VTiO3 is Ilmenite-like structured and crystallizes in the triclinic P1 space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form distorted TiO6 octahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  a faceface with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and  a faceface with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the third Ti site, Ti(3) is bonded to one O(10), one O(11), one O(12), one O(6), one O(7), and one O(9) atom to form TiO6 octahedra that share  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. In the fourth Ti site, Ti(4) is bonded to one O(10), one O(11), one O(12), one O(5), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-61°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-61°. In the third V site, V(3) is bonded to one O(11), one O(12), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Ti(4)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with four equivalent Ti(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and  a faceface with one Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-61°. In the fourth V site, V(4) is bonded to one O(10), one O(11), one O(12), one O(2), one O(6), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with four equivalent Ti(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  a faceface with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ti(1), one Ti(2), one V(1), and one V(2) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(10)Ti2V2 trigonal pyramid,  a cornercorner with one O(7)Ti2V2 trigonal pyramid,  a cornercorner with one O(9)Ti3V trigonal pyramid,  a cornercorner with one O(2)TiV3 trigonal pyramid,  a cornercorner with one O(6)TiV3 trigonal pyramid,  an edgeedge with one O(7)Ti2V2 trigonal pyramid, and  an edgeedge with one O(2)TiV3 trigonal pyramid. In the second O site, O(2) is bonded to one Ti(1), one V(1), one V(2), and one V(4) atom to form distorted OTiV3 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid,  a cornercorner with one O(12)Ti2V2 trigonal pyramid, corners with two equivalent O(6)TiV3 trigonal pyramids,  an edgeedge with one O(1)Ti2V2 trigonal pyramid,  an edgeedge with one O(10)Ti2V2 trigonal pyramid, and  an edgeedge with one O(7)Ti2V2 trigonal pyramid. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Ti(1), one Ti(2), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(4), and one V(1) atom. In the sixth O site, O(6) is bonded to one Ti(3), one V(2), one V(3), and one V(4) atom to form distorted OTiV3 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid, corners with two equivalent O(9)Ti3V trigonal pyramids, corners with two equivalent O(2)TiV3 trigonal pyramids, corners with three equivalent O(12)Ti2V2 trigonal pyramids,  an edgeedge with one O(10)Ti2V2 trigonal pyramid,  an edgeedge with one O(11)Ti2V2 trigonal pyramid, and  an edgeedge with one O(7)Ti2V2 trigonal pyramid. In the seventh O site, O(7) is bonded to one Ti(2), one Ti(3), one V(1), and one V(2) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid,  a cornercorner with one O(12)Ti2V2 trigonal pyramid, corners with two equivalent O(10)Ti2V2 trigonal pyramids, corners with two equivalent O(9)Ti3V trigonal pyramids,  an edgeedge with one O(1)Ti2V2 trigonal pyramid,  an edgeedge with one O(2)TiV3 trigonal pyramid, and  an edgeedge with one O(6)TiV3 trigonal pyramid. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1), one Ti(4), one V(3), and one V(4) atom. In the ninth O site, O(9) is bonded to one Ti(2), one Ti(3), one Ti(4), and one V(3) atom to form distorted OTi3V trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(12)Ti2V2 trigonal pyramid, corners with two equivalent O(7)Ti2V2 trigonal pyramids, corners with two equivalent O(6)TiV3 trigonal pyramids, corners with three equivalent O(11)Ti2V2 trigonal pyramids,  an edgeedge with one O(10)Ti2V2 trigonal pyramid, and  an edgeedge with one O(12)Ti2V2 trigonal pyramid. In the tenth O site, O(10) is bonded to one Ti(3), one Ti(4), one V(1), and one V(4) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid, corners with two equivalent O(7)Ti2V2 trigonal pyramids, corners with three equivalent O(12)Ti2V2 trigonal pyramids,  an edgeedge with one O(11)Ti2V2 trigonal pyramid,  an edgeedge with one O(9)Ti3V trigonal pyramid,  an edgeedge with one O(2)TiV3 