TiV3O8 crystallizes in the triclinic P1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(9), and two equivalent O(4) atoms. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(16), and two equivalent O(3) atoms. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), one O(7), one O(9), and two equivalent O(16) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 21°. In the second V site, V(2) is bonded to one O(10), one O(4), one O(5), one O(8), and two equivalent O(15) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 22°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(6), one O(8), and two equivalent O(13) atoms. In the fourth V site, V(4) is bonded to one O(12), one O(13), one O(7), one O(9), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 26°. In the fifth V site, V(5) is bonded to one O(10), one O(11), one O(14), one O(8), and two equivalent O(1) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 28°. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(7), and two equivalent O(14) atoms. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(6) and two equivalent V(5) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(4) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Ti(2), one V(1), and one V(6) atom. In the fourth O site, O(4) is bonded to two equivalent Ti(1), one V(2), and one V(3) atom to form distorted OTi2V2 trigonal pyramids that share corners with two equivalent O(4)Ti2V2 trigonal pyramids and edges with two equivalent O(13)TiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one V(6) atom. In the sixth O site, O(6) is bonded in a linear geometry to one V(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(5) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Ti(1), one V(1), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2), one V(2), and one V(5) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one Ti(1) and one V(5) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Ti(2) and one V(4) atom. In the thirteenth O site, O(13) is bonded to one Ti(1), one V(4), and two equivalent V(3) atoms to form distorted OTiV3 trigonal pyramids that share corners with two equivalent O(13)TiV3 trigonal pyramids and edges with two equivalent O(4)Ti2V2 trigonal pyramids. In the fourteenth O site, O(14) is bonded to one Ti(2), one V(5), and two equivalent V(6) atoms to form distorted corner-sharing OTiV3 trigonal pyramids. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent V(2) atoms. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent V(1) atoms.
TiV3O8 crystallizes in the triclinic P1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(9), and two equivalent O(4) atoms. The Ti(1)-O(11) bond length is 1.75 Å. The Ti(1)-O(13) bond length is 2.31 Å. The Ti(1)-O(15) bond length is 2.14 Å. The Ti(1)-O(9) bond length is 1.89 Å. Both Ti(1)-O(4) bond lengths are 1.98 Å. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(16), and two equivalent O(3) atoms. The Ti(2)-O(10) bond length is 1.89 Å. The Ti(2)-O(12) bond length is 1.74 Å. The Ti(2)-O(14) bond length is 2.36 Å. The Ti(2)-O(16) bond length is 2.17 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) Ti(2)-O(3) bond length. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), one O(7), one O(9), and two equivalent O(16) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 21°. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.98 Å. The V(1)-O(9) bond length is 1.92 Å. There is one shorter (1.77 Å) and one longer (2.07 Å) V(1)-O(16) bond length. In the second V site, V(2) is bonded to one O(10), one O(4), one O(5), one O(8), and two equivalent O(15) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 22°. The V(2)-O(10) bond length is 1.89 Å. The V(2)-O(4) bond length is 2.08 Å. The V(2)-O(5) bond length is 1.97 Å. The V(2)-O(8) bond length is 2.00 Å. There is one shorter (1.78 Å) and one longer (2.07 Å) V(2)-O(15) bond length. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(6), one O(8), and two equivalent O(13) atoms. The V(3)-O(2) bond length is 2.02 Å. The V(3)-O(4) bond length is 2.37 Å. The V(3)-O(6) bond length is 1.69 Å. The V(3)-O(8) bond length is 2.03 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) V(3)-O(13) bond length. In the fourth V site, V(4) is bonded to one O(12), one O(13), one O(7), one O(9), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 26°. The V(4)-O(12) bond length is 1.92 Å. The V(4)-O(13) bond length is 2.10 Å. The V(4)-O(7) bond length is 1.88 Å. The V(4)-O(9) bond length is 2.04 Å. There is one shorter (1.84 Å) and one longer (2.03 Å) V(4)-O(2) bond length. In the fifth V site, V(5) is bonded to one O(10), one O(11), one O(14), one O(8), and two equivalent O(1) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 28°. The V(5)-O(10) bond length is 2.10 Å. The V(5)-O(11) bond length is 1.89 Å. The V(5)-O(14) bond length is 2.06 Å. The V(5)-O(8) bond length is 1.84 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) V(5)-O(1) bond length. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(7), and two equivalent O(14) atoms. The V(6)-O(1) bond length is 1.94 Å. The V(6)-O(3) bond length is 2.43 Å. The V(6)-O(5) bond length is 1.70 Å. The V(6)-O(7) bond length is 2.02 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) V(6)-O(14) bond length. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(6) and two equivalent V(5) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(4) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Ti(2), one V(1), and one V(6) atom. In the fourth O site, O(4) is bonded to two equivalent Ti(1), one V(2), and one V(3) atom to form distorted OTi2V2 trigonal pyramids that share corners with two equivalent O(4)Ti2V2 trigonal pyramids and edges with two equivalent O(13)TiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one V(6) atom. In the sixth O site, O(6) is bonded in a linear geometry to one V(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(4), and one V(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(5) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Ti(1), one V(1), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2), one V(2), and one V(5) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one Ti(1) and one V(5) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Ti(2) and one V(4) atom. In the thirteenth O site, O(13) is bonded to one Ti(1), one V(4), and two equivalent V(3) atoms to form distorted OTiV3 trigonal pyramids that share corners with two equivalent O(13)TiV3 trigonal pyramids and edges with two equivalent O(4)Ti2V2 trigonal pyramids. In the fourteenth O site, O(14) is bonded to one Ti(2), one V(5), and two equivalent V(6) atoms to form distorted corner-sharing OTiV3 trigonal pyramids. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent V(2) atoms. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent V(1) atoms.