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BaAg crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Ba is bonded in a 7-coordinate geometry to seven equivalent Ag atoms. There are a spread of Ba–Ag bond distances ranging from 3.51–3.71 Å. Ag is bonded in a 9-coordinate geometry to seven equivalent Ba and two equivalent Ag atoms. Both Ag–Ag bond lengths are 3.02 Å.
BaAg2 is hexagonal omega structure structured and crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Ba is bonded to twelve equivalent Ag atoms to form a mixture of edge and face-sharing BaAg12 cuboctahedra. There are a spread of Ba–Ag bond distances ranging from 3.58–3.60 Å. Ag is bonded in a 9-coordinate geometry to six equivalent Ba and three equivalent Ag atoms. All Ag–Ag bond lengths are 2.85 Å.
Ba3Ag2 crystallizes in the trigonal R-3 space group. The structure is three-dimensional. there are three inequivalent Ba sites. In the first Ba site, Ba is bonded in an octahedral geometry to six equivalent Ag atoms. All Ba–Ag bond lengths are 3.58 Å. In the second Ba site, Ba is bonded in a 6-coordinate geometry to six equivalent Ag atoms. There are three shorter (3.47 Å) and three longer (3.56 Å) Ba–Ag bond lengths. In the third Ba site, Ba is bonded in a 4-coordinate geometry to five equivalent Ag atoms. There are a spread of Ba–Ag bond distances ranging from 3.54–4.22 Å. Ag is bonded in a 9-coordinate geometry to eight Ba and one Ag atom. The Ag–Ag bond length is 3.09 Å.
BaAg5 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Ba is bonded in a 6-coordinate geometry to eighteen Ag atoms. There are six shorter (3.46 Å) and twelve longer (3.77 Å) Ba–Ag bond lengths. There are two inequivalent Ag sites. In the first Ag site, Ag is bonded in a 12-coordinate geometry to three equivalent Ba and six equivalent Ag atoms. All Ag–Ag bond lengths are 2.87 Å. In the second Ag site, Ag is bonded to four equivalent Ba and eight Ag atoms to form a mixture of edge, face, and corner-sharing AgBa4Ag8 cuboctahedra. All Ag–Ag bond lengths are 2.99 Å.