Ba3ZrF10 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to two equivalent F(1), two equivalent F(4), three equivalent F(3), and four equivalent F(2) atoms. In the second Ba site, Ba(2) is bonded in a body-centered cubic geometry to four equivalent F(1) and four equivalent F(2) atoms. Zr(1) is bonded in a 8-coordinate geometry to two equivalent F(3), two equivalent F(4), and four equivalent F(2) atoms. There are four inequivalent F sites. In the first F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(1) and one Zr(1) atom. In the second F site, F(1) is bonded to two equivalent Ba(1) and two equivalent Ba(2) atoms to form FBa4 tetrahedra that share corners with two equivalent F(1)Ba4 tetrahedra, corners with twelve equivalent F(2)Ba3Zr tetrahedra, edges with two equivalent F(2)Ba3Zr tetrahedra, and edges with three equivalent F(1)Ba4 tetrahedra. In the third F site, F(2) is bonded to one Ba(2), two equivalent Ba(1), and one Zr(1) atom to form distorted FBa3Zr tetrahedra that share corners with four equivalent F(2)Ba3Zr tetrahedra, corners with six equivalent F(1)Ba4 tetrahedra,  an edgeedge with one F(1)Ba4 tetrahedra, and edges with four equivalent F(2)Ba3Zr tetrahedra. In the fourth F site, F(3) is bonded in a 1-coordinate geometry to three equivalent Ba(1) and one Zr(1) atom.
Ba3ZrF10 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 11-coordinate geometry to two equivalent F(1), two equivalent F(4), three equivalent F(3), and four equivalent F(2) atoms. Both Ba(1)-F(1) bond lengths are 2.69 Å. Both Ba(1)-F(4) bond lengths are 2.68 Å. There is one shorter (2.81 Å) and two longer (3.12 Å) Ba(1)-F(3) bond lengths. There are two shorter (2.78 Å) and two longer (2.94 Å) Ba(1)-F(2) bond lengths. In the second Ba site, Ba(2) is bonded in a body-centered cubic geometry to four equivalent F(1) and four equivalent F(2) atoms. All Ba(2)-F(1) bond lengths are 2.63 Å. All Ba(2)-F(2) bond lengths are 2.72 Å. Zr(1) is bonded in a 8-coordinate geometry to two equivalent F(3), two equivalent F(4), and four equivalent F(2) atoms. Both Zr(1)-F(3) bond lengths are 2.11 Å. Both Zr(1)-F(4) bond lengths are 2.05 Å. All Zr(1)-F(2) bond lengths are 2.17 Å. There are four inequivalent F sites. In the first F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(1) and one Zr(1) atom. In the second F site, F(1) is bonded to two equivalent Ba(1) and two equivalent Ba(2) atoms to form FBa4 tetrahedra that share corners with two equivalent F(1)Ba4 tetrahedra, corners with twelve equivalent F(2)Ba3Zr tetrahedra, edges with two equivalent F(2)Ba3Zr tetrahedra, and edges with three equivalent F(1)Ba4 tetrahedra. In the third F site, F(2) is bonded to one Ba(2), two equivalent Ba(1), and one Zr(1) atom to form distorted FBa3Zr tetrahedra that share corners with four equivalent F(2)Ba3Zr tetrahedra, corners with six equivalent F(1)Ba4 tetrahedra,  an edgeedge with one F(1)Ba4 tetrahedra, and edges with four equivalent F(2)Ba3Zr tetrahedra. In the fourth F site, F(3) is bonded in a 1-coordinate geometry to three equivalent Ba(1) and one Zr(1) atom.