A series of 3,7‐dimethyl‐9‐amino‐3,7‐diazabicyclo[3.3.1]nonane‐9‐carbonitrile and 3,7‐dimethyl‐9‐amino‐3,7‐diazabicyclo[3.3.1]nonane‐9‐carboxamide N‐substituted have been synthesized and studied by 1H and 13C nmr spectroscopy and the crystal structure of 3,7‐dimethyl‐9‐benzylamino‐3,7‐diazabicyclo[3.3.1]nonane‐9‐carboxamide dihydrochloride (IVb·2HCl) has been determined by X‐ray diffraction. The compounds studied display in deuteriochloroform, dimethyl sulfoxide‐d6 and methanol‐d4 the same preferred flattened chair‐chair conformation with the methyl groups in equatorial position. The carboxamido group lies in a plane nearly perpendicular to the bispidine skeleton. The conformation and protonation sites of IVb·2HCl in the crystal state and in deuterium oxide solution are discussed.