Yb3SbO7 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share corners with two equivalent Sb(1)O6 octahedra,  a cornercorner with one Yb(1)O7 pentagonal bipyramid, edges with two equivalent Sb(1)O6 octahedra, and edges with three equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 46-52°. In the second Yb site, Yb(2) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. Sb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Yb(1)O7 pentagonal bipyramids, and edges with four equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 38°. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Yb(1) and two equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with two equivalent O(1)Yb4 tetrahedra, corners with four equivalent O(3)Yb3Sb tetrahedra, corners with four equivalent O(4)Yb4 tetrahedra, corners with four equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(4)Yb4 tetrahedra, edges with two equivalent O(3)Yb3Sb tetrahedra,  an edgeedge with one O(2)Yb2Sb2 trigonal pyramid, and edges with two equivalent O(5)Yb3Sb trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Yb(1) and two equivalent Sb(1) atoms to form distorted OYb2Sb2 trigonal pyramids that share corners with two equivalent O(4)Yb4 tetrahedra, corners with four equivalent O(3)Yb3Sb tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with four equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(1)Yb4 tetrahedra, edges with two equivalent O(3)Yb3Sb tetrahedra, and edges with two equivalent O(5)Yb3Sb trigonal pyramids. In the third O site, O(3) is bonded to one Yb(2), two equivalent Yb(1), and one Sb(1) atom to form distorted OYb3Sb tetrahedra that share corners with two equivalent O(3)Yb3Sb tetrahedra, corners with two equivalent O(1)Yb4 tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with six equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(3)Yb3Sb tetrahedra,  an edgeedge with one O(1)Yb4 tetrahedra,  an edgeedge with one O(4)Yb4 tetrahedra,  an edgeedge with one O(2)Yb2Sb2 trigonal pyramid, and  an edgeedge with one O(5)Yb3Sb trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Yb(1) and two equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with two equivalent O(4)Yb4 tetrahedra, corners with four equivalent O(3)Yb3Sb tetrahedra, corners with four equivalent O(1)Yb4 tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with four equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(1)Yb4 tetrahedra, edges with two equivalent O(3)Yb3Sb tetrahedra, and edges with two equivalent O(5)Yb3Sb trigonal pyramids. In the fifth O site, O(5) is bonded to one Yb(2), two equivalent Yb(1), and one Sb(1) atom to form distorted OYb3Sb trigonal pyramids that share corners with two equivalent O(1)Yb4 tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra, corners with six equivalent O(3)Yb3Sb tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with two equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(3)Yb3Sb tetrahedra,  an edgeedge with one O(1)Yb4 tetrahedra,  an edgeedge with one O(4)Yb4 tetrahedra,  an edgeedge with one O(2)Yb2Sb2 trigonal pyramid, and  an edgeedge with one O(5)Yb3Sb trigonal pyramid.
Yb3SbO7 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share corners with two equivalent Sb(1)O6 octahedra,  a cornercorner with one Yb(1)O7 pentagonal bipyramid, edges with two equivalent Sb(1)O6 octahedra, and edges with three equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 46-52°. The Yb(1)-O(1) bond length is 2.32 Å. The Yb(1)-O(2) bond length is 2.34 Å. The Yb(1)-O(4) bond length is 2.23 Å. There is one shorter (2.38 Å) and one longer (2.44 Å) Yb(1)-O(3) bond length. There is one shorter (2.25 Å) and one longer (2.38 Å) Yb(1)-O(5) bond length. In the second Yb site, Yb(2) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. Both Yb(2)-O(1) bond lengths are 2.27 Å. Both Yb(2)-O(3) bond lengths are 2.52 Å. Both Yb(2)-O(4) bond lengths are 2.26 Å. Both Yb(2)-O(5) bond lengths are 2.49 Å. Sb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Yb(1)O7 pentagonal bipyramids, and edges with four equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 38°. Both Sb(1)-O(2) bond lengths are 2.04 Å. Both Sb(1)-O(3) bond lengths are 1.99 Å. Both Sb(1)-O(5) bond lengths are 1.93 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Yb(1) and two equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with two equivalent O(1)Yb4 tetrahedra, corners with four equivalent O(3)Yb3Sb tetrahedra, corners with four equivalent O(4)Yb4 tetrahedra, corners with four equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(4)Yb4 tetrahedra, edges with two equivalent O(3)Yb3Sb tetrahedra,  an edgeedge with one O(2)Yb2Sb2 trigonal pyramid, and edges with two equivalent O(5)Yb3Sb trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Yb(1) and two equivalent Sb(1) atoms to form distorted OYb2Sb2 trigonal pyramids that share corners with two equivalent O(4)Yb4 tetrahedra, corners with four equivalent O(3)Yb3Sb tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with four equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(1)Yb4 tetrahedra, edges with two equivalent O(3)Yb3Sb tetrahedra, and edges with two equivalent O(5)Yb3Sb trigonal pyramids. In the third O site, O(3) is bonded to one Yb(2), two equivalent Yb(1), and one Sb(1) atom to form distorted OYb3Sb tetrahedra that share corners with two equivalent O(3)Yb3Sb tetrahedra, corners with two equivalent O(1)Yb4 tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with six equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(3)Yb3Sb tetrahedra,  an edgeedge with one O(1)Yb4 tetrahedra,  an edgeedge with one O(4)Yb4 tetrahedra,  an edgeedge with one O(2)Yb2Sb2 trigonal pyramid, and  an edgeedge with one O(5)Yb3Sb trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Yb(1) and two equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with two equivalent O(4)Yb4 tetrahedra, corners with four equivalent O(3)Yb3Sb tetrahedra, corners with four equivalent O(1)Yb4 tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with four equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(1)Yb4 tetrahedra, edges with two equivalent O(3)Yb3Sb tetrahedra, and edges with two equivalent O(5)Yb3Sb trigonal pyramids. In the fifth O site, O(5) is bonded to one Yb(2), two equivalent Yb(1), and one Sb(1) atom to form distorted OYb3Sb trigonal pyramids that share corners with two equivalent O(1)Yb4 tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra, corners with six equivalent O(3)Yb3Sb tetrahedra, corners with two equivalent O(2)Yb2Sb2 trigonal pyramids, corners with two equivalent O(5)Yb3Sb trigonal pyramids,  an edgeedge with one O(3)Yb3Sb tetrahedra,  an edgeedge with one O(1)Yb4 tetrahedra,  an edgeedge with one O(4)Yb4 tetrahedra,  an edgeedge with one O(2)Yb2Sb2 trigonal pyramid, and  an edgeedge with one O(5)Yb3Sb trigonal pyramid.