A Variety of Phase‐Transition Behaviors in a Niccolite Series of [NH(3)(CH(2))(4)NH(3)][M(HCOO)(3)](2)

A niccolite series of [bnH(2) (2+)][M(HCOO)(3)](2) (bnH(2) (2+)=1,4‐butyldiammonium) shows four kinds of metal‐dependent phase transitions, from high temperature para‐electric phases to low‐temperature ferro‐, antiferro‐, glass‐like, and para‐electric phases. The conformational flexibility of bnH(2) (2+) and the different size, mass, and bonding character of the metal ion lead to various disorder‐order transitions of bnH(2) (2+) in the lattice and relevant framework modulations, thus different phase transitions and dielectric responses. The magnetic members display a coexistence or combination of electric and magnetic orderings in the low‐temperature region.