Unique charge ordering of manganese in a new mixed valent phosphate |
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Authors: | L Adam A Guesdon B Raveau |
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Institution: | aLaboratoire CRISMAT, ENSICAEN, UMR CNRS 6508, Université de Caen Basse-Normandie, 6 Boulevard du Maréchal Juin, 14050 CAEN Cedex, France |
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Abstract: | A new mixed-valent manganese phosphate, , has been synthesized using hydrothermal method. Its monoclinic C2/c structure (a=12.5506(16) Å, b=10.4816(18) Å, c=13.6723(10) Å, β=103.758(11)°) forms a 3D framework of MnO6 octahedra, MnO5 trigonal bipyramids, PO4 and PO3OH tetrahedra. The main structural feature of this phosphate deals with its Mn4O16]∞ chains running along , which are interconnected through PO4 and PO3OH tetrahedra, forming intersecting tunnels running along 110], and 001]. The geometry of the Mn4O16]∞ chains and the charge ordering of manganese in the latter are unique: they consist of trimeric units of divalent manganese “” alternating with single trivalent MnIIIO6 octahedra along . In each “” unit one central MnIIO6 octahedron shares two opposite edges with two MnIIO5 trigonal bipyramids. Along , one Mn(II) octahedron alternates with one Mn(III) octahedron by sharing one corner. The relationships between the structure of this unique charge ordered phosphate and other manganese phosphates are discussed. |
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Keywords: | Manganese phosphates Charge ordering Intersecting tunnel phosphates |
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