Crystal structure of 2-amino-4-phenyl-4H-benzo[h]chromene-3-carbo­nitrile

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

doi:10.1107/S2056989015011536

. 2015 Jun 27;71(Pt 7):o516–o517. doi: 10.1107/S2056989015011536

Crystal structure of 2-amino-4-phenyl-4H-benzo[h]chromene-3-carbonitrile

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

PMCID: PMC4518988 PMID: 26279939

Abstract

In the title compound, C₂₀H₁₄N₂O, the plane of the phenyl ring is almost normal to that of the naphthalene ring system, forming a dihedral angle of 83.15 (8)°. The 4H-pyran ring fused with the naphthalene ring system has a flattened boat conformation. In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an R ₂ ²(12) ring motif. The dimers are connected by C—H⋯π interactions, forming supramolecular chains along [010].

Keywords: crystal structure, aminochromene, fused chromene, hydrogen bonding, C—H⋯π interactions

Related literature

For synthesis of chromene-containing compounds, see: Elagamey et al. (1988 ▸); El-Maghraby (2014 ▸). For industrial applications of aminochromenes, see: Ellis (1977 ▸); Hafez et al. (1987 ▸). For various biological activities of fused chromenes, see: Hiramoto et al. (1997 ▸); Bianchi & Tava (1987 ▸); Eiden & Denk (1991 ▸); Smith et al. (1998 ▸); Taylor et al. (1998 ▸). For the crystal structure of the isomer of the title compound, 3-amino-1-phenyl-1H-benzo[f]chromene-2-carbonitrile, see: Akkurt et al. (2013 ▸). graphic file with name e-71-0o516-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₄N₂O
M _r = 298.33
Monoclinic,
a = 9.1662 (1) Å
b = 5.7246 (1) Å
c = 13.9177 (2) Å
β = 90.153 (1)°
V = 730.30 (2) Å³
Z = 2
Cu Kα radiation
μ = 0.67 mm⁻¹
T = 100 K
0.28 × 0.13 × 0.10 mm

Data collection

Rigaku AFC11 diffractometer
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012 ▸) T _min = 0.883, T _max = 1.000
5778 measured reflections
2201 independent reflections
2184 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.093
S = 1.09
2201 reflections
216 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack x determined using 775 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▸)
Absolute structure parameter: 0.2 (3)

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/S2056989015011536/tk5369sup1.cif

e-71-0o516-sup1.cif^{(211.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011536/tk5369Isup2.hkl

e-71-0o516-Isup2.hkl^{(121.1KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011536/tk5369Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015011536/tk5369fig1.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.^{(1.6MB, tif)}

. DOI: 10.1107/S2056989015011536/tk5369fig2.tif

View of the dimers formed by N—H⋯O hydrogen bonds.

CCDC reference: 1406770

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C15C20 phenyl ring.

DHA	DH	HA	D A	DHA
N1H1BN2ⁱ	0.91(3)	2.09(3)	2.970(2)	163(3)
C9H9Cg1ⁱⁱ	0.95	2.88	3.574(2)	131

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

Acknowledgments

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

supplementary crystallographic information

S1. Comment

Among synthetic heterocyclic compounds, aminochromenes represent an important class of organic compounds being the main components of many naturally occurring products (Elagamey et al., 1988; El-Maghraby, 2014). They are used for the chemical synthesis of cosmetics, pigments (Ellis, 1977), and potentially biodegradable agrochemicals (Hafez, et al., 1987). Fused chromene systems have displayed a broad spectrum of biological activities such as mutagenicity (Hiramoto, et al., 1997), sex pheromonal (Bianchi & Tava, 1987), central nervous system (CNS) activities (Eiden & Denk, 1991) and inhibitors for influenza virus sialidases (Smith et al., 1998; Taylor et al., 1998). In this context and following our strategy for the synthesis of bio-active molecules, we herein report the synthesis and crystal structure of the title compound.

As seen in Fig. 1, the C4–C13 naphthalene ring system of the title compound is essentially planar [maximum deviations = -0.020 (2) Å for C4 and -0.016 (2) Å for C8]. The C15–C20 phenyl ring makes a dihedral angle of 83.15 (8)° with the mean plane of the naphthalene ring. The 4H-pyran ring (O1/C1–C4/C13) in the title compound is puckered [the puckering parameters (Cremer & Pople, 1975) are Q_T = 0.177 (2) Å, θ = 98.2 (6) ° and φ = 342.9 (7) °. The structural geometric parameters of the title compound are normal and are consistent with those of the isomer compound 3-amino-1-phenyl-1H-benzo[f]chromene-2-carbonitrile (Akkurt et al., 2013). Both isomers crystallizes in the same monoclinic space group P2₁ and their unit-cell parameters are almost equal.

In the crystal, pairs of N—H···N hydrogen bonds form inversion dimers with an R₂²(12) ring motif (Table 1 and Fig. 2). In addition, C—H···π interactions are observed.

S2. Experimental

To a solution of 1-naphthol (144 mg; 1 mmol) in 10 ml absolute ethanol, an equimolar amount of benzylidene-malononitrile (154 mg; 1 mmol) was added with constant stirring. The reaction mixture was refluxed for 3 h in the presence of a catalytic amount of piperidine. The reaction progress was monitored by TLC and after cooling, the formed precipitate was filtered off, washed with cold ethanol and dried under vacuum in a desiccator for 24 h. The solid was recrystallized from ethanol. Crystals suitable for X-ray crystallography were obtained by slow evaporation of a solution of the title compound in ethanol (yield 92%; m.p. 483 K).