2-Amino-4-(4-fluoro­phen­yl)-6-meth­oxy-4H-benzo[h]chromene-3-carbonitrile

Al-Anood M Al-Dies; Abdel-Galil E Amr; Ahmed M El-Agrody; Tze Shyang Chia; Hoong-Kun Fun

doi:10.1107/S1600536812023021

. 2012 May 31;68(Pt 6):o1934–o1935. doi: 10.1107/S1600536812023021

2-Amino-4-(4-fluorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carbonitrile

Al-Anood M Al-Dies ^a, Abdel-Galil E Amr ^b,^c, Ahmed M El-Agrody ^a, Tze Shyang Chia ^d, Hoong-Kun Fun ^d,^*,^‡

PMCID: PMC3379488 PMID: 22719686

Abstract

In the title molecule, C₂₁H₁₅FN₂O₂, the dihedral angle between the fluoro-substituted benzene ring and the mean plane of the 4H-benzo[h]chromene ring system [maximum deviation = 0.109 (2) Å] is 83.35 (7)°. The pyran ring adopts a slight sofa conformation with the tertiary C(H) atom forming the flap. The methoxy group is slightly twisted from the attached benzene ring of the 4H-benzo[h]chromene moiety [C—O—C—C = −4.3 (3)°]. In the crystal, molecules are linked by intermolecular N—H⋯N hydrogen bonds into infinite wave-like chains along the b axis. The crystal packing is further stabilized by π–π interactions [centroid–centroid distance = 3.7713 (9) Å].

Related literature

For the synthesis of 4H-chromene derivatives, see: Sayed et al. (2000 ▶); Bedair et al. (2001 ▶); El-Agrody et al. (2000 ▶, 2002 ▶). For the chemical and pharmacological properties of 4H-chromene and fused 4H-chromene derivatives, see: El-Agrody et al. (2000 ▶); Abd-El-Aziz et al. (2004 ▶, 2007 ▶); Sabry et al. (2011 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶). graphic file with name e-68-o1934-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₅FN₂O₂
M _r = 346.35
Monoclinic,
a = 12.6336 (4) Å
b = 11.9333 (3) Å
c = 12.0471 (4) Å
β = 113.581 (2)°
V = 1664.56 (9) Å³
Z = 4
Cu Kα radiation
μ = 0.81 mm⁻¹
T = 296 K
0.88 × 0.68 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.537, T _max = 0.953
11390 measured reflections
3199 independent reflections
2770 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.132
S = 1.05
3199 reflections
245 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812023021/lh5476sup1.cif

e-68-o1934-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023021/lh5476Isup2.hkl

e-68-o1934-Isup2.hkl^{(157KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812023021/lh5476Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N1⋯N2ⁱ	0.89 (2)	2.17 (2)	3.054 (2)	175 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and TSC thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSC also thanks the Malaysian Government and USM for the award of a research fellowship. The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for funding the work through the research group project No. RGP-VPP-172.

supplementary crystallographic information

Comment

In our previous work, we have reported the synthesis of 4H-chromene derivatives using α-cyanocinnamonitriles and ethyl α-cyanocinnamates (Sayed et al., 2000; Bedair et al., 2001; El-Agrody et al., 2000, 2002), study of their characterization and evaluation of their antimicrobial and antitumor activities. In continuation of our interest in the chemical and pharmacological properties of 4H-chromene and fused 4H-chromene derivatives (El-Agrody et al., 2000; Abd-El-Aziz et al., 2004, 2007; Sabry et al., 2011), we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. The fluoro-substituted benzene ring (C14–C19) is approximately perpendicular to the 4H-benzo[h]chromene ring system [O1/C1–C13, maximum deviation = 0.109 (2) Å at atom C3] as indicated by the dihedral angle of 83.35 (7)°. The pyran ring (O1/C1–C5) adopts slight sofa conformation [puckering parameters (Cremer & Pople, 1975), Q = 0.0980 (16) Å, θ = 69.5 (9)° and φ = 167.7 (10)°] with C3 as the flap atom. The methoxy group (C20/O2) is slightly twisted from the attached benzene ring (C4–C6/C11–C13) of the 4H-benzo[h]chromene moiety with torsion angle C20—O2—C12—C13 of -4.3 (3)°.

In the crystal (Fig. 2), molecules are linked by intermolecular N1—H2N1···N2ⁱ hydrogen bonds (Table 1) into infinite wave-like chains along b axis. The crystal packing is further stabilized by π–π interaction with Cg1-Cg1 distance of 3.7713 (9) Å, where Cg1 is the centroid of O1/C1–C5 ring [symmetry code: 1-x, 1-y, -z].

Experimental

A solution of 4-methoxy-1-naphthol (0.01 mol) in EtOH (30 ml) was treated with α-cyano-p-fluorocinnamonitrile (0.01 mol) and piperidine (0.5 ml). The reaction mixture was heated until complete precipitation occurred (reaction time: 60 min). The solid product formed was collected by filtration and recrystallized from ethanol to give the title compound. M.p.: 493–494 K.