Cs4Zr3S14 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to one S(1), one S(2), one S(4), two equivalent S(6), two equivalent S(7), and three equivalent S(5) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one S(1), one S(5), one S(6), one S(7), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one S(1), one S(2), one S(3), one S(5), one S(7), and two equivalent S(6) atoms to form distorted ZrS7 pentagonal bipyramids that share  a cornercorner with one S(3)Cs2Zr2S trigonal bipyramid,  an edgeedge with one Zr(1)S7 pentagonal bipyramid, and  a faceface with one Zr(2)S8 hexagonal bipyramid. In the second Zr site, Zr(2) is bonded to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted face-sharing ZrS8 hexagonal bipyramids. There are seven inequivalent S sites. In the first S site, S(5) is bonded in a 6-coordinate geometry to one Cs(2), three equivalent Cs(1), one Zr(1), and one S(2) atom. In the second S site, S(6) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), and two equivalent Zr(1) atoms. In the third S site, S(7) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Zr(1), and one S(3) atom. In the fourth S site, S(1) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), one Zr(1), one Zr(2), and one S(4) atom. In the fifth S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), one Zr(1), one Zr(2), and one S(5) atom. In the sixth S site, S(3) is bonded to two equivalent Cs(2), one Zr(1), one Zr(2), and one S(7) atom to form distorted SCs2Zr2S trigonal bipyramids that share  a cornercorner with one Zr(1)S7 pentagonal bipyramid,  a cornercorner with one S(3)Cs2Zr2S trigonal bipyramid, and  an edgeedge with one S(3)Cs2Zr2S trigonal bipyramid. In the seventh S site, S(4) is bonded in a 5-coordinate geometry to one Cs(1), two equivalent Cs(2), one Zr(2), and one S(1) atom.
Cs4Zr3S14 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to one S(1), one S(2), one S(4), two equivalent S(6), two equivalent S(7), and three equivalent S(5) atoms. The Cs(1)-S(1) bond length is 3.47 Å. The Cs(1)-S(2) bond length is 3.85 Å. The Cs(1)-S(4) bond length is 3.62 Å. There is one shorter (3.46 Å) and one longer (3.90 Å) Cs(1)-S(6) bond length. There is one shorter (3.61 Å) and one longer (3.70 Å) Cs(1)-S(7) bond length. There are a spread of Cs(1)-S(5) bond distances ranging from 3.69-3.98 Å. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one S(1), one S(5), one S(6), one S(7), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. The Cs(2)-S(1) bond length is 3.62 Å. The Cs(2)-S(5) bond length is 3.53 Å. The Cs(2)-S(6) bond length is 3.83 Å. The Cs(2)-S(7) bond length is 3.68 Å. There is one shorter (3.87 Å) and one longer (4.02 Å) Cs(2)-S(2) bond length. There is one shorter (3.59 Å) and one longer (3.87 Å) Cs(2)-S(3) bond length. There is one shorter (3.58 Å) and one longer (3.64 Å) Cs(2)-S(4) bond length. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one S(1), one S(2), one S(3), one S(5), one S(7), and two equivalent S(6) atoms to form distorted ZrS7 pentagonal bipyramids that share  a cornercorner with one S(3)Cs2Zr2S trigonal bipyramid,  an edgeedge with one Zr(1)S7 pentagonal bipyramid, and  a faceface with one Zr(2)S8 hexagonal bipyramid. The Zr(1)-S(1) bond length is 2.81 Å. The Zr(1)-S(2) bond length is 2.60 Å. The Zr(1)-S(3) bond length is 2.63 Å. The Zr(1)-S(5) bond length is 2.53 Å. The Zr(1)-S(7) bond length is 2.59 Å. There is one shorter (2.45 Å) and one longer (2.58 Å) Zr(1)-S(6) bond length. In the second Zr site, Zr(2) is bonded to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted face-sharing ZrS8 hexagonal bipyramids. Both Zr(2)-S(1) bond lengths are 2.56 Å. Both Zr(2)-S(2) bond lengths are 2.73 Å. Both Zr(2)-S(3) bond lengths are 2.72 Å. Both Zr(2)-S(4) bond lengths are 2.57 Å. There are seven inequivalent S sites. In the first S site, S(5) is bonded in a 6-coordinate geometry to one Cs(2), three equivalent Cs(1), one Zr(1), and one S(2) atom. The S(5)-S(2) bond length is 2.08 Å. In the second S site, S(6) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), and two equivalent Zr(1) atoms. In the third S site, S(7) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Zr(1), and one S(3) atom. The S(7)-S(3) bond length is 2.08 Å. In the fourth S site, S(1) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), one Zr(1), one Zr(2), and one S(4) atom. The S(1)-S(4) bond length is 2.08 Å. In the fifth S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), one Zr(1), one Zr(2), and one S(5) atom. In the sixth S site, S(3) is bonded to two equivalent Cs(2), one Zr(1), one Zr(2), and one S(7) atom to form distorted SCs2Zr2S trigonal bipyramids that share  a cornercorner with one Zr(1)S7 pentagonal bipyramid,  a cornercorner with one S(3)Cs2Zr2S trigonal bipyramid, and  an edgeedge with one S(3)Cs2Zr2S trigonal bipyramid. In the seventh S site, S(4) is bonded in a 5-coordinate geometry to one Cs(1), two equivalent Cs(2), one Zr(2), and one S(1) atom.