Crystal structure of 3,5-dinitro-2-pyridone, C5H3NO(NO2)2

Abstract

Source of materialUnder stirring, 1.4 g (0.01 mol) 2-hydroxy-3-nitropyridine was dissolved in 2 ml fuming H 2SO4 (50 % SO3 content). 1.5 ml mixture ® = 1.6 g/ml) of oleum with fuming HNO 3 was added slowly and kept below 40°C. The solution was stirred at RT for 1 h and slowly rised to 90°C in 2 h, followed by keeping at 90°C for additional 4 h. The solution was cooled to RT and poured on 20 g ice. 1.05 g (75 %) pale yellow needles were obtained. Single crystals suitable for X-ray diffraction analysis were isolated after several weeks from aqueous solution (m.p. 175-176°C). DiscussionPyridone and hydroxypyridine are tautomeric organic molecules. The calculation of two tautomeric forms of unsubstituted hydroxypyridine, benzoid and quinoid structures, resulted in the difference of energies. The benzoid form is slightly more preferable than the quinoid form [1]. Nitropyridine and its derivatives have been paid much attention due to their practical applications: 2-hydroxy-3,5-dinitropyridine is extremely important as an intermediate for oxidative dyestuffs, medicines or agrochemicals [2]. Also some derivatives of the nitropyridine have nonlinear optics property [3]. A variety of substituted nitropyridine compounds are used as herbicidal chemicals to control the growth of undesired plants [4]. 2-Hydroxyl-3,5-dinitropyridine and its metal complexes have higher explosion temperature and lower sensitivity. So, they are used as energetic catalysts for solid propellants in order to adjust and improve their trajectory properties [5]. The atoms of nitropyridone moiety (including N3, O4, O5) display an almost coplanar configuration with a mean deviation to the least-squares plane of 0.0134 Å. The plane through N2, O2 and O3 has a dihedral angle of 12.5°with the above-mentioned plane. The C2N2, C2C3 and C4C5 distances are 1.462(3) Å, 1.363(4) Å and 1.360(3) Å, respectively, which agree well with the corresponding distance in compound 3-nitro-2-pyridone [6]. The distances 1.456(3) Å for C1C2 and 1.390(4) Å for C3C4 are slightly longer than the respective distances in 3-nitro-2-pyridone (1.439(3) Å and 1.371(4) Å, respectively), while the distances of 1.223(3) Å for C1O1 and 1.325(4) Å for C5N1 are slightly shorter than the corresponding distances in the same compound (1.236(3) Å and 1.339(4) Å, respectively) [6].

Bis(μ-3,5-dinitropyridin-2-olato)bis[tetraaqua(3,5-dinitropyridin-2-olato)barium(II)]

“…The bridging Ba-O bonds in the Ba 2 O 2 motif make an approximately regular parallelogram of the Ba and bridging O atoms, with a BaÁ Á ÁBa distance of 4.677 (2) Å . The mean C-O distance is slightly longer than that in the free ligand 1.223 (3) Å (Zhang et al, 2006), and indicative of the weakening of the carbonyl bond strength after coordination. The dimeric units are linked into a three-dimensional network by hydrogen bonds.…”

“…2-Hydroxyl-3,5dinitropyridine and its metal complexes are explosive and are used as energetic catalysts for solid propellants in order to adjust and improve their trajectory properties (Zhao et al, 2003). The crystal structure of the ligand 2-hydroxy-3,5dinitropyridine was reported last year (Zhang et al, 2006). The molecular structure, showing the atom-numbering scheme and displacement ellipsoids at the 40% probability level.…”

Control of supramolecular chirality in co-crystals of achiral moleculesviastacking interactions and hydrogen bonding

“…11,25 For the unsubstituted pyridine-2-one two polymorphic forms has been found, the first (CSD PYRIDO) contains dimers and the second (CSD PYRIDO12) chains. Finally, the DNP2O molecule itself crystallizes in the polar space group Pna2 1 (CSD JERVUY), 26 and molecules in crystal form H-bonded chains. It is important that the cyclicity of the amide fragment is essential, as acyclic secondary amines in trans conformation usually prefer translation for chain propagation.…”

“…b Roomtemperature data from the crystal structure of pure DNP2O, CSD refcode JERVUY. 26 c Data for two NFT co-crystals with two different compositions. d Data for crystallographically independent of co-former molecules.…”

Research Progress on the Synthesis of Energetic Pyridines

“…(2)生成热高, 代表性化合物有 CL-20, TNAZ, FOX-7, 富氮杂环含能离子盐等 [82] . 近年来, 由于富氮杂环含能 物具有相对良好的热稳定性和性能特点, 但因吡啶环中 的氮元素含量偏低, 故被选择作吡啶含能离子盐的前体 化合物较少, 仅有 2-羟基-3,5-二硝基吡啶(2HDNP), 4-羟基-3,5-二硝基吡啶(4HDNP), 4-羟基-3.5-二硝基吡啶 氮氧化物(4HDNPO)等 [93,94] . 郑玉梅等 [95]…”