Crystal structure and spin-trimer magnetism of Rb2.3(H2O)0.8Mn3[B4P6O24(O,OH)2]

Abstract

The novel borophosphate Rb_2.3(H₂O)_0.8Mn₃[B₄P₆O₂₄(O,OH)₂] was prepared under hydrothermal conditions at 553 K. Its crystal structure was determined using single-crystal X-ray diffraction data obtained from a non-merohedral twin and refined against F² to R = 0.057. The compound crystallizes in the orthorhombic space group Pbcn, with unit-cell parameters a = 20.076(2) Å, b = 9.151(1) Å, c = 12.257(1) Å, V = 2251.8(2) ų, and Z = 4. The title compound is the first example of a borophosphate with manganese ions adopting both octahedral and tetrahedral coordinations. Its unique crystal structure is formed by borophosphate slabs and chains of Mn²⁺-centered polyhedra sharing edges and vertices. These 2D and 1D fragments interconnect into a framework with open channels that accommodate Rb⁺ cations and water molecules. Topological relationships between borophosphates built from three-membered rings of two borate and one phosphate tetrahedra sharing oxygen vertices, amended by additional PO₄ and HPO₄ tetrahedra, are discussed. The temperature dependence of the magnetic susceptibility of Rb_2.3(H₂O)_0.8Mn₃[B₄P₆O₂₄(O,OH)₂] reveals predominant antiferromagnetic exchange interactions and the high-temperature effective magnetic moment corresponding to the high-spin S = 5/2 state of Mn²⁺ ions. At 12.5 K, a magnetic transition is evidenced by ac-susceptibility and specific heat measurements. A spin-trimer model with the leading exchange interaction J ∼ 3.2 K is derived from density-functional band-structure calculations and accounts for all experimental observations.