trigonal pyramid, and  an edgeedge with one O(6)TiV3 trigonal pyramid. In the eleventh O site, O(11) is bonded to one Ti(3), one Ti(4), one V(3), and one V(4) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(10)Ti2V2 trigonal pyramid,  a cornercorner with one O(7)Ti2V2 trigonal pyramid,  a cornercorner with one O(2)TiV3 trigonal pyramid,  a cornercorner with one O(6)TiV3 trigonal pyramid, corners with three equivalent O(9)Ti3V trigonal pyramids,  an edgeedge with one O(10)Ti2V2 trigonal pyramid,  an edgeedge with one O(6)TiV3 trigonal pyramid, and edges with two equivalent O(12)Ti2V2 trigonal pyramids. In the twelfth O site, O(12) is bonded to one Ti(3), one Ti(4), one V(3), and one V(4) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(7)Ti2V2 trigonal pyramid,  a cornercorner with one O(9)Ti3V trigonal pyramid,  a cornercorner with one O(2)TiV3 trigonal pyramid, corners with three equivalent O(10)Ti2V2 trigonal pyramids, corners with three equivalent O(6)TiV3 trigonal pyramids,  an edgeedge with one O(9)Ti3V trigonal pyramid, and edges with two equivalent O(11)Ti2V2 trigonal pyramids.
VTiO3 is Ilmenite-like structured and crystallizes in the triclinic P1 space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form distorted TiO6 octahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  a faceface with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The Ti(1)-O(1) bond length is 1.99 Å. The Ti(1)-O(2) bond length is 1.91 Å. The Ti(1)-O(3) bond length is 2.11 Å. The Ti(1)-O(4) bond length is 2.11 Å. The Ti(1)-O(5) bond length is 2.12 Å. The Ti(1)-O(8) bond length is 1.91 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and  a faceface with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The Ti(2)-O(1) bond length is 2.02 Å. The Ti(2)-O(3) bond length is 2.03 Å. The Ti(2)-O(4) bond length is 2.04 Å. The Ti(2)-O(5) bond length is 2.11 Å. The Ti(2)-O(7) bond length is 2.03 Å. The Ti(2)-O(9) bond length is 2.01 Å. In the third Ti site, Ti(3) is bonded to one O(10), one O(11), one O(12), one O(6), one O(7), and one O(9) atom to form TiO6 octahedra that share  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. The Ti(3)-O(10) bond length is 2.13 Å. The Ti(3)-O(11) bond length is 2.08 Å. The Ti(3)-O(12) bond length is 1.93 Å. The Ti(3)-O(6) bond length is 2.03 Å. The Ti(3)-O(7) bond length is 1.96 Å. The Ti(3)-O(9) bond length is 1.96 Å. In the fourth Ti site, Ti(4) is bonded to one O(10), one O(11), one O(12), one O(5), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The Ti(4)-O(10) bond length is 1.91 Å. The Ti(4)-O(11) bond length is 1.92 Å. The Ti(4)-O(12) bond length is 2.08 Å. The Ti(4)-O(5) bond length is 1.92 Å. The Ti(4)-O(8) bond length is 2.10 Å. The Ti(4)-O(9) bond length is 2.23 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-61°. The V(1)-O(1) bond length is 2.15 Å. The V(1)-O(10) bond length is 2.14 Å. The V(1)-O(2) bond length is 2.17 Å. The V(1)-O(4) bond length is 2.08 Å. The V(1)-O(5) bond length is 2.12 Å. The V(1)-O(7) bond length is 2.16 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-61°. The V(2)-O(1) bond length is 2.17 Å. The V(2)-O(2) bond length is 2.09 Å. The V(2)-O(3) bond length is 2.02 Å. The V(2)-O(4) bond length is 2.02 Å. The V(2)-O(6) bond length is 1.99 Å. The V(2)-O(7) bond length is 2.15 Å. In the third V site, V(3) is bonded to one O(11), one O(12), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Ti(4)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with four equivalent Ti(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and  a faceface with one Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-61°. The V(3)-O(11) bond length is 2.14 Å. The V(3)-O(12) bond length is 2.18 Å. The V(3)-O(3) bond length is 2.08 Å. The V(3)-O(6) bond length is 2.10 Å. The V(3)-O(8) bond length is 2.17 Å. The V(3)-O(9) bond length is 2.13 Å. In the fourth V site, V(4) is bonded to one O(10), one O(11), one O(12), one O(2), one O(6), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with four equivalent Ti(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  a faceface with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. The V(4)-O(10) bond length is 2.17 Å. The V(4)-O(11) bond length is 2.16 Å. The V(4)-O(12) bond length is 2.13 Å. The V(4)-O(2) bond