2-Oxochromen-4-yl 4-(dimethyl­amino)­benzoate

Akoun Abou; Abdoulaye Djandé; Bintou Sessouma; Adama Saba; Rita Kakou-Yao

doi:10.1107/S1600536811030844

. 2011 Aug 6;67(Pt 9):o2269–o2270. doi: 10.1107/S1600536811030844

2-Oxochromen-4-yl 4-(dimethylamino)benzoate

Akoun Abou ^a,^*, Abdoulaye Djandé ^b, Bintou Sessouma ^b, Adama Saba ^b, Rita Kakou-Yao ^a

PMCID: PMC3200765 PMID: 22058924

Abstract

In the title molecule, C₁₈H₁₅NO₄, the benzoate ring is oriented at a dihedral angle of 43.43 (6)° with respect to the planar [maximum deviation = 0.038 (2) Å] chromene ring. The crystal structure features R ₂ ²(12) centrosymetric dimers formed via C—H⋯O interactions and these dimeric aggregates are connected by C—H⋯π interactions.

Related literature

For the biological activity of coumarin derivatives, see: Ukhov et al. (2001 ▶); Abd Elhafez et al. (2003 ▶); Basanagouda et al. (2009 ▶); Liu et al. (2008 ▶); Trapkov et al. (1996 ▶); Vukovic et al. (2010 ▶); Emmanuel-Giota et al. (2001 ▶); Hamdi & Dixneuf (2007 ▶); Wang et al. (2001 ▶); Marchenko et al. (2006 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₈H₁₅NO₄
M _r = 309.32
Triclinic,
a = 7.4939 (2) Å
b = 10.2361 (3) Å
c = 10.6620 (3) Å
α = 92.307 (3)°
β = 103.935 (1)°
γ = 109.852 (2)°
V = 739.92 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.50 × 0.40 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer
8424 measured reflections
3590 independent reflections
2897 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.120
S = 0.98
3585 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811030844/tk2767sup1.cif

e-67-o2269-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030844/tk2767Isup2.hkl

e-67-o2269-Isup2.hkl^{(179.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811030844/tk2767Isup3.cml

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

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

Cg3 is the centroid of the C15–C18/C22/C23 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H91⋯O8ⁱ	0.96	2.49	3.449 (2)	171
C7—H71⋯Cg3ⁱⁱ	0.95	2.84	3.429 (2)	121
C20—H202⋯Cg3ⁱⁱⁱ	0.99	2.91	3.777 (2)	146

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

Acknowledgments

We thank the Laboratoire de Physique des Interactions Ioniques and Spectropôle, Université de Provence, and the Université Paul Cézanne, Faculté des Sciences et Techniques de Saint Jérôme, Marseille, France, for the use of their diffractometer.

supplementary crystallographic information

Comment

Coumarin constitutes one of the major classes of naturally occurring compounds, and interest in its chemistry continues unabated because of its usefulness as biologically active agents. It also represents the core structure of several molecules of pharmaceutical importance. Coumarin and its derivatives have been reported to serve as anti-bacterial (Ukhov et al., 2001; Abd Elhafez et al., 2003; Basanagouda et al., 2009; Liu et al., 2008), anti-oxidant (Trapkov et al., 1996; Vukovic et al., 2010), anti-inflammatory (Emmanuel-Giota et al., 2001; Hamdi & Dixneuf, 2007), anti-coagulant (Hamdi et al., 2007) and anti-tumour (Wang et al., 2001; Marchenko et al., 2006) agents. Therefore, the synthesis of new coumarin derivatives is of considerable interest. In order to study the influence of new substituents on the activity of the coumarin derivative, the title compound, (I), has been synthesized and in this paper, we present its molecular structure, Fig. 1.

In (I), the planar chromene ring system resulting from the two coupled rings (benzene and 3,6-dihydro-2H-pyran) is oriented with respect to the benzoate-benzene ring at a dihedral angle of 43.43 (6)°. Atoms O14, N19, C13 and C21 are 0.046 (1), 0.052 (1), 0.079 (2) and 0.077 (3) Å out of the plane of the benzoate-benzene ring, respectively, so, they are coplanar with this ring.

In the crystal structure, intermolecular C—H···O interactions (Table 1) link the molecules into centrosymmetric dimers through R₂²(12) ring motifs (Bernstein et al., 1995) (Fig. 2). Two weak C—H···π interactions formed between the H71 and H202 atoms and the centroid Cg3 of the benzoate-benzene ring (Table 1 and Fig. 3) further stabilize the structure.

Experimental

To a solution of 4.10^-2 mole of paradimethylamino benzoyl chloride in 150 ml of dried tetrahydrofuran, was added 0.12 mole of dried triethylamine and 4.10^-2 mole of 4-hydroxycoumarin by small portions over 30 min. The mixture was then refluxed for 3 h and poured in 300 ml of chloroform or dichloromethane. The solution was acidified with dilute hydrochloric acid until the pH was 2 or 3. The organic layer was extracted, washed with water, dried over MgSO₄ and the solvent removed. The crude product was recrystallized in chloroform. Colourless crystals of the title compound are obtained in a good yield: 82.6%; M.pt. 445 K.