Li4V2GeSiO10 crystallizes in the tetragonal P-4m2 space group. Li(1) 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(1)O6 octahedra, corners with two equivalent Ge(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. 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(3) atoms to form GeO4 tetrahedra that share corners with eight equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. Si(1) is bonded to four equivalent O(2) atoms to form SiO4 tetrahedra that share corners with eight equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to four equivalent Li(1) and one V(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form distorted OLi2VSi trigonal pyramids that share corners with two equivalent O(3)Li2VGe tetrahedra, corners with six equivalent O(2)Li2VSi trigonal pyramids, and edges with two equivalent O(3)Li2VGe tetrahedra. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and one Ge(1) atom to form distorted OLi2VGe tetrahedra that share corners with six equivalent O(3)Li2VGe tetrahedra, corners with two equivalent O(2)Li2VSi trigonal pyramids, and edges with two equivalent O(2)Li2VSi trigonal pyramids.
Li4V2GeSiO10 crystallizes in the tetragonal P-4m2 space group. Li(1) 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(1)O6 octahedra, corners with two equivalent Ge(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both Li(1)-O(1) bond lengths are 2.52 Å. Both Li(1)-O(2) bond lengths are 2.08 Å. Both Li(1)-O(3) bond lengths are 2.07 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 2.01 Å. Both V(1)-O(3) bond lengths are 1.97 Å. Ge(1) is bonded to four equivalent O(3) atoms to form GeO4 tetrahedra that share corners with eight equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. All Ge(1)-O(3) bond lengths are 1.77 Å. Si(1) is bonded to four equivalent O(2) atoms to form SiO4 tetrahedra that share corners with eight equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. All Si(1)-O(2) 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 four equivalent Li(1) and one V(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form distorted OLi2VSi trigonal pyramids that share corners with two equivalent O(3)Li2VGe tetrahedra, corners with six equivalent O(2)Li2VSi trigonal pyramids, and edges with two equivalent O(3)Li2VGe tetrahedra. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and one Ge(1) atom to form distorted OLi2VGe tetrahedra that share corners with six equivalent O(3)Li2VGe tetrahedra, corners with two equivalent O(2)Li2VSi trigonal pyramids, and edges with two equivalent O(2)Li2VSi trigonal pyramids.