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SmAg is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Sm is bonded in a body-centered cubic geometry to eight equivalent Ag atoms. All Sm–Ag bond lengths are 3.22 Å. Ag is bonded in a body-centered cubic geometry to eight equivalent Sm atoms.
SmAg(WO4)2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Sm3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Sm–O bond distances ranging from 2.38–2.61 Å. There are two inequivalent W6+ sites. In the first W6+ site, W6+ is bonded to six O2- atoms to form distorted edge-sharing WO6 octahedra. There are a spread of W–O bond distances ranging from 1.82–2.14 Å. In the second W6+ site, W6+ is bonded to six O2- atoms to form distorted edge-sharing WO6 octahedra. There are a spread of W–O bond distances ranging from 1.81–2.22 Å. Ag1+ is bonded in a 2-coordinate geometry to eight O2- atoms. There are a spread of Ag–O bond distances ranging from 2.37–3.01 Å. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to one Sm3+, two W6+, and one Ag1+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Sm3+, one W6+, and one Ag1+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Sm3+, one W6+, and one Ag1+ atom. In the fourth O2- site, O2- is bonded to three W6+ and one Ag1+ atom to form distorted edge-sharing OAgW3 tetrahedra. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent Sm3+, one W6+, and one Ag1+ atom.