Li4V3CoCu2(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(11), one O(15), one O(21), and one O(5) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(13), one O(18), one O(19), and one O(21) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(16), one O(17), and one O(18) atom. 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 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 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. Co(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 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. There are two inequivalent Cu sites. In the first Cu site, Cu(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 Cu site, Cu(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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-45°. 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-45°. 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-48°. 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-49°. 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one Cu(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Co(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 Cu(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 Cu(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 Cu(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 Cu(2), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Co(1), one Cu(1), and one P(4) atom to form distorted OLi2CoCuP trigonal bipyramids that share  an edgeedge with one O(15)LiVCuP trigonal pyramid and  a faceface with one O(21)Li2CoCuP trigonal bipyramid. 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 3-coordinate geometry to one Li(3), one Co(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 V(2), one Cu(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one V(3), one Cu(2), and one P(4) atom to form a mixture of distorted corner and edge-sharing OLiVCuP trigonal pyramids. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Co(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(4), one V(3), one Cu(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Co(1), one Cu(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(3), one Cu(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 to one Li(2), one Li(3), one Co(1), one Cu(1), and one P(6) atom to form distorted OLi2CoCuP trigonal bipyramids that share  a cornercorner with one O(15)LiVCuP trigonal pyramid and  a faceface with one O(11)Li2CoCuP trigonal bipyramid. In the twenty-second O site, O(22) is bonded in a linear 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.
Li4V3CoCu2(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 2.11 Å. The Li(1)-O(20) bond length is 2.26 Å. The Li(1)-O(24) bond length is 2.26 Å. The Li(1)-O(4) bond length is 2.43 Å. The Li(1)-O(8) bond length is 2.51 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(15), one O(21), and one O(5) atom. The Li(2)-O(11) bond length is 2.12 Å. The Li(2)-O(15) bond length is 2.19 Å. The Li(2)-O(21) bond length is 2.38 Å. The Li(2)-O(5) bond length is 2.06 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(13), one O(18), one O(19), and one O(21) atom. The Li(3)-O(13) bond length is 2.08 Å. The Li(3)-O(18) bond length is 2.42 Å. The Li(3)-O(19) bond length is 2.16 Å. The Li(3)-O(21) bond length is 2.13 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(16), one O(17), and one O(18) atom. The Li(4)-O(11) bond length is 2.35 Å. The Li(4)-O(16) bond length is 2.06 Å. The Li(4)-O(17) bond length is 2.25 Å. The Li(4)-O(18) bond length is 2.06 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 2.05 Å. The V(1)-O(22) bond length is 1.98 Å. The V(1)-O(23) bond length is 1.95 Å. The V(1)-O(24) bond length is 2.03 Å. The V(1)-O(6) bond length is 2.02 Å. The V(1)-O(8) bond length is 2.02 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 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 2.00 Å. The V(2)-O(14) bond length is 2.06 Å. The V(2)-O(20) bond length is 2.05 Å. The V(2)-O(4) bond length is 2.05 Å. The V(2)-O(7) bond length is 2.02 Å. The V(2)-O(9) bond length is 1.97 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 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 2.00 Å. The V(3)-O(15) bond length is 2.12 Å. The V(3)-O(17) bond length is 2.07 Å. The V(3)-O(19) bond length is 2.08 Å. The V(3)-O(2) bond length is 1.97 Å. The V(3)-O(3) bond length is 2.01 Å. Co(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 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(1)-O(11) bond length is 2.18 Å. The Co(1)-O(13) bond length is 2.04 Å. The Co(1)-O(16) bond length is 2.01 Å. The Co(1)-O(18) bond length is 2.16 Å. The Co(1)-O(21) bond length is 2.19 Å. The Co(1)-O(5) bond length is 2.03 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(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 Cu(1)-O(11) bond length is 2.22 Å. The Cu(1)-O(14) bond length is 2.29 Å. The Cu(1)-O(18) bond length is 2.38 Å. The Cu(1)-O(21) bond length is 2.23 Å. The Cu(1)-O(4) bond length is 2.26 Å. The Cu(1)-O(7) bond length is 2.17 Å. In the second Cu site, Cu(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 Cu(2)-O(10) bond length is 2.26 Å. The Cu(2)-O(15) bond length is 2.24 Å. The Cu(2)-O(17) bond length is 2.29 Å. The Cu(2)-O(19) bond length is 2.44 Å. The Cu(2)-O(6) bond length is 2.14 Å. The Cu(2)-O(8) bond length is 2.29 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-45°. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.56 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-45°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(13) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.57 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-48°. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(14) bond length is 1.57 Å. The P(3)-O(16) bond length is 1.53 Å. The P(3)-O(2) bond length is 1.54 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-49°. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.58 Å. The P(4)-O(23) bond length is 1.52 Å. The P(4)-O(9) 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(24) atom to form PO4 tetrahedra that share  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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. The P(5)-O(12) bond length is 1.52 Å. The P(5)-O(17) bond length is 1.59 Å. The P(5)-O(18) bond length is 1.56 Å. The P(5)-O(24) bond length is 1.54 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 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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. The P(6)-O(19) bond length is 1.58 Å. The P(6)-O(20) bond length is 1.54 Å. The P(6)-O(21) bond length is 1.57 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 distorted bent 150 degrees geometry to one V(3) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one Cu(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Co(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 Cu(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 Cu(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 Cu(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 Cu(2), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Co(1), one Cu(1), and one P(4) atom to form distorted OLi2CoCuP trigonal bipyramids that share  an edgeedge with one O(15)LiVCuP trigonal pyramid and  a faceface with one O(21)Li2CoCuP trigonal bipyramid. 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 3-coordinate geometry to one Li(3), one Co(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 V(2), one Cu(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one V(3), one Cu(2), and one P(4) atom to form a mixture of distorted corner and edge-sharing OLiVCuP trigonal pyramids. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Co(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(4), one V(3), one Cu(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Co(1), one Cu(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(3), one Cu(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 to one Li(2), one Li(3), one Co(1), one Cu(1), and one P(6) atom to form distorted OLi2CoCuP trigonal bipyramids that share  a cornercorner with one O(15)LiVCuP trigonal pyramid and  a faceface with one O(11)Li2CoCuP trigonal bipyramid. In the twenty-second O site, O(22) is bonded in a linear 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.