N,N-Diethyl-2-hy­droxy­ethanaminium 2,6-dioxo-5-(2,4,6-trinitro­phen­yl)-1,2,3,6-tetra­hydro­pyrimidin-4-olate dihydrate

Manickam Buvaneswari; Doraisamyraja Kalaivani

doi:10.1107/S1600536811017363

. 2011 May 20;67(Pt 6):o1433–o1434. doi: 10.1107/S1600536811017363

N,N-Diethyl-2-hydroxyethanaminium 2,6-dioxo-5-(2,4,6-trinitrophenyl)-1,2,3,6-tetrahydropyrimidin-4-olate dihydrate

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

PMCID: PMC3120611 PMID: 21754812

Abstract

In the title molecular salt, C₆H₁₆NO⁺·C₁₀H₄N₅O₉ ⁻·2H₂O, which crystallizes as a dihydrate, O—H⋯O hydrogen bonds link the barbiturate anion, the ethanaminium cation and the water molecules of crystallization. The dihedral angle between the rings in the anion is 43.71 (8)°. In the crystal, an R ₂ ²(8) ring motif hydrogen-bonding pattern is also found involving inversion-related barbiturate rings with N—H⋯O hydrogen bonds. As a result of the various hydrogen bonds an infinite two-dimensional network, propagating in (10 Inline graphic ), is formed.

Related literature

For the anti-epileptic properties of barbiturates, see: Tripathi (2009 ▶); Kalaivani & Malarvizhi (2009 ▶); Kalaivani et al. (2008 ▶). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₆H₁₆NO⁺·C₁₀H₄N₅O₉ ⁻·2H₂O
M _r = 492.41
Monoclinic,
a = 8.3792 (2) Å
b = 21.7673 (4) Å
c = 12.0894 (2) Å
β = 96.118 (1)°
V = 2192.46 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 1999 ▶) T _min = 0.892, T _max = 0.975
23280 measured reflections
4686 independent reflections
3492 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.131
S = 1.08
4686 reflections
338 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017363/su2264sup1.cif

e-67-o1433-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017363/su2264Isup2.hkl

e-67-o1433-Isup2.hkl^{(229.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017363/su2264Isup3.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
O10—H10⋯O2Wⁱ	0.82	2.05	2.792 (2)	150
O10—H10⋯O4ⁱⁱ	0.82	2.49	3.0648 (19)	129
N6—H6⋯O1Wⁱⁱⁱ	0.91 (3)	1.95 (3)	2.846 (2)	170 (2)
N1—H1A⋯O10^iv	0.85 (2)	2.05 (3)	2.884 (2)	166 (2)
N2—H2A⋯O2^v	0.83 (2)	2.03 (2)	2.847 (2)	173 (2)
O1W—H2W⋯O2^v	0.91 (1)	1.90 (2)	2.7431 (19)	154 (2)
O2W—H4W⋯O1W^vi	0.93 (1)	1.94 (2)	2.796 (3)	152 (3)
O1W—H1W⋯O3	0.91 (1)	1.91 (1)	2.7783 (17)	160 (2)
O2W—H3W⋯O1	0.93 (1)	1.89 (2)	2.792 (2)	162 (4)

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

Acknowledgments

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

supplementary crystallographic information

Comment

Most of the barbituric acid derivatives (barbiturates) are antiepileptic agents (Tripathi, 2009). The barbiturate prepared in our laboratory from 1-chloro-2,4-dinitrobenzene was obtained as maroon blocks when recrystallized from absolute alcohol (Kalaivani & Malarvizhi, 2009) and has antiepileptic activity (Kalaivani et al., 2008). We report here the crystal structure of a related barbiturate obtained from 1-chloro-2,4,6-trinitrobenzene (TNCB) and barbituric acid in the presence of 2(N,N-diethyl) ethanolamine. It shows an extra ordinary stability and very high solubility in dipolar aprotic solvents, such as dimethyl sulfoxide, which may be attributed to its salt-like structure.

The molecular structure of the title compound is illustrated in Fig. 1. The anion and cation are involved in O—H···O hydrogen bonds with the water molecules of crystallization (Table 1).

In the crystal a R₂²(8) ring motif hydrogen bonding pattern (Bernstein et al., 1995) is also found involving inversion-related barbiturate rings with N—H···O hydrogen bonds (Table 1 and Fig. 2). These various hydrogen bonds lead finally to the formation of an infinite two-dimensional network propagating in (10–1).

Experimental

Equimolar solutions of 1-chloro-2,4,6-trinitrobenzene (TNCB) and barbituric acid were prepared in ethanol and mixed. A three fold excess of 2(N,N-diethyl) ethanolamine was then added and the mixture was shaken well for 5–6 h. Maroon red coloured crystals were obtained after 24 hrs. The crystals were filtered and recrystallized from absolute alcohol (yield of pure crystals 70%, m.p. 507 K). 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.