Synthesis, characterization, and energetic properties of salts of the 1-cyanomethyl-1,1-dimethylhydrazinium cation

1,1-Dimethylhydrazine can be readily alkylated with bromoacetonitrile to form 1-cyanomethyl-1,1-dimethylhydrazinium bromide ([(CH(3))(2)N(CH(2)CN)NH(2)]Br, 1). The metathesis reaction of compound 1 led to the formation of a new family of energetic salts based on the [(CH(3))(2)N(CH(2)CN)NH(2)](+) cation and nitrate (2), perchlorate (3), azide (4), 5-aminotetrazolate ([H(2)N-CN(4)](-), 5), 5,5'-azobistetrazolate ([N(4)C-N=N-CN(4)](2-), 7), and picrate (8) anions. The new materials were characterized by elemental analysis, mass spectrometry, and (multinuclear) NMR and vibrational (infrared and Raman) spectroscopies. Additionally, the molecular structure of the [(CH(3))(2)N(CH(2)CN)NH(2)](+) cation in compounds 1, 3, and 8 and that of sodium 5,5'-azobistetrazolate octahydrate (NaZT·8H(2)O) were solved by X-ray diffraction techniques. The hydrogen-bonding networks found in the structure of salts 1, 3, 8, and NaZT·8H(2)O are described using graph-set analysis. The melting and decomposition points of the new compounds were determined by differential scanning calorimetry, and insight into their sensitivity towards impact, friction, and electrostatics was gained by submitting the materials to standard tests. Furthermore, we estimated some performance parameters of interest and predicted the decomposition gases formed upon decomposition of salts 2-8 and of mixtures with an oxidizer. The interesting thermal, sensitivity, and performance properties of some of the compounds described in this work make them attractive towards a prospective energetic application.