Cs2ZrCu3F12 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one F(4), one F(7), two equivalent F(1), two equivalent F(2), and two equivalent F(6) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one F(3), two equivalent F(2), two equivalent F(6), and four equivalent F(8) atoms. Zr(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(6), and two equivalent F(8) atoms to form ZrF7 pentagonal bipyramids that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(3)F6 octahedra, and edges with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-53°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form CuF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra, corners with two equivalent Cu(3)F6 octahedra, and corners with two equivalent Zr(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-43°. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, and edges with two equivalent Zr(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-52°. In the third Cu site, Cu(3) is bonded to two equivalent F(2), two equivalent F(7), and two equivalent F(8) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(3)F6 octahedra, and corners with two equivalent Zr(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-40°. There are eight inequivalent F sites. In the first F site, F(8) is bonded in a 2-coordinate geometry to two equivalent Cs(2), one Zr(1), and one Cu(3) atom. In the second F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cu(1), and one Cu(2) atom. In the third F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cs(2), one Cu(1), and one Cu(3) atom. In the fourth F site, F(3) is bonded in a 2-coordinate geometry to one Cs(2), one Zr(1), and one Cu(1) atom. In the fifth F site, F(4) is bonded in a 3-coordinate geometry to one Cs(1), one Zr(1), and one Cu(1) atom. In the sixth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Zr(1) and two equivalent Cu(2) atoms. In the seventh F site, F(6) is bonded to one Cs(1), one Cs(2), one Zr(1), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing FCs2ZrCu tetrahedra. In the eighth F site, F(7) is bonded in a distorted bent 150 degrees geometry to one Cs(1) and two equivalent Cu(3) atoms.
Cs2ZrCu3F12 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one F(4), one F(7), two equivalent F(1), two equivalent F(2), and two equivalent F(6) atoms. The Cs(1)-F(4) bond length is 3.10 Å. The Cs(1)-F(7) bond length is 3.01 Å. Both Cs(1)-F(1) bond lengths are 3.30 Å. Both Cs(1)-F(2) bond lengths are 3.25 Å. Both Cs(1)-F(6) bond lengths are 3.16 Å. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one F(3), two equivalent F(2), two equivalent F(6), and four equivalent F(8) atoms. The Cs(2)-F(3) bond length is 3.24 Å. Both Cs(2)-F(2) bond lengths are 3.29 Å. Both Cs(2)-F(6) bond lengths are 3.06 Å. There are two shorter (3.20 Å) and two longer (3.46 Å) Cs(2)-F(8) bond lengths. Zr(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(6), and two equivalent F(8) atoms to form ZrF7 pentagonal bipyramids that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(3)F6 octahedra, and edges with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-53°. The Zr(1)-F(3) bond length is 2.04 Å. The Zr(1)-F(4) bond length is 2.04 Å. The Zr(1)-F(5) bond length is 2.33 Å. Both Zr(1)-F(6) bond lengths are 2.11 Å. Both Zr(1)-F(8) bond lengths are 2.06 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form CuF6 octahedra that share corners with two equivalent Cu(2)F6 octahedra, corners with two equivalent Cu(3)F6 octahedra, and corners with two equivalent Zr(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-43°. The Cu(1)-F(3) bond length is 2.24 Å. The Cu(1)-F(4) bond length is 2.43 Å. Both Cu(1)-F(1) bond lengths are 1.97 Å. Both Cu(1)-F(2) bond lengths are 1.94 Å. In the second Cu site, Cu(2) is bonded to two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, and edges with two equivalent Zr(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-52°. Both Cu(2)-F(1) bond lengths are 1.94 Å. Both Cu(2)-F(5) bond lengths are 2.02 Å. Both Cu(2)-F(6) bond lengths are 2.23 Å. In the third Cu site, Cu(3) is bonded to two equivalent F(2), two equivalent F(7), and two equivalent F(8) atoms to form CuF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(3)F6 octahedra, and corners with two equivalent Zr(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-40°. Both Cu(3)-F(2) bond lengths are 1.96 Å. Both Cu(3)-F(7) bond lengths are 1.93 Å. Both Cu(3)-F(8) bond lengths are 2.33 Å. There are eight inequivalent F sites. In the first F site, F(8) is bonded in a 2-coordinate geometry to two equivalent Cs(2), one Zr(1), and one Cu(3) atom. In the second F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cu(1), and one Cu(2) atom. In the third F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cs(2), one Cu(1), and one Cu(3) atom. In the fourth F site, F(3) is bonded in a 2-coordinate geometry to one Cs(2), one Zr(1), and one Cu(1) atom. In the fifth F site, F(4) is bonded in a 3-coordinate geometry to one Cs(1), one Zr(1), and one Cu(1) atom. In the sixth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Zr(1) and two equivalent Cu(2) atoms. In the seventh F site, F(6) is bonded to one Cs(1), one Cs(2), one Zr(1), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing FCs2ZrCu tetrahedra. In the eighth F site, F(7) is bonded in a distorted bent 150 degrees geometry to one Cs(1) and two equivalent Cu(3) atoms.