Li2V2Sn(PO4)3 crystallizes in the monoclinic C2 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(3), two equivalent O(4), and two equivalent O(7) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(5), and two equivalent O(8) atoms. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one O(11), one O(8), and two equivalent O(12) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the second V site, V(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Sn(1) is bonded in a 3-coordinate geometry to one O(3), one O(6), and one O(7) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share 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 28-41°. In the second P site, P(2) is bonded to two equivalent O(10) and two equivalent O(7) atoms to form PO4 tetrahedra that share 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 30-44°. In the third P site, P(3) is bonded to two equivalent O(2) and two equivalent O(8) atoms to form PO4 tetrahedra that share 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 31-37°. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(12), and one O(4) atom to form PO4 tetrahedra that share 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 25-41°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Sn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Sn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Sn(1), and one P(2) 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(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(2), and one P(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Li(3), one V(2), and one P(4) atom.
Li2V2Sn(PO4)3 crystallizes in the monoclinic C2 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(3), two equivalent O(4), and two equivalent O(7) atoms. Both Li(1)-O(3) bond lengths are 2.36 Å. Both Li(1)-O(4) bond lengths are 2.56 Å. Both Li(1)-O(7) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(5), and two equivalent O(8) atoms. Both Li(2)-O(11) bond lengths are 2.54 Å. Both Li(2)-O(5) bond lengths are 2.66 Å. Both Li(2)-O(8) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one O(11), one O(8), and two equivalent O(12) atoms. The Li(3)-O(11) bond length is 2.13 Å. The Li(3)-O(8) bond length is 2.56 Å. There is one shorter (2.10 Å) and one longer (2.59 Å) Li(3)-O(12) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 2.17 Å. The V(1)-O(4) bond length is 2.07 Å. The V(1)-O(6) bond length is 2.18 Å. The V(1)-O(7) bond length is 2.16 Å. In the second V site, V(2) is bonded to one O(10), one O(11), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The V(2)-O(10) bond length is 2.06 Å. The V(2)-O(11) bond length is 2.11 Å. The V(2)-O(12) bond length is 2.15 Å. The V(2)-O(5) bond length is 2.10 Å. The V(2)-O(8) bond length is 2.09 Å. The V(2)-O(9) bond length is 2.04 Å. Sn(1) is bonded in a 3-coordinate geometry to one O(3), one O(6), and one O(7) atom. The Sn(1)-O(3) bond length is 2.35 Å. The Sn(1)-O(6) bond length is 2.23 Å. The Sn(1)-O(7) bond length is 2.34 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share 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 28-41°. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.58 Å. The P(1)-O(9) bond length is 1.52 Å. In the second P site, P(2) is bonded to two equivalent O(10) and two equivalent O(7) atoms to form PO4 tetrahedra that share 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 30-44°. Both P(2)-O(10) bond lengths are 1.53 Å. Both P(2)-O(7) bond lengths are 1.59 Å. In the third P site, P(3) is bonded to two equivalent O(2) and two equivalent O(8) atoms to form PO4 tetrahedra that share 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 31-37°. Both P(3)-O(2) bond lengths are 1.53 Å. Both P(3)-O(8) bond lengths are 1.57 Å. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(12), and one O(4) atom to form PO4 tetrahedra that share 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 25-41°. The P(4)-O(1) bond length is 1.53 Å. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(12) bond length is 1.56 Å. The P(4)-O(4) bond length is 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Sn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Sn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Sn(1), and one P(2) 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(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(2), and one P(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Li(3), one V(2), and one P(4) atom.