Abstract: Two N-amino energetic compounds—1-amino-4, 4', 5, 5'-tetranitro-2, 2'-biimidazole(ATNBI) and 1, 1'-diamino-4, 4', 5, 5'-tetranitro-2, 2'-biimidazole(DATNBI) were synthesized via N-amination using 4, 4', 5, 5'-tetranitro-2, 2'-biimidazole dehydrate (TNBI·2H₂O) as the raw material. The structures of the target compounds were confirmed by IR spectra, ¹H NMR, ¹³C NMR and elemental analysis. The single crystal of DATNBI was obtained, and its structure was analyzed. Furthermore, the thermal stability of DATNBI was tested by differential scanning calorimetry (DSC), and the two thermal decomposition peak temperatures of DATNBI were 255.8 ℃ and 268.8 ℃, respectively. Based on the crystal density and calculated (CBS-4M) solid-phase heat of DATNBI formation, the detonation parameters such as detonation velocity and pressure were calculated using Kamlet-Jacobs equations. The results are the crystal density = 1.933 g·cm^-3, detonation velocity = 8.860 km·s^-1, detonation pressure = 37.0 GPa and the heat of formation = 374.0 kJ·mol^-1, which esults indicate that DATNBI is a high energy density material with preferable detonation properties.