Crystal structure of 2-(2-bromo­phen­yl)-4-(1H-indol-3-yl)-6-(thio­phen-2-yl)pyridine-3-carbo­nitrile

R Vishnupriya; J Suresh; Shanmugavel Bharkavi; Subbu Perumal; P L Nilantha Lakshman

doi:10.1107/S1600536814017188

. 2014 Aug 1;70(Pt 9):o968–o969. doi: 10.1107/S1600536814017188

Crystal structure of 2-(2-bromophenyl)-4-(1H-indol-3-yl)-6-(thiophen-2-yl)pyridine-3-carbonitrile

R Vishnupriya ^a, J Suresh ^a, Shanmugavel Bharkavi ^b, Subbu Perumal ^b, P L Nilantha Lakshman ^c,^*

PMCID: PMC4186133 PMID: 25309284

Abstract

In the title compound, C₂₄H₁₄BrN₃S, the dihedral angles between the planes of the pyridine ring and the pendant thiophene ring, the indole ring system (r.m.s. deviation = 0.022 Å) and the bromobenzene ring are 9.37 (17), 21.90 (12) and 69.01 (15)°, respectively. The approximate coplanarity of the central ring and the indole ring system is supported by two intramolecular C—H⋯N interactions. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R ₂ ²(16) loops and the dimers are linked by C—H⋯π and aromatic π–π stacking [shortest centroid–centroid separation = 3.729 (3) Å] into a three-dimensional network.

Keywords: crystal structure, pyridine-3-carbonitrile, hydrogen bonding, π–π stacking

Related literature

For the biological activity of pyridine-3-carbonitrile derivatives, see: Kim et al. (2005 ▶); Ji et al. (2007 ▶); Brandt et al. (2010 ▶); El-Sayed et al. (2011 ▶).

Experimental

Crystal data

C₂₄H₁₄BrN₃S
M _r = 456.35
Monoclinic,
a = 10.470 (5) Å
b = 21.353 (5) Å
c = 9.292 (5) Å
β = 107.710 (5)°
V = 1978.9 (15) Å³
Z = 4
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 293 K
0.52 × 0.23 × 0.17 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.958, T _max = 0.986
17079 measured reflections
4305 independent reflections
2837 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.121
S = 1.02
4305 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.35 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814017188/hb7260sup1.cif

e-70-0o968-sup1.cif^{(27.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017188/hb7260Isup2.hkl

e-70-0o968-Isup2.hkl^{(206.7KB, hkl)}

Click here for additional data file.^{(7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017188/hb7260Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814017188/hb7260fig1.tif

The molecular structure of compound showing 30% probability displacement ellipsoids.

Click here for additional data file.^{(1.1MB, tif)}

x y z . DOI: 10.1107/S1600536814017188/hb7260fig2.tif

Partial packing view of the compound showing molecules interconnected through a C—H⋯π stacking interaction (dotted lines; symmetry code: (i) Inline graphic − x, + y, − z)

CCDC reference: 1015962

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the benzene ring of the indole moiety.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C53—H53⋯N1	0.93	2.58	3.069 (4)	114
C58—H58⋯N2	0.93	2.55	3.278 (4)	135
N3—H3⋯N2ⁱ	0.86	2.17	3.008 (4)	165
C32—H32⋯Cg1ⁱⁱ	0.93	2.89	3.761 (4)	157

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

Acknowledgments

JS and RV thank the management of the Madura College for their encouragement and support. SP thanks the Department of Science and Technology, New Delhi, for a major research project (SR/S1/OC/-50/2011) and the University Grants Commission, New Delhi, for the award of a BSR Faculty Fellowship

supplementary crystallographic information

S1. Comment

3-Cyanopyridine derivatives have been reported for their wide range of applications such as in antimicrobial, analgesic, anti-hyperglycemic, antiproliferative and antitumor activities (Brandt et al., 2010; El-Sayed et al., 2011; Ji et al., 2007; Kim et al., 2005). As part of our studies in this area, the title compound was investigated.

The deviation of the nitrile atoms (C41,N2) from the mean plane of the pyridine ring system is -0.013 (1) Å and -0.020 (5) Å. The shortening of the C—N distances [1.346 (3) and 1.345 (3) Å] and the opening of the N1–C11–C10 angle [122.83 (2)°] may be attributed to the size of the substituent at C1, correlating well with the values observed in the ortho-substituted derivative.

The crystal structure features a intermolecular N—H···N interaction between inverse related molecules generating a graph set ring motif R₂² (16) which are linked into chains through C—H···Cg1 interation (Cg1 is the centroid of the benzene ring of the indole moiety) and by π···π stacking interaction involving adjacent pyridine and pyrrole rings of the symmetry related molecule at (-x, -y, -z), with a centroid-to-centroid distance of 3.729 (3) Å·(Fig 2).

S2. Experimental

A mixture of 3-(1H-indol-3-yl)-3-oxopropanenitrile 1 (1 mmol), 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione 2 (1 mmol) and 2-bromo benzaldehyde 3 (1 mmol) in the presence of ammonium acetate (400 mmol) under solvent-free condition was heated at 110 °C for 7 h. After completion of the reaction (TLC), the reaction mixture was poured into water and extracted with dichloromethane. After removal of the solvent, the residue was chromatographed over silica gel (230–400 mesh) using petroleum ether-ethyl acetate mixture (7:3 v/v), which afforded the pure compound. Melting point 282°C, yield: 67%.