N,N-Diethyl­anilinium 2,4-dioxo-5-(2,4,6-trinitro­phen­yl)-1,2,3,4-tetra­hydro­pyrimi­din-6-olate

Manickam Buvaneswari; Doraisamyraja Kalaivani

doi:10.1107/S1600536811049506

. 2011 Nov 30;67(Pt 12):o3452. doi: 10.1107/S1600536811049506

N,N-Diethylanilinium 2,4-dioxo-5-(2,4,6-trinitrophenyl)-1,2,3,4-tetrahydropyrimidin-6-olate

Manickam Buvaneswari ^a, Doraisamyraja Kalaivani ^a,^*

PMCID: PMC3239082 PMID: 22199930

Abstract

In the crystal structure of the title molecular salt, C₁₀H₁₆N⁺·C₁₀H₄N₅O₉ ⁻, the components are linked through a N—H⋯O hydrogen bonds. R ₂ ²(8) ring motifs are formed between inversion-related barbiturate residues. Two intramoleculer N—H⋯O hydrogen bonds are observed in the anion. The dihedral angle between 2,4,6-trinitrophenyl and barbiturate rings is 53.6 (2)°. The N,N-diethylamine substituent is disordered and was modeled as two geometrically equivalent conformers with occupancies of 0.737 (2) and 0.273 (2).

Related literature

N,N-Dialkylaniline (aromatic amine) usually forms donor–acceptor adducts with electron-deficient nitro aromatics, see: Radha et al. (1987 ▶); Rizk et al. (1993 ▶). For similar structures containing the barbiturate anion, see: Buvaneswari & Kalaivani (2011 ▶); Kalaivani & Buvaneswari (2010 ▶); Kalaivani & Malarvizhi (2009 ▶); Kalaivani et al. (2008 ▶).

Experimental

Crystal data

C₁₀H₁₆N⁺·C₁₀H₄N₅O₉ ⁻
M _r = 488.42
Monoclinic,
a = 17.1903 (7) Å
b = 10.3925 (5) Å
c = 13.3613 (5) Å
β = 110.272 (2)°
V = 2239.14 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) ▶ T _min = 0.923, T _max = 0.962
3550 measured reflections
3550 independent reflections
2763 reflections with I > 2σ(I)
θ_max = 24.1°

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.105
S = 1.03
3550 reflections
337 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 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 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811049506/bv2193sup1.cif

e-67-o3452-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049506/bv2193Isup2.hkl

e-67-o3452-Isup2.hkl^{(174.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049506/bv2193Isup3.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
N1—H1A⋯O1ⁱ	0.86	2.01	2.8451 (18)	162
N2—H2A⋯O3ⁱⁱ	0.86	1.98	2.8230 (16)	167
N6A—H6AA⋯O2	0.91	1.88	2.790 (3)	175
N6B—H6BA⋯O2	0.91	1.71	2.617 (8)	174

Open in a new tab

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

Acknowledgments

The authors are thankful to the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

Comment

N,N-Dialkylaniline (aromatic amine) usually forms donor-acceptor adducts with electron-deficient nitro aromatics (Radha et al., 1987, Rizk et al., 1993). In the present investigation, it forms a different type of molecular salt (scheme) with the electron-deficient nitro aromatic compound, 1-chloro-2,4,6-trinitrobenzene (picryl chloride) in the presence of barbituric acid. We have already reported molecular salts of a similar type obtained from chlorine containing nitro aromatic compounds, barbituric acid and aliphatic amines (Kalaivani et al., 2008, Kalaivani & Malarvizhi, 2009, Kalaivani & Buvaneswari, 2010, Buvaneswari & Kalaivani, 2011). As noticed in other barbiturates, ring motifs are observed in the crystal structure of the title molecule. The protonated nitrogen atom of N,N-diethylaniline forms a hydrogen bond with the oxygen atom of the barbiturate anion and this may probably be the driving force for the formation of the title molecular salt.The negative charge on the oxygen atom of olate is delocalized over the nitro groups of the trinitrophenyl moiety and due to this extended conjugation the salt appears bright maroon red in colour.The title molecular salt is obtained with high purity in good yield (90%). Fig.1and 2 represent the ORTEP and packing view of the title molecule.

Experimental

Picryl chloride(1.3.g, 0.005 mol) was dissolved in 15 ml absolute alcohol. Barbituric acid (0.6 g, 0.005 mol)was dissolved in 30 ml of absolute alcohol. These two solutions were mixed and heated to 50°C.To this hot mixture, 4 ml of N,N-diethylaniline (0.03 mol) was added and shaken well for 3hrs. The crystals obtained were filtered, washed with 50 ml of dry ether and recrystallized from absolute alcohol (yield of pure crystals 90%, m.p.> 573 K). Maroon red block-like single crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of an ethanolic solution of the title compound at room temperature.