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Li2AgGa crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Li2AgGa ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to one Ag and one Ga atom. The Li–Ag bond length is 2.60 Å. The Li–Ga bond length is 2.78 Å. Ag is bonded in a linear geometry to two equivalent Li atoms. Ga is bonded in a linear geometry to two equivalent Li atoms.
Li2AgGa is Zintl Phase-derived structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. there are two inequivalent Li sites. In the first Li site, Li is bonded to six equivalent Ag and four equivalent Ga atoms to form distorted LiGa4Ag6 tetrahedra that share corners with eighteen LiAg4 tetrahedra and faces with sixteen LiGa4Ag6 tetrahedra. All Li–Ag bond lengths are 3.16 Å. All Li–Ga bond lengths are 2.73 Å. In the second Li site, Li is bonded to four equivalent Ag atoms to form distorted LiAg4 tetrahedra that share corners with twenty-four LiAg4 tetrahedra and faces with four equivalent LiGa4Ag6 tetrahedra. All Li–Ag bond lengths are 2.73 Å. Ag is bonded in a 8-coordinate geometry to ten Li and four equivalent Ga atoms. All Ag–Ga bond lengths are 2.73 Å. Ga is bonded in a distorted body-centered cubic geometry to four equivalent Li and four equivalent Ag atoms.