Crystal structure of 3-amino-1-(4-chloro­phen­yl)-1H-benzo[f]chromene-2-carbo­nitrile

Mehmet Akkurt; Peter N Horton; Shaaban K Mohamed; Sabry H H Younes; Mustafa R Albayati

doi:10.1107/S2056989015011159

. 2015 Jun 13;71(Pt 7):o481–o482. doi: 10.1107/S2056989015011159

Crystal structure of 3-amino-1-(4-chlorophenyl)-1H-benzo[f]chromene-2-carbonitrile

Mehmet Akkurt ^a, Peter N Horton ^b, Shaaban K Mohamed ^c,^d, Sabry H H Younes ^e, Mustafa R Albayati ^f,^*

PMCID: PMC4518915 PMID: 26279919

Abstract

In the title compound, C₂₀H₁₃ClN₂O, the chlorobenzene ring is almost perpendicular to the mean plane of the naphthalene ring system, making a dihedral angle of 81.26 (8)°. The 4H-pyran ring fused with the naphthalene ring system has a flattened boat conformation. In the crystal, N—H⋯N hydrogen bonds generate chains along the b-axis direction. Further N—H⋯N hydrogen bonds link these chains into sheets parallel to (010). The crystal packing also features C—H⋯π interactions. The crystal studied was an inversion twin with a 0.557 (16):0.443 (16) domain ratio.

Keywords: crystal structure, chromene compounds, N—H⋯N hydrogen bonds, C—H⋯π interactions

Related literature

For the synthesis and biological importance of chromene compounds, see, for example: Ellis (1977 ▸); Singh et al. (2010 ▸); Kidwai et al. (2010 ▸); Lácová et al. (2005 ▸); Dell & Smith (1993a ▸,b ▸); Al-Soud et al. (2006 ▸); Eiden & Denk (1991 ▸); Bruhlmann et al. (200); (Kesten et al. (1999 ▸); Bruhlmann et al. (2001 ▸). For a similar structure, see: Akkurt et al. (2013 ▸). graphic file with name e-71-0o481-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₃ClN₂O
M _r = 332.77
Monoclinic,
a = 10.056 (7) Å
b = 6.172 (3) Å
c = 12.751 (6) Å
β = 99.641 (17)°
V = 780.2 (8) Å³
Z = 2
Cu Kα radiation
μ = 2.23 mm⁻¹
T = 100 K
0.32 × 0.12 × 0.10 mm

Data collection

Rigaku AFC11 diffractometer
Absorption correction: multi-scan (CrystalClearSM Expert; Rigaku, 2012 ▸) T _min = 0.948, T _max = 1.000
11415 measured reflections
2558 independent reflections
2500 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.075
S = 1.06
2558 reflections
219 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Refined as an inversion twin.
Absolute structure parameter: 0.443 (16)

Data collection: CrystalClearSM Expert (Rigaku, 2012 ▸); cell refinement: CrystalClearSM Expert; data reduction: CrystalClearSM Expert; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015011159/sj5465sup1.cif

e-71-0o481-sup1.cif^{(399.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011159/sj5465Isup2.hkl

e-71-0o481-Isup2.hkl^{(140.6KB, hkl)}

Click here for additional data file.^{(5.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011159/sj5465Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015011159/sj5465fig1.tif

View of the title compound with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Click here for additional data file.^{(2.8MB, tif)}

a . DOI: 10.1107/S2056989015011159/sj5465fig2.tif

Crystal packing of the title compound viewed along the a axis, with hydrogen bonds drawn as dashed lines.

Click here for additional data file.^{(3.7MB, tif)}

b . DOI: 10.1107/S2056989015011159/sj5465fig3.tif

A view of the packing showing molecules stacked along the b axis.

CCDC reference: 1405640

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg2 and Cg3 are the centroids of the C4C8/C13 and C8C13 rings, respectively.

DHA	DH	HA	D A	DHA
N1H1AN2ⁱ	0.88	2.22	3.005(3)	148
N1H1BN2ⁱⁱ	0.88	2.32	3.129(4)	152
C6H6Cg2ⁱⁱⁱ	0.95	2.60	3.401(3)	142
C11H11Cg3^iv	0.95	2.90	3.636(3)	135

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

Acknowledgments

The authors would like to express their thanks to the National Crystallography Service (NCS), Southampton, UK, for providing the X-ray data.

supplementary crystallographic information

S1. Comment

The chromene moiety is found in natural products and exhibits various biological activities (Ellis, 1977; Singh et al., 2010; Lácová et al., 2010; Kidwai et al., 2005). Fused chromene derivatives are biologically interesting compounds showing antiproliferation activity (Dell & Smith, 1993a,b), are effective anti-HIV agents (Al-Soud et al., 2006) and impact the central nervous system (CNS) (Eiden & Denk, 1991). Moreover, they have been employed in the treatment of Alzheimer's disease (Bruhlmann et al., 2001) and the Schizophrenia disorder (Kesten et al., 1999). In this context, we report in this study the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1), the choloro-benzene ring (C15–C20) is approximately perpendicular to the naphthalene ring system [C4–C13, maximum deviation = 0.012 (2) Å at atom C4] as indicated by the dihedral angle of 81.26 (5)°. The 4H-pyran ring (O1/C1–C5) in the title compound is puckered with the puckering parameters of Q_T = 0.143 (2) Å, θ = 86.4 (8)° and φ = 167.3 (9)°. All the bond lengths and angles in the title compound are within normal ranges and comparable with those reported for a similar structure (Akkurt et al., 2013).

In the crystal structure, molecules are linked into sheets parallel to (010) by the N1—H1A···N2 and N1—H1B···N2 hydrogen bonds (Table 1, Figs 2 and 3), which generate chains along [010]. The crystal packing is further stabilized by C—H···π interactions (Table 1).

S2. Experimental

A mixture of 4-chlorobenzylidenepropanedinitrile (188.5 mg; 1 mmol) and 2-naphthol (144 mg; 1 mmol) was refluxed with stirring for 2 h at 350 K in ethanol (10 ml) in the presence of a catalytic amount of triethylamine. After cooling to room temperature, the solid product was collected by filtration, washed with cold ethanol and dried under vacuum. High quality crystals suitable for X-ray diffraction were obtained in an excellent yield (96%) by recrystallization of the crude product from ethanol. M.p. K.