LiAg5F12 is Calcite-like structured and crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with eight equivalent Ag(2)F6 octahedra and edges with two equivalent Ag(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are three inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form AgF6 octahedra that share corners with four equivalent Ag(2)F6 octahedra, corners with four equivalent Ag(3)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Ag(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. In the second Ag site, Ag(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form AgF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Ag(1)F6 octahedra,  an edgeedge with one Ag(2)F6 octahedra, and  an edgeedge with one Ag(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. In the third Ag site, Ag(3) is bonded to two equivalent F(1) and four equivalent F(4) atoms to form a mixture of edge and corner-sharing AgF6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Ag(3) and two equivalent Ag(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Ag(1), and one Ag(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ag(2) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Ag(1), one Ag(2), and one Ag(3) atom.
LiAg5F12 is Calcite-like structured and crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with eight equivalent Ag(2)F6 octahedra and edges with two equivalent Ag(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both Li(1)-F(3) bond lengths are 2.03 Å. All Li(1)-F(2) bond lengths are 2.11 Å. There are three inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form AgF6 octahedra that share corners with four equivalent Ag(2)F6 octahedra, corners with four equivalent Ag(3)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Ag(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. Both Ag(1)-F(1) bond lengths are 2.32 Å. Both Ag(1)-F(2) bond lengths are 2.25 Å. Both Ag(1)-F(4) bond lengths are 2.05 Å. In the second Ag site, Ag(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form AgF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Ag(1)F6 octahedra,  an edgeedge with one Ag(2)F6 octahedra, and  an edgeedge with one Ag(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. Both Ag(2)-F(2) bond lengths are 2.05 Å. Both Ag(2)-F(3) bond lengths are 2.15 Å. Both Ag(2)-F(4) bond lengths are 2.23 Å. In the third Ag site, Ag(3) is bonded to two equivalent F(1) and four equivalent F(4) atoms to form a mixture of edge and corner-sharing AgF6 octahedra. The corner-sharing octahedral tilt angles are 55°. Both Ag(3)-F(1) bond lengths are 2.04 Å. All Ag(3)-F(4) bond lengths are 2.31 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Ag(3) and two equivalent Ag(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Ag(1), and one Ag(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ag(2) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Ag(1), one Ag(2), and one Ag(3) atom.