V4Bi3 crystallizes in the orthorhombic Cmcm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 12-coordinate geometry to four equivalent V(4), four equivalent V(5), two equivalent Bi(3), and two equivalent Bi(4) atoms. In the second V site, V(2) is bonded to two equivalent Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form edge-sharing VBi6 octahedra. In the third V site, V(3) is bonded in a 6-coordinate geometry to one V(4), one Bi(1), one Bi(3), two equivalent Bi(2), and two equivalent Bi(4) atoms. In the fourth V site, V(4) is bonded in a 10-coordinate geometry to one V(3), two equivalent V(1), two equivalent V(5), one Bi(1), two equivalent Bi(3), and two equivalent Bi(4) atoms. In the fifth V site, V(5) is bonded in a 9-coordinate geometry to two equivalent V(1), two equivalent V(4), two equivalent Bi(3), and three equivalent Bi(4) atoms. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent V(2), two equivalent V(3), and two equivalent V(4) atoms to form distorted corner-sharing BiV6 octahedra. The corner-sharing octahedral tilt angles are 85°. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent V(2) and four equivalent V(3) atoms. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one V(1), one V(2), one V(3), two equivalent V(4), and two equivalent V(5) atoms. In the fourth Bi site, Bi(4) is bonded in a 8-coordinate geometry to one V(1), two equivalent V(3), two equivalent V(4), and three equivalent V(5) atoms.
V4Bi3 crystallizes in the orthorhombic Cmcm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 12-coordinate geometry to four equivalent V(4), four equivalent V(5), two equivalent Bi(3), and two equivalent Bi(4) atoms. All V(1)-V(4) bond lengths are 2.92 Å. All V(1)-V(5) bond lengths are 2.56 Å. Both V(1)-Bi(3) bond lengths are 2.76 Å. Both V(1)-Bi(4) bond lengths are 2.94 Å. In the second V site, V(2) is bonded to two equivalent Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form edge-sharing VBi6 octahedra. Both V(2)-Bi(1) bond lengths are 2.86 Å. Both V(2)-Bi(2) bond lengths are 2.82 Å. Both V(2)-Bi(3) bond lengths are 2.72 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one V(4), one Bi(1), one Bi(3), two equivalent Bi(2), and two equivalent Bi(4) atoms. The V(3)-V(4) bond length is 2.77 Å. The V(3)-Bi(1) bond length is 2.86 Å. The V(3)-Bi(3) bond length is 2.89 Å. Both V(3)-Bi(2) bond lengths are 2.80 Å. Both V(3)-Bi(4) bond lengths are 2.93 Å. In the fourth V site, V(4) is bonded in a 10-coordinate geometry to one V(3), two equivalent V(1), two equivalent V(5), one Bi(1), two equivalent Bi(3), and two equivalent Bi(4) atoms. There is one shorter (2.42 Å) and one longer (2.53 Å) V(4)-V(5) bond length. The V(4)-Bi(1) bond length is 3.17 Å. Both V(4)-Bi(3) bond lengths are 2.91 Å. Both V(4)-Bi(4) bond lengths are 2.95 Å. In the fifth V site, V(5) is bonded in a 9-coordinate geometry to two equivalent V(1), two equivalent V(4), two equivalent Bi(3), and three equivalent Bi(4) atoms. Both V(5)-Bi(3) bond lengths are 2.94 Å. There are two shorter (2.99 Å) and one longer (3.18 Å) V(5)-Bi(4) bond length. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent V(2), two equivalent V(3), and two equivalent V(4) atoms to form distorted corner-sharing BiV6 octahedra. The corner-sharing octahedral tilt angles are 85°. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent V(2) and four equivalent V(3) atoms. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one V(1), one V(2), one V(3), two equivalent V(4), and two equivalent V(5) atoms. In the fourth Bi site, Bi(4) is bonded in a 8-coordinate geometry to one V(1), two equivalent V(3), two equivalent V(4), and three equivalent V(5) atoms.