LiV(PO4)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(17), one O(19), and one O(3) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(12), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(13), one O(18), one O(19), one O(22), one O(23), and one O(24) atom. 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(5), one O(7), 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 second V site, V(2) is bonded to one O(14), one O(18), one O(20), one O(21), one O(23), and one O(24) 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(11), one O(15), one O(16), one O(17), 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(10), one O(18), one O(3), and one O(4) atom to form PO4 tetrahedra that share  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 15-48°. In the second P site, P(2) is bonded to one O(16), one O(23), one O(5), 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, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-42°. In the third P site, P(3) is bonded to one O(13), one O(14), one O(8), 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, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-43°. In the fourth P site, P(4) is bonded to one O(1), one O(12), one O(17), and one O(24) atom to form PO4 tetrahedra that share  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 23-42°. In the fifth P site, P(5) is bonded to one O(15), one O(21), one O(22), 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, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-45°. In the sixth P site, P(6) is bonded to one O(11), one O(19), one O(2), and one O(20) atom to form PO4 tetrahedra that share  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 7-42°. 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 P(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(6) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Li(2), one V(1), and one P(5) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(3) and one P(6) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Li(2) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Li(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(3) and one P(5) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(3) and one P(2) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(4) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(1) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one P(6) atom. In the twentieth O site, O(20) is bonded in a linear geometry to one V(2) and one P(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 120 degrees geometry to one Li(3) and one P(5) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(4) atom.
LiV(PO4)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(17), one O(19), and one O(3) atom. The Li(1)-O(17) bond length is 2.13 Å. The Li(1)-O(19) bond length is 1.94 Å. The Li(1)-O(3) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(12), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. The Li(2)-O(12) bond length is 1.99 Å. The Li(2)-O(2) bond length is 2.48 Å. The Li(2)-O(3) bond length is 2.19 Å. The Li(2)-O(6) bond length is 2.01 Å. The Li(2)-O(7) bond length is 2.65 Å. The Li(2)-O(9) bond length is 2.43 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(13), one O(18), one O(19), one O(22), one O(23), and one O(24) atom. The Li(3)-O(13) bond length is 2.00 Å. The Li(3)-O(18) bond length is 2.53 Å. The Li(3)-O(19) bond length is 2.29 Å. The Li(3)-O(22) bond length is 2.02 Å. The Li(3)-O(23) bond length is 2.53 Å. The Li(3)-O(24) bond length is 2.47 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(5), one O(7), 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(1) bond length is 1.84 Å. The V(1)-O(2) bond length is 1.94 Å. The V(1)-O(4) bond length is 1.86 Å. The V(1)-O(5) bond length is 1.84 Å. The V(1)-O(7) bond length is 1.91 Å. The V(1)-O(9) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(14), one O(18), one O(20), one O(21), one O(23), and one O(24) 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 1.84 Å. The V(2)-O(18) bond length is 1.94 Å. The V(2)-O(20) bond length is 1.87 Å. The V(2)-O(21) bond length is 1.84 Å. The V(2)-O(23) bond length is 1.92 Å. The V(2)-O(24) bond length is 1.92 Å. In the third V site, V(3) is bonded to one O(10), one O(11), one O(15), one O(16), one O(17), 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(10) bond length is 1.88 Å. The V(3)-O(11) bond length is 1.86 Å. The V(3)-O(15) bond length is 1.85 Å. The V(3)-O(16) bond length is 1.86 Å. The V(3)-O(17) bond length is 2.01 Å. The V(3)-O(8) bond length is 1.85 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(18), one O(3), and one O(4) atom to form PO4 tetrahedra that share  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 15-48°. The P(1)-O(10) bond length is 1.56 Å. The P(1)-O(18) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(16), one O(23), one O(5), 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, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-42°. The P(2)-O(16) bond length is 1.56 Å. The P(2)-O(23) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.49 Å. In the third P site, P(3) is bonded to one O(13), one O(14), one O(8), 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, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-43°. The P(3)-O(13) bond length is 1.49 Å. The P(3)-O(14) bond length is 1.58 Å. The P(3)-O(8) bond length is 1.57 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(1), one O(12), one O(17), and one O(24) atom to form PO4 tetrahedra that share  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 23-42°. The P(4)-O(1) bond length is 1.58 Å. The P(4)-O(12) bond length is 1.49 Å. The P(4)-O(17) bond length is 1.56 Å. The P(4)-O(24) bond length is 1.58 Å. In the fifth P site, P(5) is bonded to one O(15), one O(21), one O(22), 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, and  a cornercorner with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-45°. The P(5)-O(15) bond length is 1.57 Å. The P(5)-O(21) bond length is 1.58 Å. The P(5)-O(22) bond length is 1.48 Å. The P(5)-O(7) bond length is 1.56 Å. In the sixth P site, P(6) is bonded to one O(11), one O(19), one O(2), and one O(20) atom to form PO4 tetrahedra that share  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 7-42°. The P(6)-O(11) bond length is 1.56 Å. The P(6)-O(19) bond length is 1.51 Å. The P(6)-O(2) bond length is 1.56 Å. The P(6)-O(20) bond length is 1.55 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 P(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(6) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Li(2), one V(1), and one P(5) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(3) and one P(6) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Li(2) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Li(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one V(3) and one P(5) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one V(3) and one P(2) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(4) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(1) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one P(6) atom. In the twentieth O site, O(20) is bonded in a linear geometry to one V(2) and one P(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 120 degrees geometry to one Li(3) and one P(5) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one P(4) atom.