2-Oxo-2H-chromen-4-yl 4-meth­oxy­benzoate

Akoun Abou; Abdoulaye Djandé; Grégoire Danger; Adama Saba; Rita Kakou-Yao

doi:10.1107/S1600536812047666

. 2012 Nov 24;68(Pt 12):o3438–o3439. doi: 10.1107/S1600536812047666

2-Oxo-2H-chromen-4-yl 4-methoxybenzoate

Akoun Abou ^a,^*, Abdoulaye Djandé ^b, Grégoire Danger ^c, Adama Saba ^b, Rita Kakou-Yao ^a

PMCID: PMC3589019 PMID: 23476255

Abstract

In the title molecule, C₁₇H₁₂O₅, the chromen-2-one ring and the 4-methoxybenzoate side chain are inclined to one another at a dihedral angle of 69.82 (9)°. The crystal structure features parallel sheets of centrosymmetric R ₂ ²(6) dimers joined by a C(7) chain, resulting in centrosymetric tetramers of hydrogen-bonded molecules with graph-set motif R ₄ ⁴(40). These centrosymetric tetramers are connected by a pair of hydrogen bonds described by an R ₂ ²(8) ring motif and a C(7) chain via C—H⋯O interactions. In the structure, there are also π–π stacking interactions between chromene benzene and the six-membered heterocyclic rings [centroid–centroid distance = 3.691 (2) Å] and weak C=O⋯π interactions [O⋯(ring centroid) distance = 3.357 (3) Å].

Related literature

For the biological activity of coumarin derivatives, see: Basanagouda et al. (2009 ▶); Vukovic et al. (2010 ▶); Emmanuel-Giota et al. (2001 ▶); Marchenko et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For π–π stacking interactions, see: Janiak (2000 ▶).

Experimental

Crystal data

C₁₇H₁₂O₅
M _r = 296.27
Triclinic,
a = 4.371 (1) Å
b = 10.535 (4) Å
c = 15.193 (2) Å
α = 85.218 (3)°
β = 83.688 (2)°
γ = 81.893 (1)°
V = 686.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.25 × 0.15 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
5683 measured reflections
2731 independent reflections
1540 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.163
S = 1.11
2731 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97, publCIF (Westrip, 2010 ▶) and WinGX (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(24.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812047666/zs2245sup1.cif

e-68-o3438-sup1.cif^{(24.2KB, cif)}

Click here for additional data file.^{(131.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047666/zs2245Isup2.hkl

e-68-o3438-Isup2.hkl^{(131.4KB, hkl)}

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

Supplementary material file. DOI: 10.1107/S1600536812047666/zs2245Isup3.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
C8—H8⋯O2ⁱ	0.93	2.48	3.407 (4)	173
C2—H2⋯O4ⁱⁱ	0.93	2.49	3.340 (4)	151
C17—H17B⋯O5ⁱⁱⁱ	0.96	2.59	3.461 (4)	151

Open in a new tab

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

Acknowledgments

The authors thank the Spectropôle Service of the Faculty of Sciences and Techniques of Saint Jérôme (France) for the use of the diffractometer and the NMR spectrometer.

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 a biologically active agent. It also represents the core structure of several molecules of pharmaceutical importance. Coumarin and its derivatives have been reported to serve as anti-bacterial (Basanagouda et al., 2009), anti-oxidant (Vukovic et al., 2010), anti-inflammatory (Emmanuel-Giota et al., 2001) and anti-tumour agents (Marchenko, et al., 2006). 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 derivatives, the title compound, the ester C₁₇H₁₂O₅ has been synthesized and its molecular and crystal structure is reported herein.

In the title compound (Fig. 1), the side chain is tilted with respect to the chromen-2-one ring with torsion angles C1—C9—O3—C10 = -76.3 (4)° and C8—C9—O3—C10 = 107.7 (3)°. The dihedral angle between the chromene ring and the side chain is 69.82 (9) °.

In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) generate hydrogen-bonding motifs ranging from a chain to various rings. Indeed, in the methoxy group, an H atom of the methyl group (H17B) bonds to the oxygen atom of the same group on a neighbouring molecule (related by an inversion center) to form parallel sheets of centrosymetric dimers [graph set R₂²(6) (Bernstein et al., 1995)]. Also, a hydrogen of the chromene-benzene ring (H2) bonds to the oxygen atom of the carbonyl group of the side chain of a neighbouring molecule to form an infinite chain [graph set C(7)]. The combination of the C(7) chain and the R₂²(6) dimers results in a ring of hydrogen-bonded molecules described by the graph set R₄⁴(40) (Fig. 2). Further, the hydrogen of the six-membered heterocyclic ring bonds to the oxygen atom of the carbonyl group of the chromen-2-one moiety of an inversion-related neighbouring molecule to form a pair of hydrogen bonds [graph set R₂²(8)]. The latter hydrogen bonds and the C(7) chain connect the R₄⁴(40) centrosymmetric tetramers, resulting in a supramolecular aggregation (Fig. 3) which is further consolidated by weak C═ O···π interactions [O2···Cg1 (x - 1, y, z) = 3.357 (3) Å], where Cg1 is the centroid of the six-membered O containing ring, and π–π stacking between the chromene-benzene C1—C6 and the six-membered heterocyclic rings; in the latter, the centroid···centroid distance, [Cg2···Cg1 (x + 1, y, z) or Cg1···Cg2 (x - 1, y, z) = 3.691 (2) Å], is less than 3.8 Å, the maximum regarded as relevant for π–π interactions (Janiak, 2000) (Fig. 4).

Experimental

To a solution of 4-methoxybenzoyl chloride (40 mmol) in dried tetrahydrofuran (150 ml), was added dried triethylamine (120 mmol) and 4-hydroxycoumarin (40 mmol)in small portions over 30 min. The mixture was then refluxed for 3 h and poured in 300 ml of chloroform. The solution was acidified with dilute hydrochloric acid until the pH was 2–3. The organic layer was extracted, washed with water, dried over MgSO₄ and the solvent removed. The crude product was recrystallized from chloroform. Colourless crystals of the title compound were obtained in a good yield (84%); m.p. 421–422 K. ¹H NMR (Bruker TOPSPIN, CDCl₃, 400 MHz, p.p.m.) δ: 6.63 (s, 1H, H8); 7.43 (d, 1H, H2); 7.33 (t.d, 1H, H3); 7.61 (t.d,1H, H4); 7.73 (d, 1H, H5); 8.2 (d, 2H, H12 and H16); 7.05 (d, 2H, H13 and H15); 3.93 (s, 3H, CH₃). ¹³C NMR (Bruker TOPSPIN, CDCl₃, 100 MHz, p.p.m.) δ: 162 (C7); 108 (C8); 161 (C9); 127 (C2); 124 (C3); 117 (C4); 126 (C5); 153 (C6); 115 (C1); 165 (C10); 160 (C11); 133 (C12 and C16); 113 (C13 and C15); 120 (C14); 55 (C17).