Evidence of New Fluorinated Coordination Compounds in the Composition Space Diagram of FeF₃/ZnF₂–H<i>amtetraz</i>-HF_aq System

The exploration of the composition space diagram of the FeF₃/ZnF₂–H<i>amtetraz</i>-HF_aq system (H<i>amtetraz</i> = 5-aminotetrazole) by solvothermal synthesis at 160 °C for 72 h in dimethylformamide (DMF) has evidenced five new hybrid fluorides (<b>1</b>–<b>5</b>); the structures are characterized from single crystal X-ray diffraction data. [H<i>dma</i>]­·(ZnFe^III(H₂O)₄F₆) (<b>1</b>) and [H<i>dma</i>]­·[H<i>gua</i>]₂­·(Fe^IIIF₆) (<b>2</b>) contain anionic inorganic chains (<b>1</b>) or isolated octahedra (<b>2</b>) weakly hydrogen bonded (Class I hybrids) to dimethylammonium (H<i>dma</i>) and/or guanidinium (H<i>gua</i>) cations which are produced from the tetrazole ligand and solvent decomposition. [H<i>dma</i>]₂­·[H<i>gua</i>]­·[NH₄]­·[ZnFe^IIIF₅(<i>amtetraz</i>)₂]₂ (<b>3</b>), [H<i>dma</i>]₂­·[Zn_1.6Fe^II_0.4Fe^IIIF₆­(<i>amtetraz</i>)₃] (<b>4</b>), and [H<i>dma</i>]­·[Zn₄F₅(<i>amtetraz</i>)₄] (<b>5</b>) are considered as Class II hybrids in which the (<i>amtetraz</i>)⁻ anions are strongly linked to divalent metal cations via N–M bonds. In <b>3</b>, _∞{[NH₄]­·[ZnFe^IIIF₅­(<i>amtetraz</i>)₂]₂} layers are separated by [H<i>dma</i>]⁺ and [H<i>gua</i>]⁺ cations. <b>4</b> and <b>5</b> exhibit three-dimensional (3D) hybrid networks that contain small cavities where [H<i>dma</i>]⁺ cations are inserted. A porous 3D metal–organic framework intermediate is evidenced from the thermogravimetric analysis and X-ray thermodiffraction of <b>5