La3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(4), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms. In the third La site, La(3) is bonded to one S(1), one S(2), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form distorted LaS7 pentagonal bipyramids that share  a cornercorner with one Cr(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent La(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 29°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form CrS6 octahedra that share edges with two equivalent Cr(1)S6 octahedra and edges with four equivalent La(3)S7 pentagonal bipyramids. In the second Cr site, Cr(2) is bonded to two equivalent S(1) and four equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent La(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. There are six inequivalent S sites. In the first S site, S(5) is bonded to one La(2), two equivalent La(1), and two equivalent La(3) atoms to form distorted SLa5 trigonal bipyramids that share  a cornercorner with one S(4)La3Cr2 trigonal bipyramid, corners with two equivalent S(2)La5 trigonal bipyramids, corners with four equivalent S(3)La4Cr trigonal bipyramids, edges with two equivalent S(6)La3Cr2 square pyramids,  an edgeedge with one S(3)La4Cr trigonal bipyramid, edges with two equivalent S(4)La3Cr2 trigonal bipyramids, edges with two equivalent S(5)La5 trigonal bipyramids, and edges with three equivalent S(2)La5 trigonal bipyramids. In the second S site, S(6) is bonded to one La(1), two equivalent La(2), and two equivalent Cr(2) atoms to form distorted SLa3Cr2 square pyramids that share corners with two equivalent S(6)La3Cr2 square pyramids, corners with two equivalent S(3)La4Cr trigonal bipyramids, corners with three equivalent S(4)La3Cr2 trigonal bipyramids, corners with four equivalent S(2)La5 trigonal bipyramids, edges with three equivalent S(6)La3Cr2 square pyramids,  an edgeedge with one S(3)La4Cr trigonal bipyramid,  an edgeedge with one S(2)La5 trigonal bipyramid, and edges with two equivalent S(5)La5 trigonal bipyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one La(3), two equivalent La(1), and one Cr(2) atom. In the fourth S site, S(2) is bonded to one La(3), two equivalent La(1), and two equivalent La(2) atoms to form SLa5 trigonal bipyramids that share corners with four equivalent S(6)La3Cr2 square pyramids,  a cornercorner with one S(4)La3Cr2 trigonal bipyramid, corners with two equivalent S(5)La5 trigonal bipyramids, corners with four equivalent S(3)La4Cr trigonal bipyramids,  an edgeedge with one S(6)La3Cr2 square pyramid,  an edgeedge with one S(3)La4Cr trigonal bipyramid, edges with two equivalent S(4)La3Cr2 trigonal bipyramids, edges with two equivalent S(2)La5 trigonal bipyramids, and edges with three equivalent S(5)La5 trigonal bipyramids. In the fifth S site, S(3) is bonded to two equivalent La(2), two equivalent La(3), and one Cr(1) atom to form distorted SLa4Cr trigonal bipyramids that share corners with two equivalent S(6)La3Cr2 square pyramids,  a cornercorner with one S(3)La4Cr trigonal bipyramid, corners with four equivalent S(2)La5 trigonal bipyramids, corners with four equivalent S(5)La5 trigonal bipyramids,  an edgeedge with one S(6)La3Cr2 square pyramid,  an edgeedge with one S(2)La5 trigonal bipyramid,  an edgeedge with one S(5)La5 trigonal bipyramid, edges with two equivalent S(3)La4Cr trigonal bipyramids, and edges with four equivalent S(4)La3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one La(1), one La(2), one La(3), and two equivalent Cr(1) atoms to form distorted SLa3Cr2 trigonal bipyramids that share corners with three equivalent S(6)La3Cr2 square pyramids,  a cornercorner with one S(2)La5 trigonal bipyramid,  a cornercorner with one S(5)La5 trigonal bipyramid, corners with four equivalent S(4)La3Cr2 trigonal bipyramids,  an edgeedge with one S(4)La3Cr2 trigonal bipyramid, edges with two equivalent S(2)La5 trigonal bipyramids, edges with two equivalent S(5)La5 trigonal bipyramids, and edges with four equivalent S(3)La4Cr trigonal bipyramids.
