Abstract:N-Alkoxy-N-chlorocarbamates react with 4-dimethyl-aminopyridine yielding 1-alkoxyamino-4-dimethylamino-pyridinium chlorides, new type of O–N–N+ geminal systems. The XRD studies of two representative 1-alkoxyamino-pyridinium chlorides revealed the high pyramidal configuration of the central nitrogen atom in O–N–N+ geminal system.