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PbSb crystallizes in the orthorhombic Cmmm space group. The structure is three-dimensional. Pb2+ is bonded in a 8-coordinate geometry to four equivalent Sb2- atoms. All Pb–Sb bond lengths are 3.43 Å. Sb2- is bonded in a distorted body-centered cubic geometry to four equivalent Pb2+ and four equivalent Sb2- atoms. All Sb–Sb bond lengths are 3.39 Å.
PbSb is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Pb2+ is bonded to six equivalent Sb2- atoms to form a mixture of edge and corner-sharing PbSb6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Pb–Sb bond lengths are 3.18 Å. Sb2- is bonded to six equivalent Pb2+ atoms to form a mixture of edge and corner-sharing SbPb6 octahedra. The corner-sharing octahedral tilt angles are 0°.