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

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

doi:10.1107/S2056989015011020

. 2015 Jun 13;71(Pt 7):o468–o469. doi: 10.1107/S2056989015011020

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

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

PMCID: PMC4518947 PMID: 26279912

Abstract

In the title compound, C₂₁H₁₆N₂O₂, the methoxybenzene ring is almost perpendicular to the mean plane of the naphthalene ring system, making a dihedral angle of 83.62 (5)°. The 4H-pyran ring fused with the naphthalene ring system is almost planar [maximum deviation = 0.033 (1) Å]. In the crystal, molecules are linked into inversion dimers by pairs of N—H⋯N hydrogen bonds. N—H⋯O hydrogen bonds connect the dimers, forming a helical supramolecular chain along the a-axis direction. The crystal packing also features C—H⋯π interactions.

Keywords: crystal structure, chromene compounds, benzochromene, hydrogen bonding, C—H⋯π interactions

Related literature

For the biological interest of benzochromene derivatives, see: Gourdeau et al. (2004 ▸); Sangani et al. (2012 ▸); Cheng et al. (2003 ▸); Kamal et al. (2012 ▸); Denish et al. (2012 ▸); Nitin et al.. (2012 ▸); Bhat et al. (2008 ▸). For a similar structure, see: Akkurt et al. (2013 ▸). graphic file with name e-71-0o468-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₆N₂O₂
M _r = 328.36
Monoclinic,
a = 20.6017 (14) Å
b = 6.1461 (4) Å
c = 25.9689 (16) Å
β = 94.332 (4)°
V = 3278.8 (4) Å³
Z = 8
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 100 K
0.38 × 0.23 × 0.13 mm

Data collection

Rigaku AFC11 diffractometer
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012 ▸) T _min = 0.910, T _max = 1.000
12941 measured reflections
2914 independent reflections
2832 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.116
S = 1.03
2914 reflections
236 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻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/S2056989015011020/hg5445sup1.cif

e-71-0o468-sup1.cif^{(26.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011020/hg5445Isup2.hkl

e-71-0o468-Isup2.hkl^{(160.2KB, hkl)}

Click here for additional data file.^{(6.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011020/hg5445Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015011020/hg5445fig1.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.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015011020/hg5445fig2.tif

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

CCDC reference: 1405398

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

Table 1. Hydrogen-bond geometry (, ).

Cg2 is the centroid of the C4/C5/C10C13 ring.

DHA	DH	HA	D A	DHA
N1H1AN2ⁱ	0.896(18)	2.125(18)	3.0174(15)	173.8(16)
N1H1BO2ⁱⁱ	0.900(17)	2.053(17)	2.9509(14)	175.5(14)
C11H11Cg2ⁱⁱⁱ	0.95	2.56	3.3913(14)	147

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

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

Benzopyran (Chromene) is one of the important medicinal pharmacophores found in natural compounds which generated great attention because of their interesting biological activity. The natural and synthetic chromene derivatives have important biological activities such as antivascular (Gourdeau et al., 2004), antimicrobial (Sangani et al., 2012), TNF-α inhibitor (Cheng et al., 2003), anticancer (Kamal et al., 2012), anti-HIV (Denish et al., 2012), anti-inflammatory (Nitin et al., 2012), and anticonvulsant activity (Bhat et al., 2008). Based on such findings and following to our study on synthesis of bio-active heterocyclic molecules we herein report the synthesis and crystal structure of the title compound.

Fig. 1 shows the asymmetric unit of the title compound. The methoxybenzene ring (C15–C20) is approximately perpendicular to the naphthalene ring system [C4–C13, maximum deviation = 0.040 (1) Å at atom C12] as indicated by the dihedral angle of 83.62 (5)°. The pyran ring (O1/C1–C4/C13) is almost planar [maximum deviation = -0.033 (1) Å at atom C2]. The methoxy group (C21/O2) is nearly co-planar with the attached benzene ring (C15–C20) with the torsion angle C21—O2—C18—C19 of -171.07 (11)°. 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, molecules are linked into a helical supramolecular chain along the a axis, which consist of N1—H1B···O2 hydrogen bonds that connect the dimers formed by N1—H1A···N2 hydrogen bonds, to each other (Fig. 2). The crystal packing is further stabilized by C—H···π interactions (Table 1).

S2. Experimental

An ethanolic solution of 4-methoxybenzylidenepropanedinitrile (184 mg; 1 mmol) and 2-naphthol (144 mg; 1 mmol) was refluxed with stirring for 3 h at 350 K with adding two drops of piperidine. The solid product was obtained by cooling the reaction mixture to room temperature, then it was collected by filtration, washed with cold ethanol and dried under vacuum. Colourless crystals of the title compound (M.p. 465 K) suitable for X-ray diffraction were obtained in excellent yield (87%) by recrystallization of the crude product from ethanol using the slow evaporation method.