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ZnBi is SC16 CuCl, stable at 5GPa structured and crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. Zn is bonded in a 5-coordinate geometry to one Zn and four equivalent Bi atoms. The Zn–Zn bond length is 2.77 Å. There are a spread of Zn–Bi bond distances ranging from 2.80–3.03 Å. Bi is bonded in a 5-coordinate geometry to four equivalent Zn and one Bi atom. The Bi–Bi bond length is 3.05 Å.
ZnBi is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. Zn is bonded to four equivalent Bi atoms to form distorted corner-sharing ZnBi4 trigonal pyramids. There are three shorter (2.73 Å) and one longer (2.90 Å) Zn–Bi bond lengths. Bi is bonded to four equivalent Zn atoms to form distorted corner-sharing BiZn4 trigonal pyramids.