2-Amino-4-(4-chloro­phen­yl)-6-(pyrrolidin-1-yl)pyridine-3,5-dicarbonitrile

S Antony Inglebert; Jayabal Kamalraja; K Sethusankar; Gnanasambandam Vasuki

doi:10.1107/S1600536812009051

. 2012 Mar 10;68(Pt 4):o1000. doi: 10.1107/S1600536812009051

2-Amino-4-(4-chlorophenyl)-6-(pyrrolidin-1-yl)pyridine-3,5-dicarbonitrile

S Antony Inglebert ^a, Jayabal Kamalraja ^b, K Sethusankar ^c,^*, Gnanasambandam Vasuki ^b

PMCID: PMC3343967 PMID: 22589876

Abstract

In the title compound, C₁₇H₁₄ClN₅, two C atoms and their attached H atoms of the pyrrolidine ring are disordered over two sets of sites with an occupancy ratio of 0.638 (10):0.362 (10). The benzene and pyridine rings are inclined to one another by 60.57 (8)°. In the crystal, the amino group forms an N—H⋯N hydrogen bond with one of the cyano groups, linking the molecules into chains along [010].

Related literature

For a similar compound, see: Inglebert et al. (2011 ▶). For related structures, see: Chao et al. (1975 ▶); Kvick et al. (1976 ▶). For bond-length data, see: Atoji & Lipscomb (1953 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₇H₁₄ClN₅
M _r = 323.77
Triclinic,
a = 7.318 (5) Å
b = 9.060 (5) Å
c = 12.011 (5) Å
α = 87.196 (5)°
β = 80.477 (5)°
γ = 83.795 (5)°
V = 780.4 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.916, T _max = 0.939
6077 measured reflections
3570 independent reflections
1887 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.097
S = 0.85
3570 reflections
237 parameters
11 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812009051/rk2335sup1.cif

e-68-o1000-sup1.cif^{(26.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009051/rk2335Isup2.hkl

e-68-o1000-Isup2.hkl^{(175KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812009051/rk2335Isup3.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
N2—H2B⋯N4ⁱ	0.92 (1)	2.12 (1)	2.992 (3)	160 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the SAIF, IIT, Chennai, India, for the data collection. SAIB and KS also thank Dr V. Murugan, Head of of the Physics Department, RKM Vivekananda College, Chennai, India, for providing computational facilities to carry out this research work.

supplementary crystallographic information

Comment

Pyridine and its derivatives play an important role in hetrocyclic chemistry. Pyridine containing compounds are the new class of anti–HIV molecules, which particularly inhibit RNA dependent DNA polymerase or reverse transcriptace and thus act as non–nucleoside reverse transcriptace inhibitors. They also exhibit cytotoxic, anti–cancer, anti–tumour and anti–bacterial activity.

The pyrrolidine ring adopts a twisted conformation in both the major and minor conformers (occupancy factors of 0.638 (10)/0.362 (10) respectively). Puckering parameters (Cremer & Pople, 1975) are q₂ and φ₂, of 0.422 (6)Å and 273.9 (4)° for the major conformer (N5/C15/C16/C17/C18) and 0.469 (10)Å and 86.4 (6)°, respectively, for the minor conformer (N5/C15/C16'/C17'/C18).

The bond lengths of the nitrile groups attached to pyridine ring are typical (N4≡C11 = 1.148 (2)Å and C9≡N3 = 1.142 (2)Å). The nitrile groups form angles with parent C atoms: 177.1 (2)° and 174.5 (2)°. The sum angles around the atom C12 are slightly less 360° (real 358.0 (2)°) - deformed by the amino group, as seen in other aminopyridines (Chao et al., 1975; Kvick et al., 1976). This behaviour characterizes the resonance of the N2 lone pair with the aromatic ring. The effect can also be verified by the shortening of the C12—N2 bond (1.345 (2)Å) relative to a normal single C—N bond (1.483Å for C—N in methaneamine (Atoji & Lipscomb, 1953).

The amino group is planar with the pyridine ring as indicated by the torsion angle N2—C12—N1—C13 = 179.75 (16)°. The chlorine atom attached at C1 deviates by -0.0817 (3)Å from the mean plane of the phenyl ring. The title structure exhibits structural similarities with the previously reported structure (Inglebert et al., 2011).

In the crystal structure, the classical intermolecular N2—H2B···N4ⁱ hydrogen bonds link the molecules into chains along the b axis. Symmetry code: (i) x, y+1, z.

Experimental

A mixture of 4–chlorobenzaldehyde (2 mmoL, 0.28 g), malononitrile (3 mmoL, 0.198 g), pyrrolidine (1.5 mmoL, 0.1 g) was stirred without any solvent at room temperature. A solid appeared immediately which has dissolved in a minimum amount (3 ml) of ethanol and the solution was refluxed until completion of the reaction (monitered by TLC). The reaction mixture was cooled. Ethanol was evaporated under reduced pressure and the residue was extracted with dicholoromethane (3×10 ml). Evaporation of solvent left the crude solid which was subjected to silica gel column chromatography [25:75 ethyl acetate/hexane] and the product was recrysallized from dichloromethane.