V(SiO3)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(12), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra, and edges with two equivalent V(2)O6 octahedra. In the second V site, V(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(12), one O(2), one O(4), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-57°. In the second Si site, Si(2) is bonded to one O(1), one O(11), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-57°. In the third Si site, Si(3) is bonded to one O(1), one O(10), one O(3), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-61°. In the fourth Si site, Si(4) is bonded to one O(2), one O(4), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-61°. There are twelve inequivalent O sites. In the first O site, O(11) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(2) atom. In the second O site, O(12) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(1) atom. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(4) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the sixth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(4) atom. In the seventh O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one Si(1) atom. In the eighth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one Si(2) atom. In the ninth O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one Si(3) atom. In the tenth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one Si(4) atom. In the eleventh O site, O(9) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(4) atom. In the twelfth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(3) atom.
V(SiO3)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(12), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra, and edges with two equivalent V(2)O6 octahedra. The V(1)-O(10) bond length is 2.04 Å. The V(1)-O(11) bond length is 1.96 Å. The V(1)-O(12) bond length is 2.11 Å. The V(1)-O(6) bond length is 1.89 Å. The V(1)-O(8) bond length is 1.81 Å. The V(1)-O(9) bond length is 2.08 Å. In the second V site, V(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The V(2)-O(10) bond length is 2.08 Å. The V(2)-O(11) bond length is 2.11 Å. The V(2)-O(12) bond length is 1.96 Å. The V(2)-O(5) bond length is 1.89 Å. The V(2)-O(7) bond length is 1.81 Å. The V(2)-O(9) bond length is 2.04 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(12), one O(2), one O(4), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-57°. The Si(1)-O(12) bond length is 1.68 Å. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.63 Å. The Si(1)-O(5) bond length is 1.61 Å. In the second Si site, Si(2) is bonded to one O(1), one O(11), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-57°. The Si(2)-O(1) bond length is 1.63 Å. The Si(2)-O(11) bond length is 1.68 Å. The Si(2)-O(3) bond length is 1.63 Å. The Si(2)-O(6) bond length is 1.61 Å. In the third Si site, Si(3) is bonded to one O(1), one O(10), one O(3), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-61°. The Si(3)-O(1) bond length is 1.62 Å. The Si(3)-O(10) bond length is 1.66 Å. The Si(3)-O(3) bond length is 1.62 Å. The Si(3)-O(7) bond length is 1.65 Å. In the fourth Si site, Si(4) is bonded to one O(2), one O(4), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-61°. The Si(4)-O(2) bond length is 1.62 Å. The Si(4)-O(4) bond length is 1.62 Å. The Si(4)-O(8) bond length is 1.65 Å. The Si(4)-O(9) bond length is 1.66 Å. There are twelve inequivalent O sites. In the first O site, O(11) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(2) atom. In the second O site, O(12) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(1) atom. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(4) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the sixth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(4) atom. In the seventh O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one Si(1) atom. In the eighth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one Si(2) atom. In the ninth O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one Si(3) atom. In the tenth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one Si(4) atom. In the eleventh O site, O(9) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(4) atom. In the twelfth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(3) atom.