2-Amino-4-(4-meth­oxy­phen­yl)-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile 1,4-dioxane hemisolvate

Shaaban K Mohamed; Mehmet Akkurt; Muhammad N Tahir; Antar A Abdelhamid; Sabry H H Younes

doi:10.1107/S1600536812027729

. 2012 Jun 23;68(Pt 7):o2178–o2179. doi: 10.1107/S1600536812027729

2-Amino-4-(4-methoxyphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 1,4-dioxane hemisolvate

Shaaban K Mohamed ^a, Mehmet Akkurt ^b,^*, Muhammad N Tahir ^c, Antar A Abdelhamid ^a, Sabry H H Younes ^d

PMCID: PMC3393982 PMID: 22798847

Abstract

In the crystal structure of the title compound, C₁₇H₁₆N₂O₃·0.5C₄H₈O₂, pairs of N—H⋯N hydrogen bonds link molecules into dimers with R ₂ ²(12) motifs, which are connected by N—H⋯O hydrogen bonds, forming a supramolecular array in the ab plane. The 1,4-dioxane ring, which lies about an inversion center, adopts a chair conformation.

Related literature

For the biological activity of pyran and fused-pyran molecules, see: Bargagna et al. (1992 ▶); Symeonidis et al. (2009 ▶); Narender & Gupta (2009 ▶); Alvey et al. (2009 ▶); Gorlitzer et al. (1984 ▶); Han et al. (2008 ▶); Martinez & Marco (1997 ▶); Smith et al. (1998 ▶); Taylor et al. (1998 ▶). For related structures, see: Gourdeau et al. (2004 ▶); Foroumadi et al. (2007 ▶); Mohamed et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₇H₁₆N₂O₃·0.5C₄H₈O₂
M _r = 340.37
Triclinic,
a = 8.0876 (4) Å
b = 9.2013 (4) Å
c = 12.1613 (6) Å
α = 94.376 (2)°
β = 102.827 (1)°
γ = 95.972 (2)°
V = 873.01 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.35 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.973, T _max = 0.980
14186 measured reflections
4108 independent reflections
3134 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.194
S = 1.07
4108 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812027729/tk5115sup1.cif

e-68-o2178-sup1.cif^{(26.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027729/tk5115Isup2.hkl

e-68-o2178-Isup2.hkl^{(201.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027729/tk5115Isup3.cml

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
N1—H1A⋯N2ⁱ	0.86	2.27	3.123 (3)	171
N1—H1B⋯O3ⁱⁱ	0.86	2.10	2.945 (2)	167

Open in a new tab

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

Acknowledgments

We thank Manchester Metropolitan University, the University of Sargodha and Erciyes University for guidance and for instrumental support of this study. We also extend our thanks to the Egyptian Government for their financial support of this project.

supplementary crystallographic information

Comment

Pyran and fused pyran ring systems are biologically interesting compounds known for their antimicrobial and antifungal (Alvey, et al., 2009), antioxidant (Symeonidis et al., 2009), antileishmanial (Narender et al., 2009), antitumor (Han et al., 2008). In addition, fused chromene ring systems have platelet antiaggregating, local anesthetic (Bargagna et al. 1992) and antihistaminic activities (Gorlitzer et al. 1984). They also exhibit inhibitory effects on influenza virus sialidases (Smith et al. 1998; Taylor et al. 1998) and antiviral activities (Martinez & Marco, 1997). Such observations prompted us to report the synthesis and crystal structure of the title compound (I).

In (I), Fig. 1, the O2/C8—C10/C12/C13 4H-pyran and C12–C17 cyclohexene rings are puckered with puckering parameters (Cremer & Pople, 1975) of Q_T = 0.187 (2) Å, θ = 72.2 (5) °, φ = 175.7 (6) ° and Q_T = 0.455 (2) ° A, θ = 122.9 (3) °, φ = 48.5 (3) °, respectively. The centroid of the solvent 1,4-dioxane ring (O4/C18/C19/O4a/C18a/C19a) lies about an inversion center. The 1,4-dioxane ring adopts a chair conformation [puckering parameters Q_T = 0.560 (5) Å, θ = 3.46 (3) °, φ = 0.00 °]. The values of the bond lengths and angles in (I) are in normal ranges and are comparable with those of related structures (Gourdeau et al., 2004; Foroumadi et al., 2007; Mohamed et al., 2012).

In the crystal, molecules are linked by the pairs of N—H···N hydrogen bonds, forming dimers, with an R²₂(12) motif (Bernstein et al., 1995; Table 1, Fig. 2). These dimers are connected through the N—H···O hydrogen bonds with each other (Table 1, Fig. 2).

Experimental

A mixture of (4-methoxybenzylidene)propanedinitrile (184 mg, 1 mmol), cyclohexane-1,3-dione (112 mg, 1 mmol) in presence of ethanolamine (61 mg) as catalyst was refluxed in ethanol (50 ml). The reaction mixture was monitored by TLC until completion after 7 h. A solid product was deposited on cooling at ambient temperature and collected by filtration. The crude product was washed with dioxane and recrystallized from ethanol/drops of dioxane to afford the title compound in 78% yield. Single crystals suitable for X-ray analysis were grown up on slow evaporation of its mixed solvent ethanol/dioxane (9:1) solution at room temperature over three days. M.pt: 435 K.