Crystal structure of 5-(5-chloro-2-hydroxy­benzo­yl)-2-(2-methyl-1H-indol-3-yl)nicotino­nitrile

G Vimala; N Poomathi; Y AaminaNaaz; P T Perumal; A SubbiahPandi

doi:10.1107/S2056989015018058

. 2015 Oct 7;71(Pt 11):o822–o823. doi: 10.1107/S2056989015018058

Crystal structure of 5-(5-chloro-2-hydroxybenzoyl)-2-(2-methyl-1H-indol-3-yl)nicotinonitrile

G Vimala ^a, N Poomathi ^b, Y AaminaNaaz ^a, P T Perumal ^b, A SubbiahPandi ^a,^*

PMCID: PMC4645016 PMID: 26594546

Abstract

In the title compound, C₂₂H₁₄ClN₃O₂, the indole unit is essentially coplanar, with a maximum deviation of 0.035 Å for the C atom bearing the methyl group. The central pyridine ring is inclined to the indole ring system by 43.7 (1)°. The dihedral angle between the phenyl ring and the indole ring system is 15.7 (2)°, while that between the phenyl ring and the central pyridine ring is 46.3 (1)°. The molecular structure is stabilized by an intramolecular O—H⋯O hydrogen bonding, forming an S(6) ring motif. In the crystal, molecules are linked via pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an R ₂ ²(16) ring motif. The crystal structure also features C—H⋯π and π–π interactions [centroid–centroid separation = 3.688 (1) Å].

Keywords: crystal structure, nicotinonitrile, acrylate derivatives, indole unit, N—H⋯N hydrogen bonds, C—H⋯π interactions, π–π interactions

Related literature

For applications of acrylate derivatives, see: Barden (2011 ▸); Chai et al. (2006 ▸); Nieto et al. (2005 ▸); Singh et al. (2000 ▸); Andreani et al. (2001 ▸); Quetin-Leclercq (1994 ▸); Mukhopadhyay et al. (1981 ▸). For related crystal structures, see: Penthala et al. (2008 ▸). For graph-set analysis, see: Grell et al. (2000 ▸). graphic file with name e-71-0o822-scheme1.jpg

Experimental

Crystal data

C₂₂H₁₄ClN₃O₂
M _r = 387.81
Monoclinic
a = 16.0673 (15) Å
b = 7.4804 (7) Å
c = 17.0159 (15) Å
β = 113.452 (3)°
V = 1876.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.27 × 0.23 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.941, T _max = 0.960
7690 measured reflections
3638 independent reflections
2447 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.170
S = 1.01
3638 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: APEX2 and SAINT (Bruker, 2008 ▸); data reduction: SAINT and XPREP (Bruker, 2008 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015018058/zp2018sup1.cif

e-71-0o822-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018058/zp2018Isup2.hkl

e-71-0o822-Isup2.hkl^{(174.8KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015018058/zp2018Isup3.cml

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

. DOI: 10.1107/S2056989015018058/zp2018fig1.tif

The molecular structure of the title compound, with the atomic numbering scheme and displacement ellipsoids drawn at 30% probability level.

Click here for additional data file.^{(1.6MB, tif)}

b . DOI: 10.1107/S2056989015018058/zp2018fig2.tif

O—H⋯O intra and N—H⋯N intermlecular interactions (dotted lines) in the crystal structure of the title compound. The crystal packing of the molecules is viewed down the b axis.

CCDC reference: 1427861

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

Table 1. Hydrogen-bond geometry (, ).

Cg3 and Cg4 are the centroids of the C1C6 and C16C21 rings, respectively.

DHA	DH	HA	D A	DHA
O1H1O2	0.82	1.91	2.596(3)	140
N3H3AN2ⁱ	0.86	2.27	3.110(4)	164
C2H2Cg3ⁱⁱ	0.90	2.93	3.656(4)	136
C12H12Cg4ⁱⁱⁱ	0.93	2.99	3.361(4)	106

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

Acknowledgments

The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.

supplementary crystallographic information

S1. Comment

In modern times, analogs based on indole are significant players in a diverse array of markets such as dyes, plastics, agriculture, vitamin supplements, over-the-counterdrugs, flavour enhancers and perfumery (Barden, 2011). Indole derivatives exhibit antihepatitis B virus (Chai et al., 2006) and antibacterial (Nieto et al., 2005) activities. Indole derivatives have been found to exhibit antibacterial, antifungal (Singh et al., 2000) and antitumour activities (Andreani et al., 2001). Some of the indole alkaloids extracted from plants possess interesting cytotoxic, antitumour or antiparasitic properties (Quetin-Leclercq, 1994; Mukhopadhyay et al., 1981). Against this background, the crystal structure of the title compound has been determined and the results are presented herein.

In the title molecule, the indole unit is essentially co-planar with a maximum deviation of -0.035 Å for the C15 atom. The central pyridine (N1/C8—C12) ring is almost halfway to be orthogonal to the indole ring system (N3/C14—C21), making a dihedral angle of 43.7 (1)°. The carbonyl-bound phenyl ring (C16—C21) forms a dihedral angle of 15.7 (2)° with the plane of the indole ring system. The pyridine ring and the phenyl ring are inclined at an angle of 46.3 (1)°. The cyano bond distance C13≡N2 agrees well with the reported value of 1.141 (4) Å.

The crystal packing (Fig. 2 and Table 1) is stabilized by an intramolecular O—H···O hydrogen bond, forms S(6) ring motif. The molecules are linked into inversion dimers via N—H···N hydrogen bonds resulting in an R²₂(16) graph-set motif, which are stablized by C—H···π (Table 1) and π-π interactions. The Cg1···Cg2ⁱⁱ seperation is 3.688 (1) Å (Fig.2; Cg1 and Cg2 are centroids of the N3/C14—C16/C21 ring and N1/C8—C12 pyridine ring, repectively; symmetry codes: (ii) 1/2 - x, y - 1/2, 1/2 - z).

S2. Experimental

A mixture of 6-chlorol-3-formylchromone (1 mmol), cyanoacetylindole (1 mmol) and ammonium acetate (1 mmol) in DMF and a catalytic amount of SnCl2.2H2O (0.020 mol %) was added and refluxed for about 3 hrs. After completition of the reaction, the solvent was removed under reduced pressure and the residue was purified by column chromatography on siliga gel (3:97% ethylacetate and petether) to afford pure product. The purified compound was recrystalized from ethanol by using slow evaporation method. The yield of the isolated product was 92%, giving block like crystals suitable for X ray diffraction.