K(Zr3Te4)4 crystallizes in the triclinic P-1 space group. K(1) is bonded in a distorted hexagonal planar geometry to two equivalent Te(2), two equivalent Te(4), and two equivalent Te(5) atoms. There are six inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Te(1), one Te(6), one Te(7), one Te(8), and two equivalent Te(2) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. In the second Zr site, Zr(2) is bonded to one Te(2), one Te(5), one Te(7), one Te(8), and two equivalent Te(1) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the third Zr site, Zr(3) is bonded to one Te(2), one Te(3), one Te(7), one Te(8), and two equivalent Te(4) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the fourth Zr site, Zr(4) is bonded to one Te(1), one Te(4), one Te(7), one Te(8), and two equivalent Te(3) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. In the fifth Zr site, Zr(5) is bonded to one Te(4), one Te(5), one Te(7), one Te(8), and two equivalent Te(6) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. In the sixth Zr site, Zr(6) is bonded to one Te(3), one Te(6), one Te(7), one Te(8), and two equivalent Te(5) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. There are eight inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted rectangular see-saw-like geometry to one Zr(1), one Zr(4), and two equivalent Zr(2) atoms. In the second Te site, Te(2) is bonded to one K(1), one Zr(2), one Zr(3), and two equivalent Zr(1) atoms to form distorted TeKZr4 trigonal bipyramids that share corners with two equivalent Te(8)Zr6 pentagonal pyramids,  a cornercorner with one Te(2)KZr4 trigonal bipyramid,  a cornercorner with one Te(5)KZr4 trigonal bipyramid, corners with two equivalent Te(4)KZr4 trigonal bipyramids,  an edgeedge with one Te(8)Zr6 pentagonal pyramid, edges with two equivalent Te(7)Zr6 pentagonal pyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid,  an edgeedge with one Te(4)KZr4 trigonal bipyramid, and  an edgeedge with one Te(5)KZr4 trigonal bipyramid. In the third Te site, Te(3) is bonded in a distorted rectangular see-saw-like geometry to one Zr(3), one Zr(6), and two equivalent Zr(4) atoms. In the fourth Te site, Te(4) is bonded to one K(1), one Zr(4), one Zr(5), and two equivalent Zr(3) atoms to form distorted TeKZr4 trigonal bipyramids that share corners with two equivalent Te(7)Zr6 pentagonal pyramids,  a cornercorner with one Te(4)KZr4 trigonal bipyramid,  a cornercorner with one Te(5)KZr4 trigonal bipyramid, corners with two equivalent Te(2)KZr4 trigonal bipyramids,  an edgeedge with one Te(7)Zr6 pentagonal pyramid, edges with two equivalent Te(8)Zr6 pentagonal pyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid,  an edgeedge with one Te(4)KZr4 trigonal bipyramid, and  an edgeedge with one Te(5)KZr4 trigonal bipyramid. In the fifth Te site, Te(5) is bonded to one K(1), one Zr(2), one Zr(5), and two equivalent Zr(6) atoms to form distorted TeKZr4 trigonal bipyramids that share corners with two equivalent Te(7)Zr6 pentagonal pyramids,  a cornercorner with one Te(2)KZr4 trigonal bipyramid,  a cornercorner with one Te(4)KZr4 trigonal bipyramid,  a cornercorner with one Te(5)KZr4 trigonal bipyramid,  an edgeedge with one Te(7)Zr6 pentagonal pyramid, edges with two equivalent Te(8)Zr6 pentagonal pyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid,  an edgeedge with one Te(4)KZr4 trigonal bipyramid, and  an edgeedge with one Te(5)KZr4 trigonal bipyramid. In the sixth Te site, Te(6) is bonded in a distorted rectangular see-saw-like geometry to one Zr(1), one Zr(6), and two