length is 2.12 Å. The V(4)-O(6) bond length is 2.14 Å. The V(4)-O(8) bond length is 2.13 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ti(1), one Ti(2), one V(1), and one V(2) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(10)Ti2V2 trigonal pyramid,  a cornercorner with one O(7)Ti2V2 trigonal pyramid,  a cornercorner with one O(9)Ti3V trigonal pyramid,  a cornercorner with one O(2)TiV3 trigonal pyramid,  a cornercorner with one O(6)TiV3 trigonal pyramid,  an edgeedge with one O(7)Ti2V2 trigonal pyramid, and  an edgeedge with one O(2)TiV3 trigonal pyramid. In the second O site, O(2) is bonded to one Ti(1), one V(1), one V(2), and one V(4) atom to form distorted OTiV3 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid,  a cornercorner with one O(12)Ti2V2 trigonal pyramid, corners with two equivalent O(6)TiV3 trigonal pyramids,  an edgeedge with one O(1)Ti2V2 trigonal pyramid,  an edgeedge with one O(10)Ti2V2 trigonal pyramid, and  an edgeedge with one O(7)Ti2V2 trigonal pyramid. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Ti(1), one Ti(2), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(4), and one V(1) atom. In the sixth O site, O(6) is bonded to one Ti(3), one V(2), one V(3), and one V(4) atom to form distorted OTiV3 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid, corners with two equivalent O(9)Ti3V trigonal pyramids, corners with two equivalent O(2)TiV3 trigonal pyramids, corners with three equivalent O(12)Ti2V2 trigonal pyramids,  an edgeedge with one O(10)Ti2V2 trigonal pyramid,  an edgeedge with one O(11)Ti2V2 trigonal pyramid, and  an edgeedge with one O(7)Ti2V2 trigonal pyramid. In the seventh O site, O(7) is bonded to one Ti(2), one Ti(3), one V(1), and one V(2) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid,  a cornercorner with one O(12)Ti2V2 trigonal pyramid, corners with two equivalent O(10)Ti2V2 trigonal pyramids, corners with two equivalent O(9)Ti3V trigonal pyramids,  an edgeedge with one O(1)Ti2V2 trigonal pyramid,  an edgeedge with one O(2)TiV3 trigonal pyramid, and  an edgeedge with one O(6)TiV3 trigonal pyramid. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1), one Ti(4), one V(3), and one V(4) atom. In the ninth O site, O(9) is bonded to one Ti(2), one Ti(3), one Ti(4), and one V(3) atom to form distorted OTi3V trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(12)Ti2V2 trigonal pyramid, corners with two equivalent O(7)Ti2V2 trigonal pyramids, corners with two equivalent O(6)TiV3 trigonal pyramids, corners with three equivalent O(11)Ti2V2 trigonal pyramids,  an edgeedge with one O(10)Ti2V2 trigonal pyramid, and  an edgeedge with one O(12)Ti2V2 trigonal pyramid. In the tenth O site, O(10) is bonded to one Ti(3), one Ti(4), one V(1), and one V(4) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(1)Ti2V2 trigonal pyramid,  a cornercorner with one O(11)Ti2V2 trigonal pyramid, corners with two equivalent O(7)Ti2V2 trigonal pyramids, corners with three equivalent O(12)Ti2V2 trigonal pyramids,  an edgeedge with one O(11)Ti2V2 trigonal pyramid,  an edgeedge with one O(9)Ti3V trigonal pyramid,  an edgeedge with one O(2)TiV3 trigonal pyramid, and  an edgeedge with one O(6)TiV3 trigonal pyramid. In the eleventh O site, O(11) is bonded to one Ti(3), one Ti(4), one V(3), and one V(4) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(10)Ti2V2 trigonal pyramid,  a cornercorner with one O(7)Ti2V2 trigonal pyramid,  a cornercorner with one O(2)TiV3 trigonal pyramid,  a cornercorner with one O(6)TiV3 trigonal pyramid, corners with three equivalent O(9)Ti3V trigonal pyramids,  an edgeedge with one O(10)Ti2V2 trigonal pyramid,  an edgeedge with one O(6)TiV3 trigonal pyramid, and edges with two equivalent O(12)Ti2V2 trigonal pyramids. In the twelfth O site, O(12) is bonded to one Ti(3), one Ti(4), one V(3), and one V(4) atom to form distorted OTi2V2 trigonal pyramids that share  a cornercorner with one O(7)Ti2V2 trigonal pyramid,  a cornercorner with one O(9)Ti3V trigonal pyramid,  a cornercorner with one O(2)TiV3 trigonal pyramid, corners with three equivalent O(10)Ti2V2 trigonal pyramids, corners with three equivalent O(6)TiV3 trigonal pyramids,  an edgeedge with one O(9)Ti3V trigonal pyramid, and edges with two equivalent O(11)Ti2V2 trigonal pyramids.