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NaHF2 crystallizes in the trigonal R-3m space group. The structure is three-dimensional. Na1+ is bonded to six equivalent F1- atoms to form edge-sharing NaF6 octahedra. All Na–F bond lengths are 2.34 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 1-coordinate geometry to three equivalent Na1+ and one H1+ atom.
NaHF2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. Na1+ is bonded in a 2-coordinate geometry to two equivalent H1+ and eight F1- atoms. There are one shorter (2.23 Å) and one longer (2.24 Å) Na–H bond lengths. There are a spread of Na–F bond distances ranging from 2.08–2.82 Å. H1+ is bonded in a distorted bent 150 degrees geometry to two equivalent Na1+ and two F1- atoms. Both H–F bond lengths are 1.13 Å. There are two inequivalent F1- sites. In the first F1- site, F1- is bonded in a 1-coordinate geometry to four equivalent Na1+ and one H1+ atom. In the second F1- site, F1- is bonded in a 1-coordinate geometry to four equivalent Na1+ and one H1+ atom.
NaHF2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. Na1+ is bonded in a 6-coordinate geometry to six F1- atoms. There are a spread of Na–F bond distances ranging from 2.30–2.48 Å. H1+ is bonded in a linear geometry to two F1- atoms. There is one shorter (1.14 Å) and one longer (1.15 Å) H–F bond length. There are two inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted single-bond geometry to three equivalent Na1+ and one H1+ atom. In the second F1- site, F1- is bonded in a distorted single-bond geometry to three equivalent Na1+ and one H1+ atom.