjing University of Technology (39704011) and the Analysis Center of Nanjing University.

supplementary crystallographic information

Comment

Derivatives of 2-amino-3-cyanopyridine are important and useful intermediates in preparing a varity of heterocyclic compounds (Shishoo et al., 1983). Therefore, the synthesis of 2-amino-3-cyanopyridine derivatives attracts much interest in organic chemistry. Here, the single-crystal structure of the title compound (I), C₂₂H₁₄FN₃, is reported.

The title compound (Fig. 1) consists of a pyridine ring bearing a 4-fluoro phenyl at C7, a naphthyl at C10, an amino group at C9, and a cyano group at C8. The pyridine ring is twisted with respect to the benzene ring and naphthalene ring, with dihedral angles of 41.9 (1)° and 45.2 (1)°, respectively. The bond lengths and angles are within the reported values (Allen et al., 1987). Intermolecular N—H···N and C—H···F hydrogen bonds (Table 1, Fig. 2), and C—H···π and π–π stacking interactions help to stabilize the crystal structure.

Experimental

The title compound (I) was prepared from a mixture of 4-fluorobenzaldehyde (2 mmol), malononitrile (2 mmol), 1-naphthaldehyde (2 mmol) and ammonium acetate (16 mmol) under microwave irradiation (6 min, WF-4000M microwave reaction system). After cooling to room temperature, the resulting solid product was filtered off and recrystallized from methanol to give compound (I). Colorless single crystals suitable for X-ray analysis were obtained by dissolving (I) (0.5 g) in methanol (20 ml) and slowly evaporating the solvent at room temperature for a period of about two weeks.