NaCeTiNbO6F crystallizes in the orthorhombic Imma space group. Na(1) is bonded to two equivalent O(2), four equivalent O(3), and two equivalent F(1) atoms to form distorted NaO6F2 hexagonal bipyramids that share edges with two equivalent Na(1)O6F2 hexagonal bipyramids, edges with four equivalent Ce(1)O6F2 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. Ce(1) is bonded to two equivalent O(1), four equivalent O(3), and two equivalent F(1) atoms to form distorted CeO6F2 hexagonal bipyramids that share edges with two equivalent Ce(1)O6F2 hexagonal bipyramids, edges with four equivalent Na(1)O6F2 hexagonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, edges with two equivalent Na(1)O6F2 hexagonal bipyramids, and edges with four equivalent Ce(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-48°. Nb(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, edges with two equivalent Ce(1)O6F2 hexagonal bipyramids, and edges with four equivalent Na(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-45°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ce(1) and two equivalent Ti(1) atoms to form distorted OCe2Ti2 tetrahedra that share corners with two equivalent F(1)Na2Ce2 tetrahedra, corners with four equivalent O(1)Ce2Ti2 tetrahedra, and  an edgeedge with one F(1)Na2Ce2 tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Ce(1), one Ti(1), and one Nb(1) atom. F(1) is bonded to two equivalent Na(1) and two equivalent Ce(1) atoms to form FNa2Ce2 tetrahedra that share corners with two equivalent O(1)Ce2Ti2 tetrahedra, corners with four equivalent F(1)Na2Ce2 tetrahedra, and  an edgeedge with one O(1)Ce2Ti2 tetrahedra.
NaCeTiNbO6F crystallizes in the orthorhombic Imma space group. Na(1) is bonded to two equivalent O(2), four equivalent O(3), and two equivalent F(1) atoms to form distorted NaO6F2 hexagonal bipyramids that share edges with two equivalent Na(1)O6F2 hexagonal bipyramids, edges with four equivalent Ce(1)O6F2 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. Both Na(1)-O(2) bond lengths are 2.63 Å. All Na(1)-O(3) bond lengths are 2.72 Å. Both Na(1)-F(1) bond lengths are 2.20 Å. Ce(1) is bonded to two equivalent O(1), four equivalent O(3), and two equivalent F(1) atoms to form distorted CeO6F2 hexagonal bipyramids that share edges with two equivalent Ce(1)O6F2 hexagonal bipyramids, edges with four equivalent Na(1)O6F2 hexagonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Ce(1)-O(1) bond lengths are 2.61 Å. All Ce(1)-O(3) bond lengths are 2.52 Å. Both Ce(1)-F(1) bond lengths are 2.33 Å. Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, edges with two equivalent Na(1)O6F2 hexagonal bipyramids, and edges with four equivalent Ce(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-48°. Both Ti(1)-O(1) bond lengths are 1.99 Å. All Ti(1)-O(3) bond lengths are 1.99 Å. Nb(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, edges with two equivalent Ce(1)O6F2 hexagonal bipyramids, and edges with four equivalent Na(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-45°. Both Nb(1)-O(2) bond lengths are 2.02 Å. All Nb(1)-O(3) bond lengths are 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ce(1) and two equivalent Ti(1) atoms to form distorted OCe2Ti2 tetrahedra that share corners with two equivalent F(1)Na2Ce2 tetrahedra, corners with four equivalent O(1)Ce2Ti2 tetrahedra, and  an edgeedge with one F(1)Na2Ce2 tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Ce(1), one Ti(1), and one Nb(1) atom. F(1) is bonded to two equivalent Na(1) and two equivalent Ce(1) atoms to form FNa2Ce2 tetrahedra that share corners with two equivalent O(1)Ce2Ti2 tetrahedra, corners with four equivalent F(1)Na2Ce2 tetrahedra, and  an edgeedge with one O(1)Ce2Ti2 tetrahedra.