Li4CaB2O6 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), one O(3), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Ca(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 18-80°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share corners with three equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Ca(1)O6 octahedra, edges with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. Ca(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CaO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Ca(1)O6 octahedra, and edges with four equivalent Li(2)O5 trigonal bipyramids. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Li(2), one Ca(1), and one B(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one B(1) atom to form distorted OLi4B trigonal bipyramids that share corners with two equivalent O(2)Li4B trigonal bipyramids, corners with three equivalent O(3)Li2Ca2B trigonal bipyramids,  an edgeedge with one O(3)Li2Ca2B trigonal bipyramid, and  an edgeedge with one O(2)Li4B trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Ca(1), and one B(1) atom to form distorted OLi2Ca2B trigonal bipyramids that share corners with three equivalent O(2)Li4B trigonal bipyramids, corners with four equivalent O(3)Li2Ca2B trigonal bipyramids,  an edgeedge with one O(3)Li2Ca2B trigonal bipyramid, and  an edgeedge with one O(2)Li4B trigonal bipyramid.
Li4CaB2O6 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), one O(3), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Ca(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 18-80°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(3) bond length is 1.98 Å. Both Li(1)-O(2) bond lengths are 1.94 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share corners with three equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Ca(1)O6 octahedra, edges with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The Li(2)-O(3) bond length is 2.24 Å. Both Li(2)-O(1) bond lengths are 2.06 Å. There is one shorter (2.01 Å) and one longer (2.18 Å) Li(2)-O(2) bond length. Ca(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CaO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Ca(1)O6 octahedra, and edges with four equivalent Li(2)O5 trigonal bipyramids. Both Ca(1)-O(1) bond lengths are 2.45 Å. All Ca(1)-O(3) bond lengths are 2.35 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 1.39 Å. The B(1)-O(2) bond length is 1.38 Å. The B(1)-O(3) bond length is 1.40 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Li(2), one Ca(1), and one B(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one B(1) atom to form distorted OLi4B trigonal bipyramids that share corners with two equivalent O(2)Li4B trigonal bipyramids, corners with three equivalent O(3)Li2Ca2B trigonal bipyramids,  an edgeedge with one O(3)Li2Ca2B trigonal bipyramid, and  an edgeedge with one O(2)Li4B trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Ca(1), and one B(1) atom to form distorted OLi2Ca2B trigonal bipyramids that share corners with three equivalent O(2)Li4B trigonal bipyramids, corners with four equivalent O(3)Li2Ca2B trigonal bipyramids,  an edgeedge with one O(3)Li2Ca2B trigonal bipyramid, and  an edgeedge with one O(2)Li4B trigonal bipyramid.