Na5Zr2MnF15 crystallizes in the orthorhombic Cmcm space group. There are three 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(4), and four equivalent F(2) atoms. In the second Na site, Na(2) is bonded to one F(1), one F(3), one F(4), one F(5), two equivalent F(2), and two equivalent F(6) atoms to form distorted NaF8 hexagonal bipyramids that share  a cornercorner with one Na(2)F8 hexagonal bipyramid,  a cornercorner with one Zr(1)F7 pentagonal bipyramid, edges with two equivalent Mn(1)F6 octahedra, and edges with three equivalent Zr(1)F7 pentagonal bipyramids. In the third Na site, Na(3) is bonded in a distorted body-centered cubic geometry to four equivalent F(3) and four equivalent F(6) atoms. Zr(1) is bonded to one F(1), one F(3), one F(4), two equivalent F(2), and two equivalent F(6) atoms to form distorted ZrF7 pentagonal bipyramids that share  a cornercorner with one Na(2)F8 hexagonal bipyramid, corners with two equivalent Mn(1)F6 octahedra, and edges with three equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 36°. Mn(1) is bonded to two equivalent F(5) and four equivalent F(6) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent Zr(1)F7 pentagonal bipyramids, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 49°. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form a mixture of corner and edge-sharing FNa3Zr tetrahedra. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form a mixture of corner and edge-sharing FNa3Zr tetrahedra. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(3), and one Zr(1) atom to form a mixture of corner and edge-sharing FNa3Zr tetrahedra. In the fourth F site, F(4) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing FNa3Zr trigonal pyramids. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to two equivalent Na(2) and two equivalent Mn(1) atoms. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Zr(1), and one Mn(1) atom.
Na5Zr2MnF15 crystallizes in the orthorhombic Cmcm space group. There are three 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(4), and four equivalent F(2) atoms. Both Na(1)-F(1) bond lengths are 2.35 Å. Both Na(1)-F(4) bond lengths are 2.55 Å. There are two shorter (2.39 Å) and two longer (2.48 Å) Na(1)-F(2) bond lengths. In the second Na site, Na(2) is bonded to one F(1), one F(3), one F(4), one F(5), two equivalent F(2), and two equivalent F(6) atoms to form distorted NaF8 hexagonal bipyramids that share  a cornercorner with one Na(2)F8 hexagonal bipyramid,  a cornercorner with one Zr(1)F7 pentagonal bipyramid, edges with two equivalent Mn(1)F6 octahedra, and edges with three equivalent Zr(1)F7 pentagonal bipyramids. The Na(2)-F(1) bond length is 2.59 Å. The Na(2)-F(3) bond length is 2.33 Å. The Na(2)-F(4) bond length is 2.27 Å. The Na(2)-F(5) bond length is 2.85 Å. Both Na(2)-F(2) bond lengths are 2.39 Å. Both Na(2)-F(6) bond lengths are 2.71 Å. In the third Na site, Na(3) is bonded in a distorted body-centered cubic geometry to four equivalent F(3) and four equivalent F(6) atoms. All Na(3)-F(3) bond lengths are 2.47 Å. All Na(3)-F(6) bond lengths are 2.78 Å. Zr(1) is bonded to one F(1), one F(3), one F(4), two equivalent F(2), and two equivalent F(6) atoms to form distorted ZrF7 pentagonal bipyramids that share  a cornercorner with one Na(2)F8 hexagonal bipyramid, corners with two equivalent Mn(1)F6 octahedra, and edges with three equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 36°. The Zr(1)-F(1) bond length is 2.07 Å. The Zr(1)-F(3) bond length is 2.13 Å. The Zr(1)-F(4) bond length is 2.08 Å. Both Zr(1)-F(2) bond lengths are 2.07 Å. Both Zr(1)-F(6) bond lengths are 2.14 Å. Mn(1) is bonded to two equivalent F(5) and four equivalent F(6) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent Zr(1)F7 pentagonal bipyramids, and edges with four equivalent Na(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 49°. Both Mn(1)-F(5) bond lengths are 2.09 Å. All Mn(1)-F(6) bond lengths are 2.17 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form a mixture of corner and edge-sharing FNa3Zr tetrahedra. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form a mixture of corner and edge-sharing FNa3Zr tetrahedra. In the third F site, F(3) is bonded to one Na(2), two equivalent Na(3), and one Zr(1) atom to form a mixture of corner and edge-sharing FNa3Zr tetrahedra. In the fourth F site, F(4) is bonded to one Na(2), two equivalent Na(1), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing FNa3Zr trigonal pyramids. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to two equivalent Na(2) and two equivalent Mn(1) atoms. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Zr(1), and one Mn(1) atom.