14-Eth­oxy-4,6,9-trimethyl-8,12-dioxa-4,6-diaza­tetra­cyclo­[8.8.0.02,7.013,18]octa­deca-2(7),13,15,17-tetra­ene-3,5,11-trione

G Jagadeesan; D Kannan; M Bakthadoss; S Aravindhan

doi:10.1107/S1600536813000743

. 2013 Jan 23;69(Pt 2):o272. doi: 10.1107/S1600536813000743

14-Ethoxy-4,6,9-trimethyl-8,12-dioxa-4,6-diazatetracyclo[8.8.0.0^2,7.0^13,18]octadeca-2(7),13,15,17-tetraene-3,5,11-trione

G Jagadeesan ^a, D Kannan ^b, M Bakthadoss ^b, S Aravindhan ^a,^*

PMCID: PMC3569800 PMID: 23424546

Abstract

In the title compound, C₁₉H₂₀N₂O₆, the pyrone and pyran rings adopt envelope conformations with the same common C atom as the flap, the dihedral angle between the planes of the remaining ring atoms being 68.27 (4)°. The planar atoms of the pyran ring and the diazacyclic ring are almost coplanar, the dihedral angle between their mean planes being 3.29 (7)°. Moreover, the planar atoms of the pyrone ring and benzene ring of the coumarin unit are also close to coplanar, the dihedral angle between their mean planes being 8.03 (9)°. The methoxy group lies in the plane of the benzene ring, with a dihedral angle between their mean planes of 9.4 (2)°. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds resulting in sheets of molecules in the ac plane.

Related literature

For the biological activity of pyranocoumarin compounds, see: Kawaii et al. (2001 ▶); Goel et al. (1997 ▶); Su et al. (2009 ▶). For a related structure, see: Pojarová et al. (2012 ▶).

Experimental

Crystal data

C₁₉H₂₀N₂O₆
M _r = 372.37
Monoclinic,
a = 9.3526 (3) Å
b = 17.9559 (5) Å
c = 10.9158 (3) Å
β = 101.346 (1)°
V = 1797.31 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2004 ▶) T _min = 0.979, T _max = 0.983
21571 measured reflections
5615 independent reflections
3743 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.151
S = 1.03
5615 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(21.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000743/pv2613sup1.cif

e-69-0o272-sup1.cif^{(21.7KB, cif)}

Click here for additional data file.^{(269.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000743/pv2613Isup2.hkl

e-69-0o272-Isup2.hkl^{(269.4KB, hkl)}

Click here for additional data file.^{(7.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000743/pv2613Isup3.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
C2—H2⋯O6ⁱ	0.98	2.40	3.1480 (17)	132
C18—H18C⋯O3ⁱⁱ	0.96	2.45	3.252 (2)	140

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

Acknowledgments

SA thanks the UGC, India, for financial support

supplementary crystallographic information

Comment

Coumarin derivatives show strong activity against cancer cell lines (Kawaii et al., 2001) and exhibit antiulcer (Goel et al., 1997) and cytotoxic activities (Su et al., 2009). We report here in this paper the crystal structure of the title coumarin derivative.

In the title molecule (Fig. 1), the pyrone (O2/C3/C4/C9/C10/C15) and pyran (O4/C2–C6) rings adopt C3-envelope conformations with C3 displaced by 0.603 (2) and 0.668 (2) Å, respectively, from the least-square planes formed by the remaining ring atoms; the dihedral angle between the two mean-planes being 68.27 (4)°. The planar atoms of the pyran ring (O4/C2/C4–C6) and diazacyclic ring (N1/N2/C5–C8) are almost co-planar with dihedral angle between the mean-planes being 3.29 (7)°. Moreover, the planar atoms of the pyrone ring (O2/C4/C9/C10/C15) and benzene ring (C9–C14) of the coumarin moiety are also co-planar with dihedral angle between the mean-planes being 8.03 (9)°. The methoxy group (O1/C16/C17) lies in the plane of the benzene ring (C9–C14) with a dihedral angle between the mean-planes 9.4 (2)°. The crystal packing is stabilized by intermolecular C2—H2···O6 and C18—H18C···O3 hydrogen bonding interactions (Fig. 2 and Table 1).

Experimental

A mixture of 2-ethoxy-6-formylphenyl (2E)-but-2-enoate (0.234 g, 1 mmol) and N,N-dimethylbarbituric acid (0.156 g, 1 mmol) was placed in a round bottom flask and melted at 14-Ethoxy-4,6,9-trimethyl-8,12-dioxa-4,6-diazatetracyclo[8.8.0.0^2,7.0^13,18]octadeca-2(7),13,15,17-tetraene-3,5,11-trione180 °C for 1 h. After completion of the reaction as indicated by TLC, the crude product was washed with 5 ml of ethylacetate and hexane mixture (1:49 ratio) which successfully provided the pure product in 90% yield as colorless solid.