Bi4V2O11 crystallizes in the monoclinic Pc space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(3), one O(6), one O(7), and one O(8) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent Bi(1)O6 pentagonal pyramids and corners with two equivalent V(2)O4 tetrahedra. In the second V site, V(2) is bonded to one O(10), one O(7), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(1)O6 pentagonal pyramid and corners with two equivalent V(1)O5 trigonal bipyramids. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share  a cornercorner with one V(2)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(6) atom. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. In the fourth Bi site, Bi(4) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(2), and one O(5) atom. There are eleven inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1), one Bi(2), one Bi(3), and one Bi(4) atom to form edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1), one Bi(2), one Bi(3), and one Bi(4) atom to form edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Bi(1), and one Bi(3) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(1), one Bi(2), and one Bi(3) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the seventh O site, O(7) is bonded in a distorted linear geometry to one V(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2) and one Bi(1) atom. In the tenth O site, O(10) is bonded in a 1-coordinate geometry to one V(2), one Bi(2), and one Bi(4) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one V(1) and one Bi(1) atom.
Bi4V2O11 crystallizes in the monoclinic Pc space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(3), one O(6), one O(7), and one O(8) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent Bi(1)O6 pentagonal pyramids and corners with two equivalent V(2)O4 tetrahedra. The V(1)-O(11) bond length is 1.67 Å. The V(1)-O(3) bond length is 1.77 Å. The V(1)-O(6) bond length is 1.74 Å. The V(1)-O(7) bond length is 2.33 Å. The V(1)-O(8) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(10), one O(7), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(1)O6 pentagonal pyramid and corners with two equivalent V(1)O5 trigonal bipyramids. The V(2)-O(10) bond length is 1.75 Å. The V(2)-O(7) bond length is 1.71 Å. The V(2)-O(8) bond length is 1.82 Å. The V(2)-O(9) bond length is 1.74 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share  a cornercorner with one V(2)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The Bi(1)-O(1) bond length is 2.32 Å. The Bi(1)-O(11) bond length is 2.53 Å. The Bi(1)-O(2) bond length is 2.48 Å. The Bi(1)-O(3) bond length is 2.23 Å. The Bi(1)-O(4) bond length is 2.34 Å. The Bi(1)-O(9) bond length is 2.38 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(6) atom. The Bi(2)-O(1) bond length is 2.37 Å. The Bi(2)-O(10) bond length is 2.76 Å. The Bi(2)-O(2) bond length is 2.31 Å. The Bi(2)-O(4) bond length is 2.18 Å. The Bi(2)-O(5) bond length is 2.46 Å. The Bi(2)-O(6) bond length is 2.50 Å. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. The Bi(3)-O(1) bond length is 2.27 Å. The Bi(3)-O(2) bond length is 2.50 Å. The Bi(3)-O(3) bond length is 2.70 Å. The Bi(3)-O(4) bond length is 2.25 Å. The Bi(3)-O(5) bond length is 2.24 Å. In the fourth Bi site, Bi(4) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(2), and one O(5) atom. The Bi(4)-O(1) bond length is 2.44 Å. The Bi(4)-O(10) bond length is 2.36 Å. The Bi(4)-O(2) bond length is 2.18 Å. The Bi(4)-O(5) bond length is 2.16 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1), one Bi(2), one Bi(3), and one Bi(4) atom to form edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1), one Bi(2), one Bi(3), and one Bi(4) atom to form edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one Bi(1), and one Bi(3) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(1), one Bi(2), and one Bi(3) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(1) and one Bi(2) atom. In the seventh O site, O(7) is bonded in a distorted linear geometry to one V(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2) and one Bi(1) atom. In the tenth O site, O(10) is bonded in a 1-coordinate geometry to one V(2), one Bi(2), and one Bi(4) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one V(1) and one Bi(1) atom.