LiVGe2O6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Ge(2)O4 tetrahedra, corners with four equivalent Ge(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  an edgeedge with one Ge(2)O4 tetrahedra. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Ge(1)O4 tetrahedra, corners with three equivalent Ge(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(4), and two equivalent O(6) atoms to form GeO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-72°. In the second Ge site, Ge(2) is bonded to one O(1), one O(3), and two equivalent O(5) atoms to form GeO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with two equivalent Ge(2)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-61°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Ge(2) atoms. In the second O site, O(6) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ge(1) atoms. In the third O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one Ge(2) atom. In the fourth O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one Ge(1) atom. In the fifth O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Ge(2) atom to form distorted corner-sharing OLiV2Ge trigonal pyramids. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Ge(1) atom.
LiVGe2O6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Ge(2)O4 tetrahedra, corners with four equivalent Ge(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  an edgeedge with one Ge(2)O4 tetrahedra. The Li(1)-O(1) bond length is 2.33 Å. The Li(1)-O(2) bond length is 2.12 Å. The Li(1)-O(3) bond length is 2.15 Å. The Li(1)-O(4) bond length is 2.11 Å. The Li(1)-O(5) bond length is 2.19 Å. The Li(1)-O(6) bond length is 2.40 Å. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Ge(1)O4 tetrahedra, corners with three equivalent Ge(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(4) bond length is 1.98 Å. There is one shorter (2.09 Å) and one longer (2.14 Å) V(1)-O(2) bond length. There is one shorter (2.10 Å) and one longer (2.11 Å) V(1)-O(3) bond length. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(4), and two equivalent O(6) atoms to form GeO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-72°. The Ge(1)-O(2) bond length is 1.78 Å. The Ge(1)-O(4) bond length is 1.74 Å. Both Ge(1)-O(6) bond lengths are 1.80 Å. In the second Ge site, Ge(2) is bonded to one O(1), one O(3), and two equivalent O(5) atoms to form GeO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with two equivalent Ge(2)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-61°. The Ge(2)-O(1) bond length is 1.73 Å. The Ge(2)-O(3) bond length is 1.77 Å. There is one shorter (1.78 Å) and one longer (1.79 Å) Ge(2)-O(5) bond length. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Ge(2) atoms. In the second O site, O(6) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ge(1) atoms. In the third O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one Ge(2) atom. In the fourth O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one Ge(1) atom. In the fifth O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Ge(2) atom to form distorted corner-sharing OLiV2Ge trigonal pyramids. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Ge(1) atom.