La3Ge3Cl2 crystallizes in the monoclinic C2/m space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to two equivalent Ge(2), two equivalent Ge(3), one Cl(1), and three equivalent Cl(2) atoms. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent Ge(1), two equivalent Ge(2), four equivalent Ge(3), and one Cl(2) atom. In the third La site, La(3) is bonded in a 9-coordinate geometry to two equivalent Ge(2), four equivalent Ge(1), and three equivalent Cl(1) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 8-coordinate geometry to two equivalent La(2), four equivalent La(3), one Ge(1), and one Ge(2) atom. In the second Ge site, Ge(2) is bonded in a 8-coordinate geometry to two equivalent La(1), two equivalent La(2), two equivalent La(3), one Ge(1), and one Ge(3) atom. In the third Ge site, Ge(3) is bonded in a 8-coordinate geometry to two equivalent La(1), four equivalent La(2), one Ge(2), and one Ge(3) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one La(1) and three equivalent La(3) atoms to form a mixture of distorted edge and corner-sharing ClLa4 tetrahedra. In the second Cl site, Cl(2) is bonded to one La(2) and three equivalent La(1) atoms to form a mixture of distorted edge and corner-sharing ClLa4 trigonal pyramids.
La3Ge3Cl2 crystallizes in the monoclinic C2/m space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 8-coordinate geometry to two equivalent Ge(2), two equivalent Ge(3), one Cl(1), and three equivalent Cl(2) atoms. Both La(1)-Ge(2) bond lengths are 3.15 Å. Both La(1)-Ge(3) bond lengths are 3.08 Å. The La(1)-Cl(1) bond length is 2.90 Å. All La(1)-Cl(2) bond lengths are 3.04 Å. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent Ge(1), two equivalent Ge(2), four equivalent Ge(3), and one Cl(2) atom. Both La(2)-Ge(1) bond lengths are 3.16 Å. Both La(2)-Ge(2) bond lengths are 3.28 Å. There are two shorter (3.16 Å) and two longer (3.26 Å) La(2)-Ge(3) bond lengths. The La(2)-Cl(2) bond length is 3.04 Å. In the third La site, La(3) is bonded in a 9-coordinate geometry to two equivalent Ge(2), four equivalent Ge(1), and three equivalent Cl(1) atoms. Both La(3)-Ge(2) bond lengths are 3.11 Å. There are two shorter (3.17 Å) and two longer (3.42 Å) La(3)-Ge(1) bond lengths. There are two shorter (3.08 Å) and one longer (3.18 Å) La(3)-Cl(1) bond length. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 8-coordinate geometry to two equivalent La(2), four equivalent La(3), one Ge(1), and one Ge(2) atom. The Ge(1)-Ge(1) bond length is 2.53 Å. The Ge(1)-Ge(2) bond length is 2.56 Å. In the second Ge site, Ge(2) is bonded in a 8-coordinate geometry to two equivalent La(1), two equivalent La(2), two equivalent La(3), one Ge(1), and one Ge(3) atom. The Ge(2)-Ge(3) bond length is 2.53 Å. In the third Ge site, Ge(3) is bonded in a 8-coordinate geometry to two equivalent La(1), four equivalent La(2), one Ge(2), and one Ge(3) atom. The Ge(3)-Ge(3) bond length is 2.57 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one La(1) and three equivalent La(3) atoms to form a mixture of distorted edge and corner-sharing ClLa4 tetrahedra. In the second Cl site, Cl(2) is bonded to one La(2) and three equivalent La(1) atoms to form a mixture of distorted edge and corner-sharing ClLa4 trigonal pyramids.