Na7Zr6F31 crystallizes in the trigonal R3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one F(2), one F(8), one F(9), two equivalent F(5), and two equivalent F(6) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(5), one F(8), one F(9), two equivalent F(2), and two equivalent F(4) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to three equivalent F(8) and three equivalent F(9) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to one F(1), one F(3), one F(4), one F(5), one F(6), one F(8), and two equivalent F(7) atoms. In the second Zr site, Zr(2) is bonded in a 9-coordinate geometry to one F(1), one F(11), one F(2), one F(3), one F(4), one F(6), one F(9), and two equivalent F(10) atoms. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one Zr(2) atom. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Zr(2) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(4)Na2Zr2 tetrahedra, corners with two equivalent F(2)Na3Zr tetrahedra, corners with two equivalent F(5)Na3Zr tetrahedra, corners with three equivalent F(6)Na2Zr2 tetrahedra, corners with three equivalent F(8)Na3Zr tetrahedra,  an edgeedge with one F(5)Na3Zr tetrahedra, edges with two equivalent F(4)Na2Zr2 tetrahedra, and edges with two equivalent F(9)Na3Zr tetrahedra. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one Zr(2) atom. In the fourth F site, F(4) is bonded to two equivalent Na(2), one Zr(1), and one Zr(2) atom to form FNa2Zr2 tetrahedra that share  a cornercorner with one F(2)Na3Zr tetrahedra,  a cornercorner with one F(8)Na3Zr tetrahedra, corners with two equivalent F(4)Na2Zr2 tetrahedra, corners with three equivalent F(5)Na3Zr tetrahedra, corners with three equivalent F(9)Na3Zr tetrahedra,  an edgeedge with one F(6)Na2Zr2 tetrahedra,  an edgeedge with one F(8)Na3Zr tetrahedra, and edges with two equivalent F(2)Na3Zr tetrahedra. In the fifth F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(6)Na2Zr2 tetrahedra, corners with two equivalent F(2)Na3Zr tetrahedra, corners with two equivalent F(5)Na3Zr tetrahedra, corners with three equivalent F(4)Na2Zr2 tetrahedra, corners with three equivalent F(9)Na3Zr tetrahedra,  an edgeedge with one F(2)Na3Zr tetrahedra, edges with two equivalent F(6)Na2Zr2 tetrahedra, and edges with two equivalent F(8)Na3Zr tetrahedra. In the sixth F site, F(6) is bonded to two equivalent Na(1), one Zr(1), and one Zr(2) atom to form FNa2Zr2 tetrahedra that share  a cornercorner with one F(5)Na3Zr tetrahedra,  a cornercorner with one F(9)Na3Zr tetrahedra, corners with two equivalent F(6)Na2Zr2 tetrahedra, corners with three equivalent F(2)Na3Zr tetrahedra, corners with three equivalent F(8)Na3Zr tetrahedra,  an edgeedge with one F(4)Na2Zr2 tetrahedra,  an edgeedge with one F(9)Na3Zr tetrahedra, and edges with two equivalent F(5)Na3Zr tetrahedra. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to two equivalent Zr(1) atoms. In the eighth F site, F(8) is bonded to one Na(1), one Na(2), one Na(3), and one Zr(1) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(4)Na2Zr2 tetrahedra,  a cornercorner with one F(9)Na3Zr tetrahedra, corners with two equivalent F(8)Na3Zr tetrahedra, corners with three equivalent F(6)Na2Zr2 tetrahedra, corners with three equivalent F(2)Na3Zr tetrahedra,  an edgeedge with one F(4)Na2Zr2 tetrahedra, edges with two equivalent F(5)Na3Zr tetrahedra, and edges with two equivalent F(9)Na3Zr tetrahedra. In the ninth F site, F(9) is bonded to one Na(1), one Na(2), one Na(3), and one Zr(2) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(6)Na2Zr2 tetrahedra,  a cornercorner with one F(8)Na3Zr tetrahedra, corners with two equivalent F(9)Na3Zr tetrahedra, corners with three equivalent F(4)Na2Zr2 tetrahedra, corners with three equivalent F(5)Na3Zr tetrahedra,  an edgeedge with one F(6)Na2Zr2 tetrahedra, edges with two equivalent F(2)Na3Zr tetrahedra, and edges with two equivalent F(8)Na3Zr tetrahedra. In the tenth F site, F(10) is bonded in a distorted bent 120 degrees geometry to two equivalent Zr(2) atoms. In the eleventh F site, F(11) is bonded in a trigonal non-coplanar geometry to three equivalent Zr(2) atoms.
