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CsHF2 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Cs1+ is bonded in a 8-coordinate geometry to eight equivalent F1- atoms. All Cs–F bond lengths are 3.15 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 Cs1+ and one H1+ atom.
CsH2F3 crystallizes in the orthorhombic P2_12_12_1 space group. The structure is three-dimensional. there are two inequivalent Cs1+ sites. In the first Cs1+ site, Cs1+ is bonded in a 10-coordinate geometry to two H1+ and eight F1- atoms. There are one shorter (3.13 Å) and one longer (3.25 Å) Cs–H bond lengths. There are a spread of Cs–F bond distances ranging from 3.01–3.30 Å. In the second Cs1+ site, Cs1+ is bonded in a 7-coordinate geometry to seven F1- atoms. There are a spread of Cs–F bond distances ranging from 3.05–3.31 Å. There are four inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a linear geometry to one Cs1+ and two F1- atoms. There is one shorter (1.04 Å) and one longer (1.30 Å) H–F bond length. In the second H1+ site, H1+ is bonded in a linear geometry to two F1- atoms. There is one shorter (1.02 Å) and one longer (1.34 Å) H–F bond length. In the third H1+ site, H1+ is bonded in a linear geometry to one Cs1+ and two F1- atoms. There is one shorter (1.03 Å) and one longer (1.30 Å) H–F bond length. In the fourth H1+ site, H1+ is bonded in a linear geometry to two F1- atoms. There is one shorter (1.02 Å) and one longer (1.33 Å) H–F bond length. There are six inequivalent F1- sites. In the first F1- site, F1- is bonded in a single-bond geometry to three Cs1+ and one H1+ atom. In the second F1- site, F1- is bonded in a single-bond geometry to three Cs1+ and one H1+ atom. In the third F1- site, F1- is bonded in a distorted bent 150 degrees geometry to two Cs1+ and two H1+ atoms. In the fourth F1- site, F1- is bonded in a single-bond geometry to three Cs1+ and one H1+ atom. In the fifth F1- site, F1- is bonded in a single-bond geometry to three Cs1+ and one H1+ atom. In the sixth F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one Cs1+ and two H1+ atoms.