Two new high-nitrogen energetic compounds $ZTO{cdot}2H_2O$ and $ZTO(phen){cdot}H_2O$ have been synthesized (where ZTO = 4,4-azo-1,2,4-triazol-5-one and phen = 1,10-phenanthroline). The crystal structure, elemental analysis and IR spectroscopy are presented. Compound 1 $ZTO{cdot}2H_2O$ crystallizes in the orthorhombic crystal system with space group Pnna and compound 2 $ZTO(phen){cdot}H_2O$ in the triclinic crystal system with space group P-1. In $ZTO(phen){cdot}H_2O$, there is intermolecular hydrogen bonds between the -NH group of ZTO molecule (as donor) and N atom of phen molecule (as acceptor). Thermal decomposition process is studied by applying the differential scanning calorimetry (DSC) and thermo thermogravimetric differential analysis (TG-DTG). The DSC curve shows that there is one exothermic peak in $ZTO{cdot}2H_2O$ and $ZTO(phen){cdot}H_2O$, respectively. The critical temperature of thermal explosion ($T_b$) for $ZTO{cdot}2H_2O$ and $ZTO(phen){cdot}H_2O$ is $282.21^{circ}C$ and $195.94^{circ}C$, respectively.