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

R Babykala; D Kalaivani

doi:10.1107/S1600536813004352

. 2013 Feb 20;69(Pt 3):o398–o399. doi: 10.1107/S1600536813004352

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

R Babykala ^a, D Kalaivani ^a,^*

PMCID: PMC3588430 PMID: 23476581

Abstract

In the anion of the title salt, C₁₀H₁₆N⁺·C₁₀H₄ClN₄O₇ ⁻ [trivial name = N,N-diethylanilinium 5-(3-chloro-4,6,-dinitrophenyl)barbiturate], the dihedral angle between the benzene and pyrimidine rings is 45.49 (6)°. The mean plane of the nitro group, which is ortho-substituted with respect to the pyrimidine ring, is twisted by 41.57 (13)° from the benzene ring, while the mean plane of the nitro group, which is para-substituted, is twisted by 14.41 (12)° from this ring. In the crystal, N—H⋯O hydrogen bonds link cations and anions into chains along [1-10]. Within the chains, inversion-related anionic barbiturate anions form R ₂ ²(8) ring motifs.

Related literature

For different types of interactions between electron-deficient nitro aromatics and bases, see: Jackson & Gazzolo (1900 ▶); Mulliken (1952 ▶); Russell & Janzen (1962 ▶); Blake et al. (1966 ▶). For donor–acceptor interactions see: Mulliken (1952 ▶); Radha et al. (1987 ▶). For π–π stacking interactions, see: Vembu & Fronczek (2009 ▶). For the biological activity of pyrimidine and barbiturate derivatives, see: Jain et al. (2006 ▶); Tripathi (2009 ▶) and of related barbiturates, see: Kalaivani & Buvaneswari (2010 ▶). For the crystal structures of related barbiturates, see: Kalaivani & Malarvizhi (2009 ▶); Buvaneswari & Kalaivani (2011 ▶); Kalaivani & Mangaiyarkarasi (2013 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₆N⁺·C₁₀H₄ClN₄O₇ ⁻
M _r = 477.86
Triclinic,
a = 9.8040 (2) Å
b = 10.2870 (2) Å
c = 11.8260 (2) Å
α = 74.727 (1)°
β = 82.761 (1)°
γ = 71.817 (1)°
V = 1091.87 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004) ▶ T _min = 0.913, T _max = 0.985
18678 measured reflections
3836 independent reflections
3123 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.117
S = 1.04
3836 reflections
312 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(30.1KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813004352/lh5583sup1.cif

e-69-0o398-sup1.cif^{(30.1KB, cif)}

Click here for additional data file.^{(188KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813004352/lh5583Isup2.hkl

e-69-0o398-Isup2.hkl^{(188KB, hkl)}

Click here for additional data file.^{(8.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813004352/lh5583Isup3.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
N4—H4A⋯O5ⁱ	0.83 (2)	2.06 (2)	2.892 (2)	175 (2)
N3—H3A⋯O7ⁱⁱ	0.83 (2)	1.96 (2)	2.794 (2)	180 (3)
N5—H5A⋯O6ⁱⁱⁱ	0.87 (3)	1.82 (3)	2.677 (2)	168 (3)

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

Acknowledgments

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

supplementary crystallographic information

Comment

Several types of interactions have been observed between electron deficient nitro aromatic compounds and electron rich species (Jackson et al., 1900; Mulliken, 1952; Russell et al., 1962; Blake et al., 1966). Partial transfer of electrons results in the formation of charge-transfer complexes (Mulliken, 1952; Russell et al., 1962). N,N-diethylaniline usually forms charge transfer complexes with electron deficient nitroaromatics which is revealed through the existence of π···π stacking in single crystal X-ray diffraction studies (Vembu et al.,2009). The title molecular salt is formed upon mixing 1,3-dichloro-4,6-dinitrobenzene (DCDNB), N,N-diethylaniline and barbituric acid in which no significant π···π stacking is observed between nitro aromatic ring and N,N-diethylaniline ring. Barbituric acid (pyrimidine-2,4,6(1H,3H,5H)-trione) and many other pyrimidine derivatives occupy a distinct and unique place in everyday life (Jain et al., 2006). Barbiturates are mainly used to stop convulsion and they also have hypnotic property which is applied for the treatment of psychotic patients, induction of state of sleep and prolonged sleep (Tripathi et al., 2009). The related barbiturates synthesised in our laboratory also possess such properties (Kalaivani & Malarvizhi 2009; Kalaivani & Buvaneswari 2010). Single crystal X-ray analysis of the molecular salts derived from (1-chloro-2,4-dinitrobenzene/2,4,6-trinitrobenzene), N,N-diethylaniline and barbituric acid have already been reported by our group (Buvaneswari & Kalaivani 2011; Kalaivani & Mangaiyarkarasi, 2013).

The molecular structure of the title compound is shown in Fig 1. In the crystal, N—H···O hyrogen bonds link cations and anions into chains (Fig 2) along [110] which incorporate R²₂(8) rings (Bernstein et al., 1995).

Experimental

Analytical grade 1,3-dichloro-4,6-dinitrobenzene (DCDNB) and Barbituric acid (BBA) were used as supplied by Aldrich company. N,N-Diethylaniline was distilled under reduced pressure and the fraction boiling over at its boiling point was used. DCDNB (2.37g, 0.01mol) in 15ml of absolute ethanol was mixed with barbituric acid (1.28g, 0.01mol)in 30ml of absolute ethanol. N,N-diethylaniline (3g, 0.01mol) was added to the above mixture, heated to 313K, and shaken well for 5-6 hrs. The solution was kept at room temperature. After a period of two weeks dark reddish orange block-shaped crystals formed in the solution. The crystals were powdered well and washed with 2 to 5ml of ethanol and 50ml of dry ether and recrystallized from absolute alcohol (m.pt :494K ; yield :80 %). Good quality crystals (dark reddish-orange blocks) for single crystal X-ray studies were obtained by slow evaporation of ethanol solution of the title compound at room temperature.