Li4NbV3Cr2(PO4)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(14), one O(20), one O(24), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(15), and one O(17) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(15), one O(19), one O(2), and one O(21) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(3) atom. Nb(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(21), and one O(5) atom to form distorted NbO6 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 V sites. In the first V site, V(1) is bonded to one O(10), one O(22), one O(23), one O(24), one O(6), 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. In the second V site, V(2) is bonded to one O(12), one O(14), one O(20), one O(4), one O(7), and one O(9) atom to form distorted 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(1), one O(15), one O(17), one O(19), one O(2), and one O(3) atom to form distorted 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 two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) atom. In the second Cr site, Cr(2) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom. 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(6) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 24-54°. In the second P site, P(2) is bonded to one O(1), one O(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 27-54°. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 26-51°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 33-53°. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 20-50°. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 19-47°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one V(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Cr(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one Cr(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Cr(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Nb(1), one Cr(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one Cr(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one V(3), one Cr(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one V(3), one Cr(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Nb(1), one Cr(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one V(3), one Cr(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Nb(1), one Cr(1), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(5) atom.
Li4NbV3Cr2(PO4)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(14), one O(20), one O(24), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.10 Å. The Li(1)-O(14) bond length is 2.15 Å. The Li(1)-O(20) bond length is 2.10 Å. The Li(1)-O(24) bond length is 2.12 Å. The Li(1)-O(4) bond length is 2.60 Å. The Li(1)-O(8) bond length is 2.46 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(15), and one O(17) atom. The Li(2)-O(1) bond length is 1.94 Å. The Li(2)-O(11) bond length is 2.16 Å. The Li(2)-O(15) bond length is 2.05 Å. The Li(2)-O(17) bond length is 2.41 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(15), one O(19), one O(2), and one O(21) atom. The Li(3)-O(15) bond length is 2.40 Å. The Li(3)-O(19) bond length is 2.09 Å. The Li(3)-O(2) bond length is 1.94 Å. The Li(3)-O(21) bond length is 2.17 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(3) atom. The Li(4)-O(17) bond length is 2.17 Å. The Li(4)-O(18) bond length is 2.18 Å. The Li(4)-O(19) bond length is 2.42 Å. The Li(4)-O(3) bond length is 1.95 Å. Nb(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(21), and one O(5) atom to form distorted NbO6 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 Nb(1)-O(11) bond length is 2.18 Å. The Nb(1)-O(13) bond length is 1.99 Å. The Nb(1)-O(16) bond length is 2.00 Å. The Nb(1)-O(18) bond length is 2.23 Å. The Nb(1)-O(21) bond length is 2.12 Å. The Nb(1)-O(5) bond length is 2.02 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(22), one O(23), one O(24), one O(6), 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(1)-O(10) bond length is 2.15 Å. The V(1)-O(22) bond length is 2.12 Å. The V(1)-O(23) bond length is 2.11 Å. The V(1)-O(24) bond length is 2.21 Å. The V(1)-O(6) bond length is 2.21 Å. The V(1)-O(8) bond length is 2.26 Å. In the second V site, V(2) is bonded to one O(12), one O(14), one O(20), one O(4), one O(7), and one O(9) atom to form distorted 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(12) bond length is 2.09 Å. The V(2)-O(14) bond length is 2.17 Å. The V(2)-O(20) bond length is 2.19 Å. The V(2)-O(4) bond length is 2.14 Å. The V(2)-O(7) bond length is 2.21 Å. The V(2)-O(9) bond length is 2.09 Å. In the third V site, V(3) is bonded to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) atom to form distorted 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(1) bond length is 2.11 Å. The V(3)-O(15) bond length is 2.13 Å. The V(3)-O(17) bond length is 2.23 Å. The V(3)-O(19) bond length is 2.19 Å. The V(3)-O(2) bond length is 2.11 Å. The V(3)-O(3) bond length is 2.09 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) atom. The Cr(1)-O(11) bond length is 2.20 Å. The Cr(1)-O(14) bond length is 2.14 Å. The Cr(1)-O(18) bond length is 2.34 Å. The Cr(1)-O(21) bond length is 2.53 Å. The Cr(1)-O(4) bond length is 2.38 Å. The Cr(1)-O(7) bond length is 2.14 Å. In the second Cr site, Cr(2) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom. The Cr(2)-O(10) bond length is 2.41 Å. The Cr(2)-O(15) bond length is 2.43 Å. The Cr(2)-O(17) bond length is 2.24 Å. The Cr(2)-O(19) bond length is 2.20 Å. The Cr(2)-O(6) bond length is 2.09 Å. The Cr(2)-O(8) bond length is 2.18 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(6) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 24-54°. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 27-54°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(13) bond length is 1.58 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 26-51°. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(14) bond length is 1.57 Å. The P(3)-O(16) bond length is 1.57 Å. The P(3)-O(2) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 33-53°. The P(4)-O(11) bond length is 1.65 Å. The P(4)-O(15) bond length is 1.58 Å. The P(4)-O(23) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.50 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 20-50°. The P(5)-O(12) bond length is 1.50 Å. The P(5)-O(17) bond length is 1.60 Å. The P(5)-O(18) bond length is 1.62 Å. The P(5)-O(24) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(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 19-47°. The P(6)-O(19) bond length is 1.60 Å. The P(6)-O(20) bond length is 1.52 Å. The P(6)-O(21) bond length is 1.60 Å. The P(6)-O(22) bond length is 1.51 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one V(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Cr(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one Cr(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Cr(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Nb(1), one Cr(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one Cr(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one V(3), one Cr(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one V(3), one Cr(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Nb(1), one Cr(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one V(3), one Cr(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Nb(1), one Cr(1), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(5) atom.