Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT)₂(PA)₂] and [Cu(DAT)₂(HTNR)₂] with nitrogen rich 1,5-diaminotetrazole (DAT)

Abstract

2015)Synthesis, structure, and thermal decomposition of two copper coordination compounds [Cu(DAT) 2 (PA) 2 ] and [Cu(DAT) 2 (HTNR) 2 ] with nitrogen rich 1,5-diaminotetrazole (Two similar complexes combined with 1,5-diaminotetrazole (DAT) and copper trinitrophenol were characterized by elemental analysis, FT-IR spectroscopy and single crystal X-ray diffraction and the sensitivity were studied.Both [Cu(DAT) 2 (PA) 2 ] (1) and [Cu(DAT) 2 (HTNR) 2 ] (2) were prepared from 1,5-diaminotetrazole (DAT) and copper trinitrophenol, 1 for picrate (PA) and 2 for styphnate acid (2,4,6-trinitro resorcinol, TNR), and were characterized by elemental analysis, FT-IR spectroscopy, and single crystal X-ray diffraction. The space group of these compounds is P2 1 /c (monoclinic). The lattice parameters are similar [a = 11.405(3) Å, b = 14.867(3) Å, c = 8.099(2) Å for 1 and a = 12.262(3) Å, b = 14.900(3) Å, c = 7.243(2) Å for 2], except the β = 106.257(3)°in 1 and β = 92.989(4)°in 2. Both have extended structures due to hydrogen bonds, but there are some differences because of the ligands induced effect. Differential scanning calorimetry analysis shows that two exothermic processes take place in both complexes, the first peak temperatures are 488.2 K for 1 and 519.2 K Downloaded by [University of Western Ontario] at 04:29 06 February 2015 for 2. The kinetic parameters of the first exothermic process were studied by using Kissinger's method and Ozawa's method, in which the enthalpy of formation (−7346 and −5706 kJ M −1 ), critical temperature of thermal explosion (475.0 and 515.8 K), entropy of activation (ΔS ≠ ), enthalpy of activation (ΔH ≠ ), and free energy of activation (ΔG ≠ ) were calculated and obtained as −117.25 J K −1 M −1 , 140.64 kJ M −1 , 196.44 kJ M −1 and −219.1 J K −1 M −1 , 383.56 kJ M −1 , 495.34 kJ M −1 for 1 and 2, respectively. The sensitivity test results showed that both compounds were sensitive to impact (<5 J) and flame (>20 cm) rather than friction.

High-Energy Metal–Organic Frameworks with a Dicyanamide Linker for Hypergolic Fuels

“…The volumetric energy density of HEMOF- 3 is 51.3 kJ·cm –3 , which is 2.6 times that of previous reported hypergolic Co­(AIM) 2 (19.5 kJ·cm –3 ) . The energy densities of MOFs- 1 – 3 are also far greater than some energetic coordination compounds with DAT as ligand, − such as Cu­(DAT) 2 (PA) 2 (10.2 kJ·g –1 ) and Cu­(DAT) 2 (HTNR) 2 (7.6 kJ·g –1 ). This fully shows that the energy of MOFs with mixed linkers is much higher than that of ordinary energetic coordination compounds.…”

A Smart Access to the Dinitramide Anion – The Use of Dinitraminic Acid for the Preparation of Nitrogen‐Rich Energetic Copper(II) Complexes

“…The crystalline materials were filtered off, washed with a small amount of ice-cold water when necessary and dried in air overnight. The use of other common monotetrazoles such as 1amino-5H-tetrazole, [17] 1,5-dimethyltetrazole, [23] 1,5diaminotetrazole, [24] and 1-methyl-5-aminotetrazole [25] or ditetrazoles such as di(tetrazol-2-yl)propane, [9b] which have already been successfully used as ligands, did not result in isolable crystalline ECC. One factor that could play a crucial role here is that in our synthesis we were limited to the solvent water because of the ion exchange and could not use organic solvents such as acetonitrile.…”

Thermochemistry, Tautomerism, and Thermal Decomposition of 1,5-Diaminotetrazole: A High-Level ab Initio Study

“…Nitrogen-rich heterocyclic compounds are promising components of environmental friendly energetic compositions. − Among them, 1,5-diaminotetrazole (DAT, 1 ) is prominent due to its good thermal stability and high nitrogen content (∼84 wt %). − Besides that, DAT is widely used as a building block for a huge variety of novel high-energy compounds. − …”