Ti3V5O16 is Rutile-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. In the second Ti site, Ti(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent V(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the third V site, V(3) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Ti(2), one V(1), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Ti(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2) and two equivalent V(4) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(4) atoms. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2), one V(3), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent V(4) atoms. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ti(1), one V(2), and one V(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(4) atoms.
Ti3V5O16 is Rutile-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Ti(1)-O(11) bond length is 2.02 Å. The Ti(1)-O(2) bond length is 2.02 Å. The Ti(1)-O(3) bond length is 1.98 Å. The Ti(1)-O(4) bond length is 1.94 Å. The Ti(1)-O(6) bond length is 1.96 Å. The Ti(1)-O(7) bond length is 1.97 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. The Ti(2)-O(10) bond length is 1.96 Å. The Ti(2)-O(5) bond length is 1.94 Å. Both Ti(2)-O(1) bond lengths are 1.97 Å. Both Ti(2)-O(9) bond lengths are 2.02 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent V(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The V(1)-O(2) bond length is 1.92 Å. The V(1)-O(8) bond length is 1.89 Å. Both V(1)-O(1) bond lengths are 2.03 Å. Both V(1)-O(6) bond lengths are 1.98 Å. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(2)-O(3) bond length is 1.97 Å. The V(2)-O(4) bond length is 1.98 Å. Both V(2)-O(11) bond lengths are 1.95 Å. Both V(2)-O(6) bond lengths are 1.96 Å. In the third V site, V(3) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The V(3)-O(12) bond length is 1.94 Å. The V(3)-O(7) bond length is 2.01 Å. Both V(3)-O(11) bond lengths are 1.96 Å. Both V(3)-O(9) bond lengths are 1.99 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. The V(4)-O(1) bond length is 1.93 Å. The V(4)-O(10) bond length is 1.98 Å. The V(4)-O(12) bond length is 1.98 Å. The V(4)-O(5) bond length is 1.96 Å. The V(4)-O(8) bond length is 2.02 Å. The V(4)-O(9) bond length is 1.93 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Ti(2), one V(1), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Ti(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2) and two equivalent V(4) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(4) atoms. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2), one V(3), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent V(4) atoms. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ti(1), one V(2), and one V(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(4) atoms.