Li3BH6 is Ilmenite-like structured and crystallizes in the trigonal R-3 space group. Li(1) is bonded to three equivalent H(1) and three equivalent H(2) atoms to form distorted LiH6 pentagonal pyramids that share  a cornercorner with one B(1)H6 octahedra,  a cornercorner with one B(2)H6 octahedra, corners with four equivalent Li(1)H6 pentagonal pyramids,  an edgeedge with one B(1)H6 octahedra,  an edgeedge with one B(2)H6 octahedra, and edges with four equivalent Li(1)H6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 22-34°. There are two inequivalent B sites. In the first B site, B(1) is bonded to six equivalent H(1) atoms to form BH6 octahedra that share corners with six equivalent Li(1)H6 pentagonal pyramids and edges with six equivalent Li(1)H6 pentagonal pyramids. In the second B site, B(2) is bonded to six equivalent H(2) atoms to form BH6 octahedra that share corners with six equivalent Li(1)H6 pentagonal pyramids and edges with six equivalent Li(1)H6 pentagonal pyramids. There are two inequivalent H sites. In the first H site, H(1) is bonded to three equivalent Li(1) and one B(1) atom to form a mixture of corner and edge-sharing HLi3B trigonal pyramids. In the second H site, H(2) is bonded in a see-saw-like geometry to three equivalent Li(1) and one B(2) atom.
Li3BH6 is Ilmenite-like structured and crystallizes in the trigonal R-3 space group. Li(1) is bonded to three equivalent H(1) and three equivalent H(2) atoms to form distorted LiH6 pentagonal pyramids that share  a cornercorner with one B(1)H6 octahedra,  a cornercorner with one B(2)H6 octahedra, corners with four equivalent Li(1)H6 pentagonal pyramids,  an edgeedge with one B(1)H6 octahedra,  an edgeedge with one B(2)H6 octahedra, and edges with four equivalent Li(1)H6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 22-34°. There are a spread of Li(1)-H(1) bond distances ranging from 1.91-1.95 Å. There are a spread of Li(1)-H(2) bond distances ranging from 1.81-1.96 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to six equivalent H(1) atoms to form BH6 octahedra that share corners with six equivalent Li(1)H6 pentagonal pyramids and edges with six equivalent Li(1)H6 pentagonal pyramids. All B(1)-H(1) bond lengths are 1.45 Å. In the second B site, B(2) is bonded to six equivalent H(2) atoms to form BH6 octahedra that share corners with six equivalent Li(1)H6 pentagonal pyramids and edges with six equivalent Li(1)H6 pentagonal pyramids. All B(2)-H(2) bond lengths are 1.44 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded to three equivalent Li(1) and one B(1) atom to form a mixture of corner and edge-sharing HLi3B trigonal pyramids. In the second H site, H(2) is bonded in a see-saw-like geometry to three equivalent Li(1) and one B(2) atom.