YbV4O8 crystallizes in the monoclinic P2_1/c space group. Yb(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), one O(8), and two equivalent O(5) atoms. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(6), one O(8), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. In the third V site, V(3) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. There are eight inequivalent O sites. In the first O site, O(4) is bonded to one Yb(1), one V(3), and two equivalent V(4) atoms to form distorted OYbV3 trigonal pyramids that share  a cornercorner with one O(5)Yb2V3 trigonal bipyramid,  a cornercorner with one O(3)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid,  a cornercorner with one O(8)YbV3 trigonal pyramid, corners with three equivalent O(1)YbV3 trigonal pyramids, edges with two equivalent O(5)Yb2V3 trigonal bipyramids,  an edgeedge with one O(4)YbV3 trigonal pyramid, and edges with two equivalent O(3)YbV3 trigonal pyramids. In the second O site, O(5) is bonded to two equivalent Yb(1), one V(1), one V(3), and one V(4) atom to form distorted OYb2V3 trigonal bipyramids that share corners with two equivalent O(5)Yb2V3 trigonal bipyramids,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid, corners with two equivalent O(8)YbV3 trigonal pyramids, corners with three equivalent O(3)YbV3 trigonal pyramids,  an edgeedge with one O(3)YbV3 trigonal pyramid,  an edgeedge with one O(7)YbV3 trigonal pyramid,  an edgeedge with one O(8)YbV3 trigonal pyramid, edges with two equivalent O(1)YbV3 trigonal pyramids, and edges with two equivalent O(4)YbV3 trigonal pyramids. In the third O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fourth O site, O(7) is bonded to one Yb(1), one V(1), and two equivalent V(2) atoms to form OYbV3 trigonal pyramids that share  a cornercorner with one O(5)Yb2V3 trigonal bipyramid,  a cornercorner with one O(3)YbV3 trigonal pyramid,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(8)YbV3 trigonal pyramid, corners with four equivalent O(1)YbV3 trigonal pyramids,  an edgeedge with one O(5)Yb2V3 trigonal bipyramid,  an edgeedge with one O(7)YbV3 trigonal pyramid, and edges with two equivalent O(8)YbV3 trigonal pyramids. In the fifth O site, O(8) is bonded to one Yb(1), one V(2), and two equivalent V(1) atoms to form OYbV3 trigonal pyramids that share corners with two equivalent O(5)Yb2V3 trigonal bipyramids,  a cornercorner with one O(3)YbV3 trigonal pyramid,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid, corners with two equivalent O(1)YbV3 trigonal pyramids,  an edgeedge with one O(5)Yb2V3 trigonal bipyramid,  an edgeedge with one O(1)YbV3 trigonal pyramid,  an edgeedge with one O(8)YbV3 trigonal pyramid, and edges with two equivalent O(7)YbV3 trigonal pyramids. In the sixth O site, O(1) is bonded to one Yb(1), one V(1), one V(2), and one V(4) atom to form distorted OYbV3 trigonal pyramids that share corners with two equivalent O(3)YbV3 trigonal pyramids, corners with two equivalent O(8)YbV3 trigonal pyramids, corners with three equivalent O(4)YbV3 trigonal pyramids, corners with four equivalent O(7)YbV3 trigonal pyramids, edges with two equivalent O(5)Yb2V3 trigonal bipyramids, and  an edgeedge with one O(8)YbV3 trigonal pyramid. In the seventh O site, O(2) is bonded in a 4-coordinate geometry to one Yb(1), one V(1), one V(2), and one V(3) atom. In the eighth O site, O(3) is bonded to one Yb(1), one V(4), and two equivalent V(3) atoms to form distorted OYbV3 trigonal pyramids that share corners with three equivalent O(5)Yb2V3 trigonal bipyramids,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid,  a cornercorner with one O(8)YbV3 trigonal pyramid, corners with two equivalent O(1)YbV3 trigonal pyramids,  an edgeedge with one O(5)Yb2V3 trigonal bipyramid,  an edgeedge with one O(3)YbV3 trigonal pyramid, and edges with two equivalent O(4)YbV3 trigonal pyramids.
