Li8VCo3(PO4)6 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(14), one O(21), one O(24), one O(3), and one O(9) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(2), one O(3), and one O(5) atom. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(16), one O(2), and one O(8) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(20), one O(5), and one O(8) atom. In the fifth Li site, Li(5) is bonded to one O(15), one O(18), one O(2), one O(22), one O(5), and one O(8) atom to form distorted LiO6 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,  a cornercorner with one P(6)O4 tetrahedra,  a faceface with one Co(1)O6 octahedra, and  a faceface with one Co(3)O6 octahedra. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(15), one O(18), one O(4), and one O(9) atom. In the seventh Li site, Li(7) is bonded in a 3-coordinate geometry to one O(15), one O(22), one O(24), and one O(6) atom. In the eighth Li site, Li(8) is bonded in a 4-coordinate geometry to one O(10), one O(18), one O(21), and one O(22) atom. V(1) is bonded to one O(12), one O(17), one O(19), one O(21), 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. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(13), one O(16), one O(2), one O(20), one O(5), and one O(8) atom to form distorted CoO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. In the second Co site, Co(2) is bonded to one O(1), one O(11), one O(14), one O(23), one O(3), and one O(7) atom to form distorted CoO6 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 Co site, Co(3) is bonded to one O(10), one O(15), one O(18), one O(22), one O(4), and one O(6) atom to form CoO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(19), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-51°. In the second P site, P(2) is bonded to one O(12), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-51°. In the third P site, P(3) is bonded to one O(14), one O(17), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-51°. In the fourth P site, P(4) is bonded to one O(15), one O(16), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-48°. In the fifth P site, P(5) is bonded to one O(11), one O(18), one O(20), and one O(21) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-47°. In the sixth P site, P(6) is bonded to one O(13), one O(22), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-47°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Co(2), and one P(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(6), one Co(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Li(5), one Co(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(7), one Co(3), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Co(2) and one P(4) atom. In the eighth O site, O(8) is bonded in a distorted square pyramidal geometry to one Li(3), one Li(4), one Li(5), one Co(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Li(6), one V(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(8), one Co(3), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Co(2) and one P(5) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(2), one Co(1), and one P(6) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Co(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(5), one Li(6), one Li(7), one Co(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(3), one Co(1), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(5), one Li(6), one Li(8), one Co(3), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(4), one Co(1), and one P(5) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(1), one Li(8), one V(1), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(5), one Li(7), one Li(8), one Co(3), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Co(2) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one Li(1), one Li(7), one V(1), and one P(6) atom.
Li8VCo3(PO4)6 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(14), one O(21), one O(24), one O(3), and one O(9) atom. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(14) bond length is 2.10 Å. The Li(1)-O(21) bond length is 2.58 Å. The Li(1)-O(24) bond length is 2.58 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(9) bond length is 2.59 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(2), one O(3), and one O(5) atom. The Li(2)-O(13) bond length is 2.04 Å. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-O(5) bond length is 2.25 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(16), one O(2), and one O(8) atom. The Li(3)-O(1) bond length is 2.05 Å. The Li(3)-O(16) bond length is 2.03 Å. The Li(3)-O(2) bond length is 2.26 Å. The Li(3)-O(8) bond length is 2.17 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(20), one O(5), and one O(8) atom. The Li(4)-O(14) bond length is 2.05 Å. The Li(4)-O(20) bond length is 2.04 Å. The Li(4)-O(5) bond length is 2.16 Å. The Li(4)-O(8) bond length is 2.24 Å. In the fifth Li site, Li(5) is bonded to one O(15), one O(18), one O(2), one O(22), one O(5), and one O(8) atom to form distorted LiO6 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,  a cornercorner with one P(6)O4 tetrahedra,  a faceface with one Co(1)O6 octahedra, and  a faceface with one Co(3)O6 octahedra. The Li(5)-O(15) bond length is 2.46 Å. The Li(5)-O(18) bond length is 2.44 Å. The Li(5)-O(2) bond length is 2.15 Å. The Li(5)-O(22) bond length is 2.44 Å. The Li(5)-O(5) bond length is 2.15 Å. The Li(5)-O(8) bond length