La3CrS6 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The La(1)-S(4) bond length is 3.18 Å. The La(1)-S(6) bond length is 3.01 Å. Both La(1)-S(1) bond lengths are 2.91 Å. Both La(1)-S(2) bond lengths are 2.99 Å. Both La(1)-S(5) bond lengths are 2.93 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(4), one S(5), two equivalent S(2), two equivalent S(3), and two equivalent S(6) atoms. The La(2)-S(4) bond length is 3.18 Å. The La(2)-S(5) bond length is 3.15 Å. Both La(2)-S(2) bond lengths are 2.90 Å. Both La(2)-S(3) bond lengths are 3.00 Å. Both La(2)-S(6) bond lengths are 3.05 Å. In the third La site, La(3) is bonded to one S(1), one S(2), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form distorted LaS7 pentagonal bipyramids that share  a cornercorner with one Cr(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent La(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 29°. The La(3)-S(1) bond length is 2.85 Å. The La(3)-S(2) bond length is 2.98 Å. The La(3)-S(4) bond length is 2.96 Å. Both La(3)-S(3) bond lengths are 2.90 Å. Both La(3)-S(5) bond lengths are 2.87 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form CrS6 octahedra that share edges with two equivalent Cr(1)S6 octahedra and edges with four equivalent La(3)S7 pentagonal bipyramids. Both Cr(1)-S(3) bond lengths are 2.44 Å. All Cr(1)-S(4) bond lengths are 2.54 Å. In the second Cr site, Cr(2) is bonded to two equivalent S(1) and four equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent La(3)S7 pentagonal bipyramids and edges with two equivalent Cr(2)S6 octahedra. Both Cr(2)-S(1) bond lengths are 2.36 Å. All Cr(2)-S(6) bond lengths are 2.55 Å. There are six inequivalent S sites. In the first S site, S(5) is bonded to one La(2), two equivalent La(1), and two equivalent La(3) atoms to form distorted SLa5 trigonal bipyramids that share  a cornercorner with one S(4)La3Cr2 trigonal bipyramid, corners with two equivalent S(2)La5 trigonal bipyramids, corners with four equivalent S(3)La4Cr trigonal bipyramids, edges with two equivalent S(6)La3Cr2 square pyramids,  an edgeedge with one S(3)La4Cr trigonal bipyramid, edges with two equivalent S(4)La3Cr2 trigonal bipyramids, edges with two equivalent S(5)La5 trigonal bipyramids, and edges with three equivalent S(2)La5 trigonal bipyramids. In the second S site, S(6) is bonded to one La(1), two equivalent La(2), and two equivalent Cr(2) atoms to form distorted SLa3Cr2 square pyramids that share corners with two equivalent S(6)La3Cr2 square pyramids, corners with two equivalent S(3)La4Cr trigonal bipyramids, corners with three equivalent S(4)La3Cr2 trigonal bipyramids, corners with four equivalent S(2)La5 trigonal bipyramids, edges with three equivalent S(6)La3Cr2 square pyramids,  an edgeedge with one S(3)La4Cr trigonal bipyramid,  an edgeedge with one S(2)La5 trigonal bipyramid, and edges with two equivalent S(5)La5 trigonal bipyramids. In the third S site, S(1) is bonded in a 4-coordinate geometry to one La(3), two equivalent La(1), and one Cr(2) atom. In the fourth S site, S(2) is bonded to one La(3), two equivalent La(1), and two equivalent La(2) atoms to form SLa5 trigonal bipyramids that share corners with four equivalent S(6)La3Cr2 square pyramids,  a cornercorner with one S(4)La3Cr2 trigonal bipyramid, corners with two equivalent S(5)La5 trigonal bipyramids, corners with four equivalent S(3)La4Cr trigonal bipyramids,  an edgeedge with one S(6)La3Cr2 square pyramid,  an edgeedge with one S(3)La4Cr trigonal bipyramid, edges with two equivalent S(4)La3Cr2 trigonal bipyramids, edges with two equivalent S(2)La5 trigonal bipyramids, and edges with three equivalent S(5)La5 trigonal bipyramids. In the fifth S site, S(3) is bonded to two equivalent La(2), two equivalent La(3), and one Cr(1) atom to form distorted SLa4Cr trigonal bipyramids that share corners with two equivalent S(6)La3Cr2 square pyramids,  a cornercorner with one S(3)La4Cr trigonal bipyramid, corners with four equivalent S(2)La5 trigonal bipyramids, corners with four equivalent S(5)La5 trigonal bipyramids,  an edgeedge with one S(6)La3Cr2 square pyramid,  an edgeedge with one S(2)La5 trigonal bipyramid,  an edgeedge with one S(5)La5 trigonal bipyramid, edges with two equivalent S(3)La4Cr trigonal bipyramids, and edges with four equivalent S(4)La3Cr2 trigonal bipyramids. In the sixth S site, S(4) is bonded to one La(1), one La(2), one La(3), and two equivalent Cr(1) atoms to form distorted SLa3Cr2 trigonal bipyramids that share corners with three equivalent S(6)La3Cr2 square pyramids,  a cornercorner with one S(2)La5 trigonal bipyramid,  a cornercorner with one S(5)La5 trigonal bipyramid, corners with four equivalent S(4)La3Cr2 trigonal bipyramids,  an edgeedge with one S(4)La3Cr2 trigonal bipyramid, edges with two equivalent S(2)La5 trigonal bipyramids, edges with two equivalent S(5)La5 trigonal bipyramids, and edges with four equivalent S(3)La4Cr trigonal bipyramids.