Li6VSb3(PO4)6 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(19), one O(4), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(16), one O(17), one O(20), one O(5), one O(8), and one O(9) 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, and  a cornercorner with one P(6)O4 tetrahedra. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(16), one O(21), one O(22), and one O(6) atom. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(13), one O(18), one O(20), one O(22), and one O(23) atom. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(15), one O(17), one O(18), and one O(24) atom. V(1) is bonded to one O(11), one O(13), one O(15), one O(18), one O(22), 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. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(19), one O(3), and one O(7) atom. In the second Sb site, Sb(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one O(8), and one O(9) atom. In the third Sb site, Sb(3) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(20), one O(21), one O(23), and one O(24) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-38°. In the second P site, P(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-35°. In the third P site, P(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-31°. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-39°. In the sixth P site, P(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one Sb(2) and one P(6) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Sb(2) and one P(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Sb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Li(2) and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Sb(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one Sb(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Sb(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted linear geometry to one Sb(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Sb(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(6), one V(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Sb(3), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one Sb(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal bipyramidal geometry to one Li(1), one Li(5), one Li(6), one V(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one Li(2), one Sb(1), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Sb(3), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(4), one Sb(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one V(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(5), one Sb(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(6), one Sb(3), and one P(1) atom.
Li6VSb3(PO4)6 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom. The Li(1)-O(11) bond length is 2.16 Å. The Li(1)-O(14) bond length is 2.50 Å. The Li(1)-O(18) bond length is 2.26 Å. The Li(1)-O(22) bond length is 2.47 Å. The Li(1)-O(3) bond length is 2.14 Å. The Li(1)-O(7) bond length is 2.33 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(14), one O(19), one O(4), and one O(9) atom. The Li(2)-O(14) bond length is 2.16 Å. The Li(2)-O(19) bond length is 1.80 Å. The Li(2)-O(4) bond length is 1.82 Å. The Li(2)-O(9) bond length is 2.08 Å. In the third Li site, Li(3) is bonded to one O(16), one O(17), one O(20), one O(5), one O(8), and one O(9) 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, and  a cornercorner with one P(6)O4 tetrahedra. The Li(3)-O(16) bond length is 2.12 Å. The Li(3)-O(17) bond length is 2.31 Å. The Li(3)-O(20) bond length is 2.24 Å. The Li(3)-O(5) bond length is 2.20 Å. The Li(3)-O(8) bond length is 2.12 Å. The Li(3)-O(9) bond length is 2.37 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(16), one O(21), one O(22), and one O(6) atom. The Li(4)-O(11) bond length is 2.07 Å. The Li(4)-O(16) bond length is 2.13 Å. The Li(4)-O(21) bond length is 2.01 Å. The Li(4)-O(22) bond length is 2.63 Å. The Li(4)-O(6) bond length is 2.42 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(13), one O(18), one O(20), one O(22), and one O(23) atom. The Li(5)-O(13) bond length is 2.54 Å. The Li(5)-O(18) bond length is 2.47 Å. The Li(5)-O(20) bond length is 2.16 Å. The Li(5)-O(22) bond length is 2.00 Å. The Li(5)-O(23) bond length is 2.06 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one O(15), one O(17), one O(18), and one O(24) atom. The Li(6)-O(15) bond length is 2.37 Å. The Li(6)-O(17) bond length is 2.07 Å. The Li(6)-O(18) bond length is 2.04 Å. The Li(6)-O(24) bond length is 2.20 Å. V(1) is bonded to one O(11), one O(13), one O(15), one O(18), one O(22), 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(11) bond length is 2.08 Å. The V(1)-O(13) bond length is 2.05 Å. The V(1)-O(15) bond length is 2.03 Å. The V(1)-O(18) bond length is 2.10 Å. The V(1)-O(22) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.10 Å. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(19), one O(3), and one O(7) atom. The Sb(1)-O(10) bond length is 2.24 Å. The Sb(1)-O(12) bond length is 2.30 Å. The Sb(1)-O(14) bond length is 2.18 Å. The Sb(1)-O(19) bond length is 2.54 Å. The Sb(1)-O(3) bond length is 2.22 Å. The Sb(1)-O(7) bond length is 2.08 Å. In the second Sb site, Sb(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one O(8), and one O(9) atom. The Sb(2)-O(1) bond length is 2.32 Å. The Sb(2)-O(2) bond length is 2.31 Å. The Sb(2)-O(5) bond length is 2.10 Å. The Sb(2)-O(8) bond length is 2.26 Å. The Sb(2)-O(9) bond length is 2.22 Å. In the third Sb site, Sb(3) is bonded in a 6-coordinate geometry to one O(16), one O(17), one O(20), one O(21), one O(23), and one O(24) atom. The Sb(3)-O(16) bond length is 2.18 Å. The Sb(3)-O(17) bond length is 2.17 Å. The Sb(3)-O(20) bond length is 2.15 Å. The Sb(3)-O(21) bond length is 2.50 Å. The Sb(3)-O(23) bond length is 2.37 Å. The Sb(3)-O(24) bond length is 2.39 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-38°. The P(1)-O(24) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.59 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-35°. The P(2)-O(13) bond length is 1.56 Å. The P(2)-O(21) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-31°. The P(3)-O(14) bond length is 1.56 Å. The P(3)-O(15) bond length is 1.55 Å. The P(3)-O(23) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. The P(4)-O(10) bond length is 1.52 Å. The P(4)-O(11) bond length is 1.58 Å. The P(4)-O(16) bond length is 1.59 Å. The P(4)-O(2) bond length is 1.52 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-39°. The P(5)-O(12) bond length is 1.52 Å. The P(5)-O(17) bond length is 1.60 Å. The P(5)-O(18) bond length is 1.58 Å. The P(5)-O(4) bond length is 1.51 Å. In the sixth P site, P(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra and  a cornercorner with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The P(6)-O(1) bond length is 1.51 Å. The P(6)-O(19) bond length is 1.52 Å. The P(6)-O(20) bond length is 1.59 Å. The P(6)-O(22) bond length is 1.58 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one Sb(2) and one P(6) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Sb(2) and one P(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Sb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Li(2) and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Sb(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one Sb(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Sb(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted linear geometry to one Sb(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(5), one V(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Sb(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(6), one V(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Sb(3), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(3), one Li(6), one Sb(3), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal bipyramidal geometry to one Li(1), one Li(5), one Li(6), one V(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one Li(2), one Sb(1), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Sb(3), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(4), one Sb(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one V(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(5), one Sb(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(6), one Sb(3), and one P(1) atom.