is 2.15 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(15), one O(18), one O(4), and one O(9) atom. The Li(6)-O(15) bond length is 2.06 Å. The Li(6)-O(18) bond length is 2.54 Å. The Li(6)-O(4) bond length is 1.95 Å. The Li(6)-O(9) bond length is 2.11 Å. In the seventh Li site, Li(7) is bonded in a 3-coordinate geometry to one O(15), one O(22), one O(24), and one O(6) atom. The Li(7)-O(15) bond length is 2.57 Å. The Li(7)-O(22) bond length is 2.08 Å. The Li(7)-O(24) bond length is 2.09 Å. The Li(7)-O(6) bond length is 1.95 Å. In the eighth Li site, Li(8) is bonded in a 4-coordinate geometry to one O(10), one O(18), one O(21), and one O(22) atom. The Li(8)-O(10) bond length is 1.95 Å. The Li(8)-O(18) bond length is 2.07 Å. The Li(8)-O(21) bond length is 2.11 Å. The Li(8)-O(22) bond length is 2.53 Å. V(1) is bonded to one O(12), one O(17), one O(19), one O(21), 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(1)-O(12) bond length is 1.93 Å. The V(1)-O(17) bond length is 1.94 Å. The V(1)-O(19) bond length is 1.93 Å. The V(1)-O(21) bond length is 2.00 Å. The V(1)-O(24) bond length is 1.99 Å. The V(1)-O(9) bond length is 1.99 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(13), one O(16), one O(2), one O(20), one O(5), and one O(8) atom to form distorted CoO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. The Co(1)-O(13) bond length is 2.06 Å. The Co(1)-O(16) bond length is 2.04 Å. The Co(1)-O(2) bond length is 2.23 Å. The Co(1)-O(20) bond length is 2.04 Å. The Co(1)-O(5) bond length is 2.22 Å. The Co(1)-O(8) bond length is 2.21 Å. In the second Co site, Co(2) is bonded to one O(1), one O(11), one O(14), one O(23), one O(3), and one O(7) atom to form distorted CoO6 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 Co(2)-O(1) bond length is 2.18 Å. The Co(2)-O(11) bond length is 2.00 Å. The Co(2)-O(14) bond length is 2.17 Å. The Co(2)-O(23) bond length is 2.01 Å. The Co(2)-O(3) bond length is 2.18 Å. The Co(2)-O(7) bond length is 2.00 Å. In the third Co site, Co(3) is bonded to one O(10), one O(15), one O(18), one O(22), one O(4), and one O(6) atom to form CoO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. The Co(3)-O(10) bond length is 2.03 Å. The Co(3)-O(15) bond length is 2.11 Å. The Co(3)-O(18) bond length is 2.12 Å. The Co(3)-O(22) bond length is 2.12 Å. The Co(3)-O(4) bond length is 2.03 Å. The Co(3)-O(6) bond length is 2.03 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(19), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-51°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(10) bond length is 1.53 Å. The P(1)-O(19) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(12), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-51°. The P(2)-O(12) bond length is 1.57 Å. The P(2)-O(3) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(14), one O(17), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-51°. The P(3)-O(14) bond length is 1.56 Å. The P(3)-O(17) bond length is 1.56 Å. The P(3)-O(6) bond length is 1.54 Å. The P(3)-O(8) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(15), one O(16), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-48°. The P(4)-O(15) bond length is 1.56 Å. The P(4)-O(16) bond length is 1.55 Å. The P(4)-O(7) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.60 Å. In the fifth P site, P(5) is bonded to one O(11), one O(18), one O(20), and one O(21) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-47°. The P(5)-O(11) bond length is 1.51 Å. The P(5)-O(18) bond length is 1.56 Å. The P(5)-O(20) bond length is 1.55 Å. The P(5)-O(21) bond length is 1.60 Å. In the sixth P site, P(6) is bonded to one O(13), one O(22), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and  a cornercorner with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-47°. The P(6)-O(13) bond length is 1.55 Å. The P(6)-O(22) bond length is 1.56 Å. The P(6)-O(23) bond length is 1.51 Å. The P(6)-O(24) bond length is 1.61 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Co(2), and one P(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(6), one Co(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Li(5), one Co(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(7), one Co(3), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Co(2) and one P(4) atom. In the eighth O site, O(8) is bonded in a distorted square pyramidal geometry to one Li(3), one Li(4), one Li(5), one Co(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Li(6), one V(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(8), one Co(3), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Co(2) and one P(5) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(2), one Co(1), and one P(6) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Co(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(5), one Li(6), one Li(7), one Co(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(3), one Co(1), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(5), one Li(6), one Li(8), one Co(3), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(4), one Co(1), and one P(5) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(1), one Li(8), one V(1), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(5), one Li(7), one Li(8), one Co(3), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Co(2) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one Li(1), one Li(7), one V(1), and one P(6) atom.