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

D Kalaivani; M Buvaneswari; S Rajeswari

doi:10.1107/S1600536811051610

. 2011 Dec 7;68(Pt 1):o29–o30. doi: 10.1107/S1600536811051610

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

D Kalaivani ^a,^*, M Buvaneswari ^a, S Rajeswari ^b

PMCID: PMC3254393 PMID: 22259534

Abstract

In the title barbiturate salt (trivial name: trimethylammonium 2,4,6-trinitrophenylbarbiturate), C₃H₁₀N⁺·C₁₀H₄N₅O₉ ⁻, the asymmetric unit contains two sets of anion–cation moieties. The dihedral angle between the rings in the anions are 44.0 (3) and 45.7 (3)°. Adjacent anions are connected into ribbons along [100] through R ₂ ²(8) ring motifs formed by N—H⋯O hydrogen bonds involving the barbiturate rings. Attached to both sides of these ribbons via N—H⋯O hydrogen bonds are the trimethylammonium cations. C—H⋯O hydrogen bonds are also observed.

Related literature

For the biological activity of barbiturates, see: Nogrady (1988 ▶); Gitto et al. (2006 ▶). For side effects of barbiturates, see: Hardman & Limbird (2001 ▶); Rana et al. (2007 ▶). For barbiturates related to the title compound, see: Kalaivani et al. (2008 ▶); Kalaivani & Malarvizhi (2009 ▶).

Experimental

Crystal data

C₃H₁₀N⁺·C₁₀H₄N₅O₉ ⁻
M _r = 398.30
Monoclinic,
a = 11.9828 (12) Å
b = 30.802 (3) Å
c = 9.5516 (11) Å
β = 105.895 (6)°
V = 3390.6 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEX II CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.90, T _max = 0.97
31796 measured reflections
6580 independent reflections
4977 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.123
S = 1.02
6580 reflections
536 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; 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., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811051610/qk2022sup1.cif

e-68-00o29-sup1.cif^{(44KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051610/qk2022Isup2.hkl

e-68-00o29-Isup2.hkl^{(322KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811051610/qk2022Isup3.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—H4⋯O17ⁱ	0.85 (2)	1.94 (2)	2.780 (2)	170 (2)
N5—H5⋯O16	0.86 (3)	1.93 (3)	2.778 (2)	170 (2)
N9—H9⋯O8	0.85 (2)	1.95 (2)	2.790 (2)	172 (2)
N10—H10⋯O7ⁱⁱ	0.83 (2)	1.96 (2)	2.786 (2)	173 (2)
N11—H11A⋯O9ⁱⁱⁱ	0.94 (3)	1.82 (3)	2.730 (2)	160 (3)
N12—H12A⋯O18	0.94 (3)	2.02 (3)	2.803 (3)	139 (3)
N12—H12A⋯O5^iv	0.94 (3)	2.16 (3)	2.856 (3)	130 (2)
C2—H2⋯O4^v	0.93	2.58	3.265 (3)	131
C16—H16⋯O2^vi	0.93	2.27	3.146 (3)	156
C24—H24B⋯O5	0.96	2.51	3.448 (4)	164
C24—H24C⋯O10ⁱⁱⁱ	0.96	2.57	3.457 (4)	154
C26—H26B⋯O18^iv	0.96	2.50	3.400 (5)	156

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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 X-ray data collection.

supplementary crystallographic information

Comment

Barbiturates are biologically active molecules (Nogrady, 1988; Gitto et al., 2006). Many reported barbiturates have noticeable side effects (Hardman & Limbird, 2001; Rana et al., 2007). The growing interest in preparing new barbiturates prompted the present work. A barbiturate previously synthesized in our laboratory from 1-chloro-2,4-dinitrobenzene, barbituric acid and triethylamine has only one anion-cation pair in the asymmetric unit (Kalaivani et al., 2008; Kalaivani & Malarvizhi, 2009). However, the asymmetric unit of the title barbiturate (Scheme), prepared from 1-chloro-2,4,6-trinitrobenzene, barbituric acid and trimethylamine, comprises two sets of anion-cation moieties (Fig. 1). Two sets of R₂²(8) hydrogen bond motifs are noticed between the adjacent anions. The hydrogen bonds N9—H9···O8 and N5—H5···O16 form the first set of R₂²(8) motif and the hydrogen bonds N10—H10···O7 and N4—H4···O17 form the second set of R₂²(8) motif. The aggregations of these motifs form an infinite one dimensional anionic ribbon extending along [100] direction. To either side of the anionic ribbon the trimethylammonium cations are hydrogen bonded through N11—H11A···O9 and N12—H12A···O18 hydrogen bonds in the terminal positions as depicted in Fig. 2. Furthermore a number of weak C—H···O interactions (cf. Table 1) contribute to the three-dimensional coherence of the crystal structure.

Experimental

1-Chloro-2,4,6-trinitrobenzene (2.5 g, 0.01 mol) in 20 ml of absolute ethanol was mixed with barbituric acid (1.3 g, 0.01 mol) in 30 ml of absolute ethanol and heated to 40°C. Trimethylamine (3 ml ~0.05 mol) was then added and the mixture was shaken well for 2 hrs. Dark maroon red crystals obtained were filtered. The filtered crystals were powdered well and washed with 50 ml of dry ether and recrystallized from absolute ethanol (yield 80%; m.p. 245 °C). Good quality crystals, suitable for single-crystal X-ray studies were obtained by slow evaporation of the ethanolic solution of title compound at room temperature.