Influences of secondary metal-ligand subunits on molybdenum oxide structures: The hydrothermal syntheses and structures of [M(tpytrz)2Mo4O13] (M = Fe, Co, Ni, Zn; tpytrz = tripyridyltriazine), [Ni(tpytrz)Mo2O7] and [Zn2(tpytrz)Mo2O8]

Jr Rarig R.S., Jon A Zubieta

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Abstract

The hydrothermal reactions of the appropriate salts of the first row transition metal dipositive cations M′(II), MoO3 and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpytrz) yielded the bimetallic oxide hybrid solids [M′(tpytrz)2Mo4O13] [M′ = Fe (1), Co (2), Ni (3), Zn (4)], [Ni(tpytrz)Mo2O7] (6) and [Zn2(tpytrz)Mo2O8] (7) and the molecular compound [Ni(H2O)4-(Htpytrz)2][Mo8O 26]·1.2H2O (5·1.2H2O). The isomorphous series 1-4 exhibits a two-dimensional bimetallic oxide network constructed from chains of corner-sharing Mo(VI) octahedra and tetrahedra, linked by {M′O4N2} octahedra. The inorganic layers are tethered by bidentate tpytrz ligands, each of which bonds to an M′ site of one layer and an octahedral {MoO5N} site of an adjacent layer, with one pyridyl group adopting a pendant mode in the interlamellar region. In contrast, the structure of [Ni(tpytrz)Mo2O7] (6), while adopting the prototypical motif of alternating bimetallic oxide networks and bridging ligand domains, is characterized by an oxide layer constructed from bimolybdate units {Mo2O7}2- linked through {NiO4N2} octahedra. Curiously, the {Zn2Mo2O8} network of [Zn2(tpytrz)Mo2O8] (7) is constructed from {MoO4} tetrahedra linked through binuclear units of edge-sharing {ZnO4N} square pyramids.

Original languageEnglish (US)
Pages (from-to)3446-3452
Number of pages7
JournalJournal of the Chemical Society - Dalton Transactions
Issue number23
StatePublished - 2001

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  • Chemistry(all)

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