Dimethyl 2-[(acridin-9-yl)methyl­idene]malonate

Sinara M V de Almeida; Ivan R Pitta; Maria do Carmo A de Lima; Francisco J B Mendonça Junior; Carlos A de Simone

doi:10.1107/S1600536813000500

. 2013 Jan 12;69(Pt 2):o224. doi: 10.1107/S1600536813000500

Dimethyl 2-[(acridin-9-yl)methylidene]malonate

Sinara M V de Almeida ^a, Ivan R Pitta ^b, Maria do Carmo A de Lima ^b, Francisco J B Mendonça Junior ^c, Carlos A de Simone ^d,^*

PMCID: PMC3569759 PMID: 23424505

Abstract

In the title compound, C₁₉H₁₅NO₄, the acridine system is essentially planar (r.m.s. deviation = 0.015 Å). The crystal packing exhibits π–π interactions between pairs of centrosymmetric molecules, one of them between the central heterocyclic rings and others between the outer benzene rings of the acridine systems, with centroid–centroid distances of 3.692 (1) and 3.754 (1) Å, respectively. These pairs are further linked by additional π–π interactions along the a-axis direction through one of the two outer benzene ring of neighboring molecules, with a centroid–centroid distance of 3.642 (2) Å.

Related literature

For background to acridines, see: Kumar et al. (2012 ▶). For the biological activity of acridine derivatives, see: Pigatto et al. (2011 ▶); Das et al. (2011 ▶); Kumar et al. (2012 ▶). For the synthesis of acridines, see: Tomar et al. (2010 ▶). For related structures, see: Buckleton & Waters (1984 ▶).

Experimental

Crystal data

C₁₉H₁₅NO₄
M _r = 321.32
Triclinic,
a = 8.3022 (2) Å
b = 9.0208 (3) Å
c = 12.0334 (4) Å
α = 96.468 (2)°
β = 93.652 (2)°
γ = 117.422 (2)°
V = 787.98 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.32 × 0.28 × 0.22 mm

Data collection

Nonius KappaCCD diffractometer
10674 measured reflections
3626 independent reflections
2805 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.148
S = 1.05
3626 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: COLLECT (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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

Click here for additional data file.^{(17.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000500/lr2094sup1.cif

e-69-0o224-sup1.cif^{(17.2KB, cif)}

Click here for additional data file.^{(169.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000500/lr2094Isup2.hkl

e-69-0o224-Isup2.hkl^{(169.2KB, hkl)}

Click here for additional data file.^{(6.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000500/lr2094Isup3.cml

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

Acknowledgments

This work received partial support from CNPq and PROPESQ/UEPB. The authors thank the Instituto de Física de São Carlos – USP for allowing the use of the KappaCCD diffractometer.

supplementary crystallographic information

Comment

The pharmacological uses of acridine derivatives have been well documented (Kumar et al. 2012). Amongst these applications can be highlighted: Proflavin an antibacterial agent against many Gram positive bacteria; Bucricaine which is used topically for surface anesthesia (Kumar et al. 2012); Quinacrine and 9-aminoacridine that act as antimalarial and disinfectant agents respectively (Das et al. 2011); and several antitumor agents as nitracrina, amsacrine and 9-arylacridines which are potent topoisomerase inhibitors (Pigatto et al. 2011).

In this work, we report the structure of the title compound synthesized by the reaction between acridine-9-carbaldehyde and dimethyl malonate. The mean plane analysis of molecule shows that the acridine ring is essentially planar. The deviation observed is maximum for the C5 [(0.0311 (2) Å].The crystal packing exhibits π- π interactions between pairs of centrosymmetric molecules, one of them between the central heterocyclic rings and others between the side benzene rings of the acridine moieties, with centroid-centroid distances of 3.692 (1) and 3.754 (1) Årespectively. These pairs are further linked by additional π- π interactions along the a axis through one of the two side benzene ring of neighboring molecules, with centroid-centroid distance of 3.642 (2) Å.

Experimental

In a Dean-Stark apparatus, acridine-9-carbaldehyde (0.1 mmol), dimethyl malonate (0.1 mmol) and morpholine (0.01 mmol) were refluxed in toluene (10 ml). The reaction mixture was refluxed at 383 K for 24 h, and the solvent was evaporated under reduced pressure. The title compound was purified by flash chromatography on silica gel (230–400 mesh) Merck (Germany), eluting with n-hexane/ethyl acetate (9.5:0.5) to give analytically pure yellow crystals of 2-acridin-9-yl-methylene-malonic acid dimethyl ester; yield 33%, M.p. 405–407 K. Crystals suitable for suitable for single-crystal X-ray diffraction were grown by slow evaporation at 289 K of a solution of the pure title compound in absolute ethanol.

FTIR (KBr, cm^-1) Umax: 2954, 2924, 1730, 1628, 1435, 1266, 1232, 1076, 785, 749. NMR ¹H (300 MHz, DMSO-d₆) δ 3.15 (s, 3H), 3.92 (s, 3H), 7.65 (m, 2H), 7.89 (m, 2H), 7.99 (d, 2H,J = 8.6 Hz), 8.20 (d, 2H, J = 8.6 Hz), 8.70 (s, 1H). HRMS calcd for C₁₉H₁₅NO₄ = 321.1001, found = 322.0617.