equivalent Zr(5) atoms. In the seventh Te site, Te(7) is bonded to one Zr(1), one Zr(2), one Zr(3), one Zr(4), one Zr(5), and one Zr(6) atom to form distorted TeZr6 pentagonal pyramids that share corners with two equivalent Te(4)KZr4 trigonal bipyramids, corners with two equivalent Te(5)KZr4 trigonal bipyramids,  an edgeedge with one Te(4)KZr4 trigonal bipyramid,  an edgeedge with one Te(5)KZr4 trigonal bipyramid, edges with two equivalent Te(2)KZr4 trigonal bipyramids, and faces with two equivalent Te(8)Zr6 pentagonal pyramids. In the eighth Te site, Te(8) is bonded to one Zr(1), one Zr(2), one Zr(3), one Zr(4), one Zr(5), and one Zr(6) atom to form distorted TeZr6 pentagonal pyramids that share corners with two equivalent Te(2)KZr4 trigonal bipyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid, edges with two equivalent Te(4)KZr4 trigonal bipyramids, edges with two equivalent Te(5)KZr4 trigonal bipyramids, and faces with two equivalent Te(7)Zr6 pentagonal pyramids.
K(Zr3Te4)4 crystallizes in the triclinic P-1 space group. K(1) is bonded in a distorted hexagonal planar geometry to two equivalent Te(2), two equivalent Te(4), and two equivalent Te(5) atoms. Both K(1)-Te(2) bond lengths are 3.73 Å. Both K(1)-Te(4) bond lengths are 3.72 Å. Both K(1)-Te(5) bond lengths are 3.73 Å. There are six inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Te(1), one Te(6), one Te(7), one Te(8), and two equivalent Te(2) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The Zr(1)-Te(1) bond length is 2.90 Å. The Zr(1)-Te(6) bond length is 3.01 Å. The Zr(1)-Te(7) bond length is 2.93 Å. The Zr(1)-Te(8) bond length is 2.92 Å. There is one shorter (2.90 Å) and one longer (2.92 Å) Zr(1)-Te(2) bond length. In the second Zr site, Zr(2) is bonded to one Te(2), one Te(5), one Te(7), one Te(8), and two equivalent Te(1) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Zr(2)-Te(2) bond length is 2.92 Å. The Zr(2)-Te(5) bond length is 3.02 Å. The Zr(2)-Te(7) bond length is 2.93 Å. The Zr(2)-Te(8) bond length is 2.93 Å. There is one shorter (2.90 Å) and one longer (2.91 Å) Zr(2)-Te(1) bond length. In the third Zr site, Zr(3) is bonded to one Te(2), one Te(3), one Te(7), one Te(8), and two equivalent Te(4) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Zr(3)-Te(2) bond length is 3.02 Å. The Zr(3)-Te(3) bond length is 2.91 Å. The Zr(3)-Te(7) bond length is 2.93 Å. The Zr(3)-Te(8) bond length is 2.93 Å. There is one shorter (2.90 Å) and one longer (2.92 Å) Zr(3)-Te(4) bond length. In the fourth Zr site, Zr(4) is bonded to one Te(1), one Te(4), one Te(7), one Te(8), and two equivalent Te(3) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. The Zr(4)-Te(1) bond length is 3.01 Å. The Zr(4)-Te(4) bond length is 2.92 Å. The Zr(4)-Te(7) bond length is 2.92 Å. The Zr(4)-Te(8) bond length is 2.93 Å. There is one shorter (2.90 Å) and one longer (2.91 Å) Zr(4)-Te(3) bond length. In the fifth Zr site, Zr(5) is bonded to one Te(4), one Te(5), one Te(7), one Te(8), and two equivalent Te(6) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 42-53°. The Zr(5)-Te(4) bond length is 3.02 Å. The Zr(5)-Te(5) bond length is 2.92 Å. The Zr(5)-Te(7) bond length is 2.92 Å. The Zr(5)-Te(8) bond length is 2.93 Å. There is one shorter (2.90 Å) and one longer (2.91 Å) Zr(5)-Te(6) bond length. In the sixth Zr site, Zr(6) is bonded to one Te(3), one Te(6), one Te(7), one Te(8), and two equivalent Te(5) atoms to form a mixture of corner, edge, and face-sharing ZrTe6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Zr(6)-Te(3) bond length is 