Ba4Ga3Ge20 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 12-coordinate geometry to four equivalent Ga(1) and eight equivalent Ge(1) atoms. In the second Ba site, Ba(2) is bonded in a 20-coordinate geometry to eight equivalent Ge(2) and twelve equivalent Ge(1) atoms. Ga(1) is bonded to four equivalent Ba(1) and four equivalent Ge(1) atoms to form a mixture of edge and corner-sharing GaBa4Ge4 tetrahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(2) is bonded in a 5-coordinate geometry to one Ba(2), 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(2), two equivalent Ba(1), one Ga(1), one Ge(1), and two equivalent Ge(2) atoms.
Ba4Ga3Ge20 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 12-coordinate geometry to four equivalent Ga(1) and eight equivalent Ge(1) atoms. All Ba(1)-Ga(1) bond lengths are 3.91 Å. All Ba(1)-Ge(1) bond lengths are 3.72 Å. In the second Ba site, Ba(2) is bonded in a 20-coordinate geometry to eight equivalent Ge(2) and twelve equivalent Ge(1) atoms. All Ba(2)-Ge(2) bond lengths are 3.53 Å. All Ba(2)-Ge(1) bond lengths are 3.65 Å. Ga(1) is bonded to four equivalent Ba(1) and four equivalent Ge(1) atoms to form a mixture of edge and corner-sharing GaBa4Ge4 tetrahedra. All Ga(1)-Ge(1) bond lengths are 2.56 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(2) is bonded in a 5-coordinate geometry to one Ba(2), one Ge(2), and three equivalent Ge(1) atoms. The Ge(2)-Ge(2) bond length is 2.50 Å. All Ge(2)-Ge(1) bond lengths are 2.56 Å. In the second Ge site, Ge(1) is bonded in a 7-coordinate geometry to one Ba(2), two equivalent Ba(1), one Ga(1), one Ge(1), and two equivalent Ge(2) atoms. The Ge(1)-Ge(1) bond length is 2.62 Å.