Adducts of the Zinc Salt of Dinitramic Acid

Herein, we describe the synthesis of coordination compounds starting from carbohydrazide ((H2NHN)2C=O (CHZ)) and the Zn2+ salt of dinitramic acid (HDN), which are high-nitrogen substances that exhibit properties similar to those of a burning-rate inhibitor of pyrotechnic compositions. This study demonstrates that these compounds react with glyoxal to furnish adducts of metal–organic macrocyclic cages bearing the elements of carbohydrazide, complexing metals and the HDN anion, depending on the ratio of the starting reactants. The assembled macrocyclic cage has “host–guest” properties and is a safe container for the storage of HDN salts. X-ray crystallographic analysis of the resultant coordination compound, [Zn(chz)3(N(NO2)2)2]), indicated that the metal–ligand association occurs via the N and O atoms of carbohydrazide. The zinc salt of dinitramic acid, which is enclosed into adducts with a macrocycle, is thermally stable and insensitive to mechanical impacts. The complex zinc salt of dinitramide was shown herein to exhibit inhibitory activity towards the burning rate of pyrotechnic compositions.

[1]  S. Il’yasov,et al.  Macrocycle as a “Container” for Dinitramide Salts , 2022, Materials.

[2]  J. Kalman.  Are all solid propellant burning rate modifiers catalysts? , 2022, Propellants, Explosives, Pyrotechnics.

[3]  Sebastian Fischer,et al.  ADN Solid Propellants with High Burning Rates as Booster Material for Hypersonic Applications , 2022, Propellants, Explosives, Pyrotechnics.

[4]  U. Schaller,et al.  4‐Amino‐1‐Butyl‐1,2,4‐Triazolium Dinitramide – Synthesis, Characterization and Combustion of a Low‐Temperature Dinitramide‐Based Energetic Ionic Liquid (EIL) , 2022, Propellants, Explosives, Pyrotechnics.

[5]  Y. V. Gatilov,et al.  A novel energetic nickel coordination compound based on carbohydrazide and dinitramide , 2022, Mendeleev Communications.

[6]  Jie Kong,et al.  A Review on the Use of Burning Rate Suppressants in AP‐Based Composite Propellants , 2021 .

[7]  Maximilian H. H. Wurzenberger,et al.  A Smart Access to the Dinitramide Anion – The Use of Dinitraminic Acid for the Preparation of Nitrogen‐Rich Energetic Copper(II) Complexes , 2021, Chemistry.

[8]  Pratima Kumar.  An overview over dinitramide anion and compounds based on it , 2020, Indian Chemical Engineer.

[9]  K. Ghani,et al.  New Energetic Complex of Copper(II) Dinitramide Based Nitrogen‐rich Ligand Aminoguanidine(CH 6 N 4 ): Synthesis, Structural and Energetic Properties , 2019, Propellants, Explosives, Pyrotechnics.

[10]  Hongzhen Li,et al.  Synthesis, characterization and properties of a novel energetic ionic salt: dicarbohydrazide bis[3-(5-nitroimino-1,2,4-triazole)] , 2019, New Journal of Chemistry.

[11]  I. Eltsov,et al.  A New Synthetic Route to Heteroanthracenes , 2018 .

[12]  D. Trache,et al.  Effect of amide-based compounds on the combustion characteristics of composite solid rocket propellants , 2015 .

[13]  G. Sheldrick.  Crystal structure refinement with SHELXL , 2015, Acta crystallographica. Section C, Structural chemistry.

[14]  Jason Hall,et al.  Advances in Spacecraft Technologies , 2014 .

[15]  T. Klapötke,et al.  Transition metal complexes of 3-amino-1-nitroguanidine as laser ignitible primary explosives: structures and properties. , 2013, Inorganic chemistry.

[16]  L. Mishra,et al.  Template Synthesis of Macrocyclic Complexes of Bivalent CoII, NiII, PdII,ZnII and CdII Ions with Cyclic Glyoxal Carbohydrazone (1,2,4,5,8,9,11,12-octaazacyclotetradeca-5,7,12,14-tetraene-3,10-dione) , 2012 .

[17]  T. Klapötke,et al.  Explosives Based on Diaminourea , 2011 .

[18]  Niklas Wingborg,et al.  Green Propellants Based on Ammonium Dinitramide (ADN) , 2011 .

[19]  T. Klapötke,et al.  Synthesis and Characterization of 3,5-Diamino-1,2,4-triazolium Dinitramide , 2010 .

[20]  A. Lobanova,et al.  Application of dinitramide salts (Review) , 2009 .

[21]  Ruihu Wang,et al.  Nitrogen-rich nitroguanidyl-functionalized tetrazolate energetic salts. , 2009, Chemical communications.

[22]  T. Klapötke,et al.  Azidoformamidinium and 5-aminotetrazolium dinitramide-two highly energetic isomers with a balanced oxygen content. , 2009, Dalton transactions.

[23]  Li Yang,et al.  Synthesis, crystal structure and thermal decomposition character of [Zn(CHZ)3][C(NO2)3]2 · (H2O)2 (CHZ = Carbohydrazide) , 2008 .

[24]  B. Twamley,et al.  Energetic mono and dibasic 5-dinitromethyltetrazolates: synthesis, properties, and particle processing , 2007 .

[25]  M. Akiyoshi,et al.  The Thermal Behavior of the Zinc Complexes as a Non‐Azide Gas Generant for Safer Driving — Zn Complexes of the Carbohydrazide and Semicarbazide , 2000 .

[26]  R. Butcher,et al.  A new class of flexible energetic salts, part 4: The crystal structures of hexaaquomagnesium(II), hexaaquomanganese(II), and hexaaquozinc(II) dihydrate salts of dinitramide , 1998 .

[27]  O. A. Luk’yanov,et al.  Dinitramide and its salts , 1994 .

[28]  V. A. Tartakovskii,et al.  Dinitramide and its salts , 1994 .