KZrVF7 crystallizes in the orthorhombic Pnna space group. K(1) is bonded in a 10-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(4), and four equivalent F(3) atoms. Zr(1) is bonded to one F(2), two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form ZrF7 pentagonal bipyramids that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 31-42°. V(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with four equivalent Zr(1)F7 pentagonal bipyramids and  an edgeedge with one Zr(1)F7 pentagonal bipyramid. There are four inequivalent F sites. In the first F site, F(4) is bonded in a distorted bent 150 degrees geometry to one K(1), one Zr(1), and one V(1) atom. In the second F site, F(1) is bonded in a distorted bent 150 degrees geometry to one K(1), one Zr(1), and one V(1) atom. In the third F site, F(2) is bonded in a 3-coordinate geometry to two equivalent K(1) and one Zr(1) atom. In the fourth F site, F(3) is bonded in a 4-coordinate geometry to two equivalent K(1), one Zr(1), and one V(1) atom.
KZrVF7 crystallizes in the orthorhombic Pnna space group. K(1) is bonded in a 10-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(4), and four equivalent F(3) atoms. Both K(1)-F(1) bond lengths are 3.15 Å. Both K(1)-F(2) bond lengths are 2.75 Å. Both K(1)-F(4) bond lengths are 3.16 Å. There are two shorter (2.79 Å) and two longer (3.08 Å) K(1)-F(3) bond lengths. Zr(1) is bonded to one F(2), two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form ZrF7 pentagonal bipyramids that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 31-42°. The Zr(1)-F(2) bond length is 2.03 Å. Both Zr(1)-F(1) bond lengths are 2.12 Å. Both Zr(1)-F(3) bond lengths are 2.16 Å. Both Zr(1)-F(4) bond lengths are 2.06 Å. V(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with four equivalent Zr(1)F7 pentagonal bipyramids and  an edgeedge with one Zr(1)F7 pentagonal bipyramid. Both V(1)-F(1) bond lengths are 2.12 Å. Both V(1)-F(3) bond lengths are 2.13 Å. Both V(1)-F(4) bond lengths are 2.12 Å. There are four inequivalent F sites. In the first F site, F(4) is bonded in a distorted bent 150 degrees geometry to one K(1), one Zr(1), and one V(1) atom. In the second F site, F(1) is bonded in a distorted bent 150 degrees geometry to one K(1), one Zr(1), and one V(1) atom. In the third F site, F(2) is bonded in a 3-coordinate geometry to two equivalent K(1) and one Zr(1) atom. In the fourth F site, F(3) is bonded in a 4-coordinate geometry to two equivalent K(1), one Zr(1), and one V(1) atom.