Li4V3Cr2Co(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 4-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 5-coordinate geometry to one O(1), 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 5-coordinate geometry to one O(13), one O(18), 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(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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Cr(2)O6 octahedra. 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 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Cr(2)O6 octahedra. 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 to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom to form distorted CrO6 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,  a cornercorner with one P(6)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one V(3)O6 octahedra. Co(1) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(16), one O(18), one O(21), and one O(5) 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-47°. 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-46°. 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-50°. 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-48°. 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-51°. 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 Cr(2)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 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 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 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 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 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 to one Li(1), one V(1), one Cr(2), and one P(3) atom to form distorted corner-sharing OLiVCrP trigonal pyramids. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Cr(1), one Co(1), and one P(4) atom to form distorted corner-sharing OLi2CrCoP trigonal bipyramids. In the twelfth O site, O(12) is bonded in a linear 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 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 4-coordinate geometry to one Li(2), one V(3), one Cr(2), and one P(4) atom. 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 to one Li(4), one V(3), one Cr(2), and one P(5) atom to form distorted OLiVCrP trigonal pyramids that share  a cornercorner with one O(11)Li2CrCoP trigonal bipyramid and  a cornercorner with one O(10)LiVCrP trigonal pyramid. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Cr(1), one Co(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 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 5-coordinate geometry to one Li(2), one Li(3), one Cr(1), one Co(1), and one P(6) atom. 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.
Li4V3Cr2Co(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 4-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 2.06 Å. The Li(1)-O(14) bond length is 2.12 Å. The Li(1)-O(20) bond length is 2.11 Å. The Li(1)-O(24) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.60 Å. The Li(1)-O(8) bond length is 2.59 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(15), one O(21), and one O(5) atom. The Li(2)-O(1) bond length is 2.34 Å. The Li(2)-O(11) bond length is 2.16 Å. The Li(2)-O(15) bond length is 2.12 Å. The Li(2)-O(21) bond length is 2.51 Å. The Li(2)-O(5) bond length is 2.11 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(13), one O(18), one O(19), one O(2), and one O(21) atom. The Li(3)-O(13) bond length is 2.16 Å. The Li(3)-O(18) bond length is 2.51 Å. The Li(3)-O(19) bond length is 2.18 Å. The Li(3)-O(2) bond length is 2.40 Å. The Li(3)-O(21) bond length is 2.12 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 2.41 Å. The Li(4)-O(16) bond length is 2.25 Å. The Li(4)-O(17) bond length is 2.23 Å. The Li(4)-O(18) bond length is 2.12 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Cr(2)O6 octahedra. The V(1)-O(10) bond length is 2.04 Å. The V(1)-O(22) bond length is 2.01 Å. The V(1)-O(23) bond length is 1.99 Å. The V(1)-O(24) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.04 Å. The V(1)-O(8) bond length is 2.10 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 1.98 Å. The V(2)-O(14) bond length is 2.07 Å. The V(2)-O(20) bond length is 2.09 Å. The V(2)-O(4) bond length is 2.00 Å. The V(2)-O(7) bond length is 2.09 Å. The V(2)-O(9) bond length is 1.95 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Cr(2)O6 octahedra. The V(3)-O(1) bond length is 2.11 Å. The V(3)-O(15) bond length is 2.16 Å. The V(3)-O(17) bond length is 2.24 Å. The V(3)-O(19) bond length is 2.21 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 2.18 Å. The Cr(1)-O(14) bond length is 2.15 Å. The Cr(1)-O(18) bond length is 2.18 Å. The Cr(1)-O(21) bond length is 2.39 Å. The Cr(1)-O(4) bond length is 2.41 Å. The Cr(1)-O(7) bond length is 2.13 Å. In the second Cr site, Cr(2) is bonded to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom to form distorted CrO6 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,  a cornercorner with one P(6)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one V(3)O6 octahedra. The Cr(2)-O(10) bond length is 2.38 Å. The Cr(2)-O(15) bond length is 2.37 Å. The Cr(2)-O(17) bond length is 2.21 Å. The Cr(2)-O(19) bond length is 2.15 Å. The Cr(2)-O(6) bond length is 2.11 Å. The Cr(2)-O(8) bond length is 2.17 Å. Co(1) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(16), one O(18), one O(21), and one O(5) atom. The Co(1)-O(11) bond length is 2.26 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 2.34 Å. The Co(1)-O(21) bond length is 2.14 Å. The Co(1)-O(5) bond length is 2.10 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-47°. The P(1)-O(3) bond length is 1.52 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 1.58 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-46°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(13) 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 1.59 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-50°. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(14) bond length is 1.60 Å. The P(3)-O(16) bond length is 1.54 Å. The P(3)-O(2) bond length is 1.52 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-48°. The P(4)-O(11) bond length is 1.58 Å. The P(4)-O(15) bond length is 1.56 Å. The P(4)-O(23) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.53 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-51°. The P(5)-O(12) bond length is 1.51 Å. The P(5)-O(17) bond length is 1.57 Å. The P(5)-O(18) bond length is 1.58 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 Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-48°. The P(6)-O(19) bond length is 1.59 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 1.52 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 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 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 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 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 to one Li(1), one V(1), one Cr(2), and one P(3) atom to form distorted corner-sharing OLiVCrP trigonal pyramids. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Cr(1), one Co(1), and one P(4) atom to form distorted corner-sharing OLi2CrCoP trigonal bipyramids. In the twelfth O site, O(12) is bonded in a linear 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 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 4-coordinate geometry to one Li(2), one V(3), one Cr(2), and one P(4) atom. 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 to one Li(4), one V(3), one Cr(2), and one P(5) atom to form distorted OLiVCrP trigonal pyramids that share  a cornercorner with one O(11)Li2CrCoP trigonal bipyramid and  a cornercorner with one O(10)LiVCrP trigonal pyramid. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Cr(1), one Co(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 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 5-coordinate geometry to one Li(2), one Li(3), one Cr(1), one Co(1), and one P(6) atom. 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.