Zr6Ag7F31 crystallizes in the trigonal R-3 space group. Zr(1) is bonded in a 8-coordinate geometry to one F(1), one F(5), one F(6), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in an octahedral geometry to six equivalent F(5) atoms. In the second Ag site, Ag(2) is bonded in a 7-coordinate geometry to two equivalent F(4), two equivalent F(5), and three equivalent F(6) atoms. There are six inequivalent F sites. In the first F site, F(6) is bonded to one Zr(1) and three equivalent Ag(2) atoms to form distorted FZrAg3 tetrahedra that share  a cornercorner with one F(1)Zr6 octahedra, corners with three equivalent F(5)ZrAg3 tetrahedra, corners with four equivalent F(4)Zr2Ag2 tetrahedra, corners with four equivalent F(6)ZrAg3 tetrahedra,  an edgeedge with one F(6)ZrAg3 tetrahedra, edges with two equivalent F(4)Zr2Ag2 tetrahedra, and edges with two equivalent F(5)ZrAg3 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the second F site, F(1) is bonded to six equivalent Zr(1) atoms to form FZr6 octahedra that share corners with six equivalent F(5)ZrAg3 tetrahedra, corners with six equivalent F(6)ZrAg3 tetrahedra, and corners with twelve equivalent F(4)Zr2Ag2 tetrahedra. In the third F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Zr(1) atoms. In the fourth F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Zr(1) atoms. In the fifth F site, F(4) is bonded to two equivalent Zr(1) and two equivalent Ag(2) atoms to form distorted FZr2Ag2 tetrahedra that share corners with two equivalent F(1)Zr6 octahedra, corners with two equivalent F(4)Zr2Ag2 tetrahedra, corners with four equivalent F(5)ZrAg3 tetrahedra, corners with four equivalent F(6)ZrAg3 tetrahedra,  an edgeedge with one F(4)Zr2Ag2 tetrahedra,  an edgeedge with one F(5)ZrAg3 tetrahedra, and edges with two equivalent F(6)ZrAg3 tetrahedra. The corner-sharing octahedral tilt angles range from 54-56°. In the sixth F site, F(5) is bonded to one Zr(1), one Ag(1), and two equivalent Ag(2) atoms to form distorted FZrAg3 tetrahedra that share  a cornercorner with one F(1)Zr6 octahedra, corners with three equivalent F(5)ZrAg3 tetrahedra, corners with three equivalent F(6)ZrAg3 tetrahedra, corners with four equivalent F(4)Zr2Ag2 tetrahedra,  an edgeedge with one F(4)Zr2Ag2 tetrahedra, edges with two equivalent F(5)ZrAg3 tetrahedra, and edges with two equivalent F(6)ZrAg3 tetrahedra. The corner-sharing octahedral tilt angles are 58°.
Zr6Ag7F31 crystallizes in the trigonal R-3 space group. Zr(1) is bonded in a 8-coordinate geometry to one F(1), one F(5), one F(6), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. The Zr(1)-F(1) bond length is 2.87 Å. The Zr(1)-F(5) bond length is 2.07 Å. The Zr(1)-F(6) bond length is 2.06 Å. Both Zr(1)-F(2) bond lengths are 2.11 Å. There is one shorter (2.12 Å) and one longer (2.15 Å) Zr(1)-F(3) bond length. There is one shorter (2.18 Å) and one longer (2.19 Å) Zr(1)-F(4) bond length. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in an octahedral geometry to six equivalent F(5) atoms. All Ag(1)-F(5) bond lengths are 2.50 Å. In the second Ag site, Ag(2) is bonded in a 7-coordinate geometry to two equivalent F(4), two equivalent F(5), and three equivalent F(6) atoms. There is one shorter (2.59 Å) and one longer (2.63 Å) Ag(2)-F(4) bond length. There is one shorter (2.43 Å) and one longer (2.50 Å) Ag(2)-F(5) bond length. There are two shorter (2.46 Å) and one longer (2.50 Å) Ag(2)-F(6) bond length. There are six inequivalent F sites. In the first F site, F(6) is bonded to one Zr(1) and three equivalent Ag(2) atoms to form distorted FZrAg3 tetrahedra that share  a cornercorner with one F(1)Zr6 octahedra, corners with three equivalent F(5)ZrAg3 tetrahedra, corners with four equivalent F(4)Zr2Ag2 tetrahedra, corners with four equivalent F(6)ZrAg3 tetrahedra,  an edgeedge with one F(6)ZrAg3 tetrahedra, edges with two equivalent F(4)Zr2Ag2 tetrahedra, and edges with two equivalent F(5)ZrAg3 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the second F site, F(1) is bonded to six equivalent Zr(1) atoms to form FZr6 octahedra that share corners with six equivalent F(5)ZrAg3 tetrahedra, corners with six equivalent F(6)ZrAg3 tetrahedra, and corners with twelve equivalent F(4)Zr2Ag2 tetrahedra. In the third F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Zr(1) atoms. In the fourth F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Zr(1) atoms. In the fifth F site, F(4) is bonded to two equivalent Zr(1) and two equivalent Ag(2) atoms to form distorted FZr2Ag2 tetrahedra that share corners with two equivalent F(1)Zr6 octahedra, corners with two equivalent F(4)Zr2Ag2 tetrahedra, corners with four equivalent F(5)ZrAg3 tetrahedra, corners with four equivalent F(6)ZrAg3 tetrahedra,  an edgeedge with one F(4)Zr2Ag2 tetrahedra,  an edgeedge with one F(5)ZrAg3 tetrahedra, and edges with two equivalent F(6)ZrAg3 tetrahedra. The corner-sharing octahedral tilt angles range from 54-56°. In the sixth F site, F(5) is bonded to one Zr(1), one Ag(1), and two equivalent Ag(2) atoms to form distorted FZrAg3 tetrahedra that share  a cornercorner with one F(1)Zr6 octahedra, corners with three equivalent F(5)ZrAg3 tetrahedra, corners with three equivalent F(6)ZrAg3 tetrahedra, corners with four equivalent F(4)Zr2Ag2 tetrahedra,  an edgeedge with one F(4)Zr2Ag2 tetrahedra, edges with two equivalent F(5)ZrAg3 tetrahedra, and edges with two equivalent F(6)ZrAg3 tetrahedra. The corner-sharing octahedral tilt angles are 58°.