Na2ZrF6 is Baddeleyite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms to form distorted NaF7 pentagonal bipyramids that share corners with four equivalent Zr(1)F7 pentagonal bipyramids,  an edgeedge with one Na(1)F7 pentagonal bipyramid, and edges with two equivalent Zr(1)F7 pentagonal bipyramids. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(3), two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms. Zr(1) is bonded to one F(2), one F(3), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted ZrF7 pentagonal bipyramids that share corners with four equivalent Na(1)F7 pentagonal bipyramids,  an edgeedge with one Zr(1)F7 pentagonal bipyramid, and edges with two equivalent Na(1)F7 pentagonal bipyramids. There are six inequivalent F sites. In the first F site, F(6) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one Zr(1) atom. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Zr(1) atoms. In the third F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Zr(1) atom to form a mixture of distorted edge and corner-sharing FNa3Zr trigonal pyramids. In the fourth F site, F(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Zr(1) atom. In the fifth F site, F(4) is bonded to one Na(1), two equivalent Na(2), and one Zr(1) atom to form a mixture of edge and corner-sharing FNa3Zr tetrahedra. In the sixth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Zr(1) atom.
Na2ZrF6 is Baddeleyite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms to form distorted NaF7 pentagonal bipyramids that share corners with four equivalent Zr(1)F7 pentagonal bipyramids,  an edgeedge with one Na(1)F7 pentagonal bipyramid, and edges with two equivalent Zr(1)F7 pentagonal bipyramids. The Na(1)-F(1) bond length is 2.44 Å. The Na(1)-F(2) bond length is 2.47 Å. The Na(1)-F(3) bond length is 2.25 Å. The Na(1)-F(4) bond length is 2.28 Å. The Na(1)-F(5) bond length is 2.35 Å. There is one shorter (2.21 Å) and one longer (2.34 Å) Na(1)-F(6) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one F(3), two equivalent F(2), two equivalent F(4), and two equivalent F(5) atoms. The Na(2)-F(3) bond length is 2.35 Å. There is one shorter (2.24 Å) and one longer (2.29 Å) Na(2)-F(2) bond length. There is one shorter (2.27 Å) and one longer (2.33 Å) Na(2)-F(4) bond length. There is one shorter (2.33 Å) and one longer (2.67 Å) Na(2)-F(5) bond length. Zr(1) is bonded to one F(2), one F(3), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted ZrF7 pentagonal bipyramids that share corners with four equivalent Na(1)F7 pentagonal bipyramids,  an edgeedge with one Zr(1)F7 pentagonal bipyramid, and edges with two equivalent Na(1)F7 pentagonal bipyramids. The Zr(1)-F(2) bond length is 2.07 Å. The Zr(1)-F(3) bond length is 2.01 Å. The Zr(1)-F(4) bond length is 2.06 Å. The Zr(1)-F(5) bond length is 2.05 Å. The Zr(1)-F(6) bond length is 2.01 Å. There is one shorter (2.15 Å) and one longer (2.20 Å) Zr(1)-F(1) bond length. There are six inequivalent F sites. In the first F site, F(6) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one Zr(1) atom. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Zr(1) atoms. In the third F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Zr(1) atom to form a mixture of distorted edge and corner-sharing FNa3Zr trigonal pyramids. In the fourth F site, F(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Zr(1) atom. In the fifth F site, F(4) is bonded to one Na(1), two equivalent Na(2), and one Zr(1) atom to form a mixture of edge and corner-sharing FNa3Zr tetrahedra. In the sixth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Zr(1) atom.