CsSc3F10 crystallizes in the orthorhombic Pmma space group. Cs(1) is bonded to four equivalent F(1) and eight equivalent F(3) atoms to form distorted CsF12 cuboctahedra that share edges with four equivalent Sc(1)F6 octahedra, edges with eight equivalent Sc(2)F7 pentagonal bipyramids, and faces with two equivalent Cs(1)F12 cuboctahedra. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to two equivalent F(5) and four equivalent F(3) atoms to form ScF6 octahedra that share corners with two equivalent Sc(1)F6 octahedra, corners with four equivalent Sc(2)F7 pentagonal bipyramids, and edges with four equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 4°. In the second Sc site, Sc(2) is bonded to one F(2), two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form ScF7 pentagonal bipyramids that share corners with two equivalent Sc(1)F6 octahedra, corners with three equivalent Sc(2)F7 pentagonal bipyramids, edges with four equivalent Cs(1)F12 cuboctahedra, and  an edgeedge with one Sc(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 32°. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Cs(1) and two equivalent Sc(2) atoms to form a mixture of distorted edge and corner-sharing FCs2Sc2 tetrahedra. In the second F site, F(2) is bonded in a linear geometry to two equivalent Sc(2) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Cs(1), one Sc(1), and one Sc(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to two equivalent Sc(2) atoms. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent Sc(1) atoms.
CsSc3F10 crystallizes in the orthorhombic Pmma space group. Cs(1) is bonded to four equivalent F(1) and eight equivalent F(3) atoms to form distorted CsF12 cuboctahedra that share edges with four equivalent Sc(1)F6 octahedra, edges with eight equivalent Sc(2)F7 pentagonal bipyramids, and faces with two equivalent Cs(1)F12 cuboctahedra. There are two shorter (3.02 Å) and two longer (3.03 Å) Cs(1)-F(1) bond lengths. There are four shorter (3.33 Å) and four longer (3.40 Å) Cs(1)-F(3) bond lengths. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to two equivalent F(5) and four equivalent F(3) atoms to form ScF6 octahedra that share corners with two equivalent Sc(1)F6 octahedra, corners with four equivalent Sc(2)F7 pentagonal bipyramids, and edges with four equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 4°. Both Sc(1)-F(5) bond lengths are 2.03 Å. All Sc(1)-F(3) bond lengths are 2.02 Å. In the second Sc site, Sc(2) is bonded to one F(2), two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form ScF7 pentagonal bipyramids that share corners with two equivalent Sc(1)F6 octahedra, corners with three equivalent Sc(2)F7 pentagonal bipyramids, edges with four equivalent Cs(1)F12 cuboctahedra, and  an edgeedge with one Sc(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 32°. The Sc(2)-F(2) bond length is 2.05 Å. Both Sc(2)-F(1) bond lengths are 2.10 Å. Both Sc(2)-F(3) bond lengths are 2.13 Å. Both Sc(2)-F(4) bond lengths are 2.03 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Cs(1) and two equivalent Sc(2) atoms to form a mixture of distorted edge and corner-sharing FCs2Sc2 tetrahedra. In the second F site, F(2) is bonded in a linear geometry to two equivalent Sc(2) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Cs(1), one Sc(1), and one Sc(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to two equivalent Sc(2) atoms. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent Sc(1) atoms.