LiAgF2 crystallizes in the orthorhombic Pmn2_1 space group. Li(1) is bonded to one F(2) and three equivalent F(1) atoms to form LiF4 tetrahedra that share corners with six equivalent Li(1)F4 tetrahedra, corners with five equivalent Ag(1)F5 trigonal bipyramids, and  an edgeedge with one Ag(1)F5 trigonal bipyramid. Ag(1) is bonded to one F(1) and four equivalent F(2) atoms to form distorted AgF5 trigonal bipyramids that share corners with five equivalent Li(1)F4 tetrahedra, corners with four equivalent Ag(1)F5 trigonal bipyramids,  an edgeedge with one Li(1)F4 tetrahedra, and edges with four equivalent Ag(1)F5 trigonal bipyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Li(1) and one Ag(1) atom to form FLi3Ag tetrahedra that share corners with six equivalent F(1)Li3Ag tetrahedra, corners with five equivalent F(2)LiAg4 trigonal bipyramids, and  an edgeedge with one F(2)LiAg4 trigonal bipyramid. In the second F site, F(2) is bonded to one Li(1) and four equivalent Ag(1) atoms to form distorted FLiAg4 trigonal bipyramids that share corners with five equivalent F(1)Li3Ag tetrahedra, corners with four equivalent F(2)LiAg4 trigonal bipyramids,  an edgeedge with one F(1)Li3Ag tetrahedra, and edges with four equivalent F(2)LiAg4 trigonal bipyramids.
LiAgF2 crystallizes in the orthorhombic Pmn2_1 space group. Li(1) is bonded to one F(2) and three equivalent F(1) atoms to form LiF4 tetrahedra that share corners with six equivalent Li(1)F4 tetrahedra, corners with five equivalent Ag(1)F5 trigonal bipyramids, and  an edgeedge with one Ag(1)F5 trigonal bipyramid. The Li(1)-F(2) bond length is 1.88 Å. All Li(1)-F(1) bond lengths are 1.90 Å. Ag(1) is bonded to one F(1) and four equivalent F(2) atoms to form distorted AgF5 trigonal bipyramids that share corners with five equivalent Li(1)F4 tetrahedra, corners with four equivalent Ag(1)F5 trigonal bipyramids,  an edgeedge with one Li(1)F4 tetrahedra, and edges with four equivalent Ag(1)F5 trigonal bipyramids. The Ag(1)-F(1) bond length is 2.33 Å. There are a spread of Ag(1)-F(2) bond distances ranging from 2.43-2.62 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Li(1) and one Ag(1) atom to form FLi3Ag tetrahedra that share corners with six equivalent F(1)Li3Ag tetrahedra, corners with five equivalent F(2)LiAg4 trigonal bipyramids, and  an edgeedge with one F(2)LiAg4 trigonal bipyramid. In the second F site, F(2) is bonded to one Li(1) and four equivalent Ag(1) atoms to form distorted FLiAg4 trigonal bipyramids that share corners with five equivalent F(1)Li3Ag tetrahedra, corners with four equivalent F(2)LiAg4 trigonal bipyramids,  an edgeedge with one F(1)Li3Ag tetrahedra, and edges with four equivalent F(2)LiAg4 trigonal bipyramids.