Abstract: | By adding piperazine to a hydrofluoric and phosphoric acid solution of Manganese(III) fluoride, the fluoride phosphate (pipzH2)MnF2(HPO4)(H2O)](H2PO4) can be crystallized. Its structure is built by piperazinium(2+) cations, (H2PO4)? anions, and an anionic double‐chain of HPO4] tetrahedra and MnO3F2(H2O)] octahedra. The structure is triclinic, space group P , Z = 2, a = 622.97(4), b = 923.46(6), c = 1183.62(7) pm, α = 98.343(6)°, β = 100.747(7)°, γ = 107.642(5)°, R = 0.0289. It is worth noting that a ferrodistortive Jahn‐Teller order is observed with MnO3F2(H2O)] octahedra strongly elongated along the F–Mn–OH2 axes perpendicular to the chain plane. The structure is stabilized by very strong hydrogen bonds. |