Repeated methanolysis of [Zr3O](OPrn)(10) followed by extraction and crystallization from toluene yields material that is X-ray crystallographically indistinguishable from the compound previously formulated as [Zr13O8](OMe)(36). Elemental analysis and H-1 solution NMR spectroscopy strongly suggest that this material is a mixture of methyltriskaidecazirconates (MTZ) [Zr13O8](OMe)(x)(OH)(36-x) x(av) similar to 20, that readily cocrystallize from hydrocarbon solution. These species have the metal-oxygen framework structure reported for [Zr13O8](OMe)(36), where the 13 zirconium and 32 bridging oxygen atoms comprise a fragment of the fluorite structure adopted by ZrO2 at elevated temperatures. Ethanolysis of [Zr3O](OPrn)(10) yields its ethyl analogue, [Zr3O](OEt)(10). Both trizirconates display temperature-dependent H-1 solution NMR spectra that are interpreted mechanistically in terms of rearrangement mechanisms involving trigonal twists at the octahedral zirconium centers.