Mg14VBi crystallizes in the hexagonal P-6m2 space group. There are four inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Mg(4), four equivalent Mg(1), four equivalent Mg(3), and two equivalent V(1) atoms to form MgMg10V2 cuboctahedra that share corners with four equivalent Bi(1)Mg12 cuboctahedra, corners with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with two equivalent V(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Mg10V2 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with eight equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with four equivalent Mg(1)Mg10V2 cuboctahedra, and faces with ten equivalent Mg(3)Mg10VBi cuboctahedra. In the second Mg site, Mg(2) is bonded in a distorted linear geometry to two equivalent Mg(4), four equivalent Mg(3), and two equivalent Bi(1) atoms. In the third Mg site, Mg(3) is bonded to two equivalent Mg(1), two equivalent Mg(2), two equivalent Mg(4), four equivalent Mg(3), one V(1), and one Bi(1) atom to form distorted MgMg10VBi cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra, corners with fourteen equivalent Mg(3)Mg10VBi cuboctahedra, edges with two equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent V(1)Mg12 cuboctahedra, edges with two equivalent Bi(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Mg10V2 cuboctahedra, edges with four equivalent Mg(3)Mg10VBi cuboctahedra,  a faceface with one V(1)Mg12 cuboctahedra,  a faceface with one Bi(1)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with five equivalent Mg(1)Mg10V2 cuboctahedra, and faces with six equivalent Mg(3)Mg10VBi cuboctahedra. In the fourth Mg site, Mg(4) is bonded to three equivalent Mg(1), three equivalent Mg(2), and six equivalent Mg(3) atoms to form MgMg12 cuboctahedra that share corners with six equivalent Mg(4)Mg12 cuboctahedra, corners with twelve equivalent Mg(3)Mg10VBi cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with six equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with three equivalent Mg(1)Mg10V2 cuboctahedra, faces with three equivalent V(1)Mg12 cuboctahedra, faces with three equivalent Bi(1)Mg12 cuboctahedra, and faces with six equivalent Mg(3)Mg10VBi cuboctahedra. V(1) is bonded to six equivalent Mg(1) and six equivalent Mg(3) atoms to form VMg12 cuboctahedra that share corners with six equivalent V(1)Mg12 cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with twelve equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent Bi(1)Mg12 cuboctahedra, faces with six equivalent Mg(1)Mg10V2 cuboctahedra, faces with six equivalent Mg(3)Mg10VBi cuboctahedra, and faces with six equivalent Mg(4)Mg12 cuboctahedra. Bi(1) is bonded to six equivalent Mg(2) and six equivalent Mg(3) atoms to form BiMg12 cuboctahedra that share corners with six equivalent Bi(1)Mg12 cuboctahedra, corners with twelve equivalent Mg(1)Mg10V2 cuboctahedra, edges with twelve equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with six equivalent Mg(3)Mg10VBi cuboctahedra, and faces with six equivalent Mg(4)Mg12 cuboctahedra.
Mg14VBi crystallizes in the hexagonal P-6m2 space group. There are four inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Mg(4), four equivalent Mg(1), four equivalent Mg(3), and two equivalent V(1) atoms to form MgMg10V2 cuboctahedra that share corners with four equivalent Bi(1)Mg12 cuboctahedra, corners with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with two equivalent V(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Mg10V2 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with eight equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with four equivalent Mg(1)Mg10V2 cuboctahedra, and faces with ten equivalent Mg(3)Mg10VBi cuboctahedra. Both Mg(1)-Mg(4) bond lengths are 3.18 Å. There are two shorter (3.16 Å) and two longer (3.17 Å) Mg(1)-Mg(1) bond lengths. All Mg(1)-Mg(3) bond lengths are 3.10 Å. Both Mg(1)-V(1) bond lengths are 3.16 Å. In the second Mg site, Mg(2) is bonded in a distorted linear geometry to two equivalent Mg(4), four equivalent Mg(3), and two equivalent Bi(1) atoms. Both Mg(2)-Mg(4) bond lengths are 3.18 Å. All Mg(2)-Mg(3) bond lengths are 3.27 Å. Both Mg(2)-Bi(1) bond lengths are 3.16 Å. In the third Mg site, Mg(3) is bonded to two equivalent Mg(1), two equivalent Mg(2), two equivalent Mg(4), four equivalent Mg(3), one V(1), and one Bi(1) atom to form distorted MgMg10VBi cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra, corners with fourteen equivalent Mg(3)Mg10VBi cuboctahedra, edges with two equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent V(1)Mg12 cuboctahedra, edges with two equivalent Bi(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Mg10V2 cuboctahedra, edges with four equivalent Mg(3)Mg10VBi cuboctahedra,  a faceface with one V(1)Mg12 cuboctahedra,  a faceface with one Bi(1)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with five equivalent Mg(1)Mg10V2 cuboctahedra, and faces with six equivalent Mg(3)Mg10VBi cuboctahedra. Both Mg(3)-Mg(4) bond lengths are 3.17 Å. There are two shorter (3.15 Å) and two longer (3.18 Å) Mg(3)-Mg(3) bond lengths. The Mg(3)-V(1) bond length is 3.10 Å. The Mg(3)-Bi(1) bond length is 3.26 Å. In the fourth Mg site, Mg(4) is bonded to three equivalent Mg(1), three equivalent Mg(2), and six equivalent Mg(3) atoms to form MgMg12 cuboctahedra that share corners with six equivalent Mg(4)Mg12 cuboctahedra, corners with twelve equivalent Mg(3)Mg10VBi cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with six equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with three equivalent Mg(1)Mg10V2 cuboctahedra, faces with three equivalent V(1)Mg12 cuboctahedra, faces with three equivalent Bi(1)Mg12 cuboctahedra, and faces with six equivalent Mg(3)Mg10VBi cuboctahedra. V(1) is bonded to six equivalent Mg(1) and six equivalent Mg(3) atoms to form VMg12 cuboctahedra that share corners with six equivalent V(1)Mg12 cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with twelve equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent Bi(1)Mg12 cuboctahedra, faces with six equivalent Mg(1)Mg10V2 cuboctahedra, faces with six equivalent Mg(3)Mg10VBi cuboctahedra, and faces with six equivalent Mg(4)Mg12 cuboctahedra. Bi(1) is bonded to six equivalent Mg(2) and six equivalent Mg(3) atoms to form BiMg12 cuboctahedra that share corners with six equivalent Bi(1)Mg12 cuboctahedra, corners with twelve equivalent Mg(1)Mg10V2 cuboctahedra, edges with twelve equivalent Mg(3)Mg10VBi cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with six equivalent Mg(3)Mg10VBi cuboctahedra, and faces with six equivalent Mg(4)Mg12 cuboctahedra.