LiVSiO4 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(2), and one O(3) atom. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(6), one O(7), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO5 trigonal bipyramids that share  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra,  a cornercorner with one V(2)O5 trigonal bipyramid, and  an edgeedge with one Si(1)O4 tetrahedra. In the second V site, V(2) is bonded to one O(1), one O(4), one O(8), and two equivalent O(5) atoms to form VO5 trigonal bipyramids that share  a cornercorner with one Si(1)O4 tetrahedra, corners with four equivalent Si(2)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(2)O5 trigonal bipyramid. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O5 trigonal bipyramid,  a cornercorner with one V(2)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and corners with four equivalent V(2)O5 trigonal bipyramids. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(2), and one Si(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Li(2), one V(2), and one Si(1) atom.
LiVSiO4 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(2) bond length is 1.90 Å. The Li(1)-O(3) bond length is 1.89 Å. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(6), one O(7), and one O(8) atom. The Li(2)-O(6) bond length is 1.96 Å. The Li(2)-O(7) bond length is 1.86 Å. The Li(2)-O(8) bond length is 1.97 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO5 trigonal bipyramids that share  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra,  a cornercorner with one V(2)O5 trigonal bipyramid, and  an edgeedge with one Si(1)O4 tetrahedra. The V(1)-O(2) bond length is 2.05 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(4) bond length is 2.04 Å. The V(1)-O(6) bond length is 1.99 Å. The V(1)-O(7) bond length is 2.08 Å. In the second V site, V(2) is bonded to one O(1), one O(4), one O(8), and two equivalent O(5) atoms to form VO5 trigonal bipyramids that share  a cornercorner with one Si(1)O4 tetrahedra, corners with four equivalent Si(2)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(2)O5 trigonal bipyramid. The V(2)-O(1) bond length is 1.92 Å. The V(2)-O(4) bond length is 2.08 Å. The V(2)-O(8) bond length is 1.97 Å. There is one shorter (1.95 Å) and one longer (2.11 Å) V(2)-O(5) bond length. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O5 trigonal bipyramid,  a cornercorner with one V(2)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(3) bond length is 1.66 Å. The Si(1)-O(6) bond length is 1.64 Å. The Si(1)-O(8) bond length is 1.66 Å. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and corners with four equivalent V(2)O5 trigonal bipyramids. The Si(2)-O(1) bond length is 1.64 Å. The Si(2)-O(4) bond length is 1.66 Å. The Si(2)-O(5) bond length is 1.68 Å. The Si(2)-O(7) bond length is 1.62 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(2), and one Si(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Li(2), one V(2), and one Si(1) atom.