3-Nitroso-2-(2-nitrophenyl)imidazo [1.2-a] pyridine was converted to its diamino derivative (5) and the open-chain compound 2-N(2-pyridyl) benzimidoyl cyanide (6). Compound 5 was condensed with triethyl orthoformate or 2-chlorobenzaldehyde to afford the pyrido [1',2':1,2] imidazo [5,4-d] [1.3] benzodiazepines (7a, b). X-ray crystallographic analysis confirmed the structure of 7a. The structure of 7b was assigned by two-dimensional nuclear magnetic resonance techniques, 1 H− 1 H and 13 C− 1 H correlation spectroscopy