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Issue 9, 2017
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Crystal structure and spin-trimer magnetism of Rb2.3(H2O)0.8Mn3[B4P6O24(O,OH)2]

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Abstract

The novel borophosphate Rb2.3(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) Å3, 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 Rb2.3(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.

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

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Publication details

The article was received on 07 Nov 2016, accepted on 31 Jan 2017 and first published on 31 Jan 2017


Article type: Paper
DOI: 10.1039/C6DT04241D
Citation: Dalton Trans., 2017,46, 2957-2965
  • Open access: Creative Commons BY license
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    Crystal structure and spin-trimer magnetism of Rb2.3(H2O)0.8Mn3[B4P6O24(O,OH)2]

    O. V. Yakubovich, L. V. Shvanskaya, G. V. Kiriukhina, A. S. Volkov, O. V. Dimitrova, E. A. Ovchenkov, A. A. Tsirlin, A. A. Shakin, O. S. Volkova and A. N. Vasiliev, Dalton Trans., 2017, 46, 2957
    DOI: 10.1039/C6DT04241D

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