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LiHF2 crystallizes in the trigonal R-3m space group. The structure is three-dimensional. Li1+ is bonded to six equivalent F1- atoms to form edge-sharing LiF6 octahedra. All Li–F bond lengths are 2.05 Å. H1+ is bonded in a linear geometry to two equivalent F1- atoms. Both H–F bond lengths are 1.15 Å. F1- is bonded in a 4-coordinate geometry to three equivalent Li1+ and one H1+ atom.
LiHF2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Li1+ is bonded to two equivalent H1+ and six equivalent F1- atoms to form a mixture of distorted corner and edge-sharing LiH2F6 hexagonal bipyramids. Both Li–H bond lengths are 1.69 Å. There are two shorter (1.79 Å) and four longer (2.29 Å) Li–F bond lengths. H1+ is bonded in a distorted linear geometry to two equivalent Li1+ and two equivalent F1- atoms. Both H–F bond lengths are 1.14 Å. F1- is bonded in a distorted single-bond geometry to three equivalent Li1+ and one H1+ atom.
LiHF2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Li1+ is bonded to six equivalent F1- atoms to form edge-sharing LiF6 octahedra. There are two shorter (2.00 Å) and four longer (2.04 Å) Li–F bond lengths. H1+ is bonded in a linear geometry to two equivalent F1- atoms. Both H–F bond lengths are 1.14 Å. F1- is bonded to three equivalent Li1+ and one H1+ atom to form a mixture of distorted corner and edge-sharing FLi3H trigonal pyramids.