La4GeO8 crystallizes in the orthorhombic Pnma space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(6), and four equivalent O(5) atoms. In the second La site, La(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. In the third La site, La(3) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(6), and four equivalent O(4) atoms. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(5) atoms. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the second O site, O(6) is bonded to one La(1), one La(3), and two equivalent La(2) atoms to form OLa4 tetrahedra that share corners with four equivalent O(4)La4 tetrahedra, corners with three equivalent O(3)La3Ge trigonal pyramids, edges with two equivalent O(2)La4 tetrahedra, and edges with two equivalent O(4)La4 tetrahedra. In the third O site, O(1) is bonded in a 4-coordinate geometry to one La(3), two equivalent La(2), and one Ge(1) atom. In the fourth O site, O(2) is bonded to one La(1), one La(3), and two equivalent La(2) atoms to form OLa4 tetrahedra that share corners with four equivalent O(4)La4 tetrahedra, corners with three equivalent O(3)La3Ge trigonal pyramids, edges with two equivalent O(4)La4 tetrahedra, and edges with two equivalent O(6)La4 tetrahedra. In the fifth O site, O(3) is bonded to one La(1), two equivalent La(2), and one Ge(1) atom to form distorted corner-sharing OLa3Ge trigonal pyramids. In the sixth O site, O(4) is bonded to two equivalent La(2) and two equivalent La(3) atoms to form OLa4 tetrahedra that share corners with two equivalent O(2)La4 tetrahedra, corners with two equivalent O(6)La4 tetrahedra, corners with four equivalent O(4)La4 tetrahedra, corners with two equivalent O(3)La3Ge trigonal pyramids,  an edgeedge with one O(2)La4 tetrahedra,  an edgeedge with one O(6)La4 tetrahedra, and edges with two equivalent O(4)La4 tetrahedra.
La4GeO8 crystallizes in the orthorhombic Pnma space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(6), and four equivalent O(5) atoms. The La(1)-O(2) bond length is 2.28 Å. The La(1)-O(3) bond length is 2.64 Å. The La(1)-O(6) bond length is 2.29 Å. There are two shorter (2.54 Å) and two longer (2.77 Å) La(1)-O(5) bond lengths. In the second La site, La(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The La(2)-O(1) bond length is 2.60 Å. The La(2)-O(2) bond length is 2.41 Å. The La(2)-O(3) bond length is 2.62 Å. The La(2)-O(5) bond length is 2.88 Å. The La(2)-O(6) bond length is 2.38 Å. There is one shorter (2.36 Å) and one longer (2.38 Å) La(2)-O(4) bond length. In the third La site, La(3) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(6), and four equivalent O(4) atoms. The La(3)-O(1) bond length is 2.59 Å. The La(3)-O(2) bond length is 2.51 Å. The La(3)-O(6) bond length is 2.41 Å. There are two shorter (2.42 Å) and two longer (2.51 Å) La(3)-O(4) bond lengths. Ge(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(5) atoms. The Ge(1)-O(1) bond length is 1.79 Å. The Ge(1)-O(3) bond length is 1.77 Å. Both Ge(1)-O(5) bond lengths are 1.77 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the second O site, O(6) is bonded to one La(1), one La(3), and two equivalent La(2) atoms to form OLa4 tetrahedra that share corners with four equivalent O(4)La4 tetrahedra, corners with three equivalent O(3)La3Ge trigonal pyramids, edges with two equivalent O(2)La4 tetrahedra, and edges with two equivalent O(4)La4 tetrahedra. In the third O site, O(1) is bonded in a 4-coordinate geometry to one La(3), two equivalent La(2), and one Ge(1) atom. In the fourth O site, O(2) is bonded to one La(1), one La(3), and two equivalent La(2) atoms to form OLa4 tetrahedra that share corners with four equivalent O(4)La4 tetrahedra, corners with three equivalent O(3)La3Ge trigonal pyramids, edges with two equivalent O(4)La4 tetrahedra, and edges with two equivalent O(6)La4 tetrahedra. In the fifth O site, O(3) is bonded to one La(1), two equivalent La(2), and one Ge(1) atom to form distorted corner-sharing OLa3Ge trigonal pyramids. In the sixth O site, O(4) is bonded to two equivalent La(2) and two equivalent La(3) atoms to form OLa4 tetrahedra that share corners with two equivalent O(2)La4 tetrahedra, corners with two equivalent O(6)La4 tetrahedra, corners with four equivalent O(4)La4 tetrahedra, corners with two equivalent O(3)La3Ge trigonal pyramids,  an edgeedge with one O(2)La4 tetrahedra,  an edgeedge with one O(6)La4 tetrahedra, and edges with two equivalent O(4)La4 tetrahedra.