Synthesis of titanium fluorophosphates and fluorosulfates from hexafluorotitanic acid

Three new titanium-based network structures and an organic tetraazapentacenium [TiF6]2– salt were synthesized under high fluoride-concentration, hydrothermal conditions utilizing hexafluorotitanic acid as a starting material. The compositions of the new connected-structure phases obtained are CsTi2F2(PO4)(PO3F)2, [Imidazole-H][Ti3F2(PO3F)(PO4)3]·0.5H2O, and [DABCO-H][Ti(SO4)2(SO3(OH,F))]. CsTi2F2(PO4)(PO3F)2 has a sheet-like structure with interlayer Cs+ ions coordinated solely by fluoride ions, whereas [Imidazole-H] [Ti3F2(PO3F)(PO4)3]·0.5H2O has a three-dimensional framework structure with elliptical channels containing pairs of organic template molecules. The DABCO templated phase is isostructural with ferrinatrite with chains formed from titanium coordinated by six sulfate groups. Reactions using 1,2-phenylenediamine under these conditions surprisingly generates 5,12-dihydro-5,7,12,14-tetraazapentacenium cations, which crystallize as a salt with [TiF6]2–.