In10SnS14 crystallizes in the monoclinic Pm space group. There are ten inequivalent In sites. In the first In site, In(1) is bonded to one S(13), one S(3), two equivalent S(4), and two equivalent S(6) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second In site, In(2) is bonded to one S(14), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the third In site, In(3) is bonded in a 3-coordinate geometry to one S(9) and two equivalent S(12) atoms. In the fourth In site, In(4) is bonded in a 3-coordinate geometry to one S(10) and two equivalent S(11) atoms. In the fifth In site, In(5) is bonded to one S(5), one S(7), two equivalent S(4), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the sixth In site, In(6) is bonded to one S(6), one S(8), two equivalent S(3), and two equivalent S(7) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the seventh In site, In(7) is bonded to one S(1), one S(11), two equivalent S(10), and two equivalent S(2) atoms to form edge-sharing InS6 octahedra. In the eighth In site, In(8) is bonded to one S(12), one S(2), two equivalent S(1), and two equivalent S(9) atoms to form edge-sharing InS6 octahedra. In the ninth In site, In(9) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(14) atoms. In the tenth In site, In(10) is bonded in a 3-coordinate geometry to one S(2) and two equivalent S(13) atoms. Sn(1) is bonded in a distorted see-saw-like geometry to two equivalent S(12) and two equivalent S(8) atoms. There are fourteen inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one In(7), one In(9), and two equivalent In(8) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one In(10), one In(8), and two equivalent In(7) atoms. In the third S site, S(3) is bonded to one In(1), two equivalent In(2), and two equivalent In(6) atoms to form SIn5 square pyramids that share corners with two equivalent S(8)In3Sn2 trigonal bipyramids, edges with two equivalent S(3)In5 square pyramids, and edges with two equivalent S(4)In5 square pyramids. In the fourth S site, S(4) is bonded to one In(2), two equivalent In(1), and two equivalent In(5) atoms to form SIn5 square pyramids that share corners with two equivalent S(8)In3Sn2 trigonal bipyramids, edges with two equivalent S(3)In5 square pyramids, edges with two equivalent S(4)In5 square pyramids, and  an edgeedge with one S(8)In3Sn2 trigonal bipyramid. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(2) atoms. In the sixth S site, S(6) is bonded in a distorted trigonal non-coplanar geometry to one In(6) and two equivalent In(1) atoms. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(6) atoms. In the eighth S site, S(8) is bonded to one In(6), two equivalent In(5), and two equivalent Sn(1) atoms to form distorted SIn3Sn2 trigonal bipyramids that share corners with two equivalent S(12)In3Sn2 square pyramids, corners with two equivalent S(3)In5 square pyramids, corners with two equivalent S(4)In5 square pyramids,  an edgeedge with one S(12)In3Sn2 square pyramid,  an edgeedge with one S(4)In5 square pyramid, and edges with two equivalent S(8)In3Sn2 trigonal bipyramids. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one In(3) and two equivalent In(8) atoms. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one In(4) and two equivalent In(7) atoms. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one In(7) and two equivalent In(4) atoms. In the twelfth S site, S(12) is bonded to one In(8), two equivalent In(3), and two equivalent Sn(1) atoms to form a mixture of edge and corner-sharing SIn3Sn2 square pyramids. In the thirteenth S site, S(13) is bonded in a trigonal non-coplanar geometry to one In(1) and two equivalent In(10) atoms. In the fourteenth S site, S(14) is bonded in a trigonal non-coplanar geometry to one In(2) and two equivalent In(9) atoms.
