3-[1-(2-Hy­droxy­anilino)ethyl­idene]-3H-chromen-2,4-dione

Ameni Brahmia; Taicir Ben Ayed; Rached Ben Hassen

doi:10.1107/S160053681301934X

. 2013 Jul 24;69(Pt 8):o1296. doi: 10.1107/S160053681301934X

3-[1-(2-Hydroxyanilino)ethylidene]-3H-chromen-2,4-dione

Ameni Brahmia ^a, Taicir Ben Ayed ^b, Rached Ben Hassen ^a,^*

PMCID: PMC3793787 PMID: 24109374

Abstract

The title compound is a new aminocoumarin derivative, C₁₇H₁₃NO₄, and was synthesized by the condensation of 2-aminophenol and 3-acetyl-4-hydroxycoumarin. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, the molecules are linked into chains extending in the [010] direction by O—H⋯O hydrogen bonds. There is also a π–π stacking interaction between the bicyclic coumarin fragment and the phenol ring [centroid–centroid distance = 3.7510 (14) Å], and these ring systems form between them a dihedral angle of 53.3 (2)°. Intermolecular hydrogen bond C—H⋯O hydrogen bonding is also observed in the interconnection of the crystal packing.

Related literature

For related structures, see: Traven et al. (2000 ▶); Malecka et al. (2004 ▶); Mechi et al. (2009 ▶); Ghouili et al. (2011 ▶); Ketata et al. (2012 ▶). For the properties of coumarin derivatives, see: Bordin et al. (1995 ▶); Hamdi et al. (2010 ▶); Mahidol et al. (2004 ▶). graphic file with name e-69-o1296-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₃NO₄
M _r = 295.29
Monoclinic,
a = 12.5596 (4) Å
b = 7.5870 (3) Å
c = 14.3433 (6) Å
β = 94.660 (2)°
V = 1362.25 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.16 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
11784 measured reflections
3891 independent reflections
1721 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.194
S = 0.91
3891 reflections
251 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SMART; data reduction: SAINT (Bruker, 2001 ▶); 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681301934X/ff2111sup1.cif

e-69-o1296-sup1.cif^{(16.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681301934X/ff2111Isup2.hkl

e-69-o1296-Isup2.hkl^{(186.9KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681301934X/ff2111Isup3.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
O4—H12⋯O2ⁱ	0.82	1.92	2.742 (2)	175
N1—H13⋯O3	0.88 (3)	1.75 (3)	2.537 (3)	148 (3)
C8—H4⋯O2ⁱ	0.93	2.59	3.274 (3)	131

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Symmetry code: (i) Inline graphic .

Acknowledgments

Professor A. Ben Salah is acknowledged for his contribution to the X-ray diffraction data collection at the Laboratory of Materials Science and the Environment, University of Sfax, Tunisia.

supplementary crystallographic information

Comment

Coumarin derivatives have a wide range of biological properties. They possess pharmacological activities, mainly anticoagulant. They also have anti-tumor, anti-oxidants and anti-inflammatory properties (Bordin et al., 1995; Mahidol et al., 2004). In continuation of our structural and biological studies of coumarin derivatives (Mechi et al., 2009; Hamdi et al., 2010; Ghouili et al., 2011; Ketata et al., 2012), we present the crystal structure of the title compound, a new derivative of amino coumarins.

In the crystal, the title compounds adopts a conformation where the dihedral angle between the plane of the bicyclic coumarin fragment and the phenol ring is 53.3 (2)°. The structure of our solid compound is stable thanks to the intermolecular hydrogen bonds O4—H12···O2. The crystal structure of C₁₇H₁₃N₁O₄ shows a π-π stacking interaction alternating between two inverted molecules. The stacking is observed along the b axis with distance 3.361 (4) Å between the layers of coumarin and phenol rings [centroid-centroid distance 3.7510 (14) Å].

The structure exhibits intramolecular hydrogen bonding N1—H13···O3, similar to that observed in amino coumarin analogue (Malecka et al. 2004), and we observe also a strong p-electron delocalization effect when comparing with O—H···O in 3-acetyl-4-hydroxycoumarin (Traven et al. 20000). In fact, the distances C1—C2 = 1.437 (3) Å in the title compound is longer then that one of the 3-acetyl-4-hydroxycoumarin (1.399 (1) Å) and C1—C5 = 1.428 (3) Å is shorter then 1.454 (1) Å. The elongation of N1—C5; C1—C2; C1—C11 and C11—O2 distances (see the table of bond lengths) and the shortening of O4—C6, C6—C4, C4—N1, C5—C1 and C2—O3 bond lengths, in comparison with those of the compound C₁₃H₁₃N₁O₄ (Malecka et al. 2004) could be related to the electron-donor effect of the phenolic group in the title compound.

The linkage between the coumarin system and aminophenol ring exhibits bond lengths O3—C2 = 1.251 (3) Å, C2—C1 = 1.437 (3) Å, C1—C5 = 1.428 (3) Å, C5—N1 = 1.316 (3) Å and N1—C4 = 1.422 (3) Å, suggesting that all non-hydrogen atoms between the electron-donors and acceptors are highly conjugated, leading to a π-bridge for the charge transfer from aminophenol ring to coumarin system.

Experimental

The amino coumarin was synthesized by the condensation of an equimolar amount of 2-aminophenol and 3-acetyl-4-hydroxycoumarin in absolute ethanol. After four hours of reflux, the reaction mixture was left crystallizing at room temperature. The compound obtained is presented as transparent crystals of light yellow color with shape and size suitable for the structural study of X-ray single-crystal. Yield:(90%). mp= 446 K. IR: ν 3155 (NH), 2973 (OH), 1666 (>C=O), 1609 (C=C), 1102 (C—O); 1HNMR: δp.p.m.: 2.54 (s, 3H, Hmethyl), 6.51–7.14 (m, 4H, Ar—H), 7.23–8.12 (m, 4H, Ph—H), 10.45 (s, 1H, OH), 15.20 (s, 1H, NH); 13CNMR: (p.p.m.): 20.30 (C methyl), 97.11 (C3), 116.27–134.34 (C arom), 151.40 (C—OH), 161.66 (C=O lactone), 175.90 (C—N), 180.19 (C=O ketone),