RbPrF4 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 7-coordinate geometry to one F(3), two equivalent F(1), and four equivalent F(4) atoms. Pr(1) is bonded in a 9-coordinate geometry to one F(4), two equivalent F(1), three equivalent F(2), and three equivalent F(3) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Rb(1) and two equivalent Pr(1) atoms to form distorted FRb2Pr2 tetrahedra that share corners with four equivalent F(1)Rb2Pr2 tetrahedra, corners with six equivalent F(3)RbPr3 tetrahedra, and  an edgeedge with one F(3)RbPr3 tetrahedra. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Pr(1) atoms. In the third F site, F(3) is bonded to one Rb(1) and three equivalent Pr(1) atoms to form FRbPr3 tetrahedra that share corners with two equivalent F(3)RbPr3 tetrahedra, corners with six equivalent F(1)Rb2Pr2 tetrahedra,  an edgeedge with one F(1)Rb2Pr2 tetrahedra, and edges with two equivalent F(3)RbPr3 tetrahedra. In the fourth F site, F(4) is bonded in a 5-coordinate geometry to four equivalent Rb(1) and one Pr(1) atom.
RbPrF4 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 7-coordinate geometry to one F(3), two equivalent F(1), and four equivalent F(4) atoms. The Rb(1)-F(3) bond length is 2.75 Å. There is one shorter (2.71 Å) and one longer (2.82 Å) Rb(1)-F(1) bond length. There are two shorter (2.80 Å) and two longer (2.85 Å) Rb(1)-F(4) bond lengths. Pr(1) is bonded in a 9-coordinate geometry to one F(4), two equivalent F(1), three equivalent F(2), and three equivalent F(3) atoms. The Pr(1)-F(4) bond length is 2.32 Å. Both Pr(1)-F(1) bond lengths are 2.39 Å. There is one shorter (2.47 Å) and two longer (2.54 Å) Pr(1)-F(2) bond lengths. There is one shorter (2.43 Å) and two longer (2.49 Å) Pr(1)-F(3) bond lengths. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Rb(1) and two equivalent Pr(1) atoms to form distorted FRb2Pr2 tetrahedra that share corners with four equivalent F(1)Rb2Pr2 tetrahedra, corners with six equivalent F(3)RbPr3 tetrahedra, and  an edgeedge with one F(3)RbPr3 tetrahedra. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Pr(1) atoms. In the third F site, F(3) is bonded to one Rb(1) and three equivalent Pr(1) atoms to form FRbPr3 tetrahedra that share corners with two equivalent F(3)RbPr3 tetrahedra, corners with six equivalent F(1)Rb2Pr2 tetrahedra,  an edgeedge with one F(1)Rb2Pr2 tetrahedra, and edges with two equivalent F(3)RbPr3 tetrahedra. In the fourth F site, F(4) is bonded in a 5-coordinate geometry to four equivalent Rb(1) and one Pr(1) atom.