Li4V2GeSiO10 crystallizes in the orthorhombic Pccm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(2) atoms. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ge(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with four equivalent Si(1)O4 tetrahedra and edges with four equivalent Li(2)O6 octahedra. V(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. Ge(1) is bonded to four equivalent O(2) atoms to form GeO4 tetrahedra that share corners with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. Si(1) is bonded to four equivalent O(3) atoms to form SiO4 tetrahedra that share corners with four equivalent Li(2)O6 octahedra and corners with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(3), two equivalent Li(2), and one V(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one Ge(1) atom to form OLi2VGe tetrahedra that share corners with six equivalent O(2)Li2VGe tetrahedra, corners with two equivalent O(3)Li2VSi trigonal pyramids,  an edgeedge with one O(2)Li2VGe tetrahedra, and  an edgeedge with one O(3)Li2VSi trigonal pyramid. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), and one Si(1) atom to form distorted OLi2VSi trigonal pyramids that share corners with two equivalent O(2)Li2VGe tetrahedra, corners with six equivalent O(3)Li2VSi trigonal pyramids,  an edgeedge with one O(2)Li2VGe tetrahedra, and  an edgeedge with one O(3)Li2VSi trigonal pyramid.
Li4V2GeSiO10 crystallizes in the orthorhombic Pccm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1) and four equivalent O(2) atoms. Both Li(1)-O(1) bond lengths are 2.53 Å. All Li(1)-O(2) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ge(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. Both Li(2)-O(1) bond lengths are 2.51 Å. Both Li(2)-O(2) bond lengths are 2.05 Å. Both Li(2)-O(3) bond lengths are 2.09 Å. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with four equivalent Si(1)O4 tetrahedra and edges with four equivalent Li(2)O6 octahedra. Both Li(3)-O(1) bond lengths are 2.50 Å. All Li(3)-O(3) bond lengths are 2.09 Å. V(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. The V(1)-O(1) bond length is 1.68 Å. Both V(1)-O(2) bond lengths are 1.99 Å. Both V(1)-O(3) bond lengths are 1.99 Å. Ge(1) is bonded to four equivalent O(2) atoms to form GeO4 tetrahedra that share corners with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. All Ge(1)-O(2) bond lengths are 1.77 Å. Si(1) is bonded to four equivalent O(3) atoms to form SiO4 tetrahedra that share corners with four equivalent Li(2)O6 octahedra and corners with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. All Si(1)-O(3) bond lengths are 1.65 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(3), two equivalent Li(2), and one V(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one Ge(1) atom to form OLi2VGe tetrahedra that share corners with six equivalent O(2)Li2VGe tetrahedra, corners with two equivalent O(3)Li2VSi trigonal pyramids,  an edgeedge with one O(2)Li2VGe tetrahedra, and  an edgeedge with one O(3)Li2VSi trigonal pyramid. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), and one Si(1) atom to form distorted OLi2VSi trigonal pyramids that share corners with two equivalent O(2)Li2VGe tetrahedra, corners with six equivalent O(3)Li2VSi trigonal pyramids,  an edgeedge with one O(2)Li2VGe tetrahedra, and  an edgeedge with one O(3)Li2VSi trigonal pyramid.