2-Amino-4-(4-chloro­phen­yl)-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; Mustafa R Albayati

doi:10.1107/S1600536812024142

. 2012 May 31;68(Pt 6):o1965–o1966. doi: 10.1107/S1600536812024142

2-Amino-4-(4-chlorophenyl)-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, Mustafa R Albayati ^d

PMCID: PMC3379514 PMID: 22719712

Abstract

In the title compound, C₁₈H₁₇ClN₂O₂·C₃H₆O, the 4H-pyran ring is nearly planar [maximum deviation = −0.108 (1) Å] and the cyclohexene ring is puckered [puckering parameters Q _T = 0.4596 (17) Å, θ = 55.9 (2)° and ϕ = 226.5 (3)°]. The 4H-pyran ring is approximately perpendicular to the benzene ring [dihedral angle = 84.35 (7)°] and is almost coplanar with the mean plane of the cyclohexene ring [dihedral angle = 8.64 (7)°]. In the crystal, inversion-related main molecules are linked into dimers by pairs of N—H⋯N hydrogen bonds, generating an R ₂ ²(12) graph-set motif. These dimers are further connected by N—H⋯O and C—H⋯N hydrogen bonds, forming a layer structure extending parallel to the (011) plane. In addition, the molecules within the layers interact with each other via C—H⋯π interactions.

Related literature

For the synthesis of chromene compounds, see: Coujon et al. (2002 ▶). For the bioactivity of chromene compounds see: Kaye & Nocanda (2002 ▶). For similar structures, see: Hu et al. (2012 ▶); Mohamed et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-68-o1965-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₇ClN₂O₂·C₃H₆O
M _r = 386.86
Triclinic,
a = 8.1707 (2) Å
b = 9.4386 (2) Å
c = 13.5192 (4) Å
α = 84.446 (1)°
β = 82.546 (2)°
γ = 78.625 (1)°
V = 1010.76 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.28 × 0.25 × 0.23 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.942, T _max = 0.952
16320 measured reflections
4769 independent reflections
3390 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.126
S = 1.04
4769 reflections
248 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.34 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/S1600536812024142/xu5550sup1.cif

e-68-o1965-sup1.cif^{(28.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024142/xu5550Isup2.hkl

e-68-o1965-Isup2.hkl^{(233.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812024142/xu5550Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the O1/C7–C11 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.86	2.30	3.1552 (19)	171
N2—H2B⋯O2ⁱⁱ	0.86	2.15	2.9949 (18)	167
C2—H2⋯N1ⁱⁱⁱ	0.93	2.51	3.234 (2)	135
C17—H17A⋯Cg2^iv	0.96	2.93	3.8221 (18)	155

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

Acknowledgments

AAA is grateful to the Azerbaijan Academic Exchange programme for financial support of this study. We thank Manchester Metropolitan University, Erciyes University and the University of Sargodha for facilitating this work.

supplementary crystallographic information

Comment

Chromene compounds are important group of oxygen heterocycles. They have employed as useful intermediate in the synthesis of a wide range of natural products (Coujon et al., 2002). Such compounds have exhibited anti-depressant, anti-hypertensive as well as anti-ischaemic properties (Kaye & Nocanda, 2002). This triggered us to extend our on-going research program in synthesis of bioactive molecules and their pharmaceutical applications towards the synthesis of chromene nucleus containing compounds. We report in this study the synthesis and crystal structure study of 2-amino-4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile–propan-2-one (1:1).

In the title compound (I), (Fig. 1), the C10/C11/C13–C16 cyclohexene ring is puckered with the puckering parameters (Cremer & Pople, 1975) of Q_T = 0.4596 (17) Å, θ = 55.9 (2)° and φ = 226.5 (3)°. The O1/C7–C11 4H-pyran ring is nearly planar with a maximum deviation of -0.108 (1) Å for C7 and is approximately perpendicular to the C1–C6 benzene ring [dihedral angle = 84.35 (7)°] and is almost co-planar with the mean plane of the cyclohexene ring [dihedral angle = 8.64 (7) °]. Bond lengths (Allen et al., 1987) and angles of the title compound are within normal ranges and are comparable to similar structures (Hu et al., 2012; Mohamed et al., 2012).

In the crystal, a pair of intermolecular N—H···N hydrogen bonds link the main molecules into an inversion dimer, generating an R₂²(12) graph-set motif (Bernstein et al., 1995; Table 1, Fig. 2). The dimers are further connected by N—H···O and C—H···N hydrogen bonds, forming a layer of molecules parallel to (011) (Table 1, Fig. 2). The layers are interconnected by weak C—H···π interactions, producing a three-dimensional network.

Experimental

A mixture of 140 mg (1 mmol) 5,5-dimethylcyclohexane-1,3-dione, 140 mg (1 mmol) 4-chlorobenzaldehyde and 123 mg (4-aminophenyl)methanol in 50 ml ethanol was refluxed for 5 h. The excess solvent was removed under vacuum and the residual resin was washed with cold acetone. The solid that formed was filtered off, washed with cold ethanol, well drained then recrystallized from a mixture of ethanol–acetone (1:1). Crystals obtained were in good quality and suitable for X-ray diffraction (m.p. 461 K).