Li2La3Ni2Sn7 crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent La(2), two equivalent Ni(1), one Sn(4), and two equivalent Sn(2) atoms to form distorted LiLa2Ni2Sn3 hexagonal pyramids that share corners with two equivalent Li(1)La2Ni2Sn3 hexagonal pyramids, corners with two equivalent La(2)Li2Sn4 octahedra, edges with two equivalent Li(1)La2Ni2Sn3 hexagonal pyramids, and  an edgeedge with one La(2)Li2Sn4 octahedra. The corner-sharing octahedral tilt angles are 19°. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 14-coordinate geometry to two equivalent Ni(1), four equivalent Sn(1), four equivalent Sn(3), and four equivalent Sn(4) atoms. In the second La site, La(2) is bonded to two equivalent Li(1), two equivalent Sn(1), and two equivalent Sn(2) atoms to form distorted LaLi2Sn4 octahedra that share corners with two equivalent Li(1)La2Ni2Sn3 hexagonal pyramids, corners with two equivalent La(2)Li2Sn4 octahedra,  an edgeedge with one Li(1)La2Ni2Sn3 hexagonal pyramid, and edges with two equivalent La(2)Li2Sn4 octahedra. The corner-sharing octahedral tilt angles are 6°. Ni(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), one La(1), one Sn(2), two equivalent Sn(1), and two equivalent Sn(4) atoms. There are four inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), and two equivalent Ni(1) atoms. In the second Sn site, Sn(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Li(1), two equivalent La(2), and one Ni(1) atom. In the third Sn site, Sn(3) is bonded in a 4-coordinate geometry to four equivalent La(1) atoms. In the fourth Sn site, Sn(4) is bonded in a 5-coordinate geometry to one Li(1), two equivalent La(1), and two equivalent Ni(1) atoms.
Li2La3Ni2Sn7 crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent La(2), two equivalent Ni(1), one Sn(4), and two equivalent Sn(2) atoms to form distorted LiLa2Ni2Sn3 hexagonal pyramids that share corners with two equivalent Li(1)La2Ni2Sn3 hexagonal pyramids, corners with two equivalent La(2)Li2Sn4 octahedra, edges with two equivalent Li(1)La2Ni2Sn3 hexagonal pyramids, and  an edgeedge with one La(2)Li2Sn4 octahedra. The corner-sharing octahedral tilt angles are 19°. Both Li(1)-La(2) bond lengths are 2.61 Å. Both Li(1)-Ni(1) bond lengths are 2.62 Å. The Li(1)-Sn(4) bond length is 2.58 Å. Both Li(1)-Sn(2) bond lengths are 2.58 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 14-coordinate geometry to two equivalent Ni(1), four equivalent Sn(1), four equivalent Sn(3), and four equivalent Sn(4) atoms. Both La(1)-Ni(1) bond lengths are 3.65 Å. All La(1)-Sn(1) bond lengths are 3.62 Å. All La(1)-Sn(3) bond lengths are 3.45 Å. All La(1)-Sn(4) bond lengths are 3.30 Å. In the second La site, La(2) is bonded to two equivalent Li(1), two equivalent Sn(1), and two equivalent Sn(2) atoms to form distorted LaLi2Sn4 octahedra that share corners with two equivalent Li(1)La2Ni2Sn3 hexagonal pyramids, corners with two equivalent La(2)Li2Sn4 octahedra,  an edgeedge with one Li(1)La2Ni2Sn3 hexagonal pyramid, and edges with two equivalent La(2)Li2Sn4 octahedra. The corner-sharing octahedral tilt angles are 6°. Both La(2)-Sn(1) bond lengths are 3.44 Å. Both La(2)-Sn(2) bond lengths are 3.39 Å. Ni(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), one La(1), one Sn(2), two equivalent Sn(1), and two equivalent Sn(4) atoms. The Ni(1)-Sn(2) bond length is 2.58 Å. Both Ni(1)-Sn(1) bond lengths are 2.85 Å. Both Ni(1)-Sn(4) bond lengths are 2.58 Å. There are four inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), and two equivalent Ni(1) atoms. In the second Sn site, Sn(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Li(1), two equivalent La(2), and one Ni(1) atom. In the third Sn site, Sn(3) is bonded in a 4-coordinate geometry to four equivalent La(1) atoms. In the fourth Sn site, Sn(4) is bonded in a 5-coordinate geometry to one Li(1), two equivalent La(1), and two equivalent Ni(1) atoms.