La2CuBiS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one Cu(1), two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(5), and three equivalent S(3) atoms. Cu(1) is bonded to one La(1), one S(5), and three equivalent S(2) atoms to form distorted CuLaS4 tetrahedra that share corners with two equivalent S(2)La2Cu3Bi octahedra, corners with three equivalent Bi(1)S6 octahedra, corners with two equivalent S(1)La4Bi square pyramids, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(4)La3Bi2 trigonal bipyramids, corners with two equivalent S(5)La4Cu trigonal bipyramids, and edges with two equivalent Cu(1)LaS4 tetrahedra. The corner-sharing octahedral tilt angles range from 8-137°. Bi(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form BiS6 octahedra that share corners with three equivalent Cu(1)LaS4 tetrahedra and edges with two equivalent Bi(1)S6 octahedra. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent La(1), two equivalent La(2), and one Cu(1) atom to form distorted SLa4Cu trigonal bipyramids that share corners with four equivalent S(2)La2Cu3Bi octahedra, corners with four equivalent S(1)La4Bi square pyramids, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(4)La3Bi2 trigonal bipyramids, corners with four equivalent S(3)La3Bi2 trigonal bipyramids, edges with two equivalent S(1)La4Bi square pyramids,  an edgeedge with one S(3)La3Bi2 trigonal bipyramid, edges with two equivalent S(4)La3Bi2 trigonal bipyramids, edges with two equivalent S(5)La4Cu trigonal bipyramids, and  a faceface with one S(2)La2Cu3Bi octahedra. The corner-sharing octahedral tilt angles range from 56-63°. In the second S site, S(1) is bonded to two equivalent La(1), two equivalent La(2), and one Bi(1) atom to form SLa4Bi square pyramids that share corners with three equivalent S(2)La2Cu3Bi octahedra, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(3)La3Bi2 trigonal bipyramids, corners with four equivalent S(5)La4Cu trigonal bipyramids,  an edgeedge with one S(2)La2Cu3Bi octahedra, edges with two equivalent S(1)La4Bi square pyramids, edges with two equivalent S(5)La4Cu trigonal bipyramids, edges with three equivalent S(3)La3Bi2 trigonal bipyramids, and edges with four equivalent S(4)La3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-39°. In the third S site, S(2) is bonded to two equivalent La(1), three equivalent Cu(1), and one Bi(1) atom to form distorted SLa2Cu3Bi octahedra that share corners with three equivalent S(1)La4Bi square pyramids, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(3)La3Bi2 trigonal bipyramids, corners with two equivalent S(4)La3Bi2 trigonal bipyramids, corners with four equivalent S(5)La4Cu trigonal bipyramids, edges with four equivalent S(2)La2Cu3Bi octahedra,  an edgeedge with one S(1)La4Bi square pyramid, edges with two equivalent S(4)La3Bi2 trigonal bipyramids, and  a faceface with one S(5)La4Cu trigonal bipyramid. In the fourth S site, S(3) is bonded to three equivalent La(2) and two equivalent Bi(1) atoms to form distorted SLa3Bi2 trigonal bipyramids that share corners with two equivalent S(2)La2Cu3Bi octahedra, corners with two equivalent S(1)La4Bi square pyramids, corners with four equivalent S(5)La4Cu trigonal bipyramids, corners with five equivalent S(4)La3Bi2 trigonal bipyramids, edges with three equivalent S(1)La4Bi square pyramids,  an edgeedge with one S(4)La3Bi2 trigonal bipyramid,  an edgeedge with one S(5)La4Cu trigonal bipyramid, and edges with four equivalent S(3)La3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 83°. In the fifth S site, S(4) is bonded to one La(2), two equivalent La(1), and two equivalent Bi(1) atoms to form distorted SLa3Bi2 trigonal bipyramids that share corners with two equivalent S(2)La2Cu3Bi octahedra, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(5)La4Cu trigonal bipyramids, corners with four equivalent S(4)La3Bi2 trigonal bipyramids, corners with five equivalent S(3)La3Bi2 trigonal bipyramids, edges with two equivalent S(2)La2Cu3Bi octahedra, edges with four equivalent S(1)La4Bi square pyramids,  an edgeedge with one S(3)La3Bi2 trigonal bipyramid, and edges with two equivalent S(5)La4Cu trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°.
