RbCaZrF7 crystallizes in the orthorhombic Cmcm space group. Rb(1) is bonded in a 8-coordinate geometry to four equivalent F(3) and four equivalent F(4) atoms. Ca(1) is bonded to one F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form CaF7 pentagonal bipyramids that share corners with three equivalent Zr(1)F7 pentagonal bipyramids and edges with two equivalent Zr(1)F7 pentagonal bipyramids. Zr(1) is bonded to one F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form ZrF7 pentagonal bipyramids that share corners with three equivalent Ca(1)F7 pentagonal bipyramids and edges with two equivalent Ca(1)F7 pentagonal bipyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Ca(1) and one Zr(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one Zr(1) atom. In the third F site, F(3) is bonded to two equivalent Rb(1), one Ca(1), and one Zr(1) atom to form a mixture of distorted face and corner-sharing FRb2CaZr tetrahedra. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Rb(1), one Ca(1), and one Zr(1) atom.
RbCaZrF7 crystallizes in the orthorhombic Cmcm space group. Rb(1) is bonded in a 8-coordinate geometry to four equivalent F(3) and four equivalent F(4) atoms. All Rb(1)-F(3) bond lengths are 3.04 Å. All Rb(1)-F(4) bond lengths are 3.07 Å. Ca(1) is bonded to one F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form CaF7 pentagonal bipyramids that share corners with three equivalent Zr(1)F7 pentagonal bipyramids and edges with two equivalent Zr(1)F7 pentagonal bipyramids. The Ca(1)-F(1) bond length is 2.28 Å. Both Ca(1)-F(2) bond lengths are 2.28 Å. Both Ca(1)-F(3) bond lengths are 2.31 Å. Both Ca(1)-F(4) bond lengths are 2.38 Å. Zr(1) is bonded to one F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form ZrF7 pentagonal bipyramids that share corners with three equivalent Ca(1)F7 pentagonal bipyramids and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The Zr(1)-F(1) bond length is 2.07 Å. Both Zr(1)-F(2) bond lengths are 2.06 Å. Both Zr(1)-F(3) bond lengths are 2.14 Å. Both Zr(1)-F(4) bond lengths are 2.13 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Ca(1) and one Zr(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one Zr(1) atom. In the third F site, F(3) is bonded to two equivalent Rb(1), one Ca(1), and one Zr(1) atom to form a mixture of distorted face and corner-sharing FRb2CaZr tetrahedra. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Rb(1), one Ca(1), and one Zr(1) atom.