3.01 Å. The Zr(6)-Te(6) bond length is 2.91 Å. The Zr(6)-Te(7) bond length is 2.92 Å. The Zr(6)-Te(8) bond length is 2.93 Å. There is one shorter (2.90 Å) and one longer (2.91 Å) Zr(6)-Te(5) bond length. There are eight inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted rectangular see-saw-like geometry to one Zr(1), one Zr(4), and two equivalent Zr(2) atoms. In the second Te site, Te(2) is bonded to one K(1), one Zr(2), one Zr(3), and two equivalent Zr(1) atoms to form distorted TeKZr4 trigonal bipyramids that share corners with two equivalent Te(8)Zr6 pentagonal pyramids,  a cornercorner with one Te(2)KZr4 trigonal bipyramid,  a cornercorner with one Te(5)KZr4 trigonal bipyramid, corners with two equivalent Te(4)KZr4 trigonal bipyramids,  an edgeedge with one Te(8)Zr6 pentagonal pyramid, edges with two equivalent Te(7)Zr6 pentagonal pyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid,  an edgeedge with one Te(4)KZr4 trigonal bipyramid, and  an edgeedge with one Te(5)KZr4 trigonal bipyramid. In the third Te site, Te(3) is bonded in a distorted rectangular see-saw-like geometry to one Zr(3), one Zr(6), and two equivalent Zr(4) atoms. In the fourth Te site, Te(4) is bonded to one K(1), one Zr(4), one Zr(5), and two equivalent Zr(3) atoms to form distorted TeKZr4 trigonal bipyramids that share corners with two equivalent Te(7)Zr6 pentagonal pyramids,  a cornercorner with one Te(4)KZr4 trigonal bipyramid,  a cornercorner with one Te(5)KZr4 trigonal bipyramid, corners with two equivalent Te(2)KZr4 trigonal bipyramids,  an edgeedge with one Te(7)Zr6 pentagonal pyramid, edges with two equivalent Te(8)Zr6 pentagonal pyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid,  an edgeedge with one Te(4)KZr4 trigonal bipyramid, and  an edgeedge with one Te(5)KZr4 trigonal bipyramid. In the fifth Te site, Te(5) is bonded to one K(1), one Zr(2), one Zr(5), and two equivalent Zr(6) atoms to form distorted TeKZr4 trigonal bipyramids that share corners with two equivalent Te(7)Zr6 pentagonal pyramids,  a cornercorner with one Te(2)KZr4 trigonal bipyramid,  a cornercorner with one Te(4)KZr4 trigonal bipyramid,  a cornercorner with one Te(5)KZr4 trigonal bipyramid,  an edgeedge with one Te(7)Zr6 pentagonal pyramid, edges with two equivalent Te(8)Zr6 pentagonal pyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid,  an edgeedge with one Te(4)KZr4 trigonal bipyramid, and  an edgeedge with one Te(5)KZr4 trigonal bipyramid. In the sixth Te site, Te(6) is bonded in a distorted rectangular see-saw-like geometry to one Zr(1), one Zr(6), and two equivalent Zr(5) atoms. In the seventh Te site, Te(7) is bonded to one Zr(1), one Zr(2), one Zr(3), one Zr(4), one Zr(5), and one Zr(6) atom to form distorted TeZr6 pentagonal pyramids that share corners with two equivalent Te(4)KZr4 trigonal bipyramids, corners with two equivalent Te(5)KZr4 trigonal bipyramids,  an edgeedge with one Te(4)KZr4 trigonal bipyramid,  an edgeedge with one Te(5)KZr4 trigonal bipyramid, edges with two equivalent Te(2)KZr4 trigonal bipyramids, and faces with two equivalent Te(8)Zr6 pentagonal pyramids. In the eighth Te site, Te(8) is bonded to one Zr(1), one Zr(2), one Zr(3), one Zr(4), one Zr(5), and one Zr(6) atom to form distorted TeZr6 pentagonal pyramids that share corners with two equivalent Te(2)KZr4 trigonal bipyramids,  an edgeedge with one Te(2)KZr4 trigonal bipyramid, edges with two equivalent Te(4)KZr4 trigonal bipyramids, edges with two equivalent Te(5)KZr4 trigonal bipyramids, and faces with two equivalent Te(7)Zr6 pentagonal pyramids.