Solvatothermal syntheses and structural characterizations of polyoxoalkoxometalates:: The heptanuclear [{Fe(OH)(CH3CN)2}Fe6OCl6{(OCH2)3CCH2OH}4], the decanuclear [Fe10O2Cl8{(OCH2)3CCH2CH3}6], and the bimetallic [(VO)2F8O2Cl6{(OCH2)3CCH2CH3}6]

Solvatothermal syntheses have been exploited to effect the isolation of three novel polyoxoalkoxometalate clusters, [{Fe(OH)(CH3CN)(2)} Fe6OCl6{(OCH2)(3) CCH2OH}(4)] (1), [Fe10O2Cl8{(OCH2)(3)CCH2CH3}(6)] (2), and [(VO)(2)Fe8O2 Cl-6{(OCH2)(3)CCH2CH3}(6)] (3). The structure of 1 may be described as hexametalate core {Fe6OCl6}(10+), consisting of a octahedral arrangement of chloride ligands encasing an octahedron of six Fe(III) sites, with a central oxo group. The remaining four coordination sites at each octahedral iron center are occupied by doubly bridging oxygen donors from the trisalkoxo ligands. One triangular face of this substructure, defined by three oxygen atoms, from three adjacent trisalkoxo ligands, is capped by the {Fe(OH)(CH3CN)(2)}(2+) subunit. The structure of 2 is based on the decametalate core of edge-sharing octahedra. The eight peripheral Fe(III) sites of the cluster bond to four oxygen donors from the trisalkoxo ligands, a terminal Cl- ligand, and one of the mu (6)-oxo groups. The two central iron sites are linked to four oxygen donors from the trisalkoxo ligands and to both of the mu (6)-oxo groups. Cluster 3 is structurally related to 2 with two {FeCl}(2+) units replaced by {VO}(2+) groups.