BaLa(BiS3)2 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded in a 9-coordinate geometry to one S(3), one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. La(1) is bonded in a 9-coordinate geometry to one S(1), one S(6), two equivalent S(2), two equivalent S(5), and three equivalent S(4) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(5), one S(6), two equivalent S(1), and two equivalent S(3) atoms to form distorted BiS6 octahedra that share corners with four equivalent Bi(2)S5 square pyramids, edges with two equivalent Bi(1)S6 octahedra, and  an edgeedge with one Bi(2)S5 square pyramid. In the second Bi site, Bi(2) is bonded to one S(2), two equivalent S(3), and two equivalent S(6) atoms to form distorted BiS5 square pyramids that share corners with four equivalent Bi(1)S6 octahedra,  an edgeedge with one Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 8-89°. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ba(1), one La(1), and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Ba(1), two equivalent La(1), and one Bi(2) atom to form distorted SBa2La2Bi square pyramids that share corners with four equivalent S(5)Ba2La2Bi square pyramids, corners with two equivalent S(6)BaLaBi3 trigonal bipyramids, edges with two equivalent S(2)Ba2La2Bi square pyramids, edges with two equivalent S(5)Ba2La2Bi square pyramids, edges with two equivalent S(3)BaBi4 square pyramids, and edges with two equivalent S(6)BaLaBi3 trigonal bipyramids. In the third S site, S(3) is bonded to one Ba(1), two equivalent Bi(1), and two equivalent Bi(2) atoms to form distorted SBaBi4 square pyramids that share corners with five equivalent S(6)BaLaBi3 trigonal bipyramids, edges with two equivalent S(2)Ba2La2Bi square pyramids, edges with two equivalent S(5)Ba2La2Bi square pyramids, edges with two equivalent S(3)BaBi4 square pyramids, and  an edgeedge with one S(6)BaLaBi3 trigonal bipyramid. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Ba(1), three equivalent La(1), and one S(4) atom. In the fifth S site, S(5) is bonded to two equivalent Ba(1), two equivalent La(1), and one Bi(1) atom to form SBa2La2Bi square pyramids that share corners with four equivalent S(2)Ba2La2Bi square pyramids,  a cornercorner with one S(6)BaLaBi3 trigonal bipyramid, edges with two equivalent S(2)Ba2La2Bi square pyramids, edges with two equivalent S(5)Ba2La2Bi square pyramids, edges with two equivalent S(3)BaBi4 square pyramids, and edges with two equivalent S(6)BaLaBi3 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ba(1), one La(1), one Bi(1), and two equivalent Bi(2) atoms to form SBaLaBi3 trigonal bipyramids that share  a cornercorner with one S(5)Ba2La2Bi square pyramid, corners with two equivalent S(2)Ba2La2Bi square pyramids, corners with five equivalent S(3)BaBi4 square pyramids, corners with two equivalent S(6)BaLaBi3 trigonal bipyramids,  an edgeedge with one S(3)BaBi4 square pyramid, edges with two equivalent S(2)Ba2La2Bi square pyramids, and edges with two equivalent S(5)Ba2La2Bi square pyramids.
BaLa(BiS3)2 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded in a 9-coordinate geometry to one S(3), one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The Ba(1)-S(3) bond length is 3.36 Å. The Ba(1)-S(4) bond length is 3.60 Å. The Ba(1)-S(6) bond length is 3.37 Å. There is one shorter (3.20 Å) and one longer (3.63 Å) Ba(1)-S(1) bond length. There is one shorter (3.17 Å) and one longer (3.38 Å) Ba(1)-S(2) bond length. Both Ba(1)-S(5) bond lengths are 3.31 Å. La(1) is bonded in a 9-coordinate geometry to one S(1), one S(6), two equivalent S(2), two equivalent S(5), and three equivalent S(4) atoms. The La(1)-S(1) bond length is 3.03 Å. The La(1)-S(6) bond length is 3.13 Å. There is one shorter (2.94 Å) and one longer (3.23 Å) La(1)-S(2) bond length. There is one shorter (3.02 Å) and one longer (3.05 Å) La(1)-S(5) bond length. There are a spread of La(1)-S(4) bond distances ranging from 2.93-3.16 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(5), one S(6), two equivalent S(1), and two equivalent S(3) atoms to form distorted BiS6 octahedra that share corners with four equivalent Bi(2)S5 square pyramids, edges with two equivalent Bi(1)S6 octahedra, and  an edgeedge with one Bi(2)S5 square pyramid. The Bi(1)-S(5) bond length is 2.64 Å. The Bi(1)-S(6) bond length is 3.08 Å. There is one shorter (2.67 Å) and one longer (2.94 Å) Bi(1)-S(1) bond length. There is one shorter (2.79 Å) and one longer (3.14 Å) Bi(1)-S(3) bond length. In the second Bi site, Bi(2) is bonded to one S(2), two equivalent S(3), and two equivalent S(6) atoms to form distorted BiS5 square pyramids that share corners with four equivalent Bi(1)S6 octahedra,  an edgeedge with one Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 8-89°. The Bi(2)-S(2) bond length is 2.61 Å. There is one shorter (2.86 Å) and one longer (3.08 Å) Bi(2)-S(3) bond length. There is one shorter (2.68 Å) and one longer (2.87 Å) Bi(2)-S(6) bond length. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ba(1), one La(1), and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Ba(1), two equivalent La(1), and one Bi(2) atom to form distorted SBa2La2Bi square pyramids that share corners with four equivalent S(5)Ba2La2Bi square pyramids, corners with two equivalent S(6)BaLaBi3 trigonal bipyramids, edges with two equivalent S(2)Ba2La2Bi square pyramids, edges with two equivalent S(5)Ba2La2Bi square pyramids, edges with two equivalent S(3)BaBi4 square pyramids, and edges with two equivalent S(6)BaLaBi3 trigonal bipyramids. In the third S site, S(3) is bonded to one Ba(1), two equivalent Bi(1), and two equivalent Bi(2) atoms to form distorted SBaBi4 square pyramids that share corners with five equivalent S(6)BaLaBi3 trigonal bipyramids, edges with two equivalent S(2)Ba2La2Bi square pyramids, edges with two equivalent S(5)Ba2La2Bi square pyramids, edges with two equivalent S(3)BaBi4 square pyramids, and  an edgeedge with one S(6)BaLaBi3 trigonal bipyramid. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Ba(1), three equivalent La(1), and one S(4) atom. The S(4)-S(4) bond length is 2.12 Å. In the fifth S site, S(5) is bonded to two equivalent Ba(1), two equivalent La(1), and one Bi(1) atom to form SBa2La2Bi square pyramids that share corners with four equivalent S(2)Ba2La2Bi square pyramids,  a cornercorner with one S(6)BaLaBi3 trigonal bipyramid, edges with two equivalent S(2)Ba2La2Bi square pyramids, edges with two equivalent S(5)Ba2La2Bi square pyramids, edges with two equivalent S(3)BaBi4 square pyramids, and edges with two equivalent S(6)BaLaBi3 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ba(1), one La(1), one Bi(1), and two equivalent Bi(2) atoms to form SBaLaBi3 trigonal bipyramids that share  a cornercorner with one S(5)Ba2La2Bi square pyramid, corners with two equivalent S(2)Ba2La2Bi square pyramids, corners with five equivalent S(3)BaBi4 square pyramids, corners with two equivalent S(6)BaLaBi3 trigonal bipyramids,  an edgeedge with one S(3)BaBi4 square pyramid, edges with two equivalent S(2)Ba2La2Bi square pyramids, and edges with two equivalent S(5)Ba2La2Bi square pyramids.