Li4V2Co3Sn3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, corners with two equivalent Sn(2)O6 octahedra, and corners with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-65°. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Sn(2)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-70°. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form LiO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra,  an edgeedge with one Sn(2)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-63°. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Sn(2)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with four equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-66°. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with four equivalent Sn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. In the second Co site, Co(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form distorted CoO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Sn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form SnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. In the second Sn site, Sn(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form SnO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, edges with four equivalent Co(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), one Co(2), and one Sn(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(4), one V(1), and two equivalent Sn(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), and two equivalent Sn(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Co(1), and two equivalent Sn(1) atoms to form distorted corner-sharing OLiCoSn2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Co(2), and one Sn(2) atom to form corner-sharing OLiCo2Sn tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Co(1), and one Sn(1) atom to form distorted OLiVCoSn tetrahedra that share  a cornercorner with one O(6)LiVCoSn tetrahedra, corners with two equivalent O(4)LiCoSn2 tetrahedra,  a cornercorner with one O(10)LiCo2Sn trigonal pyramid, and  an edgeedge with one O(6)LiVCoSn tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent Sn(1) atoms. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(3), one V(1), and two equivalent Co(2) atoms. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one Co(2), and one Sn(2) atom. In the tenth O site, O(10) is bonded to one Li(4), two equivalent Co(2), and one Sn(2) atom to form distorted OLiCo2Sn trigonal pyramids that share corners with two equivalent O(6)LiVCoSn tetrahedra and corners with three equivalent O(5)LiCo2Sn tetrahedra. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Co(1), and one Sn(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one V(2), and two equivalent Co(2) atoms.
Li4V2Co3Sn3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, corners with two equivalent Sn(2)O6 octahedra, and corners with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-65°. The Li(1)-O(12) bond length is 2.11 Å. The Li(1)-O(3) bond length is 1.95 Å. Both Li(1)-O(9) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Sn(2)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-70°. The Li(2)-O(5) bond length is 1.85 Å. The Li(2)-O(7) bond length is 2.06 Å. Both Li(2)-O(11) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form LiO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra,  an edgeedge with one Sn(2)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-63°. The Li(3)-O(4) bond length is 1.82 Å. The Li(3)-O(8) bond length is 2.03 Å. Both Li(3)-O(1) bond lengths are 2.13 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Sn(2)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with four equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-66°. The Li(4)-O(10) bond length is 1.97 Å. The Li(4)-O(2) bond length is 2.02 Å. Both Li(4)-O(6) bond lengths are 2.08 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms. The V(1)-O(2) bond length is 2.33 Å. The V(1)-O(8) bond length is 1.74 Å. Both V(1)-O(1) bond lengths are 1.90 Å. Both V(1)-O(6) bond lengths are 2.01 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms. The V(2)-O(12) bond length is 1.76 Å. The V(2)-O(7) bond length is 2.60 Å. Both V(2)-O(11) bond lengths are 1.86 Å. Both V(2)-O(9) bond lengths are 1.99 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with four equivalent Sn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Co(1)-O(3) bond length is 2.03 Å. The Co(1)-O(4) bond length is 2.01 Å. Both Co(1)-O(11) bond lengths are 2.26 Å. Both Co(1)-O(6) bond lengths are 2.12 Å. In the second Co site, Co(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form distorted CoO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, edges with two equivalent Co(2)O6 octahedra, edges with two equivalent Sn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Co(2)-O(1) bond length is 2.20 Å. The Co(2)-O(10) bond length is 1.97 Å. The Co(2)-O(12) bond length is 2.21 Å. The Co(2)-O(5) bond length is 1.98 Å. The Co(2)-O(8) bond length is 2.24 Å. The Co(2)-O(9) bond length is 2.15 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form SnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Sn(1)-O(11) bond length is 2.20 Å. The Sn(1)-O(2) bond length is 2.08 Å. The Sn(1)-O(3) bond length is 2.06 Å. The Sn(1)-O(4) bond length is 2.07 Å. The Sn(1)-O(6) bond length is 2.10 Å. The Sn(1)-O(7) bond length is 2.07 Å. In the second Sn site, Sn(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form SnO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, edges with four equivalent Co(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Sn(2)-O(10) bond length is 2.04 Å. The Sn(2)-O(5) bond length is 2.02 Å. Both Sn(2)-O(1) bond lengths are 2.22 Å. Both Sn(2)-O(9) bond lengths are 2.11 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), one Co(2), and one Sn(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(4), one V(1), and two equivalent Sn(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), and two equivalent Sn(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Co(1), and two equivalent Sn(1) atoms to form distorted corner-sharing OLiCoSn2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Co(2), and one Sn(2) atom to form corner-sharing OLiCo2Sn tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Co(1), and one Sn(1) atom to form distorted OLiVCoSn tetrahedra that share  a cornercorner with one O(6)LiVCoSn tetrahedra, corners with two equivalent O(4)LiCoSn2 tetrahedra,  a cornercorner with one O(10)LiCo2Sn trigonal pyramid, and  an edgeedge with one O(6)LiVCoSn tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent Sn(1) atoms. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(3), one V(1), and two equivalent Co(2) atoms. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one Co(2), and one Sn(2) atom. In the tenth O site, O(10) is bonded to one Li(4), two equivalent Co(2), and one Sn(2) atom to form distorted OLiCo2Sn trigonal pyramids that share corners with two equivalent O(6)LiVCoSn tetrahedra and corners with three equivalent O(5)LiCo2Sn tetrahedra. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one Co(1), and one Sn(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one V(2), and two equivalent Co(2) atoms.