In2VO5 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(2), one O(3), one O(5), and three equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent In(1)O6 octahedra, corners with four equivalent In(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-64°. There are two inequivalent In sites. In the first In site, In(1) is bonded to one O(3), two equivalent O(4), and three equivalent O(5) atoms to form InO6 octahedra that share corners with two equivalent In(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent In(2)O6 octahedra, and edges with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-64°. In the second In site, In(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form InO6 octahedra that share corners with two equivalent In(1)O6 octahedra, corners with two equivalent In(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent In(1)O6 octahedra, and edges with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent In(2) atoms. In the third O site, O(3) is bonded to one V(1), one In(1), and two equivalent In(2) atoms to form OVIn3 tetrahedra that share corners with two equivalent O(4)In4 tetrahedra, corners with two equivalent O(3)VIn3 tetrahedra, corners with four equivalent O(5)VIn3 tetrahedra, and edges with two equivalent O(4)In4 tetrahedra. In the fourth O site, O(4) is bonded to two equivalent In(1) and two equivalent In(2) atoms to form distorted OIn4 tetrahedra that share corners with two equivalent O(3)VIn3 tetrahedra, corners with four equivalent O(4)In4 tetrahedra, corners with four equivalent O(5)VIn3 tetrahedra,  an edgeedge with one O(5)VIn3 tetrahedra, and edges with two equivalent O(3)VIn3 tetrahedra. In the fifth O site, O(5) is bonded to one V(1) and three equivalent In(1) atoms to form OVIn3 tetrahedra that share corners with two equivalent O(5)VIn3 tetrahedra, corners with four equivalent O(4)In4 tetrahedra, corners with four equivalent O(3)VIn3 tetrahedra,  an edgeedge with one O(4)In4 tetrahedra, and edges with two equivalent O(5)VIn3 tetrahedra.
In2VO5 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(2), one O(3), one O(5), and three equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent In(1)O6 octahedra, corners with four equivalent In(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-64°. The V(1)-O(2) bond length is 1.79 Å. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(5) bond length is 2.05 Å. There are two shorter (1.88 Å) and one longer (2.14 Å) V(1)-O(1) bond length. There are two inequivalent In sites. In the first In site, In(1) is bonded to one O(3), two equivalent O(4), and three equivalent O(5) atoms to form InO6 octahedra that share corners with two equivalent In(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent In(2)O6 octahedra, and edges with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-64°. The In(1)-O(3) bond length is 2.21 Å. Both In(1)-O(4) bond lengths are 2.30 Å. There is one shorter (2.22 Å) and two longer (2.24 Å) In(1)-O(5) bond lengths. In the second In site, In(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form InO6 octahedra that share corners with two equivalent In(1)O6 octahedra, corners with two equivalent In(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent In(1)O6 octahedra, and edges with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. Both In(2)-O(2) bond lengths are 2.29 Å. Both In(2)-O(3) bond lengths are 2.24 Å. There is one shorter (2.13 Å) and one longer (2.18 Å) In(2)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent In(2) atoms. In the third O site, O(3) is bonded to one V(1), one In(1), and two equivalent In(2) atoms to form OVIn3 tetrahedra that share corners with two equivalent O(4)In4 tetrahedra, corners with two equivalent O(3)VIn3 tetrahedra, corners with four equivalent O(5)VIn3 tetrahedra, and edges with two equivalent O(4)In4 tetrahedra. In the fourth O site, O(4) is bonded to two equivalent In(1) and two equivalent In(2) atoms to form distorted OIn4 tetrahedra that share corners with two equivalent O(3)VIn3 tetrahedra, corners with four equivalent O(4)In4 tetrahedra, corners with four equivalent O(5)VIn3 tetrahedra,  an edgeedge with one O(5)VIn3 tetrahedra, and edges with two equivalent O(3)VIn3 tetrahedra. In the fifth O site, O(5) is bonded to one V(1) and three equivalent In(1) atoms to form OVIn3 tetrahedra that share corners with two equivalent O(5)VIn3 tetrahedra, corners with four equivalent O(4)In4 tetrahedra, corners with four equivalent O(3)VIn3 tetrahedra,  an edgeedge with one O(4)In4 tetrahedra, and edges with two equivalent O(5)VIn3 tetrahedra.