Ce5GeBi2 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 5-coordinate geometry to two equivalent Ge(1) and three equivalent Bi(1) atoms. In the second Ce site, Ce(2) is bonded to one Ge(1) and four equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing CeGeBi4 square pyramids. In the third Ce site, Ce(3) is bonded in a 6-coordinate geometry to two equivalent Ge(1) and four equivalent Bi(1) atoms. In the fourth Ce site, Ce(4) is bonded to one Ge(1) and four equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing CeGeBi4 trigonal bipyramids. Ge(1) is bonded in a 8-coordinate geometry to one Ce(2), one Ce(4), two equivalent Ce(3), and four equivalent Ce(1) atoms. Bi(1) is bonded in a 9-coordinate geometry to two equivalent Ce(2), two equivalent Ce(3), two equivalent Ce(4), and three equivalent Ce(1) atoms.
Ce5GeBi2 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 5-coordinate geometry to two equivalent Ge(1) and three equivalent Bi(1) atoms. There is one shorter (3.02 Å) and one longer (3.17 Å) Ce(1)-Ge(1) bond length. There are a spread of Ce(1)-Bi(1) bond distances ranging from 3.43-3.48 Å. In the second Ce site, Ce(2) is bonded to one Ge(1) and four equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing CeGeBi4 square pyramids. The Ce(2)-Ge(1) bond length is 3.13 Å. There are two shorter (3.27 Å) and two longer (3.29 Å) Ce(2)-Bi(1) bond lengths. In the third Ce site, Ce(3) is bonded in a 6-coordinate geometry to two equivalent Ge(1) and four equivalent Bi(1) atoms. There is one shorter (3.08 Å) and one longer (3.58 Å) Ce(3)-Ge(1) bond length. There are two shorter (3.27 Å) and two longer (3.30 Å) Ce(3)-Bi(1) bond lengths. In the fourth Ce site, Ce(4) is bonded to one Ge(1) and four equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing CeGeBi4 trigonal bipyramids. The Ce(4)-Ge(1) bond length is 3.00 Å. There are two shorter (3.28 Å) and two longer (3.31 Å) Ce(4)-Bi(1) bond lengths. Ge(1) is bonded in a 8-coordinate geometry to one Ce(2), one Ce(4), two equivalent Ce(3), and four equivalent Ce(1) atoms. Bi(1) is bonded in a 9-coordinate geometry to two equivalent Ce(2), two equivalent Ce(3), two equivalent Ce(4), and three equivalent Ce(1) atoms.