Li4Co2C4SO16 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. In the second Li site, Li(2) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 81°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-81°. In the fourth Li site, Li(4) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-81°. Co(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form CoO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Li(4)O6 octahedra. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(6), and one O(8) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent O(4) atoms to form SO4 tetrahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Li(4)O6 octahedra. In the second S site, S(2) is bonded to four equivalent O(7) atoms to form SO4 tetrahedra that share edges with two equivalent Li(2)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Co(1), and one C(2) atom. In the second O site, O(7) is bonded in an L-shaped geometry to one Li(2) and one S(2) atom. In the third O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one C(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Co(1), and one C(2) atom. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one C(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(4), one Co(1), and one C(1) atom. In the seventh O site, O(4) is bonded to one Li(1), one Li(3), one Li(4), and one S(1) atom to form edge-sharing OLi3S trigonal pyramids. In the eighth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one C(1) atom.
Li4Co2C4SO16 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. Both Li(1)-O(2) bond lengths are 2.18 Å. Both Li(1)-O(4) bond lengths are 2.35 Å. Both Li(1)-O(8) bond lengths are 2.34 Å. In the second Li site, Li(2) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 81°. Both Li(2)-O(5) bond lengths are 2.32 Å. Both Li(2)-O(6) bond lengths are 2.25 Å. Both Li(2)-O(7) bond lengths are 2.25 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-81°. Both Li(3)-O(1) bond lengths are 2.27 Å. Both Li(3)-O(4) bond lengths are 2.42 Å. Both Li(3)-O(5) bond lengths are 2.22 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-81°. Both Li(4)-O(3) bond lengths are 2.20 Å. Both Li(4)-O(4) bond lengths are 2.42 Å. Both Li(4)-O(6) bond lengths are 2.29 Å. Co(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form CoO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Li(4)O6 octahedra. The Co(1)-O(1) bond length is 2.00 Å. The Co(1)-O(2) bond length is 2.02 Å. The Co(1)-O(3) bond length is 2.02 Å. The Co(1)-O(5) bond length is 2.09 Å. The Co(1)-O(6) bond length is 2.08 Å. The Co(1)-O(8) bond length is 2.01 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. The C(1)-O(2) bond length is 1.29 Å. The C(1)-O(3) bond length is 1.30 Å. The C(1)-O(5) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(6), and one O(8) atom. The C(2)-O(1) bond length is 1.30 Å. The C(2)-O(6) bond length is 1.31 Å. The C(2)-O(8) bond length is 1.29 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent O(4) atoms to form SO4 tetrahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Li(4)O6 octahedra. All S(1)-O(4) bond lengths are 1.50 Å. In the second S site, S(2) is bonded to four equivalent O(7) atoms to form SO4 tetrahedra that share edges with two equivalent Li(2)O6 octahedra. All S(2)-O(7) bond lengths are 1.49 Å. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Co(1), and one C(2) atom. In the second O site, O(7) is bonded in an L-shaped geometry to one Li(2) and one S(2) atom. In the third O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one C(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Co(1), and one C(2) atom. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one C(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(4), one Co(1), and one C(1) atom. In the seventh O site, O(4) is bonded to one Li(1), one Li(3), one Li(4), and one S(1) atom to form edge-sharing OLi3S trigonal pyramids. In the eighth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one C(1) atom.