2-Nitrimino-5,6-dinitrobenzimidazole (1) was synthesized by nitration of 2-aminobenzimidazole at ambient temperature in good yield. In order to explore new insensitive explosives four energetic nitrogen-rich 1:1 salts such as the guanidinium (1a), aminoguanidinium (1b), triaminoguanidinium (1c) and hydroxylammonium (1d) were synthesized either by facile acid/base or in situ metathesis reaction. In addition 2-nitrobenzimidazole (2) was synthesized by the reaction of 2-aminobenzimidazole using potassium hyperoxide in THF. Different nitration methods were tested to obtain a theoretically 2,4,5,6,7-pentanitrobenzimidazole but only the already known 4,5,6,7-tetranitrobenzimidazol-2-one (3) could be isolated. All synthesized compounds were characterized especially by low temperature X-ray diffraction, CHN elemental analysis and H-1 and C-13 NMR spectroscopy. The heat of formation of all new synthesized compounds was calculated using CBS-4M electronic enthalpies in combination with the atomization method to calculate their detonation parameters with the EXPLO 5 V5.05 computer code.