LiV(SO4)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(15), one O(20), one O(3), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. In the second Li site, Li(2) is bonded to one O(11), one O(15), one O(5), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. In the third Li site, Li(3) is bonded to one O(13), one O(20), one O(3), and one O(9) atom to form LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. In the second V site, V(2) is bonded to one O(16), one O(18), one O(19), one O(21), one O(23), and one O(24) atom to form VO6 octahedra that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra, and  a cornercorner with one S(6)O4 tetrahedra. In the third V site, V(3) is bonded to one O(10), one O(13), one O(14), one O(17), one O(22), and one O(5) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. There are six inequivalent S sites. In the first S site, S(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 24-47°. In the second S site, S(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 27-47°. In the third S site, S(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-48°. In the fourth S site, S(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  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 Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-43°. In the fifth S site, S(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. In the sixth S site, S(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  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 Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 24-48°. 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(1) and one S(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one S(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one S(5) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one S(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one S(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Li(1) and one S(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one S(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(3) and one S(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one S(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Li(1) and one S(5) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one S(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(3) and one S(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one S(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one V(2) and one S(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(3) and one S(5) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one V(2) and one S(5) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(2) and one S(6) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one S(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(2) and one S(2) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one V(3) and one S(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(2) and one S(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(2) and one S(1) atom.
LiV(SO4)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(15), one O(20), one O(3), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The Li(1)-O(11) bond length is 2.16 Å. The Li(1)-O(12) bond length is 1.94 Å. The Li(1)-O(15) bond length is 2.35 Å. The Li(1)-O(20) bond length is 2.17 Å. The Li(1)-O(3) bond length is 2.17 Å. The Li(1)-O(8) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(11), one O(15), one O(5), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. The Li(2)-O(11) bond length is 1.98 Å. The Li(2)-O(15) bond length is 1.98 Å. The Li(2)-O(5) bond length is 2.07 Å. The Li(2)-O(7) bond length is 2.05 Å. In the third Li site, Li(3) is bonded to one O(13), one O(20), one O(3), and one O(9) atom to form LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. The Li(3)-O(13) bond length is 2.09 Å. The Li(3)-O(20) bond length is 1.99 Å. The Li(3)-O(3) bond length is 2.01 Å. The Li(3)-O(9) bond length is 2.03 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-O(6) bond length is 2.06 Å. The V(1)-O(7) bond length is 2.12 Å. The V(1)-O(9) bond length is 2.15 Å. In the second V site, V(2) is bonded to one O(16), one O(18), one O(19), one O(21), one O(23), and one O(24) atom to form VO6 octahedra that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra, and  a cornercorner with one S(6)O4 tetrahedra. The V(2)-O(16) bond length is 2.01 Å. The V(2)-O(18) bond length is 2.03 Å. The V(2)-O(19) bond length is 2.03 Å. The V(2)-O(21) bond length is 2.02 Å. The V(2)-O(23) bond length is 2.03 Å. The V(2)-O(24) bond length is 2.02 Å. In the third V site, V(3) is bonded to one O(10), one O(13), one O(14), one O(17), one O(22), and one O(5) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra,  a cornercorner with one S(5)O4 tetrahedra,  a cornercorner with one S(6)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The V(3)-O(10) bond length is 2.03 Å. The V(3)-O(13) bond length is 2.12 Å. The V(3)-O(14) bond length is 2.05 Å. The V(3)-O(17) bond length is 2.02 Å. The V(3)-O(22) bond length is 2.02 Å. The V(3)-O(5) bond length is 2.12 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 24-47°. The S(1)-O(24) bond length is 1.48 Å. The S(1)-O(3) bond length is 1.46 Å. The S(1)-O(5) bond length is 1.52 Å. The S(1)-O(6) bond length is 1.49 Å. In the second S site, S(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 27-47°. The S(2)-O(13) bond length is 1.52 Å. The S(2)-O(21) bond length is 1.47 Å. The S(2)-O(7) bond length is 1.52 Å. The S(2)-O(8) bond length is 1.44 Å. In the third S site, S(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-48°. The S(3)-O(14) bond length is 1.50 Å. The S(3)-O(15) bond length is 1.47 Å. The S(3)-O(23) bond length is 1.48 Å. The S(3)-O(9) bond length is 1.51 Å. In the fourth S site, S(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  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 Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-43°. The S(4)-O(10) bond length is 1.49 Å. The S(4)-O(11) bond length is 1.47 Å. The S(4)-O(16) bond length is 1.49 Å. The S(4)-O(2) bond length is 1.48 Å. In the fifth S site, S(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. The S(5)-O(12) bond length is 1.45 Å. The S(5)-O(17) bond length is 1.50 Å. The S(5)-O(18) bond length is 1.49 Å. The S(5)-O(4) bond length is 1.52 Å. In the sixth S site, S(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  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 Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 24-48°. The S(6)-O(1) bond length is 1.48 Å. The S(6)-O(19) bond length is 1.49 Å. The S(6)-O(20) bond length is 1.47 Å. The S(6)-O(22) bond length is 1.50 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(1) and one S(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one S(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one S(5) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one S(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one S(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Li(1) and one S(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one S(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(3) and one S(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one S(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Li(1) and one S(5) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one S(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(3) and one S(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one S(3) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one V(2) and one S(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(3) and one S(5) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one V(2) and one S(5) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(2) and one S(6) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one S(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(2) and one S(2) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one V(3) and one S(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(2) and one S(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one V(2) and one S(1) atom.