Li5V(PO4)3 crystallizes in the triclinic P1 space group. There are ten inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(2), one O(20), and one O(5) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(18), one O(21), one O(3), and one O(5) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(10), one O(17), one O(18), one O(3), one O(4), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(22), one O(3), one O(5), and one O(9) atom. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(11), one O(16), one O(17), one O(19), one O(3), and one O(7) atom. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(18), one O(21), one O(4), and one O(6) atom. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one O(15), one O(18), one O(20), one O(4), and one O(8) atom. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(20), one O(21), one O(3), and one O(7) atom. In the ninth Li site, Li(9) is bonded in a 3-coordinate geometry to one O(13), one O(22), and one O(8) atom. In the tenth Li site, Li(10) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(22), one O(4), and one O(6) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(13), one O(19), one O(2), one O(23), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the second V site, V(2) is bonded to one O(1), one O(12), one O(14), one O(20), one O(24), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(15), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-34°. In the second P site, P(2) is bonded to one O(19), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-44°. In the third P site, P(3) is bonded to one O(10), one O(20), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-40°. In the fourth P site, P(4) is bonded to one O(1), one O(13), one O(16), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-38°. In the fifth P site, P(5) is bonded to one O(17), one O(18), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-33°. In the sixth P site, P(6) is bonded to one O(11), one O(12), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-40°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Li(8), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(10), one Li(3), one Li(6), one Li(7), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(10), one Li(6), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(5), one Li(8), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(7), one Li(9), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(3), one Li(6), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one Li(5), one Li(8), one V(1), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Li(9), one V(1), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(8), one V(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(1), one Li(10), one Li(2), one Li(6), one Li(7), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to one Li(10), one Li(2), one Li(4), one Li(5), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal bipyramidal geometry to one Li(10), one Li(3), one Li(4), one Li(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(6), one Li(7), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one P(2) atom. In the twentieth O site, O(20) is bonded in a 2-coordinate geometry to one Li(1), one Li(7), one Li(8), one V(2), and one P(3) atom. In the twenty-first O site, O(21) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(6), one Li(8), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Li(10), one Li(4), one Li(9), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(1) and one P(5) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom.
Li5V(PO4)3 crystallizes in the triclinic P1 space group. There are ten inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(2), one O(20), and one O(5) atom. The Li(1)-O(12) bond length is 2.37 Å. The Li(1)-O(15) bond length is 2.53 Å. The Li(1)-O(2) bond length is 2.07 Å. The Li(1)-O(20) bond length is 2.50 Å. The Li(1)-O(5) bond length is 2.28 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(18), one O(21), one O(3), and one O(5) atom. The Li(2)-O(15) bond length is 2.11 Å. The Li(2)-O(16) bond length is 2.56 Å. The Li(2)-O(18) bond length is 2.55 Å. The Li(2)-O(21) bond length is 2.24 Å. The Li(2)-O(3) bond length is 2.15 Å. The Li(2)-O(5) bond length is 2.48 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(10), one O(17), one O(18), one O(3), one O(4), and one O(9) atom. The Li(3)-O(10) bond length is 2.14 Å. The Li(3)-O(17) bond length is 2.22 Å. The Li(3)-O(18) bond length is 2.13 Å. The Li(3)-O(3) bond length is 2.57 Å. The Li(3)-O(4) bond length is 2.51 Å. The Li(3)-O(9) bond length is 2.36 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(22), one O(3), one O(5), and one O(9) atom. The Li(4)-O(16) bond length is 2.56 Å. The Li(4)-O(17) bond length is 2.35 Å. The Li(4)-O(22) bond length is 2.02 Å. The Li(4)-O(3) bond length is 2.48 Å. The Li(4)-O(5) bond length is 2.06 Å. The Li(4)-O(9) bond length is 2.00 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(11), one O(16), one O(17), one O(19), one O(3), and one O(7) atom. The Li(5)-O(11) bond length is 2.58 Å. The Li(5)-O(16) bond length is 1.99 Å. The Li(5)-O(17) bond length is 2.02 Å. The Li(5)-O(19) bond length is 2.44 Å. The Li(5)-O(3) bond length is 2.09 Å. The Li(5)-O(7) bond length is 2.53 Å. