K4ZnBi2 crystallizes in the orthorhombic C222_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to four equivalent Bi(1) atoms to form KBi4 trigonal pyramids that share corners with four equivalent Zn(1)K3Bi2 trigonal bipyramids, corners with six equivalent K(1)Bi4 trigonal pyramids, and edges with three equivalent K(1)Bi4 trigonal pyramids. In the second K site, K(2) is bonded in a 6-coordinate geometry to six equivalent Bi(1) atoms. In the third K site, K(3) is bonded in a distorted trigonal planar geometry to three equivalent Zn(1) atoms. Zn(1) is bonded to three equivalent K(3) and two equivalent Bi(1) atoms to form distorted ZnK3Bi2 trigonal bipyramids that share corners with six equivalent Zn(1)K3Bi2 trigonal bipyramids and corners with eight equivalent K(1)Bi4 trigonal pyramids. Bi(1) is bonded in a 5-coordinate geometry to three equivalent K(2), four equivalent K(1), and one Zn(1) atom.
K4ZnBi2 crystallizes in the orthorhombic C222_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to four equivalent Bi(1) atoms to form KBi4 trigonal pyramids that share corners with four equivalent Zn(1)K3Bi2 trigonal bipyramids, corners with six equivalent K(1)Bi4 trigonal pyramids, and edges with three equivalent K(1)Bi4 trigonal pyramids. There are a spread of K(1)-Bi(1) bond distances ranging from 3.53-3.67 Å. In the second K site, K(2) is bonded in a 6-coordinate geometry to six equivalent Bi(1) atoms. There are two shorter (3.97 Å) and four longer (4.05 Å) K(2)-Bi(1) bond lengths. In the third K site, K(3) is bonded in a distorted trigonal planar geometry to three equivalent Zn(1) atoms. There is one shorter (3.54 Å) and two longer (3.57 Å) K(3)-Zn(1) bond lengths. Zn(1) is bonded to three equivalent K(3) and two equivalent Bi(1) atoms to form distorted ZnK3Bi2 trigonal bipyramids that share corners with six equivalent Zn(1)K3Bi2 trigonal bipyramids and corners with eight equivalent K(1)Bi4 trigonal pyramids. Both Zn(1)-Bi(1) bond lengths are 2.56 Å. Bi(1) is bonded in a 5-coordinate geometry to three equivalent K(2), four equivalent K(1), and one Zn(1) atom.