Li4V2Si(PO6)2 crystallizes in the monoclinic C2 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(11), one O(2), one O(3), and one O(4) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(6), one O(8), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(12), one O(3), one O(4), one O(7), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one V(2)O6 octahedra. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(10), two equivalent O(4), and two equivalent O(7) atoms. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to two equivalent O(12) and two equivalent O(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one Li(3)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(12), one O(5), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one Li(3)O6 octahedra. Si(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form SiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. There are three inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-43°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-46°. In the third P site, P(3) is bonded to two equivalent O(12) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(3) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), one V(1), and one Si(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(5), one V(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one Si(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one V(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(2), and one P(3) atom.
Li4V2Si(PO6)2 crystallizes in the monoclinic C2 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(11), one O(2), one O(3), and one O(4) atom. The Li(1)-O(11) bond length is 2.22 Å. The Li(1)-O(2) bond length is 2.38 Å. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(4) bond length is 2.13 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(6), one O(8), and one O(9) atom. The Li(2)-O(1) bond length is 2.46 Å. The Li(2)-O(6) bond length is 2.09 Å. The Li(2)-O(8) bond length is 2.06 Å. The Li(2)-O(9) bond length is 2.12 Å. In the third Li site, Li(3) is bonded to one O(12), one O(3), one O(4), one O(7), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one V(2)O6 octahedra. The Li(3)-O(12) bond length is 2.25 Å. The Li(3)-O(3) bond length is 2.12 Å. The Li(3)-O(4) bond length is 2.12 Å. The Li(3)-O(7) bond length is 2.21 Å. The Li(3)-O(8) bond length is 2.34 Å. The Li(3)-O(9) bond length is 2.26 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(10), two equivalent O(4), and two equivalent O(7) atoms. Both Li(4)-O(10) bond lengths are 2.37 Å. Both Li(4)-O(4) bond lengths are 2.58 Å. Both Li(4)-O(7) bond lengths are 2.11 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to two equivalent O(12) and two equivalent O(5) atoms. Both Li(5)-O(12) bond lengths are 2.13 Å. Both Li(5)-O(5) bond lengths are 2.24 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one Li(3)O6 octahedra. The V(1)-O(10) bond length is 2.04 Å. The V(1)-O(11) bond length is 2.06 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-O(7) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(1), one O(12), one O(5), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one Li(3)O6 octahedra. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(12) bond length is 2.12 Å. The V(2)-O(5) bond length is 1.93 Å. The V(2)-O(6) bond length is 1.94 Å. The V(2)-O(8) bond length is 2.11 Å. The V(2)-O(9) bond length is 2.10 Å. Si(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form SiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. The Si(1)-O(3) bond length is 1.66 Å. The Si(1)-O(4) bond length is 1.66 Å. The Si(1)-O(5) bond length is 1.63 Å. The Si(1)-O(6) bond length is 1.63 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-43°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(7) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-46°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(11) bond length is 1.53 Å. The P(2)-O(8) bond length is 1.57 Å. The P(2)-O(9) bond length is 1.57 Å. In the third P site, P(3) is bonded to two equivalent O(12) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. Both P(3)-O(12) bond lengths are 1.57 Å. Both P(3)-O(2) bond lengths are 1.54 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(3) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), one V(1), and one Si(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(5), one V(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one Si(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one V(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(2), and one P(3) atom.