NaTi2O4 crystallizes in the orthorhombic Imm2 space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(4), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO5 trigonal bipyramids. In the second Ti site, Ti(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing TiO5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a square co-planar geometry to one Na(1), one Ti(2), and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Ti(2) atoms to form distorted ONa2Ti2 tetrahedra that share corners with four equivalent O(2)Na2Ti2 tetrahedra and edges with four equivalent O(4)Na2Ti3 trigonal bipyramids. In the third O site, O(3) is bonded in a bent 120 degrees geometry to two equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Na(1), one Ti(1), and two equivalent Ti(2) atoms to form ONa2Ti3 trigonal bipyramids that share corners with four equivalent O(4)Na2Ti3 trigonal bipyramids and edges with four equivalent O(2)Na2Ti2 tetrahedra.
NaTi2O4 crystallizes in the orthorhombic Imm2 space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.42 Å. Both Na(1)-O(2) bond lengths are 2.31 Å. Both Na(1)-O(4) bond lengths are 2.55 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(4), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO5 trigonal bipyramids. The Ti(1)-O(4) bond length is 1.94 Å. Both Ti(1)-O(1) bond lengths are 2.05 Å. Both Ti(1)-O(3) bond lengths are 1.89 Å. In the second Ti site, Ti(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing TiO5 trigonal bipyramids. The Ti(2)-O(1) bond length is 1.90 Å. Both Ti(2)-O(2) bond lengths are 1.89 Å. Both Ti(2)-O(4) bond lengths are 2.05 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a square co-planar geometry to one Na(1), one Ti(2), and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Ti(2) atoms to form distorted ONa2Ti2 tetrahedra that share corners with four equivalent O(2)Na2Ti2 tetrahedra and edges with four equivalent O(4)Na2Ti3 trigonal bipyramids. In the third O site, O(3) is bonded in a bent 120 degrees geometry to two equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Na(1), one Ti(1), and two equivalent Ti(2) atoms to form ONa2Ti3 trigonal bipyramids that share corners with four equivalent O(4)Na2Ti3 trigonal bipyramids and edges with four equivalent O(2)Na2Ti2 tetrahedra.