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The title compound, (C3H10N2)2[AlF6]F·3H2O, was obtained using the solvothermal method with aluminium hydroxide, HF and propane-1,3-di­amine as precursors in ethanol as solvent. The structure consists of isolated [AlF6]3- octa­hedra, diprotonated propane-1,3-di­amine cations [(H2dap)2+], free fluoride ions and water mol­ecules of solvation. The Al-F bond lengths in the octa­hedral [AlF6]3- anions range from 1.7690 (19) to 1.8130 (19) Å, with an average value of 1.794 Å. Each [AlF6]3- anion is surrounded by three water mol­ecules and by six diprotonated amine cations. The `free' fluoride ion is hydrogen bonded to four H atoms belonging to four dications and has a distorted tetra­hedral geometry. The three water mol­ecules are connected by hydrogen bonds, forming trimers that connect the AlF6 octa­hedra and dications into a three-dimensional framework.

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In the crystal structure of bis­(propane-1,3-di­ammonium) hexa­fluorido­aluminate di­aqua­tetra­fluorido­aluminate tetra­hydrate, two different environments of the Al3+ cations are observed, namely, AlF6 and AlF4(H2O)2.
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