Na7Zr6F31 crystallizes in the trigonal R3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one F(2), one F(8), one F(9), two equivalent F(5), and two equivalent F(6) atoms. The Na(1)-F(2) bond length is 2.49 Å. The Na(1)-F(8) bond length is 2.44 Å. The Na(1)-F(9) bond length is 2.33 Å. There is one shorter (2.41 Å) and one longer (2.45 Å) Na(1)-F(5) bond length. There is one shorter (2.55 Å) and one longer (2.56 Å) Na(1)-F(6) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(5), one F(8), one F(9), two equivalent F(2), and two equivalent F(4) atoms. The Na(2)-F(5) bond length is 2.50 Å. The Na(2)-F(8) bond length is 2.41 Å. The Na(2)-F(9) bond length is 2.36 Å. There is one shorter (2.39 Å) and one longer (2.40 Å) Na(2)-F(2) bond length. There is one shorter (2.56 Å) and one longer (2.57 Å) Na(2)-F(4) bond length. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to three equivalent F(8) and three equivalent F(9) atoms. All Na(3)-F(8) bond lengths are 2.48 Å. All Na(3)-F(9) bond lengths are 2.52 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to one F(1), one F(3), one F(4), one F(5), one F(6), one F(8), and two equivalent F(7) atoms. The Zr(1)-F(1) bond length is 2.19 Å. The Zr(1)-F(3) bond length is 2.16 Å. The Zr(1)-F(4) bond length is 2.18 Å. The Zr(1)-F(5) bond length is 2.06 Å. The Zr(1)-F(6) bond length is 2.17 Å. The Zr(1)-F(8) bond length is 2.07 Å. There is one shorter (2.15 Å) and one longer (2.16 Å) Zr(1)-F(7) bond length. In the second Zr site, Zr(2) is bonded in a 9-coordinate geometry to one F(1), one F(11), one F(2), one F(3), one F(4), one F(6), one F(9), and two equivalent F(10) atoms. The Zr(2)-F(1) bond length is 2.14 Å. The Zr(2)-F(11) bond length is 2.55 Å. The Zr(2)-F(2) bond length is 2.09 Å. The Zr(2)-F(3) bond length is 2.18 Å. The Zr(2)-F(4) bond length is 2.27 Å. The Zr(2)-F(6) bond length is 2.26 Å. The Zr(2)-F(9) bond length is 2.09 Å. There is one shorter (2.14 Å) and one longer (2.16 Å) Zr(2)-F(10) bond length. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one Zr(2) atom. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Zr(2) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(4)Na2Zr2 tetrahedra, corners with two equivalent F(2)Na3Zr tetrahedra, corners with two equivalent F(5)Na3Zr tetrahedra, corners with three equivalent F(6)Na2Zr2 tetrahedra, corners with three equivalent F(8)Na3Zr tetrahedra,  an edgeedge with one F(5)Na3Zr tetrahedra, edges with two equivalent F(4)Na2Zr2 tetrahedra, and edges with two equivalent F(9)Na3Zr tetrahedra. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one Zr(2) atom. In the fourth F site, F(4) is bonded to two equivalent Na(2), one Zr(1), and one Zr(2) atom to form FNa2Zr2 tetrahedra that share  a cornercorner with one F(2)Na3Zr tetrahedra,  a cornercorner with one F(8)Na3Zr tetrahedra, corners with two equivalent F(4)Na2Zr2 tetrahedra, corners with three equivalent F(5)Na3Zr tetrahedra, corners with three equivalent F(9)Na3Zr tetrahedra,  an edgeedge with one F(6)Na2Zr2 tetrahedra,  an edgeedge with one F(8)Na3Zr tetrahedra, and edges with two equivalent F(2)Na3Zr tetrahedra. In the fifth F site, F(5) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(6)Na2Zr2 tetrahedra, corners with two equivalent F(2)Na3Zr tetrahedra, corners with two equivalent F(5)Na3Zr tetrahedra, corners with three equivalent F(4)Na2Zr2 tetrahedra, corners with three equivalent F(9)Na3Zr tetrahedra,  an edgeedge with one F(2)Na3Zr tetrahedra, edges with two equivalent F(6)Na2Zr2 tetrahedra, and edges with two equivalent F(8)Na3Zr tetrahedra. In the sixth F site, F(6) is bonded to two equivalent Na(1), one Zr(1), and one Zr(2) atom to form FNa2Zr2 tetrahedra that share  a cornercorner with one F(5)Na3Zr tetrahedra,  a cornercorner with one F(9)Na3Zr tetrahedra, corners with two equivalent F(6)Na2Zr2 tetrahedra, corners with three equivalent F(2)Na3Zr tetrahedra, corners with three equivalent F(8)Na3Zr tetrahedra,  an edgeedge with one F(4)Na2Zr2 tetrahedra,  an edgeedge with one F(9)Na3Zr tetrahedra, and edges with two equivalent F(5)Na3Zr tetrahedra. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to two equivalent Zr(1) atoms. In the eighth F site, F(8) is bonded to one Na(1), one Na(2), one Na(3), and one Zr(1) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(4)Na2Zr2 tetrahedra,  a cornercorner with one F(9)Na3Zr tetrahedra, corners with two equivalent F(8)Na3Zr tetrahedra, corners with three equivalent F(6)Na2Zr2 tetrahedra, corners with three equivalent F(2)Na3Zr tetrahedra,  an edgeedge with one F(4)Na2Zr2 tetrahedra, edges with two equivalent F(5)Na3Zr tetrahedra, and edges with two equivalent F(9)Na3Zr tetrahedra. In the ninth F site, F(9) is bonded to one Na(1), one Na(2), one Na(3), and one Zr(2) atom to form FNa3Zr tetrahedra that share  a cornercorner with one F(6)Na2Zr2 tetrahedra,  a cornercorner with one F(8)Na3Zr tetrahedra, corners with two equivalent F(9)Na3Zr tetrahedra, corners with three equivalent F(4)Na2Zr2 tetrahedra, corners with three equivalent F(5)Na3Zr tetrahedra,  an edgeedge with one F(6)Na2Zr2 tetrahedra, edges with two equivalent F(2)Na3Zr tetrahedra, and edges with two equivalent F(8)Na3Zr tetrahedra. In the tenth F site, F(10) is bonded in a distorted bent 120 degrees geometry to two equivalent Zr(2) atoms. In the eleventh F site, F(11) is bonded in a trigonal non-coplanar geometry to three equivalent Zr(2) atoms.