K4Ti3S14 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one S(3), one S(4), one S(5), two equivalent S(1), two equivalent S(7), and three equivalent S(6) atoms. In the second K site, K(2) is bonded in a 9-coordinate geometry to one S(1), one S(3), one S(4), one S(6), one S(7), two equivalent S(2), and two equivalent S(5) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(2), one S(3), one S(4), one S(6), one S(7), and two equivalent S(1) atoms to form distorted TiS7 pentagonal bipyramids that share  an edgeedge with one Ti(1)S7 pentagonal bipyramid and  a faceface with one Ti(2)S8 hexagonal bipyramid. In the second Ti site, Ti(2) is bonded to two equivalent S(2), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms to form distorted face-sharing TiS8 hexagonal bipyramids. There are seven inequivalent S sites. In the first S site, S(2) is bonded in a 4-coordinate geometry to two equivalent K(2), one Ti(1), one Ti(2), and one S(7) atom. In the second S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ti(1), one Ti(2), and one S(5) atom. In the third S site, S(4) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ti(1), one Ti(2), and one S(6) atom. In the fourth S site, S(5) is bonded in a 5-coordinate geometry to one K(1), two equivalent K(2), one Ti(2), and one S(3) atom. In the fifth S site, S(6) is bonded in a 6-coordinate geometry to one K(2), three equivalent K(1), one Ti(1), and one S(4) atom. In the sixth S site, S(7) is bonded in a 5-coordinate geometry to one K(2), two equivalent K(1), one Ti(1), and one S(2) atom. In the seventh S site, S(1) is bonded in a 5-coordinate geometry to one K(2), two equivalent K(1), and two equivalent Ti(1) atoms.
K4Ti3S14 crystallizes in the monoclinic C2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one S(3), one S(4), one S(5), two equivalent S(1), two equivalent S(7), and three equivalent S(6) atoms. The K(1)-S(3) bond length is 3.20 Å. The K(1)-S(4) bond length is 3.51 Å. The K(1)-S(5) bond length is 3.39 Å. There is one shorter (3.14 Å) and one longer (3.56 Å) K(1)-S(1) bond length. There is one shorter (3.35 Å) and one longer (3.43 Å) K(1)-S(7) bond length. There are a spread of K(1)-S(6) bond distances ranging from 3.46-3.66 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one S(1), one S(3), one S(4), one S(6), one S(7), two equivalent S(2), and two equivalent S(5) atoms. The K(2)-S(1) bond length is 3.45 Å. The K(2)-S(3) bond length is 3.30 Å. The K(2)-S(4) bond length is 3.53 Å. The K(2)-S(6) bond length is 3.20 Å. The K(2)-S(7) bond length is 3.42 Å. There is one shorter (3.21 Å) and one longer (3.80 Å) K(2)-S(2) bond length. There is one shorter (3.31 Å) and one longer (3.37 Å) K(2)-S(5) bond length. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(2), one S(3), one S(4), one S(6), one S(7), and two equivalent S(1) atoms to form distorted TiS7 pentagonal bipyramids that share  an edgeedge with one Ti(1)S7 pentagonal bipyramid and  a faceface with one Ti(2)S8 hexagonal bipyramid. The Ti(1)-S(2) bond length is 2.49 Å. The Ti(1)-S(3) bond length is 2.67 Å. The Ti(1)-S(4) bond length is 2.46 Å. The Ti(1)-S(6) bond length is 2.39 Å. The Ti(1)-S(7) bond length is 2.47 Å. There is one shorter (2.29 Å) and one longer (2.49 Å) Ti(1)-S(1) bond length. In the second Ti site, Ti(2) is bonded to two equivalent S(2), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms to form distorted face-sharing TiS8 hexagonal bipyramids. Both Ti(2)-S(2) bond lengths are 2.58 Å. Both Ti(2)-S(3) bond lengths are 2.44 Å. Both Ti(2)-S(4) bond lengths are 2.61 Å. Both Ti(2)-S(5) bond lengths are 2.46 Å. There are seven inequivalent S sites. In the first S site, S(2) is bonded in a 4-coordinate geometry to two equivalent K(2), one Ti(1), one Ti(2), and one S(7) atom. The S(2)-S(7) bond length is 2.06 Å. In the second S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ti(1), one Ti(2), and one S(5) atom. The S(3)-S(5) bond length is 2.06 Å. In the third S site, S(4) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ti(1), one Ti(2), and one S(6) atom. The S(4)-S(6) bond length is 2.06 Å. In the fourth S site, S(5) is bonded in a 5-coordinate geometry to one K(1), two equivalent K(2), one Ti(2), and one S(3) atom. In the fifth S site, S(6) is bonded in a 6-coordinate geometry to one K(2), three equivalent K(1), one Ti(1), and one S(4) atom. In the sixth S site, S(7) is bonded in a 5-coordinate geometry to one K(2), two equivalent K(1), one Ti(1), and one S(2) atom. In the seventh S site, S(1) is bonded in a 5-coordinate geometry to one K(2), two equivalent K(1), and two equivalent Ti(1) atoms.