New extended clusters in ternary molybdenum oxides

R. E. McCarley, K. H. Lii, P. A. Edwards, L. F. Brough

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Three new compounds representative of different structure types in the family of ternary metal oxides with extended metal-metal bonded arrays are discussed. InMo4O6 (isomorphous with NaMo4O6) contains infinite anion chains of condensed octahedral cluster units, (Mo4O6-), crosslinked to form channels where In+ cations reside in sites of square pyramidal coordination to oxygen. The linear array of In atoms in the channels, with d(In-In)=2.8628(4) Å, suggests some degree of In-In bonding, and these interactions may contribute to the metallic conductivity determined for this compound over the range 2-300 K. Infinite chains with Mo2O4 repeat units condensed as rhomboidal clusters fused on opposite edges are the outstanding structural feature of NaMo2O4. The compound also has a doublelayer lattice MoO2 with Na+ ions fractionally occupying octahedral coordination sites between alternate layers. The compound Ca5.45Mo18O32 contains three different kinds of cluster chains with Mo1, Mo2, and Mo4 repeat units. Metal cluster electron counts on the three different repeat units, estimated from Mo-O bond strength-bond distance relations, are reflected in the formula Ca5.45(MoO32.26-)2(Mo2 O3.50.22-)4(Mo4O62.65-)2.

Original languageEnglish
Pages (from-to)17-24
Number of pages8
JournalJournal of Solid State Chemistry
Issue number1
StatePublished - 15 Mar 1985


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