K3Zn2Cl7 crystallizes in the triclinic P-1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one Cl(1), one Cl(6), one Cl(7), two equivalent Cl(3), and two equivalent Cl(5) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to one Cl(1), one Cl(3), one Cl(5), one Cl(6), one Cl(7), and two equivalent Cl(4) atoms. In the third K site, K(3) is bonded in a 6-coordinate geometry to one Cl(3), one Cl(5), one Cl(6), one Cl(7), and two equivalent Cl(2) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one Cl(1), one Cl(3), one Cl(5), and two equivalent Cl(4) atoms to form distorted ZnCl5 square pyramids that share  a cornercorner with one Zn(2)Cl4 tetrahedra and  an edgeedge with one Zn(1)Cl5 square pyramid. In the second Zn site, Zn(2) is bonded to one Cl(1), one Cl(2), one Cl(6), and one Cl(7) atom to form corner-sharing ZnCl4 tetrahedra. There are seven inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to one K(1), one K(2), one Zn(1), and one Zn(2) atom. In the second Cl site, Cl(2) is bonded in a 1-coordinate geometry to two equivalent K(3) and one Zn(2) atom. In the third Cl site, Cl(3) is bonded to one K(2), one K(3), two equivalent K(1), and one Zn(1) atom to form distorted ClK4Zn square pyramids that share corners with four equivalent Cl(6)K3Zn tetrahedra,  an edgeedge with one Cl(3)K4Zn square pyramid, edges with two equivalent Cl(5)K4Zn square pyramids, and  a faceface with one Cl(5)K4Zn square pyramid. In the fourth Cl site, Cl(4) is bonded in a distorted L-shaped geometry to two equivalent K(2) and two equivalent Zn(1) atoms. In the fifth Cl site, Cl(5) is bonded to one K(2), one K(3), two equivalent K(1), and one Zn(1) atom to form distorted ClK4Zn square pyramids that share corners with four equivalent Cl(6)K3Zn tetrahedra,  an edgeedge with one Cl(5)K4Zn square pyramid, edges with two equivalent Cl(3)K4Zn square pyramids, and  a faceface with one Cl(3)K4Zn square pyramid. In the sixth Cl site, Cl(6) is bonded to one K(1), one K(2), one K(3), and one Zn(2) atom to form corner-sharing ClK3Zn tetrahedra. In the seventh Cl site, Cl(7) is bonded in a 4-coordinate geometry to one K(1), one K(2), one K(3), and one Zn(2) atom.
K3Zn2Cl7 crystallizes in the triclinic P-1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one Cl(1), one Cl(6), one Cl(7), two equivalent Cl(3), and two equivalent Cl(5) atoms. The K(1)-Cl(1) bond length is 3.39 Å. The K(1)-Cl(6) bond length is 3.11 Å. The K(1)-Cl(7) bond length is 3.47 Å. There is one shorter (3.25 Å) and one longer (3.33 Å) K(1)-Cl(3) bond length. There is one shorter (3.27 Å) and one longer (3.33 Å) K(1)-Cl(5) bond length. In the second K site, K(2) is bonded in a 7-coordinate geometry to one Cl(1), one Cl(3), one Cl(5), one Cl(6), one Cl(7), and two equivalent Cl(4) atoms. The K(2)-Cl(1) bond length is 3.34 Å. The K(2)-Cl(3) bond length is 3.14 Å. The K(2)-Cl(5) bond length is 3.13 Å. The K(2)-Cl(6) bond length is 3.08 Å. The K(2)-Cl(7) bond length is 3.17 Å. There is one shorter (3.54 Å) and one longer (3.58 Å) K(2)-Cl(4) bond length. In the third K site, K(3) is bonded in a 6-coordinate geometry to one Cl(3), one Cl(5), one Cl(6), one Cl(7), and two equivalent Cl(2) atoms. The K(3)-Cl(3) bond length is 3.18 Å. The K(3)-Cl(5) bond length is 3.17 Å. The K(3)-Cl(6) bond length is 3.12 Å. The K(3)-Cl(7) bond length is 3.20 Å. There is one shorter (3.41 Å) and one longer (3.51 Å) K(3)-Cl(2) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one Cl(1), one Cl(3), one Cl(5), and two equivalent Cl(4) atoms to form distorted ZnCl5 square pyramids that share  a cornercorner with one Zn(2)Cl4 tetrahedra and  an edgeedge with one Zn(1)Cl5 square pyramid. The Zn(1)-Cl(1) bond length is 2.79 Å. The Zn(1)-Cl(3) bond length is 2.35 Å. The Zn(1)-Cl(5) bond length is 2.35 Å. There is one shorter (2.44 Å) and one longer (2.45 Å) Zn(1)-Cl(4) bond length. In the second Zn site, Zn(2) is bonded to one Cl(1), one Cl(2), one Cl(6), and one Cl(7) atom to form corner-sharing ZnCl4 tetrahedra. The Zn(2)-Cl(1) bond length is 2.30 Å. The Zn(2)-Cl(2) bond length is 2.29 Å. The Zn(2)-Cl(6) bond length is 2.31 Å. The Zn(2)-Cl(7) bond length is 2.30 Å. There are seven inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to one K(1), one K(2), one Zn(1), and one Zn(2) atom. In the second Cl site, Cl(2) is bonded in a 1-coordinate geometry to two equivalent K(3) and one Zn(2) atom. In the third Cl site, Cl(3) is bonded to one K(2), one K(3), two equivalent K(1), and one Zn(1) atom to form distorted ClK4Zn square pyramids that share corners with four equivalent Cl(6)K3Zn tetrahedra,  an edgeedge with one Cl(3)K4Zn square pyramid, edges with two equivalent Cl(5)K4Zn square pyramids, and  a faceface with one Cl(5)K4Zn square pyramid. In the fourth Cl site, Cl(4) is bonded in a distorted L-shaped geometry to two equivalent K(2) and two equivalent Zn(1) atoms. In the fifth Cl site, Cl(5) is bonded to one K(2), one K(3), two equivalent K(1), and one Zn(1) atom to form distorted ClK4Zn square pyramids that share corners with four equivalent Cl(6)K3Zn tetrahedra,  an edgeedge with one Cl(5)K4Zn square pyramid, edges with two equivalent Cl(3)K4Zn square pyramids, and  a faceface with one Cl(3)K4Zn square pyramid. In the sixth Cl site, Cl(6) is bonded to one K(1), one K(2), one K(3), and one Zn(2) atom to form corner-sharing ClK3Zn tetrahedra. In the seventh Cl site, Cl(7) is bonded in a 4-coordinate geometry to one K(1), one K(2), one K(3), and one Zn(2) atom.