Li3VSiO5 is Stannite-like structured and crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent Si(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, and corners with four equivalent V(1)O4 tetrahedra. V(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form VO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with four equivalent Li(3)O4 tetrahedra. Si(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent V(1) atoms to form OLi2V2 tetrahedra that share  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(1)Li2V2 tetrahedra, corners with two equivalent O(2)Li3Si tetrahedra, corners with three equivalent O(5)Li2VSi tetrahedra, and corners with four equivalent O(4)Li2VSi tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one Si(1) atom to form OLi3Si tetrahedra that share corners with two equivalent O(1)Li2V2 tetrahedra, corners with three equivalent O(4)Li2VSi tetrahedra, corners with three equivalent O(5)Li2VSi tetrahedra, and corners with four equivalent O(3)Li3Si tetrahedra. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and one Si(1) atom to form OLi3Si tetrahedra that share  a cornercorner with one O(1)Li2V2 tetrahedra,  a cornercorner with one O(4)Li2VSi tetrahedra, corners with two equivalent O(3)Li3Si tetrahedra, corners with four equivalent O(5)Li2VSi tetrahedra, and corners with four equivalent O(2)Li3Si tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Li(3), one V(1), and one Si(1) atom to form distorted OLi2VSi tetrahedra that share  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(4)Li2VSi tetrahedra, corners with two equivalent O(5)Li2VSi tetrahedra, corners with three equivalent O(2)Li3Si tetrahedra, and corners with four equivalent O(1)Li2V2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(1), and one Si(1) atom to form OLi2VSi tetrahedra that share corners with two equivalent O(4)Li2VSi tetrahedra, corners with three equivalent O(1)Li2V2 tetrahedra, corners with three equivalent O(2)Li3Si tetrahedra, and corners with four equivalent O(3)Li3Si tetrahedra.
Li3VSiO5 is Stannite-like structured and crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(5) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent Si(1)O4 tetrahedra. The Li(2)-O(2) bond length is 2.00 Å. The Li(2)-O(5) bond length is 2.09 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, and corners with four equivalent V(1)O4 tetrahedra. The Li(3)-O(1) bond length is 2.03 Å. The Li(3)-O(2) bond length is 1.95 Å. There is one shorter (2.08 Å) and one longer (2.11 Å) Li(3)-O(4) bond length. V(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form VO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with four equivalent Li(3)O4 tetrahedra. The V(1)-O(4) bond length is 1.99 Å. The V(1)-O(5) bond length is 1.93 Å. There is one shorter (1.90 Å) and one longer (1.91 Å) V(1)-O(1) bond length. Si(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.62 Å. The Si(1)-O(4) bond length is 1.70 Å. The Si(1)-O(5) bond length is 1.68 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent V(1) atoms to form OLi2V2 tetrahedra that share  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(1)Li2V2 tetrahedra, corners with two equivalent O(2)Li3Si tetrahedra, corners with three equivalent O(5)Li2VSi tetrahedra, and corners with four equivalent O(4)Li2VSi tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one Si(1) atom to form OLi3Si tetrahedra that share corners with two equivalent O(1)Li2V2 tetrahedra, corners with three equivalent O(4)Li2VSi tetrahedra, corners with three equivalent O(5)Li2VSi tetrahedra, and corners with four equivalent O(3)Li3Si tetrahedra. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and one Si(1) atom to form OLi3Si tetrahedra that share  a cornercorner with one O(1)Li2V2 tetrahedra,  a cornercorner with one O(4)Li2VSi tetrahedra, corners with two equivalent O(3)Li3Si tetrahedra, corners with four equivalent O(5)Li2VSi tetrahedra, and corners with four equivalent O(2)Li3Si tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Li(3), one V(1), and one Si(1) atom to form distorted OLi2VSi tetrahedra that share  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(4)Li2VSi tetrahedra, corners with two equivalent O(5)Li2VSi tetrahedra, corners with three equivalent O(2)Li3Si tetrahedra, and corners with four equivalent O(1)Li2V2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(1), and one Si(1) atom to form OLi2VSi tetrahedra that share corners with two equivalent O(4)Li2VSi tetrahedra, corners with three equivalent O(1)Li2V2 tetrahedra, corners with three equivalent O(2)Li3Si tetrahedra, and corners with four equivalent O(3)Li3Si tetrahedra.