Yb4(GeO5)3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(7), two equivalent O(2), and two equivalent O(5) atoms. In the second Yb site, Yb(2) is bonded to one O(1), one O(6), one O(7), and four equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share  a cornercorner with one Yb(2)O7 pentagonal bipyramid, corners with two equivalent Ge(1)O4 tetrahedra, and edges with two equivalent Yb(2)O7 pentagonal bipyramids. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(7), and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with two equivalent Ge(2)O6 octahedra and corners with two equivalent Yb(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 60°. In the second Ge site, Ge(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form GeO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra and corners with four equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. There are seven inequivalent O sites. In the first O site, O(2) is bonded in a trigonal planar geometry to one Yb(1), one Ge(1), and one Ge(2) atom. In the second O site, O(3) is bonded to two equivalent Yb(1) and two equivalent Ge(2) atoms to form distorted corner-sharing OYb2Ge2 tetrahedra. In the third O site, O(4) is bonded in a distorted single-bond geometry to one O(6) atom. In the fourth O site, O(5) is bonded in a trigonal planar geometry to one Yb(1) and two equivalent Yb(2) atoms. In the fifth O site, O(6) is bonded in a distorted T-shaped geometry to two equivalent Yb(2) and one O(4) atom. In the sixth O site, O(7) is bonded in a trigonal planar geometry to one Yb(1), one Yb(2), and one Ge(1) atom. In the seventh O site, O(1) is bonded in a 3-coordinate geometry to one Yb(1), one Yb(2), and one Ge(1) atom.
Yb4(GeO5)3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(7), two equivalent O(2), and two equivalent O(5) atoms. The Yb(1)-O(1) bond length is 2.41 Å. The Yb(1)-O(3) bond length is 2.50 Å. The Yb(1)-O(7) bond length is 2.23 Å. Both Yb(1)-O(2) bond lengths are 2.34 Å. Both Yb(1)-O(5) bond lengths are 2.35 Å. In the second Yb site, Yb(2) is bonded to one O(1), one O(6), one O(7), and four equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share  a cornercorner with one Yb(2)O7 pentagonal bipyramid, corners with two equivalent Ge(1)O4 tetrahedra, and edges with two equivalent Yb(2)O7 pentagonal bipyramids. The Yb(2)-O(1) bond length is 2.34 Å. The Yb(2)-O(6) bond length is 2.57 Å. The Yb(2)-O(7) bond length is 2.14 Å. There are two shorter (2.38 Å) and two longer (2.44 Å) Yb(2)-O(5) bond lengths. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(7), and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with two equivalent Ge(2)O6 octahedra and corners with two equivalent Yb(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 60°. The Ge(1)-O(1) bond length is 1.76 Å. The Ge(1)-O(7) bond length is 1.73 Å. Both Ge(1)-O(2) bond lengths are 1.80 Å. In the second Ge site, Ge(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form GeO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra and corners with four equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. Both Ge(2)-O(3) bond lengths are 1.89 Å. All Ge(2)-O(2) bond lengths are 1.94 Å. There are seven inequivalent O sites. In the first O site, O(2) is bonded in a trigonal planar geometry to one Yb(1), one Ge(1), and one Ge(2) atom. In the second O site, O(3) is bonded to two equivalent Yb(1) and two equivalent Ge(2) atoms to form distorted corner-sharing OYb2Ge2 tetrahedra. In the third O site, O(4) is bonded in a distorted single-bond geometry to one O(6) atom. The O(4)-O(6) bond length is 1.27 Å. In the fourth O site, O(5) is bonded in a trigonal planar geometry to one Yb(1) and two equivalent Yb(2) atoms. In the fifth O site, O(6) is bonded in a distorted T-shaped geometry to two equivalent Yb(2) and one O(4) atom. In the sixth O site, O(7) is bonded in a trigonal planar geometry to one Yb(1), one Yb(2), and one Ge(1) atom. In the seventh O site, O(1) is bonded in a 3-coordinate geometry to one Yb(1), one Yb(2), and one Ge(1) atom.