Li5V5Cl16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Aem2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(4), one Cl(8), and two equivalent Cl(10) atoms to form LiCl4 tetrahedra that share  a cornercorner with one Li(2)Cl6 octahedra,  a cornercorner with one V(2)Cl6 octahedra, corners with two equivalent V(1)Cl6 octahedra, corners with four equivalent Li(3)Cl6 octahedra, and corners with four equivalent V(3)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. In the second Li site, Li(2) is bonded to one Cl(1), one Cl(8), two equivalent Cl(2), and two equivalent Cl(6) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent V(1)Cl6 octahedra, edges with two equivalent V(2)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the third Li site, Li(3) is bonded to one Cl(5), one Cl(9), two equivalent Cl(10), and two equivalent Cl(7) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(3)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the fourth Li site, Li(4) is bonded to two equivalent Cl(6) and two equivalent Cl(9) atoms to form LiCl4 tetrahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with two equivalent Li(3)Cl6 octahedra, corners with two equivalent V(2)Cl6 octahedra, corners with two equivalent V(3)Cl6 octahedra, and corners with four equivalent V(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one Cl(1), one Cl(10), one Cl(2), one Cl(3), and two equivalent Cl(9) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(1)Cl6 octahedra. In the second V site, V(2) is bonded to one Cl(3), one Cl(4), two equivalent Cl(2), and two equivalent Cl(6) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the third V site, V(3) is bonded to one Cl(4), one Cl(6), one Cl(7), one Cl(8), and two equivalent Cl(5) atoms to form VCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. There are ten inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(2) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth Cl site, Cl(4) is bonded to one Li(1), one V(2), and two equivalent V(3) atoms to form distorted ClLiV3 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the fifth Cl site, Cl(5) is bonded in a distorted T-shaped geometry to one Li(3) and two equivalent V(3) atoms. In the sixth Cl site, Cl(6) is bonded to one Li(2), one Li(4), one V(2), and one V(3) atom to form distorted ClLi2V2 trigonal pyramids that share  a cornercorner with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and  an edgeedge with one Cl(4)LiV3 trigonal pyramid. In the seventh Cl site, Cl(7) is bonded in a distorted T-shaped geometry to two equivalent Li(3) and one V(3) atom. In the eighth Cl site, Cl(8) is bonded to one Li(1), one Li(2), and two equivalent V(3) atoms to form distorted ClLi2V2 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(4)LiV3 trigonal pyramid,  an edgeedge with one Cl(4)LiV3 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the ninth Cl site, Cl(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), and two equivalent V(1) atoms. In the tenth Cl site, Cl(10) is bonded to one Li(1), two equivalent Li(3), and one V(1) atom to form distorted ClLi3V tetrahedra that share  a cornercorner with one Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  a cornercorner with one Cl(4)LiV3 trigonal pyramid, and  an edgeedge with one Cl(10)Li3V tetrahedra.
Li5V5Cl16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Aem2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(4), one Cl(8), and two equivalent Cl(10) atoms to form LiCl4 tetrahedra that share  a cornercorner with one Li(2)Cl6 octahedra,  a cornercorner with one V(2)Cl6 octahedra, corners with two equivalent V(1)Cl6 octahedra, corners with four equivalent Li(3)Cl6 octahedra, and corners with four equivalent V(3)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. The Li(1)-Cl(4) bond length is 2.57 Å. The Li(1)-Cl(8) bond length is 2.47 Å. Both Li(1)-Cl(10) bond lengths are 2.34 Å. In the second Li site, Li(2) is bonded to one Cl(1), one Cl(8), two equivalent Cl(2), and two equivalent Cl(6) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent V(1)Cl6 octahedra, edges with two equivalent V(2)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. The Li(2)-Cl(1) bond length is 2.53 Å. The Li(2)-Cl(8) bond length is 2.63 Å. Both Li(2)-Cl(2) bond lengths are 2.52 Å. Both Li(2)-Cl(6) bond lengths are 2.62 Å. In the third Li site, Li(3) is bonded to one Cl(5), one Cl(9), two equivalent Cl(10), and two equivalent Cl(7) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(3)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. The Li(3)-Cl(5) bond length is 2.57 Å. The Li(3)-Cl(9) bond length is 2.68 Å. There is one shorter (2.60 Å) and one longer (2.62 Å) Li(3)-Cl(10) bond length. There is one shorter (2.48 Å) and one longer (2.49 Å) Li(3)-Cl(7) bond length. In the fourth Li site, Li(4) is bonded to two equivalent Cl(6) and two equivalent Cl(9) atoms to form LiCl4 tetrahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with two equivalent Li(3)Cl6 octahedra, corners with two equivalent V(2)Cl6 octahedra, corners with two equivalent V(3)Cl6 octahedra, and corners with four equivalent V(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. Both Li(4)-Cl(6) bond lengths are 2.41 Å. Both Li(4)-Cl(9) bond lengths are 2.41 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one Cl(1), one Cl(10), one Cl(2), one Cl(3), and two equivalent Cl(9) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(1)Cl6 octahedra. The V(1)-Cl(1) bond length is 2.44 Å. The V(1)-Cl(10) bond length is 2.45 Å. The V(1)-Cl(2) bond length is 2.46 Å. The V(1)-Cl(3) bond length is 2.50 Å. There is one shorter (2.49 Å) and one longer (2.52 Å) V(1)-Cl(9) bond length. In the second V site, V(2) is bonded to one Cl(3), one Cl(4), two equivalent Cl(2), and two equivalent Cl(6) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. The V(2)-Cl(3) bond length is 2.48 Å. The V(2)-Cl(4) bond length is 2.53 Å. Both V(2)-Cl(2) bond lengths are 2.44 Å. Both V(2)-Cl(6) bond lengths are 2.50 Å. In the third V site, V(3) is bonded to one Cl(4), one Cl(6), one Cl(7), one Cl(8), and two equivalent Cl(5) atoms to form VCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. The V(3)-Cl(4) bond length is 2.57 Å. The V(3)-Cl(6) bond length is 2.54 Å. The V(3)-Cl(7) bond length is 2.38 Å. The V(3)-Cl(8) bond length is 2.52 Å. There is one shorter (2.43 Å) and one longer (2.44 Å) V(3)-Cl(5) bond length. There are ten inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(2) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth Cl site, Cl(4) is bonded to one Li(1), one V(2), and two equivalent V(3) atoms to form distorted ClLiV3 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the fifth Cl site, Cl(5) is bonded in a distorted T-shaped geometry to one Li(3) and two equivalent V(3) atoms. In the sixth Cl site, Cl(6) is bonded to one Li(2), one Li(4), one V(2), and one V(3) atom to form distorted ClLi2V2 trigonal pyramids that share  a cornercorner with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and  an edgeedge with one Cl(4)LiV3 trigonal pyramid. In the seventh Cl site, Cl(7) is bonded in a distorted T-shaped geometry to two equivalent Li(3) and one V(3) atom. In the eighth Cl site, Cl(8) is bonded to one Li(1), one Li(2), and two equivalent V(3) atoms to form distorted ClLi2V2 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(4)LiV3 trigonal pyramid,  an edgeedge with one Cl(4)LiV3 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the ninth Cl site, Cl(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), and two equivalent V(1) atoms. In the tenth Cl site, Cl(10) is bonded to one Li(1), two equivalent Li(3), and one V(1) atom to form distorted ClLi3V tetrahedra that share  a cornercorner with one Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  a cornercorner with one Cl(4)LiV3 trigonal pyramid, and  an edgeedge with one Cl(10)Li3V tetrahedra.