Cs2Na2SnGeF12 crystallizes in the orthorhombic Pmc2_1 space group. Cs(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(1), one F(3), one F(5), one F(7), and two equivalent F(10) atoms to form NaF6 octahedra that share corners with two equivalent Sn(1)F6 octahedra, corners with two equivalent Ge(1)F6 octahedra, and  an edgeedge with one Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-37°. In the second Na site, Na(2) is bonded to one F(2), one F(4), one F(6), one F(8), and two equivalent F(9) atoms to form NaF6 octahedra that share corners with two equivalent Sn(1)F6 octahedra, corners with two equivalent Ge(1)F6 octahedra, and  an edgeedge with one Sn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-41°. Sn(1) is bonded to one F(2), one F(4), one F(6), one F(8), and two equivalent F(10) atoms to form SnF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Na(2)F6 octahedra, and  an edgeedge with one Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-41°. Ge(1) is bonded to one F(1), one F(3), one F(5), one F(7), and two equivalent F(9) atoms to form GeF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Na(2)F6 octahedra, and  an edgeedge with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-37°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Na(1) and one Ge(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Na(2) and one Sn(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Cs(1), one Na(1), and one Ge(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to two equivalent Cs(1), one Na(2), and one Sn(1) atom. In the fifth F site, F(5) is bonded to two equivalent Cs(1), one Na(1), and one Ge(1) atom to form distorted corner-sharing FCs2NaGe tetrahedra. In the sixth F site, F(6) is bonded to two equivalent Cs(1), one Na(2), and one Sn(1) atom to form distorted corner-sharing FCs2NaSn tetrahedra. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Na(1), and one Ge(1) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Na(2), and one Sn(1) atom. In the ninth F site, F(9) is bonded in a distorted linear geometry to one Na(2) and one Ge(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Na(1) and one Sn(1) atom.
Cs2Na2SnGeF12 crystallizes in the orthorhombic Pmc2_1 space group. Cs(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom. The Cs(1)-F(3) bond length is 3.22 Å. The Cs(1)-F(4) bond length is 3.20 Å. The Cs(1)-F(5) bond length is 3.10 Å. The Cs(1)-F(6) bond length is 3.09 Å. The Cs(1)-F(7) bond length is 3.20 Å. The Cs(1)-F(8) bond length is 3.14 Å. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(1), one F(3), one F(5), one F(7), and two equivalent F(10) atoms to form NaF6 octahedra that share corners with two equivalent Sn(1)F6 octahedra, corners with two equivalent Ge(1)F6 octahedra, and  an edgeedge with one Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-37°. The Na(1)-F(1) bond length is 2.33 Å. The Na(1)-F(3) bond length is 2.33 Å. The Na(1)-F(5) bond length is 2.35 Å. The Na(1)-F(7) bond length is 2.47 Å. Both Na(1)-F(10) bond lengths are 2.33 Å. In the second Na site, Na(2) is bonded to one F(2), one F(4), one F(6), one F(8), and two equivalent F(9) atoms to form NaF6 octahedra that share corners with two equivalent Sn(1)F6 octahedra, corners with two equivalent Ge(1)F6 octahedra, and  an edgeedge with one Sn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-41°. The Na(2)-F(2) bond length is 2.19 Å. The Na(2)-F(4) bond length is 2.22 Å. The Na(2)-F(6) bond length is 2.29 Å. The Na(2)-F(8) bond length is 2.42 Å. Both Na(2)-F(9) bond lengths are 2.49 Å. Sn(1) is bonded to one F(2), one F(4), one F(6), one F(8), and two equivalent F(10) atoms to form SnF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Na(2)F6 octahedra, and  an edgeedge with one Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-41°. The Sn(1)-F(2) bond length is 1.99 Å. The Sn(1)-F(4) bond length is 2.00 Å. The Sn(1)-F(6) bond length is 2.02 Å. The Sn(1)-F(8) bond length is 2.01 Å. Both Sn(1)-F(10) bond lengths are 1.99 Å. Ge(1) is bonded to one F(1), one F(3), one F(5), one F(7), and two equivalent F(9) atoms to form GeF6 octahedra that share corners with two equivalent Na(1)F6 octahedra, corners with two equivalent Na(2)F6 octahedra, and  an edgeedge with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-37°. The Ge(1)-F(1) bond length is 1.84 Å. The Ge(1)-F(3) bond length is 1.85 Å. The Ge(1)-F(5) bond length is 1.86 Å. The Ge(1)-F(7) bond length is 1.85 Å. Both Ge(1)-F(9) bond lengths are 1.83 Å. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Na(1) and one Ge(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Na(2) and one Sn(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Cs(1), one Na(1), and one Ge(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to two equivalent Cs(1), one Na(2), and one Sn(1) atom. In the fifth F site, F(5) is bonded to two equivalent Cs(1), one Na(1), and one Ge(1) atom to form distorted corner-sharing FCs2NaGe tetrahedra. In the sixth F site, F(6) is bonded to two equivalent Cs(1), one Na(2), and one Sn(1) atom to form distorted corner-sharing FCs2NaSn tetrahedra. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Na(1), and one Ge(1) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Na(2), and one Sn(1) atom. In the ninth F site, F(9) is bonded in a distorted linear geometry to one Na(2) and one Ge(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Na(1) and one Sn(1) atom.