3-(4-Meth­oxy­benzo­yl)-6-nitro­coumarin

Saleta Vazquez-Rodriguez; Eugenio Uriarte; Lourdes Santana

doi:10.1107/S1600536813002948

. 2013 Feb 6;69(Pt 3):o345. doi: 10.1107/S1600536813002948

3-(4-Methoxybenzoyl)-6-nitrocoumarin

Saleta Vazquez-Rodriguez ^a,^*, Eugenio Uriarte ^a, Lourdes Santana ^a

PMCID: PMC3588552 PMID: 23476538

Abstract

In the title coumarin derivative (also known as 2H-chromen-2-one or 2H-1-benzopyran-2-one), C₁₇H₁₁NO₆, the coumarin ring system is nearly planar, with a dihedral angle of 3.35 (9)° between the pyrone and the benzene rings. The dihedral angle between the planes formed by the coumarin ring system and the benzene substituent is 54.60 (7)°, clearly showing the non-coplanarity of the whole aromatic system. The crystal studied was a non-merohedral twin; the minor component refined to approximately 0.44.

Related literature

For the synthesis of the title compound, see: Raju et al. (2010 ▶). For examples of the biological activity of coumarin derivatives, see: Borges et al. (2009 ▶), Matos et al. (2011a ▶,b ▶,c ▶), Viña et al. (2012a ▶,b ▶); Vazquez-Rodriguez et al. (2013 ▶). graphic file with name e-69-0o345-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₁NO₆
M _r = 325.27
Monoclinic,
a = 8.875 (3) Å
b = 17.266 (5) Å
c = 9.174 (3) Å
β = 95.401 (15)°
V = 1399.6 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.67 × 0.14 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.604, T _max = 0.745
30736 measured reflections
2864 independent reflections
2200 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.126
S = 0.91
2864 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); 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

Click here for additional data file.^{(18.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813002948/go2080sup1.cif

e-69-0o345-sup1.cif^{(18.6KB, cif)}

Click here for additional data file.^{(137.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002948/go2080Isup2.hkl

e-69-0o345-Isup2.hkl^{(137.7KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813002948/go2080Isup3.cml

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

Acknowledgments

This work was partially supported by the funds of the Xunta da Galicia (09CSA030203PR) and the Ministerio de Sanidad y Consumo (PS09/00501). SVR thanks the FPU program for her PhD grant AP2008–04263.

supplementary crystallographic information

Comment

Coumarin derivative compounds present a great interest in the medicinal chemistry field due to the displayed biological properties that they present (Borges et al. 2009, Matos et al. 2011a, Matos et al. 2011b, Matos et al. 2011c, Vazquez-Rodriguez et al. 2013, Viña et al. 2012a and Viña et al. 2012b). The title structure is a 3-substituted coumarin derivative containing a 4-methoxybenzoyl ring at the mentioned position and a nitro group at position 6 of the coumarin scaffold. Therefore, the X-ray analysis of this compound (figure 1) aims to contribute to the elucidation of structural requirements needed to understand the partial planarity of the compound (coumarin nucleus) and the torsion of the 3-benzoyl moiety regarding to this nucleus. From the single-crystal diffraction measurements one can conclude that both the pyrone and benzene rings in the coumarin motif are essentially planar, presenting dihedral angle of 3.35 (9)°. The planarity of the coumarin moiety is also evident by the torsion angle value between their carbons C3—C2—C7—C8 (-175.89 (18)°).

In addition, the torsion angles of the carbonyl group versus the coumarin moiety and the phenyl ring are C10—C9—C15—O16 (43.2 (2)°) and O16—C15—C17—C18 (-152.9 (2)°) respectively. These values are typical of the torsion permitted by the rotation present at position 3. Presence of the carbonyl group at position 3 provokes a non coplanarity of the benzoyl moiety regarding to the coumarin scaffold. This fact is evident taking into account the dihedral angles formed by the planes of the coumarin, the carbonyl and the phenyl groups. Dihedral angle between the coumarin moiety and the carbonyl group is 38.66 (9)°; between the carbonyl and the phenyl group is 25.76 (10)° and between the coumarin scaffold and the phenyl group is 54.60 (7)°.

Experimental

3-(4-Methoxybenzoyl)-6-nitrocoumarin was prepared according to the following protocol: to a solution of 2-hydroxy-5-nitrobenzaldehyde (1 mmol) and ethyl 4-methoxybenzoylacetate (1 mmol) in ethanol (4 ml), a catalytic amount of piperidine (5%) was added dropwise and the reaction was stirred at refluxed for 4 h. The precipitated was filtered and the solid obtained was recrystallized in dichlomethane/methanol in a 73% yield. Mp 257–259 °C.