Yb4OCl6 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 1-coordinate geometry to one O(1), three equivalent Cl(2), and six equivalent Cl(1) atoms. In the second Yb site, Yb(2) is bonded in a 8-coordinate geometry to one O(1), three equivalent Cl(2), and four equivalent Cl(1) atoms. O(1) is bonded to one Yb(1) and three equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with six equivalent Cl(2)Yb4 trigonal pyramids and edges with three equivalent Cl(2)Yb4 trigonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to two equivalent Yb(1) and four equivalent Yb(2) atoms. In the second Cl site, Cl(2) is bonded to one Yb(1) and three equivalent Yb(2) atoms to form distorted ClYb4 trigonal pyramids that share corners with two equivalent O(1)Yb4 tetrahedra, corners with eight equivalent Cl(2)Yb4 trigonal pyramids, and  an edgeedge with one O(1)Yb4 tetrahedra.
Yb4OCl6 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 1-coordinate geometry to one O(1), three equivalent Cl(2), and six equivalent Cl(1) atoms. The Yb(1)-O(1) bond length is 2.16 Å. All Yb(1)-Cl(2) bond lengths are 3.01 Å. There are three shorter (2.76 Å) and three longer (3.42 Å) Yb(1)-Cl(1) bond lengths. In the second Yb site, Yb(2) is bonded in a 8-coordinate geometry to one O(1), three equivalent Cl(2), and four equivalent Cl(1) atoms. The Yb(2)-O(1) bond length is 2.18 Å. There is one shorter (2.74 Å) and two longer (2.81 Å) Yb(2)-Cl(2) bond lengths. There are two shorter (2.82 Å) and two longer (3.07 Å) Yb(2)-Cl(1) bond lengths. O(1) is bonded to one Yb(1) and three equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with six equivalent Cl(2)Yb4 trigonal pyramids and edges with three equivalent Cl(2)Yb4 trigonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to two equivalent Yb(1) and four equivalent Yb(2) atoms. In the second Cl site, Cl(2) is bonded to one Yb(1) and three equivalent Yb(2) atoms to form distorted ClYb4 trigonal pyramids that share corners with two equivalent O(1)Yb4 tetrahedra, corners with eight equivalent Cl(2)Yb4 trigonal pyramids, and  an edgeedge with one O(1)Yb4 tetrahedra.