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Au4Mn crystallizes in the tetragonal I4/m space group. The structure is three-dimensional. Mn2+ is bonded to twelve equivalent Au+0.50- atoms to form a mixture of face and edge-sharing MnAu12 cuboctahedra. There are eight shorter (2.89 Å) and four longer (2.93 Å) Mn–Au bond lengths. Au+0.50- is bonded to three equivalent Mn2+ atoms to form a mixture of distorted edge and corner-sharing AuMn3 cuboctahedra.
Au4Mn crystallizes in the trigonal R-3m space group. The structure is three-dimensional. Mn2+ is bonded in a distorted hexagonal planar geometry to six equivalent Au+0.50- atoms. All Mn–Au bond lengths are 2.72 Å. There are two inequivalent Au+0.50- sites. In the first Au+0.50- site, Au+0.50- is bonded in a 12-coordinate geometry to three equivalent Mn2+ and three equivalent Au+0.50- atoms. All Au–Au bond lengths are 2.96 Å. In the second Au+0.50- site, Au+0.50- is bonded to twelve Au+0.50- atoms to form a mixture of face, edge, and corner-sharing AuAu12 cuboctahedra. There are three shorter (2.96 Å) and six longer (3.00 Å) Au–Au bond lengths.