In10SnS14 crystallizes in the monoclinic Pm space group. There are ten inequivalent In sites. In the first In site, In(1) is bonded to one S(13), one S(3), two equivalent S(4), and two equivalent S(6) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 5°. The In(1)-S(13) bond length is 2.57 Å. The In(1)-S(3) bond length is 2.65 Å. Both In(1)-S(4) bond lengths are 2.88 Å. Both In(1)-S(6) bond lengths are 2.56 Å. In the second In site, In(2) is bonded to one S(14), one S(4), two equivalent S(3), and two equivalent S(5) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 4°. The In(2)-S(14) bond length is 2.64 Å. The In(2)-S(4) bond length is 2.59 Å. Both In(2)-S(3) bond lengths are 2.76 Å. Both In(2)-S(5) bond lengths are 2.63 Å. In the third In site, In(3) is bonded in a 3-coordinate geometry to one S(9) and two equivalent S(12) atoms. The In(3)-S(9) bond length is 2.50 Å. Both In(3)-S(12) bond lengths are 2.72 Å. In the fourth In site, In(4) is bonded in a 3-coordinate geometry to one S(10) and two equivalent S(11) atoms. The In(4)-S(10) bond length is 2.62 Å. Both In(4)-S(11) bond lengths are 2.56 Å. In the fifth In site, In(5) is bonded to one S(5), one S(7), two equivalent S(4), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 5°. The In(5)-S(5) bond length is 2.53 Å. The In(5)-S(7) bond length is 2.48 Å. Both In(5)-S(4) bond lengths are 2.71 Å. Both In(5)-S(8) bond lengths are 2.82 Å. In the sixth In site, In(6) is bonded to one S(6), one S(8), two equivalent S(3), and two equivalent S(7) atoms to form a mixture of edge and corner-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 4°. The In(6)-S(6) bond length is 2.53 Å. The In(6)-S(8) bond length is 2.66 Å. Both In(6)-S(3) bond lengths are 2.91 Å. Both In(6)-S(7) bond lengths are 2.57 Å. In the seventh In site, In(7) is bonded to one S(1), one S(11), two equivalent S(10), and two equivalent S(2) atoms to form edge-sharing InS6 octahedra. The In(7)-S(1) bond length is 2.78 Å. The In(7)-S(11) bond length is 2.56 Å. Both In(7)-S(10) bond lengths are 2.69 Å. Both In(7)-S(2) bond lengths are 2.69 Å. In the eighth In site, In(8) is bonded to one S(12), one S(2), two equivalent S(1), and two equivalent S(9) atoms to form edge-sharing InS6 octahedra. The In(8)-S(12) bond length is 2.69 Å. The In(8)-S(2) bond length is 2.60 Å. Both In(8)-S(1) bond lengths are 2.69 Å. Both In(8)-S(9) bond lengths are 2.63 Å. In the ninth In site, In(9) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(14) atoms. The In(9)-S(1) bond length is 2.57 Å. Both In(9)-S(14) bond lengths are 2.58 Å. In the tenth In site, In(10) is bonded in a 3-coordinate geometry to one S(2) and two equivalent S(13) atoms. The In(10)-S(2) bond length is 2.67 Å. Both In(10)-S(13) bond lengths are 2.55 Å. Sn(1) is bonded in a distorted see-saw-like geometry to two equivalent S(12) and two equivalent S(8) atoms. Both Sn(1)-S(12) bond lengths are 2.96 Å. Both Sn(1)-S(8) bond lengths are 2.85 Å. There are fourteen inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one In(7), one In(9), and two equivalent In(8) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one In(10), one In(8), and two equivalent In(7) atoms. In the third S site, S(3) is bonded to one In(1), two equivalent In(2), and two equivalent In(6) atoms to form SIn5 square pyramids that share corners with two equivalent S(8)In3Sn2 trigonal bipyramids, edges with two equivalent S(3)In5 square pyramids, and edges with two equivalent S(4)In5 square pyramids. In the fourth S site, S(4) is bonded to one In(2), two equivalent In(1), and two equivalent In(5) atoms to form SIn5 square pyramids that share corners with two equivalent S(8)In3Sn2 trigonal bipyramids, edges with two equivalent S(3)In5 square pyramids, edges with two equivalent S(4)In5 square pyramids, and  an edgeedge with one S(8)In3Sn2 trigonal bipyramid. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(2) atoms. In the sixth S site, S(6) is bonded in a distorted trigonal non-coplanar geometry to one In(6) and two equivalent In(1) atoms. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(6) atoms. In the eighth S site, S(8) is bonded to one In(6), two equivalent In(5), and two equivalent Sn(1) atoms to form distorted SIn3Sn2 trigonal bipyramids that share corners with two equivalent S(12)In3Sn2 square pyramids, corners with two equivalent S(3)In5 square pyramids, corners with two equivalent S(4)In5 square pyramids,  an edgeedge with one S(12)In3Sn2 square pyramid,  an edgeedge with one S(4)In5 square pyramid, and edges with two equivalent S(8)In3Sn2 trigonal bipyramids. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one In(3) and two equivalent In(8) atoms. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one In(4) and two equivalent In(7) atoms. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one In(7) and two equivalent In(4) atoms. In the twelfth S site, S(12) is bonded to one In(8), two equivalent In(3), and two equivalent Sn(1) atoms to form a mixture of edge and corner-sharing SIn3Sn2 square pyramids. In the thirteenth S site, S(13) is bonded in a trigonal non-coplanar geometry to one In(1) and two equivalent In(10) atoms. In the fourteenth S site, S(14) is bonded in a trigonal non-coplanar geometry to one In(2) and two equivalent In(9) atoms.