LiV4(GeO4)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(15), one O(16), and one O(4) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(16), one O(2), one O(4), and one O(7) atom to form distorted VO6 octahedra that share corners with two equivalent Ge(3)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra,  an edgeedge with one Ge(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. In the second V site, V(2) is bonded to one O(11), one O(14), one O(3), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(1)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra,  an edgeedge with one Ge(3)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the third V site, V(3) is bonded to one O(12), one O(14), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(4)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra,  an edgeedge with one Ge(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(4) atom to form VO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra,  an edgeedge with one Ge(4)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-56°. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(12), one O(14), one O(16), one O(6), one O(7), and one O(8) atom to form GeO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. In the second Ge site, Ge(2) is bonded to one O(12), one O(15), one O(16), one O(4), one O(6), and one O(7) atom to form distorted GeO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-59°. In the third Ge site, Ge(3) is bonded to one O(1), one O(10), one O(11), one O(13), one O(2), and one O(5) atom to form GeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the fourth Ge site, Ge(4) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(9) atom to form GeO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(4), one Ge(3), and one Ge(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one Ge(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(4), and one Ge(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(4), one Ge(3), and one Ge(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one V(4), and one Ge(3) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(4), and one Ge(2) atom. In the sixteenth O site, O(16) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one Ge(1), and one Ge(2) atom.
LiV4(GeO4)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(15), one O(16), and one O(4) atom. The Li(1)-O(13) bond length is 1.69 Å. The Li(1)-O(15) bond length is 1.98 Å. The Li(1)-O(16) bond length is 2.02 Å. The Li(1)-O(4) bond length is 1.68 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(16), one O(2), one O(4), and one O(7) atom to form distorted VO6 octahedra that share corners with two equivalent Ge(3)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra,  an edgeedge with one Ge(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The V(1)-O(13) bond length is 2.11 Å. The V(1)-O(15) bond length is 1.93 Å. The V(1)-O(16) bond length is 2.09 Å. The V(1)-O(2) bond length is 2.10 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.89 Å. In the second V site, V(2) is bonded to one O(11), one O(14), one O(3), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(1)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra,  an edgeedge with one Ge(3)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The V(2)-O(11) bond length is 1.90 Å. The V(2)-O(14) bond length is 2.05 Å. The V(2)-O(3) bond length is 1.91 Å. The V(2)-O(5) bond length is 1.92 Å. The V(2)-O(8) bond length is 2.06 Å. The V(2)-O(9) bond length is 1.90 Å. In the third V site, V(3) is bonded to one O(12), one O(14), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(4)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra,  an edgeedge with one Ge(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(3)-O(12) bond length is 1.94 Å. The V(3)-O(14) bond length is 1.91 Å. The V(3)-O(3) bond length is 2.03 Å. The V(3)-O(6) bond length is 1.92 Å. The V(3)-O(8) bond length is 1.88 Å. The V(3)-O(9) bond length is 2.04 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(4) atom to form VO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra,  an edgeedge with one Ge(4)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-56°. The V(4)-O(1) bond length is 1.96 Å. The V(4)-O(10) bond length is 1.92 Å. The V(4)-O(13) bond length is 2.01 Å. The V(4)-O(15) bond length is 2.18 Å. The V(4)-O(2) bond length is 1.86 Å. The V(4)-O(4) bond length is 2.03 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(12), one O(14), one O(16), one O(6), one O(7), and one O(8) atom to form GeO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The Ge(1)-O(12) bond length is 1.96 Å. The Ge(1)-O(14) bond length is 1.92 Å. The Ge(1)-O(16) bond length is 1.94 Å. The Ge(1)-O(6) bond length is 1.95 Å. The Ge(1)-O(7) bond length is 1.99 Å. The Ge(1)-O(8) bond length is 1.98 Å. In the second Ge site, Ge(2) is bonded to one O(12), one O(15), one O(16), one O(4), one O(6), and one O(7) atom to form distorted GeO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-59°. The Ge(2)-O(12) bond length is 1.90 Å. The Ge(2)-O(15) bond length is 1.98 Å. The Ge(2)-O(16) bond length is 2.04 Å. The Ge(2)-O(4) bond length is 2.01 Å. The Ge(2)-O(6) bond length is 1.92 Å. The Ge(2)-O(7) bond length is 1.90 Å. In the third Ge site, Ge(3) is bonded to one O(1), one O(10), one O(11), one O(13), one O(2), and one O(5) atom to form GeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The Ge(3)-O(1) bond length is 1.99 Å. The Ge(3)-O(10) bond length is 1.98 Å. The Ge(3)-O(11) bond length is 1.94 Å. The Ge(3)-O(13) bond length is 1.88 Å. The Ge(3)-O(2) bond length is 1.93 Å. The Ge(3)-O(5) bond length is 1.94 Å. In the fourth Ge site, Ge(4) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(9) atom to form GeO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Ge(4)-O(1) bond length is 1.96 Å. The Ge(4)-O(10) bond length is 1.95 Å. The Ge(4)-O(11) bond length is 1.96 Å. The Ge(4)-O(3) bond length is 1.93 Å. The Ge(4)-O(5) bond length is 1.98 Å. The Ge(4)-O(9) bond length is 1.94 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(4), one Ge(3), and one Ge(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one Ge(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(4), and one Ge(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(4), one Ge(3), and one Ge(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one V(4), and one Ge(3) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(4), and one Ge(2) atom. In the sixteenth O site, O(16) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one Ge(1), and one Ge(2) atom.