Na2ThF6 is Fluorite-derived structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to two equivalent F(1), two equivalent F(3), and four equivalent F(2) atoms. In the second Na site, Na(2) is bonded in a body-centered cubic geometry to two equivalent F(1), two equivalent F(2), and four equivalent F(3) atoms. Th(1) is bonded in a body-centered cubic geometry to two equivalent F(2), two equivalent F(3), and four equivalent F(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), one Na(2), and two equivalent Th(1) atoms to form FNa2Th2 tetrahedra that share corners with four equivalent F(1)Na2Th2 tetrahedra, corners with six equivalent F(2)Na3Th tetrahedra, corners with six equivalent F(3)Na3Th tetrahedra, edges with two equivalent F(1)Na2Th2 tetrahedra, edges with two equivalent F(2)Na3Th tetrahedra, and edges with two equivalent F(3)Na3Th tetrahedra. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Th(1) atom to form FNa3Th tetrahedra that share corners with four equivalent F(2)Na3Th tetrahedra, corners with six equivalent F(1)Na2Th2 tetrahedra, corners with six equivalent F(3)Na3Th tetrahedra, edges with two equivalent F(1)Na2Th2 tetrahedra, edges with two equivalent F(2)Na3Th tetrahedra, and edges with two equivalent F(3)Na3Th tetrahedra. In the third F site, F(3) is bonded to one Na(1), two equivalent Na(2), and one Th(1) atom to form FNa3Th tetrahedra that share corners with four equivalent F(3)Na3Th tetrahedra, corners with six equivalent F(1)Na2Th2 tetrahedra, corners with six equivalent F(2)Na3Th tetrahedra, edges with two equivalent F(1)Na2Th2 tetrahedra, edges with two equivalent F(2)Na3Th tetrahedra, and edges with two equivalent F(3)Na3Th tetrahedra.
Na2ThF6 is Fluorite-derived structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to two equivalent F(1), two equivalent F(3), and four equivalent F(2) atoms. Both Na(1)-F(1) bond lengths are 2.49 Å. Both Na(1)-F(3) bond lengths are 2.40 Å. There are two shorter (2.38 Å) and two longer (2.45 Å) Na(1)-F(2) bond lengths. In the second Na site, Na(2) is bonded in a body-centered cubic geometry to two equivalent F(1), two equivalent F(2), and four equivalent F(3) atoms. Both Na(2)-F(1) bond lengths are 2.48 Å. Both Na(2)-F(2) bond lengths are 2.38 Å. There are two shorter (2.42 Å) and two longer (2.44 Å) Na(2)-F(3) bond lengths. Th(1) is bonded in a body-centered cubic geometry to two equivalent F(2), two equivalent F(3), and four equivalent F(1) atoms. Both Th(1)-F(2) bond lengths are 2.27 Å. Both Th(1)-F(3) bond lengths are 2.26 Å. There are two shorter (2.39 Å) and two longer (2.43 Å) Th(1)-F(1) bond lengths. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), one Na(2), and two equivalent Th(1) atoms to form FNa2Th2 tetrahedra that share corners with four equivalent F(1)Na2Th2 tetrahedra, corners with six equivalent F(2)Na3Th tetrahedra, corners with six equivalent F(3)Na3Th tetrahedra, edges with two equivalent F(1)Na2Th2 tetrahedra, edges with two equivalent F(2)Na3Th tetrahedra, and edges with two equivalent F(3)Na3Th tetrahedra. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Th(1) atom to form FNa3Th tetrahedra that share corners with four equivalent F(2)Na3Th tetrahedra, corners with six equivalent F(1)Na2Th2 tetrahedra, corners with six equivalent F(3)Na3Th tetrahedra, edges with two equivalent F(1)Na2Th2 tetrahedra, edges with two equivalent F(2)Na3Th tetrahedra, and edges with two equivalent F(3)Na3Th tetrahedra. In the third F site, F(3) is bonded to one Na(1), two equivalent Na(2), and one Th(1) atom to form FNa3Th tetrahedra that share corners with four equivalent F(3)Na3Th tetrahedra, corners with six equivalent F(1)Na2Th2 tetrahedra, corners with six equivalent F(2)Na3Th tetrahedra, edges with two equivalent F(1)Na2Th2 tetrahedra, edges with two equivalent F(2)Na3Th tetrahedra, and edges with two equivalent F(3)Na3Th tetrahedra.