Ca5Ge3 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a square co-planar geometry to four equivalent Ge(2) atoms. In the second Ca site, Ca(2) is bonded to two equivalent Ge(1) and three equivalent Ge(2) atoms to form a mixture of distorted face, corner, and edge-sharing CaGe5 trigonal bipyramids. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 8-coordinate geometry to eight equivalent Ca(2) atoms. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to two equivalent Ca(1), six equivalent Ca(2), and one Ge(2) atom.
Ca5Ge3 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a square co-planar geometry to four equivalent Ge(2) atoms. All Ca(1)-Ge(2) bond lengths are 3.09 Å. In the second Ca site, Ca(2) is bonded to two equivalent Ge(1) and three equivalent Ge(2) atoms to form a mixture of distorted face, corner, and edge-sharing CaGe5 trigonal bipyramids. Both Ca(2)-Ge(1) bond lengths are 3.27 Å. There is one shorter (3.02 Å) and two longer (3.11 Å) Ca(2)-Ge(2) bond lengths. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 8-coordinate geometry to eight equivalent Ca(2) atoms. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to two equivalent Ca(1), six equivalent Ca(2), and one Ge(2) atom. The Ge(2)-Ge(2) bond length is 2.56 Å.