A series of end-to-end azido-bridged perovskite-type compounds [(CH3)(n)NH4-n][Mn(N-3)(3)] (n = 1-4) were synthesized and characterized. Structural phase transitions indicating the general lattice flexibility were observed and confirmed by the crystal structures of different phases. These materials show cation-dependent magnetic ordering at up to 92 K and magnetic bistability near room temperature.