Ba4Ge23 crystallizes in the cubic Pm-3n space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 20-coordinate geometry to eight equivalent Ge(2) and twelve equivalent Ge(1) atoms. In the second Ba site, Ba(2) is bonded in a 12-coordinate geometry to four equivalent Ge(3) and eight equivalent Ge(1) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ge(2), and three equivalent Ge(1) atoms. In the second Ge site, Ge(1) is bonded in a 7-coordinate geometry to one Ba(1), two equivalent Ba(2), one Ge(1), one Ge(3), and two equivalent Ge(2) atoms. In the third Ge site, Ge(3) is bonded to four equivalent Ba(2) and four equivalent Ge(1) atoms to form a mixture of distorted corner and edge-sharing GeBa4Ge4 tetrahedra.
Ba4Ge23 crystallizes in the cubic Pm-3n space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 20-coordinate geometry to eight equivalent Ge(2) and twelve equivalent Ge(1) atoms. All Ba(1)-Ge(2) bond lengths are 3.56 Å. All Ba(1)-Ge(1) bond lengths are 3.67 Å. In the second Ba site, Ba(2) is bonded in a 12-coordinate geometry to four equivalent Ge(3) and eight equivalent Ge(1) atoms. All Ba(2)-Ge(3) bond lengths are 3.94 Å. All Ba(2)-Ge(1) bond lengths are 3.76 Å. There are three inequivalent Ge sites. In the first Ge site, Ge(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ge(2), and three equivalent Ge(1) atoms. The Ge(2)-Ge(2) bond length is 2.53 Å. All Ge(2)-Ge(1) bond lengths are 2.58 Å. In the second Ge site, Ge(1) is bonded in a 7-coordinate geometry to one Ba(1), two equivalent Ba(2), one Ge(1), one Ge(3), and two equivalent Ge(2) atoms. The Ge(1)-Ge(1) bond length is 2.65 Å. The Ge(1)-Ge(3) bond length is 2.60 Å. In the third Ge site, Ge(3) is bonded to four equivalent Ba(2) and four equivalent Ge(1) atoms to form a mixture of distorted corner and edge-sharing GeBa4Ge4 tetrahedra.