Li3BiS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share corners with two equivalent Li(2)BiS4 tetrahedra, corners with six equivalent Li(1)S4 trigonal pyramids, and  an edgeedge with one Li(1)S4 trigonal pyramid. In the second Li site, Li(2) is bonded to one Bi(1), two equivalent S(1), and two equivalent S(2) atoms to form distorted LiBiS4 tetrahedra that share corners with two equivalent Li(2)BiS4 tetrahedra,  a cornercorner with one S(3)Li4Bi trigonal bipyramid, and corners with four equivalent Li(1)S4 trigonal pyramids. Bi(1) is bonded in a 5-coordinate geometry to one Li(2), one S(1), one S(3), and two equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Li(2) and one Bi(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Bi(1), and one S(2) atom. In the third S site, S(3) is bonded to four equivalent Li(1) and one Bi(1) atom to form distorted SLi4Bi trigonal bipyramids that share  a cornercorner with one Li(2)BiS4 tetrahedra and edges with two equivalent S(3)Li4Bi trigonal bipyramids.
Li3BiS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share corners with two equivalent Li(2)BiS4 tetrahedra, corners with six equivalent Li(1)S4 trigonal pyramids, and  an edgeedge with one Li(1)S4 trigonal pyramid. There is one shorter (2.54 Å) and one longer (2.90 Å) Li(1)-S(2) bond length. There is one shorter (2.49 Å) and one longer (2.51 Å) Li(1)-S(3) bond length. In the second Li site, Li(2) is bonded to one Bi(1), two equivalent S(1), and two equivalent S(2) atoms to form distorted LiBiS4 tetrahedra that share corners with two equivalent Li(2)BiS4 tetrahedra,  a cornercorner with one S(3)Li4Bi trigonal bipyramid, and corners with four equivalent Li(1)S4 trigonal pyramids. The Li(2)-Bi(1) bond length is 3.28 Å. There is one shorter (2.32 Å) and one longer (2.38 Å) Li(2)-S(1) bond length. Both Li(2)-S(2) bond lengths are 2.50 Å. Bi(1) is bonded in a 5-coordinate geometry to one Li(2), one S(1), one S(3), and two equivalent S(2) atoms. The Bi(1)-S(1) bond length is 2.50 Å. The Bi(1)-S(3) bond length is 2.60 Å. Both Bi(1)-S(2) bond lengths are 2.87 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Li(2) and one Bi(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Bi(1), and one S(2) atom. The S(2)-S(2) bond length is 2.11 Å. In the third S site, S(3) is bonded to four equivalent Li(1) and one Bi(1) atom to form distorted SLi4Bi trigonal bipyramids that share  a cornercorner with one Li(2)BiS4 tetrahedra and edges with two equivalent S(3)Li4Bi trigonal bipyramids.