NaTi6O12 crystallizes in the orthorhombic Pmn2_1 space group. Na(1) is bonded in a 4-coordinate geometry to one O(2), one O(6), and two equivalent O(3) atoms. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(4), one O(5), one O(8), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the second Ti site, Ti(2) is bonded to one O(6), one O(8), two equivalent O(3), and two equivalent O(7) atoms to form a mixture of distorted corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the third Ti site, Ti(3) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(1) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. In the fourth Ti site, Ti(4) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 44-49°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ti(4) and two equivalent Ti(3) atoms. In the second O site, O(2) is bonded to one Na(1), one Ti(4), and two equivalent Ti(3) atoms to form a mixture of corner and edge-sharing ONaTi3 trigonal pyramids. In the third O site, O(3) is bonded in a see-saw-like geometry to one Na(1), one Ti(1), one Ti(2), and one Ti(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Ti(4) and two equivalent Ti(1) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(3), and one Ti(4) atom. In the sixth O site, O(6) is bonded to one Na(1), one Ti(2), and two equivalent Ti(3) atoms to form a mixture of corner and edge-sharing ONaTi3 tetrahedra. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ti(2) and two equivalent Ti(1) atoms. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Ti(2) and two equivalent Ti(1) atoms.
NaTi6O12 crystallizes in the orthorhombic Pmn2_1 space group. Na(1) is bonded in a 4-coordinate geometry to one O(2), one O(6), and two equivalent O(3) atoms. The Na(1)-O(2) bond length is 2.32 Å. The Na(1)-O(6) bond length is 2.05 Å. Both Na(1)-O(3) bond lengths are 2.21 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(4), one O(5), one O(8), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Ti(1)-O(3) bond length is 1.92 Å. The Ti(1)-O(4) bond length is 1.95 Å. The Ti(1)-O(5) bond length is 2.03 Å. The Ti(1)-O(8) bond length is 2.06 Å. There is one shorter (1.99 Å) and one longer (2.03 Å) Ti(1)-O(7) bond length. In the second Ti site, Ti(2) is bonded to one O(6), one O(8), two equivalent O(3), and two equivalent O(7) atoms to form a mixture of distorted corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Ti(2)-O(6) bond length is 2.04 Å. The Ti(2)-O(8) bond length is 1.94 Å. Both Ti(2)-O(3) bond lengths are 2.06 Å. Both Ti(2)-O(7) bond lengths are 1.96 Å. In the third Ti site, Ti(3) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(1) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. The Ti(3)-O(2) bond length is 2.04 Å. The Ti(3)-O(3) bond length is 2.07 Å. The Ti(3)-O(5) bond length is 1.96 Å. The Ti(3)-O(6) bond length is 1.97 Å. There is one shorter (1.98 Å) and one longer (2.01 Å) Ti(3)-O(1) bond length. In the fourth Ti site, Ti(4) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 44-49°. The Ti(4)-O(2) bond length is 1.99 Å. The Ti(4)-O(4) bond length is 1.99 Å. Both Ti(4)-O(1) bond lengths are 2.06 Å. Both Ti(4)-O(5) bond lengths are 1.93 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ti(4) and two equivalent Ti(3) atoms. In the second O site, O(2) is bonded to one Na(1), one Ti(4), and two equivalent Ti(3) atoms to form a mixture of corner and edge-sharing ONaTi3 trigonal pyramids. In the third O site, O(3) is bonded in a see-saw-like geometry to one Na(1), one Ti(1), one Ti(2), and one Ti(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Ti(4) and two equivalent Ti(1) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(3), and one Ti(4) atom. In the sixth O site, O(6) is bonded to one Na(1), one Ti(2), and two equivalent Ti(3) atoms to form a mixture of corner and edge-sharing ONaTi3 tetrahedra. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ti(2) and two equivalent Ti(1) atoms. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Ti(2) and two equivalent Ti(1) atoms.