La2CuInS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(5), two equivalent S(1), two equivalent S(4), and three equivalent S(3) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. Cu(1) is bonded in a 4-coordinate geometry to one S(1) and three equivalent S(2) atoms. In(1) is bonded to one S(2), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form edge-sharing InS6 octahedra. There are five inequivalent S sites. In the first S site, S(5) is bonded to one La(1), two equivalent La(2), and two equivalent In(1) atoms to form distorted SLa3In2 trigonal bipyramids that share corners with two equivalent S(2)La2InCu3 octahedra, corners with two equivalent S(1)La4Cu square pyramids, corners with four equivalent S(5)La3In2 trigonal bipyramids, corners with five equivalent S(3)La3In2 trigonal bipyramids, edges with two equivalent S(2)La2InCu3 octahedra, edges with two equivalent S(1)La4Cu square pyramids, edges with four equivalent S(4)La4In square pyramids, and  an edgeedge with one S(3)La3In2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 46°. In the second S site, S(1) is bonded to two equivalent La(1), two equivalent La(2), and one Cu(1) atom to form SLa4Cu square pyramids that share corners with four equivalent S(2)La2InCu3 octahedra, corners with four equivalent S(4)La4In square pyramids, corners with two equivalent S(5)La3In2 trigonal bipyramids, corners with four equivalent S(3)La3In2 trigonal bipyramids, edges with two equivalent S(1)La4Cu square pyramids, edges with two equivalent S(4)La4In square pyramids,  an edgeedge with one S(3)La3In2 trigonal bipyramid, edges with two equivalent S(5)La3In2 trigonal bipyramids, and  a faceface with one S(2)La2InCu3 octahedra. The corner-sharing octahedral tilt angles range from 58-64°. In the third S site, S(2) is bonded to two equivalent La(2), three equivalent Cu(1), and one In(1) atom to form distorted SLa2InCu3 octahedra that share corners with three equivalent S(4)La4In square pyramids, corners with four equivalent S(1)La4Cu square pyramids, corners with two equivalent S(3)La3In2 trigonal bipyramids, corners with two equivalent S(5)La3In2 trigonal bipyramids, edges with four equivalent S(2)La2InCu3 octahedra,  an edgeedge with one S(4)La4In square pyramid, edges with two equivalent S(5)La3In2 trigonal bipyramids, and  a faceface with one S(1)La4Cu square pyramid. In the fourth S site, S(3) is bonded to three equivalent La(1) and two equivalent In(1) atoms to form SLa3In2 trigonal bipyramids that share corners with two equivalent S(2)La2InCu3 octahedra, corners with two equivalent S(4)La4In square pyramids, corners with four equivalent S(1)La4Cu square pyramids, corners with five equivalent S(5)La3In2 trigonal bipyramids,  an edgeedge with one S(1)La4Cu square pyramid, edges with three equivalent S(4)La4In square pyramids,  an edgeedge with one S(5)La3In2 trigonal bipyramid, and edges with four equivalent S(3)La3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 88°. In the fifth S site, S(4) is bonded to two equivalent La(1), two equivalent La(2), and one In(1) atom to form SLa4In square pyramids that share corners with three equivalent S(2)La2InCu3 octahedra, corners with four equivalent S(1)La4Cu square pyramids, corners with two equivalent S(3)La3In2 trigonal bipyramids,  an edgeedge with one S(2)La2InCu3 octahedra, edges with two equivalent S(1)La4Cu square pyramids, edges with two equivalent S(4)La4In square pyramids, edges with three equivalent S(3)La3In2 trigonal bipyramids, and edges with four equivalent S(5)La3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 6-36°.
