Two novel metal phosphonates, Al(5)F(C(4)H(9)PO(3))(6)(OH)(2)(C(4)N(2)H(6))(2) and Ga(4)F(2)(C(4)H(9)PO(3))(8)H(5).(C(7)N(2)H(11)) have been prepared using an ionothermal approach and their structures solved using single-crystal X-ray diffraction. In , the breakdown of the ionic liquid solvent has occurred and a fragment of the cation coordinates to the aluminium in the structure. In , the ionic liquid cation acts as the template and is occluded. Compound is a chain structure while compound is molecular, unlike the vast majority of hydrothermally synthesised phosphonates, which are layered.