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(18), one O(21), one O(4), and one O(6) atom. The Li(6)-O(10) bond length is 2.00 Å. The Li(6)-O(15) bond length is 2.56 Å. The Li(6)-O(18) bond length is 2.43 Å. The Li(6)-O(21) bond length is 2.05 Å. The Li(6)-O(4) bond length is 2.41 Å. The Li(6)-O(6) bond length is 2.02 Å. In the seventh Li site, Li(7) is bonded in a 5-coordinate geometry to one O(15), one O(18), one O(20), one O(4), and one O(8) atom. The Li(7)-O(15) bond length is 2.02 Å. The Li(7)-O(18) bond length is 1.95 Å. The Li(7)-O(20) bond length is 2.52 Å. The Li(7)-O(4) bond length is 2.05 Å. The Li(7)-O(8) bond length is 2.49 Å. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(20), one O(21), one O(3), and one O(7) atom. The Li(8)-O(11) bond length is 2.40 Å. The Li(8)-O(14) bond length is 2.06 Å. The Li(8)-O(20) bond length is 2.62 Å. The Li(8)-O(21) bond length is 2.28 Å. The Li(8)-O(3) bond length is 2.57 Å. The Li(8)-O(7) bond length is 2.34 Å. In the ninth Li site, Li(9) is bonded in a 3-coordinate geometry to one O(13), one O(22), and one O(8) atom. The Li(9)-O(13) bond length is 2.02 Å. The Li(9)-O(22) bond length is 2.25 Å. The Li(9)-O(8) bond length is 2.22 Å. In the tenth Li site, Li(10) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(22), one O(4), and one O(6) atom. The Li(10)-O(15) bond length is 2.66 Å. The Li(10)-O(16) bond length is 2.16 Å. The Li(10)-O(17) bond length is 2.45 Å. The Li(10)-O(22) bond length is 2.53 Å. The Li(10)-O(4) bond length is 2.14 Å. The Li(10)-O(6) bond length is 2.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(13), one O(19), one O(2), one O(23), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The V(1)-O(11) bond length is 1.94 Å. The V(1)-O(13) bond length is 1.94 Å. The V(1)-O(19) bond length is 1.92 Å. The V(1)-O(2) bond length is 1.98 Å. The V(1)-O(23) bond length is 1.86 Å. The V(1)-O(7) bond length is 1.94 Å. In the second V site, V(2) is bonded to one O(1), one O(12), one O(14), one O(20), one O(24), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The V(2)-O(1) bond length is 1.89 Å. The V(2)-O(12) bond length is 1.93 Å. The V(2)-O(14) bond length is 1.95 Å. The V(2)-O(20) bond length is 1.94 Å. The V(2)-O(24) bond length is 1.90 Å. The V(2)-O(8) bond length is 1.97 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(15), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-34°. The P(1)-O(14) bond length is 1.56 Å. The P(1)-O(15) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(19), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-44°. The P(2)-O(19) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.60 Å. The P(2)-O(9) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(10), one O(20), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-40°. The P(3)-O(10) bond length is 1.52 Å. The P(3)-O(20) bond length is 1.59 Å. The P(3)-O(5) bond length is 1.53 Å. The P(3)-O(7) bond length is 1.59 Å. In the fourth P site, P(4) is bonded to one O(1), one O(13), one O(16), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-38°. The P(4)-O(1) bond length is 1.55 Å. The P(4)-O(13) bond length is 1.57 Å. The P(4)-O(16) bond length is 1.53 Å. The P(4)-O(4) bond length is 1.54 Å. In the fifth P site, P(5) is bonded to one O(17), one O(18), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-33°. The P(5)-O(17) bond length is 1.53 Å. The P(5)-O(18) bond length is 1.53 Å. The P(5)-O(23) bond length is 1.56 Å. The P(5)-O(24) bond length is 1.56 Å. In the sixth P site, P(6) is bonded to one O(11), one O(12), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-40°. The P(6)-O(11) bond length is 1.57 Å. The P(6)-O(12) bond length is 1.59 Å. The P(6)-O(21) bond length is 1.54 Å. The P(6)-O(22) bond length is 1.53 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Li(8), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(10), one Li(3), one Li(6), one Li(7), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(10), one Li(6), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(5), one Li(8), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(7), one Li(9), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(3), one Li(6), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one Li(5), one Li(8), one V(1), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Li(9), one V(1), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(8), one V(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(1), one Li(10), one Li(2), one Li(6), one Li(7), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to one Li(10), one Li(2), one Li(4), one Li(5), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal bipyramidal geometry to one Li(10), one Li(3), one Li(4), one Li(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(6), one Li(7), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one P(2) atom. In the twentieth O site, O(20) is bonded in a 2-coordinate geometry to one Li(1), one Li(7), one Li(8), one V(2), and one P(3) atom. In the twenty-first O site, O(21) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(6), one Li(8), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Li(10), one Li(4), one Li(9), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(1) and one P(5) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom.