Li4Sn(BO3)2 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share corners with three equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Sn(1)O6 octahedra, edges with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Sn(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-83°. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. Sn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form SnO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, edges with two equivalent Sn(1)O6 octahedra, and edges with four equivalent Li(1)O5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one B(1), and two equivalent Sn(1) atoms to form a mixture of distorted corner and edge-sharing OLi2Sn2B trigonal bipyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one B(1), and one Sn(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one B(1) atom.
Li4Sn(BO3)2 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share corners with three equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Sn(1)O6 octahedra, edges with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Li(1)-O(1) bond length is 2.21 Å. Both Li(1)-O(2) bond lengths are 2.08 Å. There is one shorter (2.06 Å) and one longer (2.37 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Sn(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-83°. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(2) bond length is 1.98 Å. Both Li(2)-O(3) bond lengths are 1.99 Å. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.41 Å. The B(1)-O(2) bond length is 1.40 Å. The B(1)-O(3) bond length is 1.38 Å. Sn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form SnO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, edges with two equivalent Sn(1)O6 octahedra, and edges with four equivalent Li(1)O5 trigonal bipyramids. Both Sn(1)-O(2) bond lengths are 2.59 Å. All Sn(1)-O(1) bond lengths are 2.44 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one B(1), and two equivalent Sn(1) atoms to form a mixture of distorted corner and edge-sharing OLi2Sn2B trigonal bipyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one B(1), and one Sn(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one B(1) atom.