CaTi4O6 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-38°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ti(2) and four equivalent Ti(1) atoms to form OTi6 octahedra that share corners with four equivalent O(3)CaTi5 octahedra, edges with two equivalent O(1)Ti6 octahedra, edges with six equivalent O(3)CaTi5 octahedra, and edges with four equivalent O(2)Ca2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. In the second O site, O(2) is bonded to two equivalent Ca(1), one Ti(1), and two equivalent Ti(2) atoms to form distorted OCa2Ti3 trigonal bipyramids that share corners with five equivalent O(3)CaTi5 octahedra, corners with two equivalent O(2)Ca2Ti3 trigonal bipyramids, edges with two equivalent O(1)Ti6 octahedra, edges with three equivalent O(3)CaTi5 octahedra, and edges with three equivalent O(2)Ca2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 3-41°. In the third O site, O(3) is bonded to one Ca(1), two equivalent Ti(2), and three equivalent Ti(1) atoms to form distorted OCaTi5 octahedra that share  a cornercorner with one O(3)CaTi5 octahedra, corners with two equivalent O(1)Ti6 octahedra, corners with five equivalent O(2)Ca2Ti3 trigonal bipyramids, edges with three equivalent O(1)Ti6 octahedra, edges with four equivalent O(3)CaTi5 octahedra, and edges with three equivalent O(2)Ca2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-50°. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Ti(2) atoms.
CaTi4O6 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. Both Ca(1)-O(3) bond lengths are 2.61 Å. Both Ca(1)-O(4) bond lengths are 2.35 Å. All Ca(1)-O(2) bond lengths are 2.41 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Ti(1)-O(2) bond length is 2.06 Å. Both Ti(1)-O(1) bond lengths are 2.22 Å. There are two shorter (2.07 Å) and one longer (2.19 Å) Ti(1)-O(3) bond length. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-38°. The Ti(2)-O(1) bond length is 2.17 Å. The Ti(2)-O(4) bond length is 1.98 Å. Both Ti(2)-O(2) bond lengths are 2.09 Å. Both Ti(2)-O(3) bond lengths are 2.09 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ti(2) and four equivalent Ti(1) atoms to form OTi6 octahedra that share corners with four equivalent O(3)CaTi5 octahedra, edges with two equivalent O(1)Ti6 octahedra, edges with six equivalent O(3)CaTi5 octahedra, and edges with four equivalent O(2)Ca2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. In the second O site, O(2) is bonded to two equivalent Ca(1), one Ti(1), and two equivalent Ti(2) atoms to form distorted OCa2Ti3 trigonal bipyramids that share corners with five equivalent O(3)CaTi5 octahedra, corners with two equivalent O(2)Ca2Ti3 trigonal bipyramids, edges with two equivalent O(1)Ti6 octahedra, edges with three equivalent O(3)CaTi5 octahedra, and edges with three equivalent O(2)Ca2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 3-41°. In the third O site, O(3) is bonded to one Ca(1), two equivalent Ti(2), and three equivalent Ti(1) atoms to form distorted OCaTi5 octahedra that share  a cornercorner with one O(3)CaTi5 octahedra, corners with two equivalent O(1)Ti6 octahedra, corners with five equivalent O(2)Ca2Ti3 trigonal bipyramids, edges with three equivalent O(1)Ti6 octahedra, edges with four equivalent O(3)CaTi5 octahedra, and edges with three equivalent O(2)Ca2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-50°. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Ti(2) atoms.