V3(Bi4O11)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the second V site, V(2) is bonded to two equivalent O(5), two equivalent O(7), and two equivalent O(9) atoms to form corner-sharing VO6 octahedra. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to one O(3), one O(5), one O(7), one O(9), two equivalent O(1), and two equivalent O(11) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(10), one O(4), one O(8), and two equivalent O(2) atoms. 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(3), one O(4), and one O(5) atom. In the fourth Bi site, Bi(4) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(6), one O(7), one O(8), and one O(9) atom. There are eleven inequivalent O sites. In the first O site, O(1) is bonded to one Bi(3), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Bi(3), one Bi(4), and two equivalent Bi(2) atoms. 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 bent 120 degrees geometry to one Bi(2) and one Bi(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one Bi(1), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Bi(4) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one V(1), one V(2), one Bi(1), and one Bi(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(1), one Bi(2), and one Bi(4) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2), one Bi(1), and one Bi(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the eleventh O site, O(11) is bonded to one Bi(3), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.
V3(Bi4O11)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form corner-sharing VO4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The V(1)-O(3) bond length is 1.80 Å. The V(1)-O(6) bond length is 1.70 Å. The V(1)-O(7) bond length is 1.81 Å. The V(1)-O(8) bond length is 1.69 Å. In the second V site, V(2) is bonded to two equivalent O(5), two equivalent O(7), and two equivalent O(9) atoms to form corner-sharing VO6 octahedra. Both V(2)-O(5) bond lengths are 1.92 Å. Both V(2)-O(7) bond lengths are 2.03 Å. Both V(2)-O(9) bond lengths are 1.83 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 8-coordinate geometry to one O(3), one O(5), one O(7), one O(9), two equivalent O(1), and two equivalent O(11) atoms. The Bi(1)-O(3) bond length is 2.73 Å. The Bi(1)-O(5) bond length is 2.45 Å. The Bi(1)-O(7) bond length is 2.59 Å. The Bi(1)-O(9) bond length is 2.42 Å. There is one shorter (2.33 Å) and one longer (2.65 Å) Bi(1)-O(1) bond length. There is one shorter (2.34 Å) and one longer (2.49 Å) Bi(1)-O(11) bond length. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(10), one O(4), one O(8), and two equivalent O(2) atoms. The Bi(2)-O(10) bond length is 2.53 Å. The Bi(2)-O(4) bond length is 2.20 Å. The Bi(2)-O(8) bond length is 2.70 Å. There is one shorter (2.22 Å) and one longer (2.25 Å) Bi(2)-O(2) bond length. 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(3), one O(4), and one O(5) atom. The Bi(3)-O(1) bond length is 2.21 Å. The Bi(3)-O(10) bond length is 2.16 Å. The Bi(3)-O(11) bond length is 2.18 Å. The Bi(3)-O(2) bond length is 2.70 Å. The Bi(3)-O(3) bond length is 2.29 Å. The Bi(3)-O(4) bond length is 2.04 Å. The Bi(3)-O(5) bond length is 2.27 Å. In the fourth Bi site, Bi(4) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(6), one O(7), one O(8), and one O(9) atom. The Bi(4)-O(1) bond length is 2.45 Å. The Bi(4)-O(10) bond length is 2.29 Å. The Bi(4)-O(11) bond length is 2.42 Å. The Bi(4)-O(2) bond length is 2.29 Å. The Bi(4)-O(6) bond length is 2.34 Å. The Bi(4)-O(7) bond length is 2.81 Å. The Bi(4)-O(8) bond length is 2.65 Å. The Bi(4)-O(9) bond length is 2.52 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded to one Bi(3), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Bi(3), one Bi(4), and two equivalent Bi(2) atoms. 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 bent 120 degrees geometry to one Bi(2) and one Bi(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one Bi(1), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Bi(4) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one V(1), one V(2), one Bi(1), and one Bi(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(1), one Bi(2), and one Bi(4) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2), one Bi(1), and one Bi(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the eleventh O site, O(11) is bonded to one Bi(3), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.