A MIXED-VALENT MOLYBDENUM MONOPHOSPHATE WITH A BUTTERFLY-SHAPED TUNNEL STRUCTURE CS6MO7O9(PO4)7.H2O

被引:14
作者
GUESDON, A
BOREL, MM
LECLAIRE, A
GRANDIN, A
RAVEAU, B
机构
[1] Laboratoire CRISMAT, Associé au CNRS, ISMRA, 1450 Caen Cedex, Boulevard Marechal Juin
关键词
D O I
10.1006/jssc.1994.1233
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A new mixed-valent molybdenum monophosphate Cs6Mo7O9(PO4)7 . H2O has been isolated by solid state chemistry, It crystallizes in the space group Pnma with a = 10.084(1) angstrom, b = 21.297(3) angstrom, c = 17.491(1) angstrom. Its framework [Mo7P7O37]infinity consists of two kinds of structural units formulated Mo4P6O30 and Mo3PO16. The Mo4P6O30 units are built up from two edge-sharing MoO6 octahedra sharing their corners with two other MoO6 octahedra and six PO4 tetrahedra, whereas the Mo3PO16 units, which also exhibit two edge-sharing octahedra, can be derived from the first type of units by removing one octahedron and five tetrahedra. The structure can then be described by the association of [Mo4P6O28]infinity layers, built up of corner-sharing Mo4P6O30 units, with [Mo3PO15]infinity chains, built up of corner-sharing Mo3PO16 units. A comparison with leucophosphite is made. The host lattice [Mo7P7O37]infinity delimits two kinds of tunnels running along a: a large butterfly-shaped tunnel where the Cs+ ions and H2O molecules are located, and smaller tunnels occupied by Cs+ ions only. Besides these tunnels, cages are also obtained, fully occupied by Cs+ ions. The ordered distribution of Mo(V) and Mo(IV) species is also demonstrated: Mo(V) sits in MoO6 octahedra that exhibit one free apex, whereas Mo(IV) sits in the edge-sharing octahedra of the MoP6O30 units. (C) 1994 Academic Press, Inc.
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页码:315 / 321
页数:7
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