Na8MgTi2O8 is Chalcostibite-derived structured and crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(3) atom. In the second Na site, Na(2) is bonded in a distorted trigonal non-coplanar geometry to one O(1) and two equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(4) atoms. Mg(1) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form distorted MgO4 tetrahedra that share corners with two equivalent Ti(2)O4 tetrahedra and  an edgeedge with one Ti(1)O4 tetrahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form TiO4 tetrahedra that share  an edgeedge with one Mg(1)O4 tetrahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form TiO4 tetrahedra that share corners with two equivalent Mg(1)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), and one Ti(2) atom to form distorted ONa3Ti tetrahedra that share  a cornercorner with one O(1)Na3Ti tetrahedra and corners with two equivalent O(2)Na3MgTi trigonal bipyramids. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), one Mg(1), and one Ti(1) atom to form distorted ONa3MgTi trigonal bipyramids that share corners with two equivalent O(1)Na3Ti tetrahedra and  an edgeedge with one O(2)Na3MgTi trigonal bipyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one Ti(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Mg(1), and one Ti(2) atom.
Na8MgTi2O8 is Chalcostibite-derived structured and crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(3) atom. The Na(1)-O(1) bond length is 2.24 Å. The Na(1)-O(2) bond length is 2.57 Å. The Na(1)-O(3) bond length is 2.52 Å. In the second Na site, Na(2) is bonded in a distorted trigonal non-coplanar geometry to one O(1) and two equivalent O(3) atoms. The Na(2)-O(1) bond length is 2.25 Å. Both Na(2)-O(3) bond lengths are 2.42 Å. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(4) atoms. The Na(3)-O(2) bond length is 2.29 Å. Both Na(3)-O(4) bond lengths are 2.43 Å. Mg(1) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form distorted MgO4 tetrahedra that share corners with two equivalent Ti(2)O4 tetrahedra and  an edgeedge with one Ti(1)O4 tetrahedra. Both Mg(1)-O(2) bond lengths are 2.04 Å. Both Mg(1)-O(4) bond lengths are 2.01 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form TiO4 tetrahedra that share  an edgeedge with one Mg(1)O4 tetrahedra. Both Ti(1)-O(2) bond lengths are 1.88 Å. Both Ti(1)-O(3) bond lengths are 1.84 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form TiO4 tetrahedra that share corners with two equivalent Mg(1)O4 tetrahedra. Both Ti(2)-O(1) bond lengths are 1.80 Å. Both Ti(2)-O(4) bond lengths are 1.91 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), and one Ti(2) atom to form distorted ONa3Ti tetrahedra that share  a cornercorner with one O(1)Na3Ti tetrahedra and corners with two equivalent O(2)Na3MgTi trigonal bipyramids. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), one Mg(1), and one Ti(1) atom to form distorted ONa3MgTi trigonal bipyramids that share corners with two equivalent O(1)Na3Ti tetrahedra and  an edgeedge with one O(2)Na3MgTi trigonal bipyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one Ti(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Mg(1), and one Ti(2) atom.