NaMgTi2BiO6 crystallizes in the trigonal R3 space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. Mg(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form MgO6 octahedra that share edges with three equivalent Ti(1)O6 octahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form TiO6 octahedra that share edges with three equivalent Mg(1)O6 octahedra. In the second Ti site, Ti(2) is bonded in a trigonal planar geometry to three equivalent O(2) atoms. Bi(1) is bonded in a distorted trigonal planar geometry to three equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Mg(1), one Ti(1), and one Bi(1) atom to form distorted ONaMgTiBi tetrahedra that share corners with four equivalent O(1)NaMgTiBi tetrahedra, corners with seven equivalent O(2)NaMgTi2 tetrahedra,  an edgeedge with one O(2)NaMgTi2 tetrahedra, and edges with two equivalent O(1)NaMgTiBi tetrahedra. In the second O site, O(2) is bonded to one Na(1), one Mg(1), one Ti(1), and one Ti(2) atom to form distorted ONaMgTi2 tetrahedra that share corners with four equivalent O(2)NaMgTi2 tetrahedra, corners with seven equivalent O(1)NaMgTiBi tetrahedra,  an edgeedge with one O(1)NaMgTiBi tetrahedra, and edges with two equivalent O(2)NaMgTi2 tetrahedra.
NaMgTi2BiO6 crystallizes in the trigonal R3 space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. All Na(1)-O(1) bond lengths are 2.49 Å. All Na(1)-O(2) bond lengths are 2.49 Å. Mg(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form MgO6 octahedra that share edges with three equivalent Ti(1)O6 octahedra. All Mg(1)-O(1) bond lengths are 2.05 Å. All Mg(1)-O(2) bond lengths are 2.21 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form TiO6 octahedra that share edges with three equivalent Mg(1)O6 octahedra. All Ti(1)-O(1) bond lengths are 1.88 Å. All Ti(1)-O(2) bond lengths are 2.21 Å. In the second Ti site, Ti(2) is bonded in a trigonal planar geometry to three equivalent O(2) atoms. All Ti(2)-O(2) bond lengths are 1.84 Å. Bi(1) is bonded in a distorted trigonal planar geometry to three equivalent O(1) atoms. All Bi(1)-O(1) bond lengths are 2.33 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Mg(1), one Ti(1), and one Bi(1) atom to form distorted ONaMgTiBi tetrahedra that share corners with four equivalent O(1)NaMgTiBi tetrahedra, corners with seven equivalent O(2)NaMgTi2 tetrahedra,  an edgeedge with one O(2)NaMgTi2 tetrahedra, and edges with two equivalent O(1)NaMgTiBi tetrahedra. In the second O site, O(2) is bonded to one Na(1), one Mg(1), one Ti(1), and one Ti(2) atom to form distorted ONaMgTi2 tetrahedra that share corners with four equivalent O(2)NaMgTi2 tetrahedra, corners with seven equivalent O(1)NaMgTiBi tetrahedra,  an edgeedge with one O(1)NaMgTiBi tetrahedra, and edges with two equivalent O(2)NaMgTi2 tetrahedra.