Ti3V2O9 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 60°. In the second Ti site, Ti(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form TiO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O5 trigonal bipyramids, and  an edgeedge with one Ti(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 33°. V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), and three equivalent O(3) atoms. There are five inequivalent O sites. In the first O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent Ti(2) atoms. In the second O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Ti(1) and two equivalent V(1) atoms. In the third O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(1) atom. In the fourth O site, O(2) is bonded in a T-shaped geometry to two equivalent Ti(2) and one V(1) atom. In the fifth O site, O(3) is bonded to one Ti(1) and three equivalent V(1) atoms to form a mixture of edge and corner-sharing OTiV3 trigonal pyramids.
Ti3V2O9 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent Ti(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 60°. Both Ti(1)-O(1) bond lengths are 1.86 Å. Both Ti(1)-O(3) bond lengths are 2.12 Å. Both Ti(1)-O(5) bond lengths are 2.00 Å. In the second Ti site, Ti(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form TiO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O5 trigonal bipyramids, and  an edgeedge with one Ti(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 33°. The Ti(2)-O(1) bond length is 1.97 Å. There is one shorter (1.85 Å) and one longer (2.00 Å) Ti(2)-O(2) bond length. There is one shorter (1.85 Å) and one longer (1.90 Å) Ti(2)-O(4) bond length. V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), and three equivalent O(3) atoms. The V(1)-O(1) bond length is 1.92 Å. The V(1)-O(2) bond length is 2.22 Å. The V(1)-O(5) bond length is 2.44 Å. There are a spread of V(1)-O(3) bond distances ranging from 2.00-2.25 Å. There are five inequivalent O sites. In the first O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent Ti(2) atoms. In the second O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Ti(1) and two equivalent V(1) atoms. In the third O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(1) atom. In the fourth O site, O(2) is bonded in a T-shaped geometry to two equivalent Ti(2) and one V(1) atom. In the fifth O site, O(3) is bonded to one Ti(1) and three equivalent V(1) atoms to form a mixture of edge and corner-sharing OTiV3 trigonal pyramids.