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Pb3Sb crystallizes in the hexagonal P6_3/mmc space group. The structure is one-dimensional and consists of two Pb3Sb ribbons oriented in the (0, 0, 1) direction. Pb is bonded in a 2-coordinate geometry to two equivalent Sb atoms. Both Pb–Sb bond lengths are 3.38 Å. Sb is bonded in a 12-coordinate geometry to six equivalent Pb atoms.
Pb3Sb is beta-derived structured and crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. there are two inequivalent Pb sites. In the first Pb site, Pb is bonded to twelve Pb atoms to form PbPb12 cuboctahedra that share corners with six equivalent PbPb12 cuboctahedra, corners with twelve equivalent SbSb6Pb6 cuboctahedra, edges with eighteen PbPb12 cuboctahedra, faces with two equivalent SbSb6Pb6 cuboctahedra, and faces with eighteen PbPb12 cuboctahedra. There are six shorter (3.46 Å) and six longer (3.59 Å) Pb–Pb bond lengths. In the second Pb site, Pb is bonded to nine Pb and three equivalent Sb atoms to form distorted PbSb3Pb9 cuboctahedra that share corners with eighteen equivalent PbSb3Pb9 cuboctahedra, edges with six equivalent SbSb6Pb6 cuboctahedra, edges with twelve PbPb12 cuboctahedra, faces with six equivalent SbSb6Pb6 cuboctahedra, and faces with fourteen PbPb12 cuboctahedra. All Pb–Pb bond lengths are 3.46 Å. All Pb–Sb bond lengths are 3.51 Å. Sb is bonded to six equivalent Pb and six equivalent Sb atoms to form distorted SbSb6Pb6 cuboctahedra that share corners with six equivalent SbSb6Pb6 cuboctahedra, corners with twelve equivalent PbPb12 cuboctahedra, edges with six equivalent SbSb6Pb6 cuboctahedra, edges with twelve equivalent PbSb3Pb9 cuboctahedra, faces with six equivalent SbSb6Pb6 cuboctahedra, and faces with fourteen PbPb12 cuboctahedra. All Sb–Sb bond lengths are 3.46 Å.