Li3VSiO5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-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), two equivalent O(3), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-19°. In the second Li site, Li(2) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-19°. In the third Li site, Li(3) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-16°. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. Si(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form SiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Si(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), one V(1), and one Si(1) atom to form distorted OLi4VSi octahedra that share  a cornercorner with one O(3)Li3VSi2 octahedra,  a cornercorner with one O(2)Li4VSi octahedra, corners with two equivalent O(5)Li3V2Si octahedra, corners with two equivalent O(4)Li4VSi octahedra,  an edgeedge with one O(1)Li4VSi octahedra, edges with two equivalent O(5)Li3V2Si octahedra, edges with three equivalent O(3)Li3VSi2 octahedra, edges with three equivalent O(2)Li4VSi octahedra, and edges with three equivalent O(4)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 4-18°. In the second O site, O(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), one V(1), and one Si(1) atom to form distorted OLi4VSi octahedra that share  a cornercorner with one O(5)Li3V2Si octahedra,  a cornercorner with one O(1)Li4VSi octahedra, corners with two equivalent O(3)Li3VSi2 octahedra, corners with two equivalent O(4)Li4VSi octahedra,  an edgeedge with one O(2)Li4VSi octahedra, edges with two equivalent O(3)Li3VSi2 octahedra, edges with three equivalent O(5)Li3V2Si octahedra, edges with three equivalent O(1)Li4VSi octahedra, and edges with three equivalent O(4)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 3-14°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one V(1), and two equivalent Si(1) atoms to form OLi3VSi2 octahedra that share  a cornercorner with one O(1)Li4VSi octahedra,  a cornercorner with one O(4)Li4VSi octahedra, corners with two equivalent O(5)Li3V2Si octahedra, corners with two equivalent O(2)Li4VSi octahedra, edges with two equivalent O(3)Li3VSi2 octahedra, edges with two equivalent O(2)Li4VSi octahedra, edges with two equivalent O(4)Li4VSi octahedra, edges with three equivalent O(5)Li3V2Si octahedra, and edges with three equivalent O(1)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 2-18°. In the fourth O site, O(4) is bonded to two equivalent Li(2), two equivalent Li(3), one V(1), and one Si(1) atom to form OLi4VSi octahedra that share  a cornercorner with one O(5)Li3V2Si octahedra,  a cornercorner with one O(3)Li3VSi2 octahedra, corners with two equivalent O(1)Li4VSi octahedra, corners with two equivalent O(2)Li4VSi octahedra, edges with two equivalent O(5)Li3V2Si octahedra, edges with two equivalent O(3)Li3VSi2 octahedra, edges with two equivalent O(4)Li4VSi octahedra, edges with three equivalent O(1)Li4VSi octahedra, and edges with three equivalent O(2)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent V(1), and one Si(1) atom to form OLi3V2Si octahedra that share  a cornercorner with one O(2)Li4VSi octahedra,  a cornercorner with one O(4)Li4VSi octahedra, corners with two equivalent O(3)Li3VSi2 octahedra, corners with two equivalent O(1)Li4VSi octahedra, edges with two equivalent O(5)Li3V2Si octahedra, edges with two equivalent O(1)Li4VSi octahedra, edges with two equivalent O(4)Li4VSi octahedra, edges with three equivalent O(3)Li3VSi2 octahedra, and edges with three equivalent O(2)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 2-14°.
