Mg6WBi crystallizes in the orthorhombic Amm2 space group. There are four inequivalent Mg sites. In the first Mg site, Mg(1) is bonded in a 4-coordinate geometry to two equivalent Mg(4), two equivalent W(1), and two equivalent Bi(1) atoms. In the second Mg site, Mg(2) is bonded in a distorted linear geometry to two equivalent Mg(4) and two equivalent W(1) atoms. In the third Mg site, Mg(3) is bonded in a 4-coordinate geometry to two equivalent Mg(4), two equivalent W(1), and two equivalent Bi(1) atoms. In the fourth Mg site, Mg(4) is bonded to two equivalent Mg(2), four equivalent Mg(1), four equivalent Mg(3), and two equivalent Bi(1) atoms to form distorted MgMg10Bi2 cuboctahedra that share corners with four equivalent Bi(1)Mg10W2 cuboctahedra, corners with six equivalent Mg(4)Mg10Bi2 cuboctahedra, edges with two equivalent Bi(1)Mg10W2 cuboctahedra, faces with two equivalent Mg(4)Mg10Bi2 cuboctahedra, faces with two equivalent Bi(1)Mg10W2 cuboctahedra, and faces with six equivalent W(1)Mg10Bi2 cuboctahedra. W(1) is bonded to two equivalent Mg(2), four equivalent Mg(1), four equivalent Mg(3), and two equivalent Bi(1) atoms to form WMg10Bi2 cuboctahedra that share corners with six equivalent W(1)Mg10Bi2 cuboctahedra, edges with four equivalent Bi(1)Mg10W2 cuboctahedra, faces with two equivalent W(1)Mg10Bi2 cuboctahedra, faces with two equivalent Bi(1)Mg10W2 cuboctahedra, and faces with six equivalent Mg(4)Mg10Bi2 cuboctahedra. Bi(1) is bonded to two equivalent Mg(4), four equivalent Mg(1), four equivalent Mg(3), and two equivalent W(1) atoms to form BiMg10W2 cuboctahedra that share corners with four equivalent Mg(4)Mg10Bi2 cuboctahedra, corners with six equivalent Bi(1)Mg10W2 cuboctahedra, edges with two equivalent Mg(4)Mg10Bi2 cuboctahedra, edges with four equivalent W(1)Mg10Bi2 cuboctahedra, faces with two equivalent Mg(4)Mg10Bi2 cuboctahedra, faces with two equivalent W(1)Mg10Bi2 cuboctahedra, and faces with two equivalent Bi(1)Mg10W2 cuboctahedra.
Mg6WBi crystallizes in the orthorhombic Amm2 space group. There are four inequivalent Mg sites. In the first Mg site, Mg(1) is bonded in a 4-coordinate geometry to two equivalent Mg(4), two equivalent W(1), and two equivalent Bi(1) atoms. Both Mg(1)-Mg(4) bond lengths are 3.10 Å. There is one shorter (3.00 Å) and one longer (3.17 Å) Mg(1)-W(1) bond length. Both Mg(1)-Bi(1) bond lengths are 3.18 Å. In the second Mg site, Mg(2) is bonded in a distorted linear geometry to two equivalent Mg(4) and two equivalent W(1) atoms. Both Mg(2)-Mg(4) bond lengths are 3.12 Å. Both Mg(2)-W(1) bond lengths are 3.12 Å. In the third Mg site, Mg(3) is bonded in a 4-coordinate geometry to two equivalent Mg(4), two equivalent W(1), and two equivalent Bi(1) atoms. There is one shorter (3.07 Å) and one longer (3.10 Å) Mg(3)-Mg(4) bond length. Both Mg(3)-W(1) bond lengths are 3.06 Å. There is one shorter (2.96 Å) and one longer (3.20 Å) Mg(3)-Bi(1) bond length. In the fourth Mg site, Mg(4) is bonded to two equivalent Mg(2), four equivalent Mg(1), four equivalent Mg(3), and two equivalent Bi(1) atoms to form distorted MgMg10Bi2 cuboctahedra that share corners with four equivalent Bi(1)Mg10W2 cuboctahedra, corners with six equivalent Mg(4)Mg10Bi2 cuboctahedra, edges with two equivalent Bi(1)Mg10W2 cuboctahedra, faces with two equivalent Mg(4)Mg10Bi2 cuboctahedra, faces with two equivalent Bi(1)Mg10W2 cuboctahedra, and faces with six equivalent W(1)Mg10Bi2 cuboctahedra. Both Mg(4)-Bi(1) bond lengths are 3.12 Å. W(1) is bonded to two equivalent Mg(2), four equivalent Mg(1), four equivalent Mg(3), and two equivalent Bi(1) atoms to form WMg10Bi2 cuboctahedra that share corners with six equivalent W(1)Mg10Bi2 cuboctahedra, edges with four equivalent Bi(1)Mg10W2 cuboctahedra, faces with two equivalent W(1)Mg10Bi2 cuboctahedra, faces with two equivalent Bi(1)Mg10W2 cuboctahedra, and faces with six equivalent Mg(4)Mg10Bi2 cuboctahedra. Both W(1)-Bi(1) bond lengths are 3.10 Å. Bi(1) is bonded to two equivalent Mg(4), four equivalent Mg(1), four equivalent Mg(3), and two equivalent W(1) atoms to form BiMg10W2 cuboctahedra that share corners with four equivalent Mg(4)Mg10Bi2 cuboctahedra, corners with six equivalent Bi(1)Mg10W2 cuboctahedra, edges with two equivalent Mg(4)Mg10Bi2 cuboctahedra, edges with four equivalent W(1)Mg10Bi2 cuboctahedra, faces with two equivalent Mg(4)Mg10Bi2 cuboctahedra, faces with two equivalent W(1)Mg10Bi2 cuboctahedra, and faces with two equivalent Bi(1)Mg10W2 cuboctahedra.