4-(2,4-Dichloro­phen­yl)-6-(1H-indol-3-yl)-2,2′-bipyridine-5-carbonitrile

P Ramesh; S S Sundaresan; P Thirumurugan; Paramasivan T Perumal; M N Ponnuswamy

doi:10.1107/S1600536809012392

. 2009 Apr 8;65(Pt 5):o996–o997. doi: 10.1107/S1600536809012392

4-(2,4-Dichlorophenyl)-6-(1H-indol-3-yl)-2,2′-bipyridine-5-carbonitrile

P Ramesh ^a, S S Sundaresan ^b, P Thirumurugan ^c, Paramasivan T Perumal ^c, M N Ponnuswamy ^b,^*

PMCID: PMC2977688 PMID: 21584031

Abstract

The title compound, C₂₅H₁₄Cl₂N₄, crystallizes with two independent molecules in the asymmetric unit. The two pyridine rings are almost coplanar, making dihedral angles of 3.2 (1) and 8.6 (1)° in the two independent molecules. The dichlorophenyl and indole rings are twisted away from the bipyridine ring by 64.32 (5) and 18.46 (4)°, respectively in the first molecule and by 51.0 (1) and 27.99 (5)°, respectively in the second molecule. The crystal packing is stabilized by C—H⋯N, C—H⋯Cl, N—H⋯N and C—H⋯π interactions.

Related literature

For the use of pyridine derivatives containing cyano, amino, carboxyl and hydroxyl groups as drugs, see: Zhou et al. (2008 ▶); Stevenson et al. (2000 ▶); Harris & Uhle (1960 ▶); Ho et al. (1986 ▶); Rajeswaran et al. (1999 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₅H₁₄Cl₂N₄
M _r = 441.30
Monoclinic,
a = 10.0307 (12) Å
b = 22.446 (3) Å
c = 17.932 (3) Å
β = 90.991 (4)°
V = 4036.7 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.902, T _max = 0.934
38628 measured reflections
7874 independent reflections
5586 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.141
S = 1.06
7874 reflections
567 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809012392/bt2890sup1.cif

e-65-0o996-sup1.cif^{(34.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012392/bt2890Isup2.hkl

e-65-0o996-Isup2.hkl^{(377.5KB, 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
C9—H9⋯N1	0.93	2.55	3.052 (3)	114
C9′—H9′⋯N1′	0.93	2.50	2.993 (3)	113
C15—H15⋯N17	0.93	2.52	3.280 (4)	139
C15′—H15′⋯N17′	0.93	2.61	3.334 (3)	135
C5—H5⋯Cl2′ⁱ	0.93	2.81	3.727 (3)	169
N14—H14⋯N17′ⁱⁱ	0.73 (3)	2.36 (3)	3.075 (3)	166 (3)
N14′—H14′⋯N17ⁱⁱⁱ	0.86 (3)	2.33 (3)	3.157 (3)	160 (3)
C15′—H15′⋯Cg5	0.93	3.13	3.798 (3)	131
C23—H23⋯Cg8	0.93	2.76	3.620 (3)	155
C23′—H23′⋯Cg7	0.93	2.83	3.633 (3)	145

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg5, Cg7 and Cg8 are the centroids of the C24–N29, C8–C13 and C8A–C13A rings, respectively.

Acknowledgments

PR thanks Dr Babu Varghese, SAIF, IIT-Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Pyridine derivatives containing multi-functional groups can be used as drugs such as streptonigrin, streptonigrone and lavendamycin which are reported as anticancer drugs, and itavastatin, cerivastatin are reported as the HMG-CoA enzyme inhibitors (Zhou et al., 2008). Indole derivatives are used as bioactive drugs (Stevenson et al., 2000) and they exhibit anti-allergic, central nervous system depressant and muscle relaxant properties (Harris & Uhle 1960; Ho et al., 1986). Indoles have been proved to display high aldose reductase inhibitory activity (Rajeswaran et al., 1999).

The ORTEP diagram of the title compound is shown in Fig. 1. In the title compound, there are two crystallographically independent molecules in the asymmetric unit. The two pyridine rings lie in the same plane as can be seen from the dihedral angle of 3.2 (1)° and 8.6 (1)°. The dichlorophenyl and indole rings are twisted away from the bipyridine ring by 64.32 (5)° and 18.46 (4)°, respectively. In the benzene ring of the indole ring system, the endocyclic angels at C12 and C12' are contracted to 117.7 (2)° and 117.9 (3)°, while those at C13 and C13' are expanded to 123.0 (2)° and 122.2 (3)°, respectively. This would appear to be a real effect caused by the fusion of the pyrrole with benzene ring resulting in an angular distortion. The sum of the bond angles around N14(359.3)° and N14'(360.3)° are in accordance with sp² hybridization. The bond angles of C3—C16—N17 (178.0 (3))° and C3'-C16'-N17' (178.0 (3))° show the linearity of the cyano group, a feature observed in carbonitrile compounds.

The crystal packing is controlled by C—H···N, C—H···Cl, N—H···N and C—H···π types of intra and intermolecular interactions in addition to van der Waals forces. Atoms N14 and N14' at (x, y, z) donate one proton each to N17 (-x, y + 1/2, -z + 1/2) and N17'(-x, y - 1/2, -z + 1/2) which connects the molecules to form a dimer with a graph-set-motiff R²₂(16) (Bernstein et al., 1995). These dimers are linked into a zigzag chain running along b axis through intermolecular C5—H5···Cl2' hydrogen bond which is shown in Fig. 2.

Experimental

A mixture of 4-(2,4-dichlorophenyl)-6-(1H-indol-3-yl)-1,4-dihydro -2,2'-bipyridine-5-carbonitrile (1 mmol) and urea oxalate (20 mol%) was irradiated in a microwave oven in ethanol for 5 min. After the completion of the reaction (as monitored by TLC), it was poured into water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under vacuo. The crude product was chromatographed and isolated in 86% yield (90:10, petroleum ether: ethyl acetate). The compound was recrystallized in ethanol.