Li3VSiO5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-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), two equivalent O(3), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-19°. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(2) bond length is 1.99 Å. There is one shorter (2.04 Å) and one longer (2.31 Å) Li(1)-O(3) bond length. There is one shorter (2.08 Å) and one longer (2.43 Å) Li(1)-O(5) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-19°. The Li(2)-O(1) bond length is 2.34 Å. The Li(2)-O(5) bond length is 2.02 Å. There is one shorter (2.02 Å) and one longer (2.34 Å) Li(2)-O(2) bond length. There is one shorter (2.09 Å) and one longer (2.13 Å) Li(2)-O(4) bond length. In the third Li site, Li(3) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-16°. The Li(3)-O(2) bond length is 2.09 Å. The Li(3)-O(3) bond length is 2.11 Å. There is one shorter (2.01 Å) and one longer (2.05 Å) Li(3)-O(1) bond length. There is one shorter (2.13 Å) and one longer (2.19 Å) Li(3)-O(4) bond length. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(2) bond length is 2.04 Å. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(4) bond length is 2.00 Å. Both V(1)-O(5) bond lengths are 2.07 Å. Si(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form SiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Si(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The Si(1)-O(1) bond length is 1.78 Å. The Si(1)-O(2) bond length is 1.78 Å. The Si(1)-O(4) bond length is 1.77 Å. The Si(1)-O(5) bond length is 1.88 Å. There is one shorter (1.87 Å) and one longer (1.95 Å) Si(1)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), one V(1), and one Si(1) atom to form distorted OLi4VSi octahedra that share  a cornercorner with one O(3)Li3VSi2 octahedra,  a cornercorner with one O(2)Li4VSi octahedra, corners with two equivalent O(5)Li3V2Si octahedra, corners with two equivalent O(4)Li4VSi octahedra,  an edgeedge with one O(1)Li4VSi octahedra, edges with two equivalent O(5)Li3V2Si octahedra, edges with three equivalent O(3)Li3VSi2 octahedra, edges with three equivalent O(2)Li4VSi octahedra, and edges with three equivalent O(4)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 4-18°. In the second O site, O(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), one V(1), and one Si(1) atom to form distorted OLi4VSi octahedra that share  a cornercorner with one O(5)Li3V2Si octahedra,  a cornercorner with one O(1)Li4VSi octahedra, corners with two equivalent O(3)Li3VSi2 octahedra, corners with two equivalent O(4)Li4VSi octahedra,  an edgeedge with one O(2)Li4VSi octahedra, edges with two equivalent O(3)Li3VSi2 octahedra, edges with three equivalent O(5)Li3V2Si octahedra, edges with three equivalent O(1)Li4VSi octahedra, and edges with three equivalent O(4)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 3-14°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one V(1), and two equivalent Si(1) atoms to form OLi3VSi2 octahedra that share  a cornercorner with one O(1)Li4VSi octahedra,  a cornercorner with one O(4)Li4VSi octahedra, corners with two equivalent O(5)Li3V2Si octahedra, corners with two equivalent O(2)Li4VSi octahedra, edges with two equivalent O(3)Li3VSi2 octahedra, edges with two equivalent O(2)Li4VSi octahedra, edges with two equivalent O(4)Li4VSi octahedra, edges with three equivalent O(5)Li3V2Si octahedra, and edges with three equivalent O(1)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 2-18°. In the fourth O site, O(4) is bonded to two equivalent Li(2), two equivalent Li(3), one V(1), and one Si(1) atom to form OLi4VSi octahedra that share  a cornercorner with one O(5)Li3V2Si octahedra,  a cornercorner with one O(3)Li3VSi2 octahedra, corners with two equivalent O(1)Li4VSi octahedra, corners with two equivalent O(2)Li4VSi octahedra, edges with two equivalent O(5)Li3V2Si octahedra, edges with two equivalent O(3)Li3VSi2 octahedra, edges with two equivalent O(4)Li4VSi octahedra, edges with three equivalent O(1)Li4VSi octahedra, and edges with three equivalent O(2)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent V(1), and one Si(1) atom to form OLi3V2Si octahedra that share  a cornercorner with one O(2)Li4VSi octahedra,  a cornercorner with one O(4)Li4VSi octahedra, corners with two equivalent O(3)Li3VSi2 octahedra, corners with two equivalent O(1)Li4VSi octahedra, edges with two equivalent O(5)Li3V2Si octahedra, edges with two equivalent O(1)Li4VSi octahedra, edges with two equivalent O(4)Li4VSi octahedra, edges with three equivalent O(3)Li3VSi2 octahedra, and edges with three equivalent O(2)Li4VSi octahedra. The corner-sharing octahedral tilt angles range from 2-14°.