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RbHF2 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Rb1+ is bonded in a 8-coordinate geometry to eight equivalent F1- atoms. All Rb–F bond lengths are 2.96 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 single-bond geometry to four equivalent Rb1+ and one H1+ atom.
RbHF2 crystallizes in the orthorhombic Ima2 space group. The structure is three-dimensional. Rb1+ is bonded in a 8-coordinate geometry to eight F1- atoms. There are a spread of Rb–F bond distances ranging from 2.91–3.05 Å. H1+ is bonded in a linear geometry to two F1- atoms. There is one shorter (1.14 Å) and one longer (1.16 Å) H–F bond length. There are two inequivalent F1- sites. In the first F1- site, F1- is bonded in a single-bond geometry to four equivalent Rb1+ and one H1+ atom. In the second F1- site, F1- is bonded in a single-bond geometry to four equivalent Rb1+ and one H1+ atom.