La2CuInS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to one S(5), two equivalent S(1), two equivalent S(4), and three equivalent S(3) atoms. The La(1)-S(5) bond length is 3.25 Å. Both La(1)-S(1) bond lengths are 2.93 Å. Both La(1)-S(4) bond lengths are 2.99 Å. There are two shorter (2.97 Å) and one longer (3.04 Å) La(1)-S(3) bond length. In the second La site, La(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms. Both La(2)-S(1) bond lengths are 2.94 Å. Both La(2)-S(2) bond lengths are 3.01 Å. Both La(2)-S(4) bond lengths are 2.96 Å. There is one shorter (3.13 Å) and one longer (3.19 Å) La(2)-S(5) bond length. Cu(1) is bonded in a 4-coordinate geometry to one S(1) and three equivalent S(2) atoms. The Cu(1)-S(1) bond length is 2.27 Å. There are two shorter (2.32 Å) and one longer (2.62 Å) Cu(1)-S(2) bond length. In(1) is bonded to one S(2), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form edge-sharing InS6 octahedra. The In(1)-S(2) bond length is 2.62 Å. The In(1)-S(4) bond length is 2.59 Å. Both In(1)-S(3) bond lengths are 2.81 Å. Both In(1)-S(5) bond lengths are 2.60 Å. There are five inequivalent S sites. In the first S site, S(5) is bonded to one La(1), two equivalent La(2), and two equivalent In(1) atoms to form distorted SLa3In2 trigonal bipyramids that share corners with two equivalent S(2)La2InCu3 octahedra, corners with two equivalent S(1)La4Cu square pyramids, corners with four equivalent S(5)La3In2 trigonal bipyramids, corners with five equivalent S(3)La3In2 trigonal bipyramids, edges with two equivalent S(2)La2InCu3 octahedra, edges with two equivalent S(1)La4Cu square pyramids, edges with four equivalent S(4)La4In square pyramids, and  an edgeedge with one S(3)La3In2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 46°. In the second S site, S(1) is bonded to two equivalent La(1), two equivalent La(2), and one Cu(1) atom to form SLa4Cu square pyramids that share corners with four equivalent S(2)La2InCu3 octahedra, corners with four equivalent S(4)La4In square pyramids, corners with two equivalent S(5)La3In2 trigonal bipyramids, corners with four equivalent S(3)La3In2 trigonal bipyramids, edges with two equivalent S(1)La4Cu square pyramids, edges with two equivalent S(4)La4In square pyramids,  an edgeedge with one S(3)La3In2 trigonal bipyramid, edges with two equivalent S(5)La3In2 trigonal bipyramids, and  a faceface with one S(2)La2InCu3 octahedra. The corner-sharing octahedral tilt angles range from 58-64°. In the third S site, S(2) is bonded to two equivalent La(2), three equivalent Cu(1), and one In(1) atom to form distorted SLa2InCu3 octahedra that share corners with three equivalent S(4)La4In square pyramids, corners with four equivalent S(1)La4Cu square pyramids, corners with two equivalent S(3)La3In2 trigonal bipyramids, corners with two equivalent S(5)La3In2 trigonal bipyramids, edges with four equivalent S(2)La2InCu3 octahedra,  an edgeedge with one S(4)La4In square pyramid, edges with two equivalent S(5)La3In2 trigonal bipyramids, and  a faceface with one S(1)La4Cu square pyramid. In the fourth S site, S(3) is bonded to three equivalent La(1) and two equivalent In(1) atoms to form SLa3In2 trigonal bipyramids that share corners with two equivalent S(2)La2InCu3 octahedra, corners with two equivalent S(4)La4In square pyramids, corners with four equivalent S(1)La4Cu square pyramids, corners with five equivalent S(5)La3In2 trigonal bipyramids,  an edgeedge with one S(1)La4Cu square pyramid, edges with three equivalent S(4)La4In square pyramids,  an edgeedge with one S(5)La3In2 trigonal bipyramid, and edges with four equivalent S(3)La3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 88°. In the fifth S site, S(4) is bonded to two equivalent La(1), two equivalent La(2), and one In(1) atom to form SLa4In square pyramids that share corners with three equivalent S(2)La2InCu3 octahedra, corners with four equivalent S(1)La4Cu square pyramids, corners with two equivalent S(3)La3In2 trigonal bipyramids,  an edgeedge with one S(2)La2InCu3 octahedra, edges with two equivalent S(1)La4Cu square pyramids, edges with two equivalent S(4)La4In square pyramids, edges with three equivalent S(3)La3In2 trigonal bipyramids, and edges with four equivalent S(5)La3In2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 6-36°.