Mg2Bi3 crystallizes in the trigonal P-3m1 space group. Mg(1) is bonded in a body-centered cubic geometry to three equivalent Bi(2) and five equivalent Bi(1) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to five equivalent Mg(1) atoms to form a mixture of distorted corner and edge-sharing BiMg5 trigonal bipyramids. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to six equivalent Mg(1) atoms.
Mg2Bi3 crystallizes in the trigonal P-3m1 space group. Mg(1) is bonded in a body-centered cubic geometry to three equivalent Bi(2) and five equivalent Bi(1) atoms. All Mg(1)-Bi(2) bond lengths are 3.25 Å. There are three shorter (3.09 Å) and two longer (3.27 Å) Mg(1)-Bi(1) bond lengths. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to five equivalent Mg(1) atoms to form a mixture of distorted corner and edge-sharing BiMg5 trigonal bipyramids. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to six equivalent Mg(1) atoms.