6-(1H-Indol-3-yl)-4-phenyl-2,2′-bi­pyridine-5-carbonitrile

Weijun Zhu; Yan Xiang; Songlei Zhu

doi:10.1107/S1600536809016195

. 2009 May 7;65(Pt 6):o1187. doi: 10.1107/S1600536809016195

6-(1H-Indol-3-yl)-4-phenyl-2,2′-bipyridine-5-carbonitrile

Weijun Zhu ^a,^*, Yan Xiang ^b, Songlei Zhu ^c

PMCID: PMC2969709 PMID: 21583060

Abstract

In the molecule of the title compound, C₂₅H₁₆N₄, the pyridine rings are oriented at a dihedral angle of 0.92 (3)°, while the dihedral angle between the benzene ring and the adjacent pyridine ring is 56.51 (3)°. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers, forming R ₂ ²(16) ring motifs. π–π contacts between the pyridine ring and the indole ring system and between the pyridine rings [centroid–centroid distances = 3.923 (2) and 3.724 (2) Å] may further stabilize the structure. Two weak C—H⋯π interactions are also present.

Related literature

For general background, see: da Silva et al. (2001 ▶); Joshi & Chand (1982 ▶); Namba et al. (2005 ▶). For a related structure, see: Zhu et al., (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring-motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₅H₁₆N₄
M _r = 372.42
Triclinic,
a = 9.7744 (16) Å
b = 9.7927 (11) Å
c = 11.233 (2) Å
α = 73.121 (13)°
β = 86.008 (16)°
γ = 63.853 (10)°
V = 921.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 K
0.55 × 0.35 × 0.30 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (ABSCOR; Jacobson, 1998 ▶) T _min = 0.966, T _max = 0.976
8987 measured reflections
3349 independent reflections
2614 reflections with I > 2/s(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.126
S = 1.12
3349 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016195/hk2679sup1.cif

e-65-o1187-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016195/hk2679Isup2.hkl

e-65-o1187-Isup2.hkl^{(164.2KB, 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
N4—H4⋯N3ⁱ	0.86	2.23	3.066 (2)	164
C12—H12⋯Cg5ⁱⁱ	0.93	2.84	3.649 (3)	146
C23—H23⋯Cg4ⁱⁱⁱ	0.93	2.91	3.711 (3)	145

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg4 and Cg5 are the centroids of the C11–C16 and C20–C25 rings, respectively.

Acknowledgments

This work was sponsored by the ‘Qing Lan’ Project of Jiangsu Province for Excellent Young Teachers of XuZhou College of Industrial Technology, and the Special Foundation of the President of Xuzhou Medical College.

supplementary crystallographic information

Comment

Indole nucleus is a well known heterocycle (da Silva et al., 2001). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activities (Joshi & Chand, 1982). Moreover, the bipyridines and the related complexes have also found numerous applications in asymmetric catalysis, photoinduced electron transfer, and polymer and dendrimer science (Namba et al., 2005). As a part of our programme devoted to the preparation of functionalized indole derivatives, we synthesized a series of indole substituted heterocycles (Zhu et al., 2008). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The indole ring system A (N4/C18-C25) is planar with a maximum deviation of -0.021 (3) Å for atom C25. Rings B (N1/C1-C5), C (N2/C6-C10) and D (C11-C16) are, of course, planar, and they are oriented at dihedral angles of A/B = 23.01 (3), A/C = 23.61 (3), A/D = 74.90 (3), B/C = 0.92 (3), B/D = 56.51 (3) and C/D = 56.51 (3) °. So, rings B and C are nearly coplanar.

In the crystal structure, intermolecular N-H···N hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers forming R₂²(16) ring motifs (Fig. 2) (Bernstein et al., 1995), in which they may be effective in the stabilization of the structure. The π–π contacts between the pyridine ring and the indole ring system and the pyridine rings, Cg1—Cg2ⁱ and Cg2—Cg3ⁱⁱ [symmetry codes: (i) -x, 2 - y, 1 - z, (ii) -x, 1 - y, 1 - z, where Cg1, Cg2 and Cg3 are centroids of the rings (N4/C18-C20/C25), B (N1/C1-C5) and C (N2/C6-C10), respectively] may further stabilize the structure, with centroid-centroid distances of 3.923 (2) and 3.724 (2) Å. There also exist two weak C—H···π interactions (Table 1).

Experimental

The title compound was prepared by one-pot reaction of 3-cyanoacetyl indole (2 mmol), benzaldehyde (2 mmol) and 2-acetyl pyridine (2 mmol) in present of ammonium acetate in ethanol. After refluxing for 5 h, the reaction mixture was cooled and washed with small amount of cool ethanol. The crude product was filtered and single crystals of the title compound were obtained from ethanol solution by slow evaporation at room temperature (yield; 80%, m.p. 567-568 K). Spectroscopic analysis: IR (KBr, n, cm^-1): 3337, 3050, 2218, 1573, 1535, 1438, 1214, 1145, 850, 745, 703. ¹H NMR (400 MHz, DMSO-d₆): 11.89 (br s, 1H, NH), 8.78 (d, J = 4.4 Hz, 1H, ArH), 8.58 (d, J = 8.0 Hz, 1H, ArH), 8.41 (d, J = 5.2 Hz, 2H, ArH), 8.31 (s, 1H, ArH), 8.11 (m, 1H, ArH), 7.79-7.81 (m, 2H, ArH), 7.56-7.66 (m, 5H, ArH), 7.24-7.29 (m, 2H, ArH)