YbV4O8 crystallizes in the triclinic P-1 space group. Yb(1) is bonded to one O(5), one O(7), two equivalent O(1), and two equivalent O(4) atoms to form distorted YbO6 pentagonal pyramids that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(4)O5 trigonal bipyramids,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Yb(1)O6 pentagonal pyramids, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-55°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Yb(1)O6 pentagonal pyramid, corners with two equivalent V(4)O5 trigonal bipyramids, and  an edgeedge with one Yb(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 48-71°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(6), one O(8), and two equivalent O(7) atoms. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one O(8), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with two equivalent Yb(1)O6 pentagonal pyramids, corners with two equivalent V(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Yb(1)O6 pentagonal pyramid, and edges with two equivalent V(4)O5 trigonal bipyramids. In the fourth V site, V(4) is bonded to one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Yb(1)O6 pentagonal pyramids, corners with two equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Yb(1) and one V(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to two equivalent Yb(1), one V(1), and one V(3) atom to form distorted edge-sharing OYb2V2 trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Yb(1), one V(4), and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(4) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Yb(1), one V(1), one V(4), and two equivalent V(2) atoms. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom.
YbV4O8 crystallizes in the triclinic P-1 space group. Yb(1) is bonded to one O(5), one O(7), two equivalent O(1), and two equivalent O(4) atoms to form distorted YbO6 pentagonal pyramids that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(4)O5 trigonal bipyramids,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Yb(1)O6 pentagonal pyramids, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-55°. The Yb(1)-O(5) bond length is 2.26 Å. The Yb(1)-O(7) bond length is 2.49 Å. Both Yb(1)-O(1) bond lengths are 2.34 Å. There is one shorter (2.47 Å) and one longer (2.50 Å) Yb(1)-O(4) bond length. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Yb(1)O6 pentagonal pyramid, corners with two equivalent V(4)O5 trigonal bipyramids, and  an edgeedge with one Yb(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 48-71°. The V(1)-O(2) bond length is 1.74 Å. The V(1)-O(3) bond length is 1.87 Å. The V(1)-O(4) bond length is 1.81 Å. The V(1)-O(7) bond length is 1.95 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(6), one O(8), and two equivalent O(7) atoms. The V(2)-O(1) bond length is 1.71 Å. The V(2)-O(3) bond length is 1.95 Å. The V(2)-O(6) bond length is 1.96 Å. The V(2)-O(8) bond length is 1.98 Å. There is one shorter (2.25 Å) and one longer (2.41 Å) V(2)-O(7) bond length. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one O(8), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with two equivalent Yb(1)O6 pentagonal pyramids, corners with two equivalent V(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Yb(1)O6 pentagonal pyramid, and edges with two equivalent V(4)O5 trigonal bipyramids. The V(3)-O(3) bond length is 1.99 Å. The V(3)-O(4) bond length is 2.15 Å. The V(3)-O(6) bond length is 2.18 Å. The V(3)-O(8) bond length is 2.03 Å. There is one shorter (1.99 Å) and one longer (2.13 Å) V(3)-O(5) bond length. In the fourth V site, V(4) is bonded to one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Yb(1)O6 pentagonal pyramids, corners with two equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. The V(4)-O(2) bond length is 1.93 Å. The V(4)-O(5) bond length is 2.07 Å. The V(4)-O(6) bond length is 1.88 Å. The V(4)-O(7) bond length is 2.19 Å. The V(4)-O(8) bond length is 1.87 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Yb(1) and one V(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to two equivalent Yb(1), one V(1), and one V(3) atom to form distorted edge-sharing OYb2V2 trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Yb(1), one V(4), and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(4) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Yb(1), one V(1), one V(4), and two equivalent V(2) atoms. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom.