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Crystal growth and crystal structures of six novel phases in the Mn/As/O/Cl(Br) system, as well as magnetic properties of α-Mn 3 (AsO 4 ) 2

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Abstract Chemical vapour transport reactions (900 °C → 820 °C, Cl2 or Br2 as transport agent) of in situ formed Mn3(AsO4)2 yielded the orthoarsenates(V) α-Mn3(AsO4)2 and β-Mn3(AsO4)2 as well as the oxoarsenate(V) halide compounds… Click to show full abstract

Abstract Chemical vapour transport reactions (900 °C → 820 °C, Cl2 or Br2 as transport agent) of in situ formed Mn3(AsO4)2 yielded the orthoarsenates(V) α-Mn3(AsO4)2 and β-Mn3(AsO4)2 as well as the oxoarsenate(V) halide compounds Mn7(AsO4)4Cl2, Mn11(AsO4)7Cl, Mn11(AsO4)7Br and Mn5(AsO4)3Cl. The crystal structures of all six phases were determined from single crystal X-ray diffraction data. The crystal structures of α-and β-Mn3(AsO4)2 are isotypic with the corresponding phosphate phases γ- and α-Mn3(PO4)2, respectively, and are reported here for the first time. A comparative discussion with other structures of general composition M3(AsO4)2 (М = Mg; divalent first-row transition metal) is given. The unique crystal structures of Mn7(AsO4)4Cl2 and that of the two isotypic Mn11(AsO4)7X (X = Cl, Br) structures are composed of two [MnO5] polyhedra, two [MnO4Cl2] polyhedra (one with site symmetry 1 ¯ ), two AsO4 tetrahedra, and one [MnO5] polyhedron, three [MnO6] octahedra (one with site symmetry.m.), one [MnO4X], one [MnO5X] polyhedron and four AsO4 tetrahedra, respectively. The various polyhedra of the three arsenate(V) halides are condensed into three-dimensional framework structures by corner- and edge-sharing. Mn5(AsO4)3Cl adopts the chloroapatite structure. The magnetic and thermal properties of pure polycrystalline samples of a-Mn3(AsO4)2 were investigated in more detail. The magnetic susceptibility proves all Mn atoms to be in the oxidation state +2 yielding an effective magnetic moment per Mn atom of 5.9 μB. Long-range antiferromagnetic ordering is observed below 8.2 K consistent with the negative Curie-Weiss temperature of −50 K derived from the high temperature susceptibility data.

Keywords: crystal growth; mn3 aso4; structures six; crystal structures; aso4; mn11 aso4

Journal Title: Journal of Solid State Chemistry
Year Published: 2017

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