Li7V4(PO4)6 crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(13), one O(23), and one O(7) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(16), one O(20), one O(3), and one O(9) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(16), one O(17), one O(19), and one O(22) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(14), one O(17), one O(18), and one O(9) atom. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(4), and one O(7) atom. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(10), one O(18), one O(23), and one O(6) atom. In the seventh Li site, Li(7) is bonded in a 4-coordinate geometry to one O(14), one O(19), one O(24), and one O(3) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(13), one O(18), 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 second V site, V(2) is bonded to one O(14), one O(17), one O(20), one O(22), one O(24), 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. In the third V site, V(3) is bonded to one O(10), one O(15), one O(2), one O(23), 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 fourth V site, V(4) is bonded to one O(12), one O(16), one O(19), one O(21), one O(3), 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(3), one O(4), one O(5), 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 25-46°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(24), 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 28-45°. In the third P site, P(3) is bonded to one O(12), one O(13), one O(20), 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 26-45°. In the fourth P site, P(4) is bonded to one O(14), one O(15), one O(19), and one O(6) 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 27-45°. In the fifth P site, P(5) is bonded to one O(1), one O(16), one O(17), and one O(2) 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 28-45°. In the sixth P site, P(6) is bonded to one O(18), one O(21), one O(22), and one O(23) 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 25-46°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(3) and one P(5) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(7), one V(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one P(4) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(5), one V(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(4) and one P(2) atom. In the ninth O site, O(9) is bonded to one Li(2), one Li(4), one V(2), and one P(1) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the tenth O site, O(10) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(6), one V(3), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(5), one V(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(4) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(7), one V(2), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(3) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(4), and one P(5) atom. In the seventeenth O site, O(17) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one V(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded to one Li(4), one Li(6), one V(1), and one P(6) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the nineteenth O site, O(19) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(7), one V(4), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one P(3) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(4) and one P(6) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(6), one V(3), and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(7), one V(2), and one P(2) atom.
Li7V4(PO4)6 crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(13), one O(23), and one O(7) atom. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(13) bond length is 2.10 Å. The Li(1)-O(23) bond length is 2.08 Å. The Li(1)-O(7) bond length is 2.22 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(16), one O(20), one O(3), and one O(9) atom. The Li(2)-O(16) bond length is 2.06 Å. The Li(2)-O(20) bond length is 2.06 Å. The Li(2)-O(3) bond length is 2.19 Å. The Li(2)-O(9) bond length is 2.12 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(16), one O(17), one O(19), and one O(22) atom. The Li(3)-O(16) bond length is 2.22 Å. The Li(3)-O(17) bond length is 2.09 Å. The Li(3)-O(19) bond length is 2.07 Å. The Li(3)-O(22) bond length is 2.07 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(14), one O(17), one O(18), and one O(9) atom. The Li(4)-O(11) bond length is 2.44 Å. The Li(4)-O(13) bond length is 2.42 Å. The Li(4)-O(14) bond length is 2.36 Å. The Li(4)-O(17) bond length is 2.34 Å. The Li(4)-O(18) bond length is 2.39 Å. The Li(4)-O(9) bond length is 2.36 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(4), and one O(7) atom. The Li(5)-O(10) bond length is 2.22 Å. The Li(5)-O(11) bond length is 2.08 Å. The Li(5)-O(4) bond length is 2.11 Å. The Li(5)-O(7) bond length is 2.10 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(10), one O(18), one O(23), and one O(6) atom. The Li(6)-O(10) bond length is 2.08 Å. The Li(6)-O(18) bond length is 2.12 Å. The Li(6)-O(23) bond length is 2.18 Å. The Li(6)-O(6) bond length is 2.10 Å. In the seventh Li site, Li(7) is bonded in a 4-coordinate geometry to one O(14), one O(19), one O(24), and one O(3) atom. The Li(7)-O(14) bond length is 2.09 Å. The Li(7)-O(19) bond length is 2.24 Å. The Li(7)-O(24) bond length is 2.08 Å. The Li(7)-O(3) bond length is 2.06 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(13), one O(18), 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(1)-O(1) bond length is 2.08 Å. The V(1)-O(11) bond length is 2.10 Å. The V(1)-O(13) bond length is 2.09 Å. The V(1)-O(18) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.09 Å. In the second V site, V(2) is bonded to one O(14), one O(17), one O(20), one O(22), one O(24), 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(2)-O(14) bond length is 2.11 Å. The V(2)-O(17) bond length is 2.13 Å. The V(2)-O(20) bond length is 2.11 Å. The V(2)-O(22) bond length is 2.09 Å. The V(2)-O(24) bond length is 2.10 Å. The V(2)-O(9) bond length is 2.11 Å. In the third V site, V(3) is bonded to one O(10), one O(15), one O(2), one O(23), 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(3)-O(10) bond length is 2.06 Å. The V(3)-O(15) bond length is 2.00 Å. The V(3)-O(2) bond length is 1.97 Å. The V(3)-O(23) bond length is 2.08 Å. The V(3)-O(5) bond length is 1.97 Å. The V(3)-O(7) bond length is 2.05 Å. In the fourth V site, V(4) is bonded to one O(12), one O(16), one O(19), one O(21), one O(3), 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(4)-O(12) bond length is 2.00 Å. The V(4)-O(16) bond length is 2.08 Å. The V(4)-O(19) bond length is 2.06 Å. The V(4)-O(21) bond length is 1.98 Å. The V(4)-O(3) bond length is 2.10 Å. The V(4)-O(8) bond length is 1.98 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), 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 25-46°. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.52 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(24), 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 28-45°. The P(2)-O(10) bond length is 1.57 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(24) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.53 Å. In the third P site, P(3) is bonded to one O(12), one O(13), one O(20), 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 26-45°. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(13) bond length is 1.56 Å. The P(3)-O(20) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.58 Å. In the fourth P site, P(4) is bonded to one O(14), one O(15), one O(19), and one O(6) 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 27-45°. The P(4)-O(14) bond length is 1.55 Å. The P(4)-O(15) bond length is 1.52 Å. The P(4)-O(19) bond length is 1.58 Å. The P(4)-O(6) bond length is 1.55 Å. In the fifth P site, P(5) is bonded to one O(1), one O(16), one O(17), and one O(2) 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 28-45°. The P(5)-O(1) bond length is 1.55 Å. The P(5)-O(16) bond length is 1.58 Å. The P(5)-O(17) bond length is 1.55 Å. The P(5)-O(2) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(18), one O(21), one O(22), and one O(23) 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 25-46°. The P(6)-O(18) bond length is 1.56 Å. The P(6)-O(21) bond length is 1.53 Å. The P(6)-O(22) bond length is 1.54 Å. The P(6)-O(23) bond length is 1.57 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(3) and one P(5) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(7), one V(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one P(4) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(5), one V(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(4) and one P(2) atom. In the ninth O site, O(9) is bonded to one Li(2), one Li(4), one V(2), and one P(1) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the tenth O site, O(10) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(6), one V(3), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(5), one V(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(4) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(7), one V(2), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(3) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(4), and one P(5) atom. In the seventeenth O site, O(17) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one V(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded to one Li(4), one Li(6), one V(1), and one P(6) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the nineteenth O site, O(19) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(7), one V(4), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one P(3) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(4) and one P(6) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(6), one V(3), and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(7), one V(2), and one P(2) atom.