Bi4V2O11 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a distorted tetrahedral geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(6), one O(8), and one O(9) atom. In the third V site, V(3) is bonded in a tetrahedral geometry to two equivalent O(11) and two equivalent O(9) atoms. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to one O(10), one O(2), one O(5), and one O(7) atom. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(5), one O(6), and one O(7) atom. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(11), one O(6), one O(8), two equivalent O(10), and two equivalent O(7) atoms. There are eleven inequivalent O sites. In the first O site, O(9) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the second O site, O(10) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(11) is bonded in a distorted single-bond geometry to one V(3), one Bi(3), and one Bi(4) atom. In the fourth O site, O(1) is bonded in a distorted single-bond geometry to one V(1), one Bi(1), and one Bi(3) atom. In the fifth O site, O(2) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh O site, O(4) is bonded in a distorted single-bond geometry to one V(2) and one Bi(1) atom. In the eighth O site, O(5) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the ninth O site, O(6) is bonded in a single-bond geometry to one V(2), one Bi(1), one Bi(3), and one Bi(4) atom. In the tenth O site, O(7) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the eleventh O site, O(8) is bonded in a distorted single-bond geometry to one V(2) and one Bi(4) atom.
Bi4V2O11 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a distorted tetrahedral geometry to two equivalent O(1) and two equivalent O(3) atoms. Both V(1)-O(1) bond lengths are 1.77 Å. Both V(1)-O(3) bond lengths are 1.77 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(6), one O(8), and one O(9) atom. The V(2)-O(3) bond length is 2.06 Å. The V(2)-O(4) bond length is 1.74 Å. The V(2)-O(6) bond length is 1.71 Å. The V(2)-O(8) bond length is 1.74 Å. The V(2)-O(9) bond length is 2.09 Å. In the third V site, V(3) is bonded in a tetrahedral geometry to two equivalent O(11) and two equivalent O(9) atoms. Both V(3)-O(11) bond lengths are 1.76 Å. Both V(3)-O(9) bond lengths are 1.77 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms. The Bi(1)-O(1) bond length is 2.35 Å. The Bi(1)-O(4) bond length is 2.47 Å. The Bi(1)-O(6) bond length is 2.84 Å. There is one shorter (2.21 Å) and one longer (2.62 Å) Bi(1)-O(2) bond length. There is one shorter (2.31 Å) and one longer (2.53 Å) Bi(1)-O(5) bond length. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to one O(10), one O(2), one O(5), and one O(7) atom. The Bi(2)-O(10) bond length is 2.33 Å. The Bi(2)-O(2) bond length is 2.29 Å. The Bi(2)-O(5) bond length is 2.35 Å. The Bi(2)-O(7) bond length is 2.29 Å. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(5), one O(6), and one O(7) atom. The Bi(3)-O(1) bond length is 2.58 Å. The Bi(3)-O(10) bond length is 2.29 Å. The Bi(3)-O(11) bond length is 2.61 Å. The Bi(3)-O(2) bond length is 2.33 Å. The Bi(3)-O(5) bond length is 2.29 Å. The Bi(3)-O(6) bond length is 2.81 Å. The Bi(3)-O(7) bond length is 2.35 Å. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(11), one O(6), one O(8), two equivalent O(10), and two equivalent O(7) atoms. The Bi(4)-O(11) bond length is 2.37 Å. The Bi(4)-O(6) bond length is 2.82 Å. The Bi(4)-O(8) bond length is 2.46 Å. There is one shorter (2.33 Å) and one longer (2.50 Å) Bi(4)-O(10) bond length. There is one shorter (2.22 Å) and one longer (2.55 Å) Bi(4)-O(7) bond length. There are eleven inequivalent O sites. In the first O site, O(9) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the second O site, O(10) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(11) is bonded in a distorted single-bond geometry to one V(3), one Bi(3), and one Bi(4) atom. In the fourth O site, O(1) is bonded in a distorted single-bond geometry to one V(1), one Bi(1), and one Bi(3) atom. In the fifth O site, O(2) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh O site, O(4) is bonded in a distorted single-bond geometry to one V(2) and one Bi(1) atom. In the eighth O site, O(5) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the ninth O site, O(6) is bonded in a single-bond geometry to one V(2), one Bi(1), one Bi(3), and one Bi(4) atom. In the tenth O site, O(7) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the eleventh O site, O(8) is bonded in a distorted single-bond geometry to one V(2) and one Bi(4) atom.