Diethyl 2-(2-nitro­benzyl­idene)malonate

S Thenmozhi; S Ranjith; A SubbiahPandi; V Dhayalan; A K MohanaKrishnan

doi:10.1107/S1600536809032668

. 2009 Aug 22;65(Pt 9):o2209. doi: 10.1107/S1600536809032668

Diethyl 2-(2-nitrobenzylidene)malonate

S Thenmozhi ^a, S Ranjith ^a, A SubbiahPandi ^a,^*, V Dhayalan ^b, A K MohanaKrishnan ^b

PMCID: PMC2969968 PMID: 21577610

Abstract

In the title compound, C₁₄H₁₅NO₆, the ethoxycarbonyl groups adopt extended conformations. In the crystal, molecules are linked into centrosymmetric dimers via pairs of C—H⋯O hydrogen bonds with a R ₂ ²(20) motif.

Related literature

For biological activity of nitrogen-containing building blocks derived from α-methylene-β-hydroxy esters, see: Singh & Batra (2008 ▶); Masson et al. (2007 ▶); Basavaiah et al. (2003 ▶); Youngme et al. (2007 ▶); Ma et al. (2005 ▶); Soldatov et al. (2003 ▶); Hinckley (1969 ▶).

Experimental

Crystal data

C₁₄H₁₅NO₆
M _r = 293.27
Triclinic,
a = 7.8410 (2) Å
b = 8.5571 (2) Å
c = 12.3533 (4) Å
α = 80.866 (2)°
β = 75.037 (1)°
γ = 64.402 (1)°
V = 721.10 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.17 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.978, T _max = 0.982
19570 measured reflections
4226 independent reflections
3259 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.145
S = 1.06
4226 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032668/bt5022sup1.cif

e-65-o2209-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032668/bt5022Isup2.hkl

e-65-o2209-Isup2.hkl^{(202.9KB, hkl)}

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⋯O3ⁱ	0.93	2.47	3.1683 (18)	132

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Symmetry code: (i) Inline graphic .

Acknowledgments

ST and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray data collection.

supplementary crystallographic information

Comment

Nitrogen-containing building blocks derived from a-methylene-β-hydroxy esters (Morita-Baylis-Hillman adducts) have been widely employed in modern organic chemistry for the synthesis of natural products and heterocycles of biological relevance (Singh & Batra, 2008; Masson et al., 2007; Basavaiah et al., 2003). β-Diketone as an excellent chelating group has been widely used in supramolecular chemistry. It can form a variety of complexes with various transition-metals (e.g. Cu, Co, Ni, Mn, Pd) or rare-earth metals (e.g. Eu, Sm, La, Gd) (Youngme et al., 2007; Ma et al., 2005). These metal complexes have significant applications in material science or act as chemical shift reagents (Soldatov et al., 2003; Hinckley, 1969). In view of this importance, the crystal structure determination of the title compound (Fig.1) has been carried out.

A perspective view of the title compound with the atom-numbering scheme is shown in Fig. 1. The deviations of the atoms N, O1 and O2 from the least-squares plane of the phenyl rings are -0.080 (1), 0.296 (2) and -0.527 (1) Å. The ethoxycarbonyl groups adopt extended conformation as can be seen from the torsion angles C8- C9- O6- C10 [175.6 (1)°], C9- O6- C10- C11 [-79.9 (2)°], C8- C12- O5- C13[178.6 (1)°] and C12- O5- C13- C14 [178.5 (1)°]. The C2–H2···O3 hydrogen bonds form a cyclic centrosymmetric dimer [R₂²(20)] shown in Fig.2.

Experimental

A mixture of 2-nitrobenzaldehyde (5 g, 33.11 mmol) in dry xylene (50 ml), ethylene diamine di acetate (1.2 g, 6.66 mmol) and diethyl malonate (6.36 g, 39.7 mmol) were added. The reaction was then refluxed for 12 h, it was then poured over ice - water (100 ml), extracted with CHCl₃ (60 ml) and dried (Na₂ SO₄). The removal of solvent followed by recrystallization from methanol. Single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution in methanol.