2-Amino-4-(4-meth­oxy­phen­yl)-7,7-di­methyl-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile propan-2-one monosolvate

Shaaban K Mohamed; Mehmet Akkurt; Muhammad N Tahir; Antar A Abdelhamid; M A Allahverdiyev

doi:10.1107/S160053681202781X

. 2012 Jun 27;68(Pt 7):o2206–o2207. doi: 10.1107/S160053681202781X

2-Amino-4-(4-methoxyphenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile propan-2-one monosolvate

Shaaban K Mohamed ^a, Mehmet Akkurt ^b,^*, Muhammad N Tahir ^c, Antar A Abdelhamid ^a, M A Allahverdiyev ^d

PMCID: PMC3394003 PMID: 22798868

Abstract

In the crystal structure of the title compound, C₁₉H₂₀N₂O₃·C₃H₆O, molecules are linked into inversion dimers with an R ₂ ²(12) motif by pairs of N—H⋯N hydrogen bonds. These dimers are further connected into chains running along the a axis by N—H⋯O hydrogen bonds. C—H⋯N and C—H⋯π interactions also feature in the packing. The cyclohexene ring adopts nearly an envelope conformation [puckering parameters are Q _T = 0.456 (2) Å, θ = 54.6 (3)° and ϕ = 225.2 (3)°].

Related literature

For pharmacological properties of 4H-chromene and fused 4H-chromene derivatives, see: Kemnitzer et al. (2007 ▶, 2008 ▶); Abd-El-Aziz et al. (2004 ▶, 2007 ▶); Sabry et al. (2011 ▶); Gourdeau et al. (2004 ▶); Mahdavi et al. (2011 ▶); Brühlmann et al. (2001 ▶). For a related structure, see: Mohamed et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₂₀N₂O₃·C₃H₆O
M _r = 382.45
Triclinic,
a = 8.2037 (4) Å
b = 9.5319 (4) Å
c = 13.8390 (7) Å
α = 77.743 (2)°
β = 87.307 (3)°
γ = 80.672 (2)°
V = 1043.43 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.978, T _max = 0.983
16752 measured reflections
4917 independent reflections
3284 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.182
S = 1.04
4917 reflections
246 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.50 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/S160053681202781X/bt5943sup1.cif

e-68-o2206-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202781X/bt5943Isup2.hkl

e-68-o2206-Isup2.hkl^{(240.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681202781X/bt5943Isup3.cml

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

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

Cg2 is the centroid of the O2/C8–C10/C12/C13) 4H-pyran ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.86	2.30	3.142 (3)	168
N2—H2B⋯O3ⁱⁱ	0.86	2.19	3.029 (2)	165
C6—H6⋯N1ⁱⁱⁱ	0.93	2.51	3.258 (3)	137
C18—H18A⋯Cg2^iv	0.96	2.77	3.677 (2)	158

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

Acknowledgments

The financial support of the Egyptian Goverment to carry out this study is gratefully acknowledged. We also thank Manchester Metropolitan University and Erciyes University for guidance and instrumental support of the study.

supplementary crystallographic information

Comment

Compounds such as 4H-chromenes and fused 4H-chromenes are a great class of organic drugs due to their wide applications in chemo therapy. They exhibited anticancer activities (Kemnitzer et al., 2007, 2008; Abd-El-Aziz et al., 2004, 2007; Gourdeau et al., 2004; Sabry et al., 2011; Mahdavi et al., 2011) and have used in treatment of Alzheimer's disease and Schizophrenia disorder (Brühlmann et al., 2001). In this context and further to our on-going study in synthesis and biological investigation of 4H-chromene compounds (Mohamed et al. 2012), we report in this study the structure and synthesis of the title compound (I).

In the title compound (I) shown in Fig. 1, the C12–C17 cyclohexene and O2/C8—C10/C12/C13 4H-pyran rings are puckered with the puckering parameters (Cremer & Pople, 1975) of Q_T = 0.456 (2) ° A, θ = 54.6 (3) °, φ = 225.2 (3) °, and Q_T = 0.201 (2) Å, θ = 108.1 (5) °, φ = 354.7 (6) °, respectively. The bond lengths and bond angles in (I) are normal and are comparable with those of a related structure previously reported (Mohamed et al., 2012).

In the crystal structure, adjacent molecules are connected 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 further connected to chains running along the a axis by N—H···O hydrogen bonds. Furthermore, C—H···π interactions contribute to the stabilization of the crystal packing (Table 1, Fig. 2).

Experimental

To a solution of 184 mg (1 mmol) (4-methoxybenzylidene)propanedinitrile in 50 ml ethanol, 140 mg (1 mmol) 5,5-dimethylcyclohexane-1,3-dione was added in presence of 123 mg (1 mmol) (4-aminophenyl)methanol as catalyst. The reaction mixture was refluxed at 350 K for 5 h, then cooled at ambient temperature. The resin product that formed was solidified by washing with acetone then filtered off under vacuum and recrystallized from ethanol. Single crystals suitable for X-ray diffraction were produced by slow evaporation of ethanol/acetone solution (1:1) of (I) over two days at room temperature. Yield is 86%, M.p. 443 K.