La4S4OCl2 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 1-coordinate geometry to one S(1), one S(3), four equivalent S(2), one O(1), and two equivalent Cl(1) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(3), four equivalent S(2), one O(1), and two equivalent Cl(1) atoms. In the third La site, La(3) is bonded in a 8-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(2), one O(1), and two equivalent Cl(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one La(1) and four equivalent La(3) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), and two equivalent La(3) atoms. In the third S site, S(3) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form distorted SLa4 trigonal pyramids that share corners with two equivalent O(1)La4 tetrahedra, corners with eight equivalent Cl(1)La4 trigonal pyramids, and  an edgeedge with one O(1)La4 tetrahedra. O(1) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form OLa4 tetrahedra that share corners with two equivalent S(3)La4 trigonal pyramids, corners with four equivalent Cl(1)La4 trigonal pyramids,  an edgeedge with one S(3)La4 trigonal pyramid, and edges with two equivalent Cl(1)La4 trigonal pyramids. Cl(1) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form distorted ClLa4 trigonal pyramids that share corners with two equivalent O(1)La4 tetrahedra, corners with four equivalent S(3)La4 trigonal pyramids, corners with four equivalent Cl(1)La4 trigonal pyramids, and  an edgeedge with one O(1)La4 tetrahedra.
La4S4OCl2 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 1-coordinate geometry to one S(1), one S(3), four equivalent S(2), one O(1), and two equivalent Cl(1) atoms. The La(1)-S(1) bond length is 2.92 Å. The La(1)-S(3) bond length is 3.14 Å. There are two shorter (2.85 Å) and two longer (3.54 Å) La(1)-S(2) bond lengths. The La(1)-O(1) bond length is 2.47 Å. Both La(1)-Cl(1) bond lengths are 3.35 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(3), four equivalent S(2), one O(1), and two equivalent Cl(1) atoms. The La(2)-S(3) bond length is 2.83 Å. There are two shorter (3.02 Å) and two longer (3.20 Å) La(2)-S(2) bond lengths. The La(2)-O(1) bond length is 2.35 Å. Both La(2)-Cl(1) bond lengths are 2.94 Å. In the third La site, La(3) is bonded in a 8-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(2), one O(1), and two equivalent Cl(1) atoms. The La(3)-S(3) bond length is 2.86 Å. There is one shorter (2.94 Å) and one longer (3.39 Å) La(3)-S(1) bond length. There is one shorter (2.92 Å) and one longer (3.21 Å) La(3)-S(2) bond length. The La(3)-O(1) bond length is 2.40 Å. There is one shorter (2.97 Å) and one longer (3.01 Å) La(3)-Cl(1) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one La(1) and four equivalent La(3) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), and two equivalent La(3) atoms. In the third S site, S(3) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form distorted SLa4 trigonal pyramids that share corners with two equivalent O(1)La4 tetrahedra, corners with eight equivalent Cl(1)La4 trigonal pyramids, and  an edgeedge with one O(1)La4 tetrahedra. O(1) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form OLa4 tetrahedra that share corners with two equivalent S(3)La4 trigonal pyramids, corners with four equivalent Cl(1)La4 trigonal pyramids,  an edgeedge with one S(3)La4 trigonal pyramid, and edges with two equivalent Cl(1)La4 trigonal pyramids. Cl(1) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form distorted ClLa4 trigonal pyramids that share corners with two equivalent O(1)La4 tetrahedra, corners with four equivalent S(3)La4 trigonal pyramids, corners with four equivalent Cl(1)La4 trigonal pyramids, and  an edgeedge with one O(1)La4 tetrahedra.