Li3V4(PO4)6 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(20), one O(5), one O(7), and one O(9) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(17), one O(4), one O(5), and one O(7) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(19), one O(21), one O(4), and one O(6) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(12), one O(16), one O(2), one O(3), one O(5), 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(10), one O(14), one O(17), one O(4), and one O(6) 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 third V site, V(3) is bonded to one O(11), one O(15), one O(19), one O(21), 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. In the fourth V site, V(4) is bonded to one O(13), one O(18), one O(20), one O(22), one O(23), and one O(9) 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(22), one O(24), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-47°. In the second P site, P(2) is bonded to one O(16), one O(23), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-41°. In the third P site, P(3) is bonded to one O(13), one O(15), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-47°. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(18), and one O(19) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-47°. In the fifth P site, P(5) is bonded to one O(17), one O(2), one O(21), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-38°. In the sixth P site, P(6) is bonded to one O(1), one O(11), one O(20), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-46°. 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(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(5) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(6) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one V(4), and one P(5) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(4) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(1), one V(4), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one V(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one V(4) and one P(1) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(4) and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom.
Li3V4(PO4)6 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(16), one O(18), one O(20), one O(5), one O(7), and one O(9) atom. The Li(1)-O(16) bond length is 2.20 Å. The Li(1)-O(18) bond length is 2.18 Å. The Li(1)-O(20) bond length is 2.16 Å. The Li(1)-O(5) bond length is 2.28 Å. The Li(1)-O(7) bond length is 2.36 Å. The Li(1)-O(9) bond length is 2.35 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(17), one O(4), one O(5), and one O(7) atom. The Li(2)-O(12) bond length is 2.33 Å. The Li(2)-O(14) bond length is 2.22 Å. The Li(2)-O(17) bond length is 2.20 Å. The Li(2)-O(4) bond length is 2.38 Å. The Li(2)-O(5) bond length is 2.11 Å. The Li(2)-O(7) bond length is 2.22 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(19), one O(21), one O(4), and one O(6) atom. The Li(3)-O(11) bond length is 2.23 Å. The Li(3)-O(14) bond length is 2.29 Å. The Li(3)-O(19) bond length is 2.27 Å. The Li(3)-O(21) bond length is 2.27 Å. The Li(3)-O(4) bond length is 2.33 Å. The Li(3)-O(6) bond length is 2.21 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(12), one O(16), one O(2), one O(3), one O(5), 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(12) bond length is 2.03 Å. The V(1)-O(16) bond length is 2.02 Å. The V(1)-O(2) bond length is 1.95 Å. The V(1)-O(3) bond length is 1.94 Å. The V(1)-O(5) bond length is 2.06 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(10), one O(14), one O(17), one O(4), and one O(6) 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 1.87 Å. The V(2)-O(10) bond length is 1.89 Å. The V(2)-O(14) bond length is 2.02 Å. The V(2)-O(17) bond length is 1.99 Å. The V(2)-O(4) bond length is 2.04 Å. The V(2)-O(6) bond length is 1.99 Å. In the third V site, V(3) is bonded to one O(11), one O(15), one O(19), one O(21), 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(3)-O(11) bond length is 1.97 Å. The V(3)-O(15) bond length is 1.91 Å. The V(3)-O(19) bond length is 1.96 Å. The V(3)-O(21) bond length is 1.96 Å. The V(3)-O(24) bond length is 1.90 Å. The V(3)-O(8) bond length is 1.91 Å. In the fourth V site, V(4) is bonded to one O(13), one O(18), one O(20), one O(22), one O(23), and one O(9) 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(4)-O(13) bond length is 1.91 Å. The V(4)-O(18) bond length is 1.98 Å. The V(4)-O(20) bond length is 1.99 Å. The V(4)-O(22) bond length is 1.94 Å. The V(4)-O(23) bond length is 1.92 Å. The V(4)-O(9) bond length is 1.96 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(22), one O(24), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-47°. The P(1)-O(14) bond length is 1.57 Å. The P(1)-O(22) bond length is 1.53 Å. The P(1)-O(24) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(16), one O(23), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-41°. The P(2)-O(16) bond length is 1.53 Å. The P(2)-O(23) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(13), one O(15), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-47°. The P(3)-O(13) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.53 Å. The P(3)-O(6) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(18), and one O(19) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-47°. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(12) bond length is 1.53 Å. The P(4)-O(18) bond length is 1.55 Å. The P(4)-O(19) bond length is 1.55 Å. In the fifth P site, P(5) is bonded to one O(17), one O(2), one O(21), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-38°. The P(5)-O(17) bond length is 1.56 Å. The P(5)-O(2) bond length is 1.52 Å. The P(5)-O(21) bond length is 1.55 Å. The P(5)-O(9) bond length is 1.55 Å. In the sixth P site, P(6) is bonded to one O(1), one O(11), one O(20), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-46°. The P(6)-O(1) bond length is 1.57 Å. The P(6)-O(11) bond length is 1.55 Å. The P(6)-O(20) bond length is 1.55 Å. The P(6)-O(3) bond length is 1.52 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(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(5) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(6) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one V(4), and one P(5) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(4) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(1), one V(4), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one V(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one V(4) and one P(1) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(4) and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom.