6-(4-Amino­phen­yl)-4-(4-eth­oxy­phen­yl)-2-meth­oxy­nicotinonitrile

Thitipone Suwunwong; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536812036276

. 2012 Aug 31;68(Pt 9):o2812–o2813. doi: 10.1107/S1600536812036276

6-(4-Aminophenyl)-4-(4-ethoxyphenyl)-2-methoxynicotinonitrile

Thitipone Suwunwong ^a, Suchada Chantrapromma ^b,^*,^‡, Hoong-Kun Fun ^c,^§

PMCID: PMC3435837 PMID: 22969683

Abstract

In the title molecule, C₂₁H₁₉N₃O₂, the central pyridine ring makes dihedral angles of 14.46 (9) and 34.67 (8)° with the 4-amino- and 4-ethoxy-substituted benzene rings, respectively. The ethoxy group is essentially coplanar with the attached benzene ring [C—O—C—C torsion angle = 178.70 (16)°] as is the methoxy group with the pyridine ring [C—O—C—N torsion angle = −3.0 (3)°]. In the crystal, molecules are linked by N—H⋯N hydrogen bonds into chains along [201]. Weak C—H⋯O hydrogen bonds and C—H⋯π interactions are also present.

Related literature

The title nicotinonitrile derivative is a cyclized product of a chalcone and a malononitrile in the present of sodium methoxide. For the synthesis and applications of substituted pyridines and nicotinonitrile derivatives, see: Al-Jaber et al. (2012 ▶); Brandt et al. (2010 ▶); El-Sayed et al. (2011 ▶); Goda et al. (2004 ▶); Ji et al. (2007 ▶); Kamal et al. (2007 ▶); Kim et al. (2005 ▶); Kolev et al. (2005 ▶); Koner et al. (2012 ▶); Zhou et al. (2006 ▶). For a related structure, see: Chantrapromma et al. (2010 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₁₉N₃O₂
M _r = 345.39
Monoclinic,
a = 5.3924 (2) Å
b = 16.5111 (5) Å
c = 20.1415 (6) Å
β = 91.315 (2)°
V = 1792.82 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.54 × 0.25 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.956, T _max = 0.982
17814 measured reflections
5216 independent reflections
3013 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.159
S = 1.04
5216 reflections
245 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036276/lh5514sup1.cif

e-68-o2812-sup1.cif^{(27.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036276/lh5514Isup2.hkl

e-68-o2812-Isup2.hkl^{(255.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812036276/lh5514Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg is the centroid of the C12–C17 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯N2ⁱ	0.88 (3)	2.20 (3)	3.084 (3)	177 (2)
C21—H21A⋯O1ⁱⁱ	0.96	2.52	3.439 (2)	160
C18—H18A⋯Cg ⁱⁱⁱ	0.96	2.84	3.7135 (18)	151

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

Acknowledgments

TS thanks the Thailand Research Fund through the Royal Golden Jubilee PhD Program and the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Office of the Higher Education, Ministry of Education, Thailand for financial support. The authors thank the Thailand Research Fund (grant No. RSA 5280033), Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Pyridines have been reported for their applications in a number of areas (Goda et al., 2004; Kamal et al., 2007; Kolev et al., 2005). There are several methods reported for the synthesis of substituted pyridine derivatives including nicotinonitrile derivatives (Al-Jaber et al., 2012; Zhou et al., 2006). Nicotinonitrile derivatives have a wide range of applications such as antitumor, antimicrobial, analgesic, anti-hyperglycemic and antiproliferative activities (Brandt et al., 2010; El-Sayed et al., 2011; Ji et al., 2007; Kim et al., 2005) and fluorescent materials (Koner et al., 2012). Our research is aimed at the synthesis and preliminary fluorescent and antibacterial screening of nicotinonitrile derivatives. The title compound (I) was synthesized by the cyclization of a chalcone derivative with malononitrile to investigate its fluorescent properties. It was found that (I) exhibits fluorescence with the maximum emission at 498 nm when was excited at 370 nm in DMSO.

The molecular structure of the title compound is shown in Fig. 1. The central pyridine ring is inclined to the 4-aminophenyl and 4-ethoxyphenyl rings with the dihedral angles of 14.46 (9) and 34.67 (8)°, respectively. The dihedral angle between these two substituted benzene rings is 44.84 (9)°. The ethoxy substituent of the 4-ethoxyphenyl group is essentially co-planar with the attached benzene ring with the torsion angle C15–O1–C18–C19 = 178.70 (16)° and C18–O1–C15–C16 = 1.8 (3)°. The methoxy group is also approximately co-planar to the pyridine ring as indictated by the torsion angle C21–O2–C11–N1 = -3.0 (3)°. The bond distances agree with the literature values (Allen et al., 1987) and are comparable with those for a related structure (Chantrapromma et al., 2010).

In the crystal (Fig. 2), molecules are linked by N—H···N hydrogen bonds into chains along [201]. Weak C—H···O hydrogen bonds and C—H···π interactions are also present (Table 1).

Experimental

The title compound (I) was synthesized by stirring the solution of (E)-1-(4-aminophenyl)-3-(4-ethoxyphenyl)prop-2-en-1-one (0.27 g, 1 mmol) in methanol (10 ml) with a freshly prepared sodium methoxide (1.0 mmol of sodium in 20 ml of methanol). Excess malononitrile (0.13 g, 2.0 mmol) was then added with continuous stirring at room temperature until the precipitate was separated out. The resulting solid was filtered. Pale brown block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from methanol/ethanol (1:1 v/v) by the slow evaporation of the solvent at room temperature over several days, Mp. 477–478 K.