Partial hydrolysis of a sample of [Mg(dme)3][Al(hfip)4]2 crystals led to the formation of the title complex, [Mg(dme)2{HOAl(hfip)2OAl(hfip)3}] (dme = dimethoxyethane and hfipH = hexafluoroisopropanol) or [Mg(C4H10O2)2O(OH)Al2(C3HF6O)5]. The magnesium cation exhibits a distorted octahedral coordination with two bidentate dimethoxyethane molecules and a dinuclear aluminate anion, coordinated to Mg2+
via oxido and hydroxido units. The anion is an oxido-bridged species, [HOAl(hfip)2(μ-O)Al(hfip)3]2–, with one Al3+ cation tetrahedrally coordinated by an oxido (O2–) anion, a hydroxido anion, and two hfip groups, whereas the second Al3+ cation is coordinated by the oxido anion and three hfip groups.