La2CuBiS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one Cu(1), two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. The La(1)-Cu(1) bond length is 3.28 Å. Both La(1)-S(1) bond lengths are 2.97 Å. Both La(1)-S(2) bond lengths are 3.00 Å. There is one shorter (3.20 Å) and one longer (3.40 Å) La(1)-S(4) bond length. Both La(1)-S(5) bond lengths are 2.96 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(5), and three equivalent S(3) atoms. The La(2)-S(4) bond length is 3.17 Å. Both La(2)-S(1) bond lengths are 3.02 Å. Both La(2)-S(5) bond lengths are 2.98 Å. There are two shorter (2.98 Å) and one longer (3.02 Å) La(2)-S(3) bond length. Cu(1) is bonded to one La(1), one S(5), and three equivalent S(2) atoms to form distorted CuLaS4 tetrahedra that share corners with two equivalent S(2)La2Cu3Bi octahedra, corners with three equivalent Bi(1)S6 octahedra, corners with two equivalent S(1)La4Bi square pyramids, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(4)La3Bi2 trigonal bipyramids, corners with two equivalent S(5)La4Cu trigonal bipyramids, and edges with two equivalent Cu(1)LaS4 tetrahedra. The corner-sharing octahedral tilt angles range from 8-137°. The Cu(1)-S(5) bond length is 2.27 Å. There are two shorter (2.34 Å) and one longer (2.49 Å) Cu(1)-S(2) bond length. Bi(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form BiS6 octahedra that share corners with three equivalent Cu(1)LaS4 tetrahedra and edges with two equivalent Bi(1)S6 octahedra. The Bi(1)-S(1) bond length is 2.77 Å. The Bi(1)-S(2) bond length is 2.80 Å. Both Bi(1)-S(3) bond lengths are 2.92 Å. Both Bi(1)-S(4) bond lengths are 2.71 Å. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent La(1), two equivalent La(2), and one Cu(1) atom to form distorted SLa4Cu trigonal bipyramids that share corners with four equivalent S(2)La2Cu3Bi octahedra, corners with four equivalent S(1)La4Bi square pyramids, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(4)La3Bi2 trigonal bipyramids, corners with four equivalent S(3)La3Bi2 trigonal bipyramids, edges with two equivalent S(1)La4Bi square pyramids,  an edgeedge with one S(3)La3Bi2 trigonal bipyramid, edges with two equivalent S(4)La3Bi2 trigonal bipyramids, edges with two equivalent S(5)La4Cu trigonal bipyramids, and  a faceface with one S(2)La2Cu3Bi octahedra. The corner-sharing octahedral tilt angles range from 56-63°. In the second S site, S(1) is bonded to two equivalent La(1), two equivalent La(2), and one Bi(1) atom to form SLa4Bi square pyramids that share corners with three equivalent S(2)La2Cu3Bi octahedra, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(3)La3Bi2 trigonal bipyramids, corners with four equivalent S(5)La4Cu trigonal bipyramids,  an edgeedge with one S(2)La2Cu3Bi octahedra, edges with two equivalent S(1)La4Bi square pyramids, edges with two equivalent S(5)La4Cu trigonal bipyramids, edges with three equivalent S(3)La3Bi2 trigonal bipyramids, and edges with four equivalent S(4)La3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-39°. In the third S site, S(2) is bonded to two equivalent La(1), three equivalent Cu(1), and one Bi(1) atom to form distorted SLa2Cu3Bi octahedra that share corners with three equivalent S(1)La4Bi square pyramids, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(3)La3Bi2 trigonal bipyramids, corners with two equivalent S(4)La3Bi2 trigonal bipyramids, corners with four equivalent S(5)La4Cu trigonal bipyramids, edges with four equivalent S(2)La2Cu3Bi octahedra,  an edgeedge with one S(1)La4Bi square pyramid, edges with two equivalent S(4)La3Bi2 trigonal bipyramids, and  a faceface with one S(5)La4Cu trigonal bipyramid. In the fourth S site, S(3) is bonded to three equivalent La(2) and two equivalent Bi(1) atoms to form distorted SLa3Bi2 trigonal bipyramids that share corners with two equivalent S(2)La2Cu3Bi octahedra, corners with two equivalent S(1)La4Bi square pyramids, corners with four equivalent S(5)La4Cu trigonal bipyramids, corners with five equivalent S(4)La3Bi2 trigonal bipyramids, edges with three equivalent S(1)La4Bi square pyramids,  an edgeedge with one S(4)La3Bi2 trigonal bipyramid,  an edgeedge with one S(5)La4Cu trigonal bipyramid, and edges with four equivalent S(3)La3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 83°. In the fifth S site, S(4) is bonded to one La(2), two equivalent La(1), and two equivalent Bi(1) atoms to form distorted SLa3Bi2 trigonal bipyramids that share corners with two equivalent S(2)La2Cu3Bi octahedra, corners with two equivalent Cu(1)LaS4 tetrahedra, corners with two equivalent S(5)La4Cu trigonal bipyramids, corners with four equivalent S(4)La3Bi2 trigonal bipyramids, corners with five equivalent S(3)La3Bi2 trigonal bipyramids, edges with two equivalent S(2)La2Cu3Bi octahedra, edges with four equivalent S(1)La4Bi square pyramids,  an edgeedge with one S(3)La3Bi2 trigonal bipyramid, and edges with two equivalent S(5)La4Cu trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°.