2-Amino-4-(4-chloro­phen­yl)-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile

Shaaban K Mohamed; Mehmet Akkurt; Antar A Abdelhamid; Kuldip Singh; M A Allahverdiyev

doi:10.1107/S1600536812015838

. 2012 Apr 18;68(Pt 5):o1414–o1415. doi: 10.1107/S1600536812015838

2-Amino-4-(4-chlorophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile

Shaaban K Mohamed ^a, Mehmet Akkurt ^b,^*, Antar A Abdelhamid ^a, Kuldip Singh ^c, M A Allahverdiyev ^d

PMCID: PMC3344539 PMID: 22590301

Abstract

In the title moleclue, C₁₆H₁₃ClN₂O₂, the cyclohexene ring is in a sofa conformation. The pyran ring is essentialy planar [maximum deviation = 0.038 (2) Å] and forms a dihedral angle of 89.68 (10)° with the benzene ring. In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with R ₂ ²(12) ring motifs. These dimers are further linked by N—H⋯O hydrogen bonds into chains along [110]. Weak C—H⋯O hydrogen bonds are also present.

Related literature

For pharmaceutical background to 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile derivatives, see: Gao et al. (2001 ▶); Xu et al. (2011 ▶); Luan et al. (2011 ▶); Wang & Zhu, (2007 ▶); O’Callaghan et al. (1995 ▶). For similar structures, see: Tu et al. (2001 ▶); Qiao et al. (2011 ▶); Kong et al. (2011 ▶); Hu et al. (2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For geometric analysis, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶).

Experimental

Crystal data

C₁₆H₁₃ClN₂O₂
M _r = 300.73
Monoclinic,
a = 13.753 (4) Å
b = 11.077 (3) Å
c = 19.370 (6) Å
β = 107.856 (5)°
V = 2808.7 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 150 K
0.43 × 0.27 × 0.07 mm

Data collection

Bruker APEX 2000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.914, T _max = 0.981
10643 measured reflections
2755 independent reflections
2124 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.122
S = 1.02
2755 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536812015838/lh5452sup1.cif

e-68-o1414-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015838/lh5452Isup2.hkl

e-68-o1414-Isup2.hkl^{(135.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812015838/lh5452Isup3.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	0.88	2.25	3.132 (3)	177
N1—H1B⋯O1ⁱⁱ	0.88	2.15	2.955 (2)	151
C3—H3⋯N2ⁱⁱⁱ	0.95	2.48	3.226 (3)	135

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

Acknowledgments

The authors gratefully thank the Higher Education Ministries in both the Arab Republic of Egypt and the Republic of Azerbaijan for their financial support to conduct this project. They also extend their thanks to Manchester Metropolitan University for facilitating this study.

supplementary crystallographic information

Comment

The existence of an amino group and cyano group in tetrahydrochromenone compounds make them great substrates for building up multi organic transformations (Luan et al., 2011), preparing poly-functionalized substituted pyran derivatives (Wang & Zhu, 2007) and designing of poly-heterocyclic compounds (O'Callaghan et al.,1995). Moreover, such derivatives of tetrahydrochromenones have attracted strong interests of pharmacists and biologists because of their potential application in the treatment of psoriatic arthritis and rheumatoid arthritis (Xu et al., 2011). They also have wide biological applications such as anti-anaphylaxis, anti-achondroplasty and anti-cancer activity (Gao et al., 2001). To continue to our interest in the synthesis of biologically active compounds we report herein the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The (C8–C13) cyclohexene ring is in a sofa conformation with puckering parameters (Cremer & Pople, 1975) of Q_T = 0.466 (3) Å, θ = 58.3 (2) ° and φ = 173.5 (3) °. The pyran ring (O2/C7/C8/C13—C15) is essentialy planar with a maximum deviation of 0.038 (2) Å for C7, and forms a dihedral angle of 89.68 (10)° with the benzene ring (C1-C6). The bond lengths (Allen et al., 1987) and angles are similar to those for reported structures (Tu et al., 2001; Qiao et al., 2011; Kong et al., 2011; Hu et al., 2012).

In the crystal, molecules are linked by pairs of intermolecular N—H···N hydrogen bonds, forming inversion dimers with R₂²(12) ring motifs (Bernstein et al., 1995; Etter et al., 1990), and these dimers are connected by weak C—H···N and N—H···O hydrogen bonds, generating one-dimensional chains along [110] (Table 1, Fig. 2).

Experimental

The title compound (I) was formed during a three component reaction of an equimolar ratios of (4-chlorobenzylidene)propanedinitrile (1 mmol), (4-aminophenyl)methanol (1 mmol) and cyclohexane-1,3-dione (1 mmol). The reaction mixture was heated in ethanol at 351 K. The reaction was monitored with TLC until completed after 5 h, then left in fume cupboard at room temperature until solvent evaporated. The resulting solid mass was recrystallized from ethanol to afford good quality crystals suitable for X-ray diffraction. [Yield: 83%, m.p.: 513 K].