YbV4O8 crystallizes in the monoclinic P2_1/c space group. Yb(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), one O(8), and two equivalent O(5) atoms. The Yb(1)-O(1) bond length is 2.51 Å. The Yb(1)-O(2) bond length is 2.52 Å. The Yb(1)-O(3) bond length is 2.32 Å. The Yb(1)-O(4) bond length is 2.35 Å. The Yb(1)-O(7) bond length is 2.35 Å. The Yb(1)-O(8) bond length is 2.35 Å. There is one shorter (2.54 Å) and one longer (2.55 Å) Yb(1)-O(5) bond length. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), one O(7), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The V(1)-O(1) bond length is 1.98 Å. The V(1)-O(2) bond length is 1.91 Å. The V(1)-O(5) bond length is 2.03 Å. The V(1)-O(7) bond length is 1.94 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) V(1)-O(8) bond length. In the second V site, V(2) is bonded to one O(1), one O(2), one O(6), one O(8), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. The V(2)-O(1) bond length is 2.10 Å. The V(2)-O(2) bond length is 2.08 Å. The V(2)-O(6) bond length is 1.99 Å. The V(2)-O(8) bond length is 2.09 Å. There is one shorter (2.02 Å) and one longer (2.09 Å) V(2)-O(7) bond length. In the third V site, V(3) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. The V(3)-O(2) bond length is 2.02 Å. The V(3)-O(4) bond length is 2.07 Å. The V(3)-O(5) bond length is 2.06 Å. The V(3)-O(6) bond length is 2.06 Å. Both V(3)-O(3) bond lengths are 2.04 Å. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The V(4)-O(1) bond length is 2.02 Å. The V(4)-O(3) bond length is 1.97 Å. The V(4)-O(5) bond length is 2.03 Å. The V(4)-O(6) bond length is 1.85 Å. There is one shorter (1.96 Å) and one longer (2.03 Å) V(4)-O(4) bond length. There are eight inequivalent O sites. In the first O site, O(4) is bonded to one Yb(1), one V(3), and two equivalent V(4) atoms to form distorted OYbV3 trigonal pyramids that share  a cornercorner with one O(5)Yb2V3 trigonal bipyramid,  a cornercorner with one O(3)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid,  a cornercorner with one O(8)YbV3 trigonal pyramid, corners with three equivalent O(1)YbV3 trigonal pyramids, edges with two equivalent O(5)Yb2V3 trigonal bipyramids,  an edgeedge with one O(4)YbV3 trigonal pyramid, and edges with two equivalent O(3)YbV3 trigonal pyramids. In the second O site, O(5) is bonded to two equivalent Yb(1), one V(1), one V(3), and one V(4) atom to form distorted OYb2V3 trigonal bipyramids that share corners with two equivalent O(5)Yb2V3 trigonal bipyramids,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid, corners with two equivalent O(8)YbV3 trigonal pyramids, corners with three equivalent O(3)YbV3 trigonal pyramids,  an edgeedge with one O(3)YbV3 trigonal pyramid,  an edgeedge with one O(7)YbV3 trigonal pyramid,  an edgeedge with one O(8)YbV3 trigonal pyramid, edges with two equivalent O(1)YbV3 trigonal pyramids, and edges with two equivalent O(4)YbV3 trigonal pyramids. In the third O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fourth O site, O(7) is bonded to one Yb(1), one V(1), and two equivalent V(2) atoms to form OYbV3 trigonal pyramids that share  a cornercorner with one O(5)Yb2V3 trigonal bipyramid,  a cornercorner with one O(3)YbV3 trigonal pyramid,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(8)YbV3 trigonal pyramid, corners with four equivalent O(1)YbV3 trigonal pyramids,  an edgeedge with one O(5)Yb2V3 trigonal bipyramid,  an edgeedge with one O(7)YbV3 trigonal pyramid, and edges with two equivalent O(8)YbV3 trigonal pyramids. In the fifth O site, O(8) is bonded to one Yb(1), one V(2), and two equivalent V(1) atoms to form OYbV3 trigonal pyramids that share corners with two equivalent O(5)Yb2V3 trigonal bipyramids,  a cornercorner with one O(3)YbV3 trigonal pyramid,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid, corners with two equivalent O(1)YbV3 trigonal pyramids,  an edgeedge with one O(5)Yb2V3 trigonal bipyramid,  an edgeedge with one O(1)YbV3 trigonal pyramid,  an edgeedge with one O(8)YbV3 trigonal pyramid, and edges with two equivalent O(7)YbV3 trigonal pyramids. In the sixth O site, O(1) is bonded to one Yb(1), one V(1), one V(2), and one V(4) atom to form distorted OYbV3 trigonal pyramids that share corners with two equivalent O(3)YbV3 trigonal pyramids, corners with two equivalent O(8)YbV3 trigonal pyramids, corners with three equivalent O(4)YbV3 trigonal pyramids, corners with four equivalent O(7)YbV3 trigonal pyramids, edges with two equivalent O(5)Yb2V3 trigonal bipyramids, and  an edgeedge with one O(8)YbV3 trigonal pyramid. In the seventh O site, O(2) is bonded in a 4-coordinate geometry to one Yb(1), one V(1), one V(2), and one V(3) atom. In the eighth O site, O(3) is bonded to one Yb(1), one V(4), and two equivalent V(3) atoms to form distorted OYbV3 trigonal pyramids that share corners with three equivalent O(5)Yb2V3 trigonal bipyramids,  a cornercorner with one O(4)YbV3 trigonal pyramid,  a cornercorner with one O(7)YbV3 trigonal pyramid,  a cornercorner with one O(8)YbV3 trigonal pyramid, corners with two equivalent O(1)YbV3 trigonal pyramids,  an edgeedge with one O(5)Yb2V3 trigonal bipyramid,  an edgeedge with one O(3)YbV3 trigonal pyramid, and edges with two equivalent O(4)YbV3 trigonal pyramids.