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MgPb3 crystallizes in the hexagonal P6_3/mmc space group. The structure is two-dimensional and consists of two MgPb3 sheets oriented in the (0, 0, 1) direction. Mg is bonded in a distorted hexagonal planar geometry to six equivalent Pb atoms. All Mg–Pb bond lengths are 3.34 Å. Pb is bonded in a distorted linear geometry to two equivalent Mg atoms.
MgPb3 is Uranium Silicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Mg is bonded to twelve Pb atoms to form MgPb12 cuboctahedra that share corners with four equivalent MgPb12 cuboctahedra, edges with eight equivalent MgPb12 cuboctahedra, edges with sixteen equivalent PbMg4Pb8 cuboctahedra, faces with four equivalent MgPb12 cuboctahedra, and faces with eight equivalent PbMg4Pb8 cuboctahedra. There are four shorter (3.41 Å) and eight longer (3.50 Å) Mg–Pb bond lengths. There are two inequivalent Pb sites. In the first Pb site, Pb is bonded in a square co-planar geometry to four equivalent Mg and eight equivalent Pb atoms. All Pb–Pb bond lengths are 3.50 Å. In the second Pb site, Pb is bonded to four equivalent Mg and eight Pb atoms to form distorted PbMg4Pb8 cuboctahedra that share corners with twelve equivalent PbMg4Pb8 cuboctahedra, edges with eight equivalent MgPb12 cuboctahedra, edges with eight equivalent PbMg4Pb8 cuboctahedra, faces with four equivalent MgPb12 cuboctahedra, and faces with ten equivalent PbMg4Pb8 cuboctahedra. All Pb–Pb bond lengths are 3.41 Å.
MgPb3 crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. Mg is bonded in a 12-coordinate geometry to six equivalent Pb atoms. All Mg–Pb bond lengths are 3.26 Å. There are two inequivalent Pb sites. In the first Pb site, Pb is bonded in a 12-coordinate geometry to three equivalent Mg and three equivalent Pb atoms. All Pb–Pb bond lengths are 3.59 Å. In the second Pb site, Pb is bonded to twelve Pb atoms to form a mixture of face, edge, and corner-sharing PbPb12 cuboctahedra. All Pb–Pb bond lengths are 3.55 Å.