V3Si3O10 crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(2), one O(3), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-64°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(6), one O(8), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-63°. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-64°. In the fourth V site, V(4) is bonded to two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-63°. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. In the second Si site, Si(2) is bonded to one O(10), one O(5), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the third Si site, Si(3) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-61°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(2), one Si(1), and one Si(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), one V(3), and one Si(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one Si(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Si(1) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(1) and one Si(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), one V(4), and one Si(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Si(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(1), one Si(2), and one Si(3) atom.
V3Si3O10 crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(2), one O(3), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-64°. The V(1)-O(10) bond length is 2.43 Å. The V(1)-O(2) bond length is 2.13 Å. The V(1)-O(3) bond length is 2.18 Å. The V(1)-O(5) bond length is 2.17 Å. The V(1)-O(7) bond length is 2.04 Å. The V(1)-O(8) bond length is 2.23 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(6), one O(8), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-63°. The V(2)-O(1) bond length is 2.33 Å. The V(2)-O(3) bond length is 2.14 Å. The V(2)-O(4) bond length is 1.89 Å. The V(2)-O(6) bond length is 2.13 Å. The V(2)-O(8) bond length is 2.05 Å. The V(2)-O(9) bond length is 2.12 Å. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-64°. Both V(3)-O(2) bond lengths are 2.04 Å. Both V(3)-O(3) bond lengths are 2.19 Å. Both V(3)-O(6) bond lengths are 2.05 Å. In the fourth V site, V(4) is bonded to two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-63°. Both V(4)-O(5) bond lengths are 2.00 Å. Both V(4)-O(8) bond lengths are 2.20 Å. Both V(4)-O(9) bond lengths are 2.07 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. The Si(1)-O(1) bond length is 1.67 Å. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.69 Å. The Si(1)-O(6) bond length is 1.62 Å. In the second Si site, Si(2) is bonded to one O(10), one O(5), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Si(2)-O(10) bond length is 1.66 Å. The Si(2)-O(5) bond length is 1.62 Å. The Si(2)-O(8) bond length is 1.70 Å. The Si(2)-O(9) bond length is 1.64 Å. In the third Si site, Si(3) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-61°. The Si(3)-O(1) bond length is 1.71 Å. The Si(3)-O(10) bond length is 1.70 Å. The Si(3)-O(4) bond length is 1.64 Å. The Si(3)-O(7) bond length is 1.58 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(2), one Si(1), and one Si(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), one V(3), and one Si(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one Si(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Si(1) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(1) and one Si(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), one V(4), and one Si(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Si(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(1), one Si(2), and one Si(3) atom.