Synthesis and structure of ternary molybdenum oxides MMo8O10 (M = Li or Zn) having orthogonal nonintersecting octahedral cluster chains

Kwang Hwa Lii, Robert E. McCarley, Sangsoo Kim, Robert A. Jacobson

研究成果: 雜誌貢獻期刊論文同行評審

31 引文 斯高帕斯(Scopus)

摘要

The new compounds LiMo8O10 (I) and ZnMo8O10 (II) have been prepared via reactions in sealed Motubes at 1370-1450°C between Li2MoO4, MoO3, and Mo (3:16:29 mole ratio), and ZnO, MoO3, and Mo (1:3:5 mole ratio), respectively. The isomorphous compounds are tetragonal, space group I41md, Z = 4, with lattice constants a = 5.8515(6) Å, c = 24.783(3)Å for I, and a = 5.8961(4) Å, c = 24.840(3)Å for II, as determined from Guinier X-ray powder patterns. Single crystal structure determination shows that these compounds are constructed from infinite chains consisting of edge-shared octahedral cluster units. The structure can be viewed as a stacking along the c axis of layers consisting of parallel chains, with the chains in successive layers oriented alternately along the a and b axes. Intra- and interlayer crosslinking of the chains by MoOMo bonds is represented in the connective formula [(Mo2Mo 4 2O 6 2O 4 3)O 2 3] for the octahedral cluster subunits. MoMo bonding within the subunits is strong, but very irregular compared to analogous compounds containing such chains. Subunit MoMo bond order sums indicate that the bond distortions are effective in accommodating a higher electron count in metal-metal bonding states. It is shown that the structures are related to the spinel and rock salt structures through an ordered-defect arrangement of the Mo and O atoms.

原文???core.languages.en_GB???
頁(從 - 到)347-358
頁數12
期刊Journal of Solid State Chemistry
64
發行號3
DOIs
出版狀態已出版 - 10月 1986

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