V3Bi2 crystallizes in the tetragonal P4/m space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 9-coordinate geometry to two equivalent V(1), two equivalent V(5), one Bi(1), and four equivalent Bi(2) atoms. In the second V site, V(2) is bonded in a 9-coordinate geometry to two equivalent V(2), two equivalent V(4), one Bi(2), and four equivalent Bi(1) atoms. In the third V site, V(3) is bonded to two equivalent Bi(1) and four equivalent Bi(2) atoms to form VBi6 octahedra that share corners with two equivalent V(4)V8Bi4 cuboctahedra, corners with four equivalent V(5)V8Bi4 cuboctahedra, and edges with two equivalent V(3)Bi6 octahedra. In the fourth V site, V(4) is bonded to eight equivalent V(2) and four equivalent Bi(1) atoms to form VV8Bi4 cuboctahedra that share corners with four equivalent V(3)Bi6 octahedra and faces with two equivalent V(4)V8Bi4 cuboctahedra. The corner-sharing octahedral tilt angles are 51°. In the fifth V site, V(5) is bonded to eight equivalent V(1) and four equivalent Bi(2) atoms to form VV8Bi4 cuboctahedra that share corners with eight equivalent V(3)Bi6 octahedra and faces with two equivalent V(5)V8Bi4 cuboctahedra. The corner-sharing octahedral tilt angles are 52°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one V(1), one V(3), one V(4), and four equivalent V(2) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one V(2), one V(5), two equivalent V(3), and four equivalent V(1) atoms.
V3Bi2 crystallizes in the tetragonal P4/m space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 9-coordinate geometry to two equivalent V(1), two equivalent V(5), one Bi(1), and four equivalent Bi(2) atoms. Both V(1)-V(1) bond lengths are 2.47 Å. Both V(1)-V(5) bond lengths are 2.66 Å. The V(1)-Bi(1) bond length is 2.84 Å. There are two shorter (2.93 Å) and two longer (3.00 Å) V(1)-Bi(2) bond lengths. In the second V site, V(2) is bonded in a 9-coordinate geometry to two equivalent V(2), two equivalent V(4), one Bi(2), and four equivalent Bi(1) atoms. Both V(2)-V(2) bond lengths are 2.51 Å. Both V(2)-V(4) bond lengths are 2.68 Å. The V(2)-Bi(2) bond length is 3.01 Å. There are two shorter (2.85 Å) and two longer (2.86 Å) V(2)-Bi(1) bond lengths. In the third V site, V(3) is bonded to two equivalent Bi(1) and four equivalent Bi(2) atoms to form VBi6 octahedra that share corners with two equivalent V(4)V8Bi4 cuboctahedra, corners with four equivalent V(5)V8Bi4 cuboctahedra, and edges with two equivalent V(3)Bi6 octahedra. Both V(3)-Bi(1) bond lengths are 2.75 Å. All V(3)-Bi(2) bond lengths are 3.03 Å. In the fourth V site, V(4) is bonded to eight equivalent V(2) and four equivalent Bi(1) atoms to form VV8Bi4 cuboctahedra that share corners with four equivalent V(3)Bi6 octahedra and faces with two equivalent V(4)V8Bi4 cuboctahedra. The corner-sharing octahedral tilt angles are 51°. All V(4)-Bi(1) bond lengths are 2.85 Å. In the fifth V site, V(5) is bonded to eight equivalent V(1) and four equivalent Bi(2) atoms to form VV8Bi4 cuboctahedra that share corners with eight equivalent V(3)Bi6 octahedra and faces with two equivalent V(5)V8Bi4 cuboctahedra. The corner-sharing octahedral tilt angles are 52°. All V(5)-Bi(2) bond lengths are 3.03 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one V(1), one V(3), one V(4), and four equivalent V(2) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one V(2), one V(5), two equivalent V(3), and four equivalent V(1) atoms.