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Cd(AuF4)2 crystallizes in the tetragonal P4/mcc space group. The structure is three-dimensional. Au3+ is bonded in a square co-planar geometry to four equivalent F1- atoms. All Au–F bond lengths are 1.97 Å. Cd2+ is bonded in a 8-coordinate geometry to eight equivalent F1- atoms. All Cd–F bond lengths are 2.37 Å. F1- is bonded in a distorted bent 120 degrees geometry to one Au3+ and one Cd2+ atom.
Cd(AuF6)2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Au5+ is bonded to six F1- atoms to form AuF6 octahedra that share corners with three equivalent CdF6 octahedra. The corner-sharing octahedra tilt angles range from 45–48°. There are a spread of Au–F bond distances ranging from 1.92–1.99 Å. Cd2+ is bonded to six F1- atoms to form CdF6 octahedra that share corners with six equivalent AuF6 octahedra. The corner-sharing octahedra tilt angles range from 45–48°. There are two shorter (2.27 Å) and four longer (2.28 Å) Cd–F bond lengths. There are six inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one Au5+ and one Cd2+ atom. In the second F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one Au5+ and one Cd2+ atom. In the third F1- site, F1- is bonded in a single-bond geometry to one Au5+ atom. In the fourth F1- site, F1- is bonded in a single-bond geometry to one Au5+ atom. In the fifth F1- site, F1- is bonded in a distorted bent 120 degrees geometry to one Au5+ and one Cd2+ atom. In the sixth F1- site, F1- is bonded in a single-bond geometry to one Au5+ atom.