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SF4 is Silicon tetrafluoride-like structured and crystallizes in the tetragonal I-42m space group. The structure is zero-dimensional and consists of two sulfur tetrafluoride molecules. S4+ is bonded in a distorted trigonal pyramidal geometry to four equivalent F1- atoms. All S–F bond lengths are 1.73 Å. F1- is bonded in a single-bond geometry to one S4+ atom.
SF4 is beta-like structured and crystallizes in the orthorhombic P2_12_12_1 space group. The structure is zero-dimensional and consists of eight sulfur tetrafluoride molecules. S4+ is bonded in a rectangular see-saw-like geometry to four F1- atoms. There are a spread of S–F bond distances ranging from 1.58–1.72 Å. There are four inequivalent F1- sites. In the first F1- site, F1- is bonded in a single-bond geometry to one S4+ atom. In the second F1- site, F1- is bonded in a single-bond geometry to one S4+ atom. In the third F1- site, F1- is bonded in a single-bond geometry to one S4+ atom. In the fourth F1- site, F1- is bonded in a single-bond geometry to one S4+ atom.