Li4V3SiO10 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(10), one O(5), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(4), one O(6), one O(7), and one O(9) atom to form LiO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and corners with two equivalent V(3)O4 tetrahedra. In the second V site, V(2) is bonded to one O(10), one O(2), one O(3), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. In the third V site, V(3) is bonded to one O(1), one O(7), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and corners with two equivalent V(1)O4 tetrahedra. Si(1) is bonded to one O(10), one O(2), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and corners with two equivalent V(2)O4 tetrahedra. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), and one V(1) atom to form OLi3V tetrahedra that share corners with two equivalent O(5)Li3V tetrahedra, corners with two equivalent O(7)Li3V tetrahedra, and  an edgeedge with one O(6)Li3Si tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), and one V(2) atom to form OLi3V tetrahedra that share corners with two equivalent O(6)Li3Si tetrahedra, corners with two equivalent O(4)Li3V tetrahedra, and  an edgeedge with one O(7)Li3V tetrahedra. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one Li(4), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLi3Si tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Li(4), and one V(3) atom to form distorted OLi3V tetrahedra that share corners with two equivalent O(6)Li3Si tetrahedra, corners with two equivalent O(4)Li3V tetrahedra, and  an edgeedge with one O(5)Li3V tetrahedra. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one Si(1) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(4), one V(1), and one V(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one Si(1) atom.
Li4V3SiO10 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-O(4) bond length is 1.97 Å. The Li(1)-O(5) bond length is 2.00 Å. The Li(1)-O(7) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The Li(2)-O(2) bond length is 2.05 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-O(5) bond length is 2.02 Å. The Li(2)-O(6) bond length is 1.97 Å. In the third Li site, Li(3) is bonded to one O(10), one O(5), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Li(3)-O(10) bond length is 1.98 Å. The Li(3)-O(5) bond length is 2.04 Å. The Li(3)-O(6) bond length is 1.97 Å. The Li(3)-O(7) bond length is 2.10 Å. In the fourth Li site, Li(4) is bonded to one O(4), one O(6), one O(7), and one O(9) atom to form LiO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Li(4)-O(4) bond length is 2.03 Å. The Li(4)-O(6) bond length is 2.00 Å. The Li(4)-O(7) bond length is 2.01 Å. The Li(4)-O(9) bond length is 1.98 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and corners with two equivalent V(3)O4 tetrahedra. The V(1)-O(1) bond length is 1.86 Å. The V(1)-O(3) bond length is 1.83 Å. The V(1)-O(4) bond length is 1.74 Å. The V(1)-O(9) bond length is 1.87 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(3), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. The V(2)-O(10) bond length is 1.90 Å. The V(2)-O(2) bond length is 1.89 Å. The V(2)-O(3) bond length is 1.81 Å. The V(2)-O(5) bond length is 1.73 Å. In the third V site, V(3) is bonded to one O(1), one O(7), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and corners with two equivalent V(1)O4 tetrahedra. The V(3)-O(1) bond length is 1.88 Å. The V(3)-O(7) bond length is 1.74 Å. The V(3)-O(8) bond length is 1.83 Å. The V(3)-O(9) bond length is 1.87 Å. Si(1) is bonded to one O(10), one O(2), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, and corners with two equivalent V(2)O4 tetrahedra. The Si(1)-O(10) bond length is 1.67 Å. The Si(1)-O(2) bond length is 1.68 Å. The Si(1)-O(6) bond length is 1.61 Å. The Si(1)-O(8) bond length is 1.65 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), and one V(1) atom to form OLi3V tetrahedra that share corners with two equivalent O(5)Li3V tetrahedra, corners with two equivalent O(7)Li3V tetrahedra, and  an edgeedge with one O(6)Li3Si tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), and one V(2) atom to form OLi3V tetrahedra that share corners with two equivalent O(6)Li3Si tetrahedra, corners with two equivalent O(4)Li3V tetrahedra, and  an edgeedge with one O(7)Li3V tetrahedra. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one Li(4), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLi3Si tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Li(4), and one V(3) atom to form distorted OLi3V tetrahedra that share corners with two equivalent O(6)Li3Si tetrahedra, corners with two equivalent O(4)Li3V tetrahedra, and  an edgeedge with one O(5)Li3V tetrahedra. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one Si(1) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(4), one V(1), and one V(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one Si(1) atom.