RbMg14Bi crystallizes in the hexagonal P-6m2 space group. Rb(1) is bonded to six equivalent Mg(1) and six Mg(3,3) atoms to form RbMg12 cuboctahedra that share corners with six equivalent Rb(1)Mg12 cuboctahedra; corners with twelve equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with six equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with twelve Mg(3,3)RbMg10Bi cuboctahedra; faces with two equivalent Bi(1)Mg12 cuboctahedra; faces with six equivalent Mg(4)Mg12 cuboctahedra; faces with six equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. There are five inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Rb(1), two equivalent Mg(4), four equivalent Mg(1), and four equivalent Mg(3) atoms to form distorted MgRb2Mg10 cuboctahedra that share corners with four equivalent Bi(1)Mg12 cuboctahedra; corners with six equivalent Mg(1)Rb2Mg10 cuboctahedra; corners with eight equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with two equivalent Rb(1)Mg12 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with four equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with eight equivalent Mg(3)RbMg10Bi cuboctahedra; faces with two equivalent Rb(1)Mg12 cuboctahedra; faces with two equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with four equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with ten Mg(3,3)RbMg10Bi cuboctahedra. In the second Mg site, Mg(2) is bonded to two equivalent Mg(4), four equivalent Mg(2), four equivalent Mg(3), and two equivalent Bi(1) atoms to form distorted MgMg10Bi2 cuboctahedra that share corners with four equivalent Rb(1)Mg12 cuboctahedra; corners with six equivalent Mg(2)Mg10Bi2 cuboctahedra; corners with eight equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with two equivalent Bi(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with eight equivalent Mg(3)RbMg10Bi cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with two equivalent Mg(1)Rb2Mg10 cuboctahedra; faces with two equivalent Bi(1)Mg12 cuboctahedra; faces with four equivalent Mg(2)Mg10Bi2 cuboctahedra; and faces with ten Mg(3,3)RbMg10Bi cuboctahedra. In the third Mg site, Mg(3) is bonded to one Rb(1); two equivalent Mg(1); two equivalent Mg(2); two equivalent Mg(4); four Mg(3,3); and one Bi(1) atom to form distorted MgRbMg10Bi cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra; corners with fourteen Mg(3,3)RbMg10Bi cuboctahedra; edges with two equivalent Rb(1)Mg12 cuboctahedra; edges with two equivalent Mg(4)Mg12 cuboctahedra; edges with two equivalent Bi(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with four equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with four Mg(3,3)RbMg10Bi cuboctahedra;  a faceface with one Rb(1)Mg12 cuboctahedra;  a faceface with one Bi(1)Mg12 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with five equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with five equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. In the fourth Mg site, Mg(3) is bonded to one Rb(1), two equivalent Mg(1), two equivalent Mg(2), two equivalent Mg(4), four equivalent Mg(3), and one Bi(1) atom to form distorted MgRbMg10Bi cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra; corners with fourteen Mg(3,3)RbMg10Bi cuboctahedra; edges with two equivalent Rb(1)Mg12 cuboctahedra; edges with two equivalent Mg(4)Mg12 cuboctahedra; edges with two equivalent Bi(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with four equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with four equivalent Mg(3)RbMg10Bi cuboctahedra;  a faceface with one Rb(1)Mg12 cuboctahedra;  a faceface with one Bi(1)Mg12 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with five equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with five equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. In the fifth Mg site, Mg(4) is bonded to three equivalent Mg(1); three equivalent Mg(2); and six Mg(3,3) atoms to form MgMg12 cuboctahedra that share corners with six equivalent Mg(4)Mg12 cuboctahedra; corners with twelve Mg(3,3)RbMg10Bi cuboctahedra; edges with six equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with six equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with six Mg(3,3)RbMg10Bi cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with three equivalent Rb(1)Mg12 cuboctahedra; faces with three equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with three equivalent Mg(1)Rb2Mg10 cuboctahedra; faces with three equivalent Bi(1)Mg12 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. Bi(1) is bonded to six equivalent Mg(2) and six Mg(3,3) atoms to form BiMg12 cuboctahedra that share corners with six equivalent Bi(1)Mg12 cuboctahedra; corners with twelve equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with six equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with twelve Mg(3,3)RbMg10Bi cuboctahedra; faces with two equivalent Rb(1)Mg12 cuboctahedra; faces with six equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with six equivalent Mg(4)Mg12 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra.
RbMg14Bi crystallizes in the hexagonal P-6m2 space group. Rb(1) is bonded to six equivalent Mg(1) and six Mg(3,3) atoms to form RbMg12 cuboctahedra that share corners with six equivalent Rb(1)Mg12 cuboctahedra; corners with twelve equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with six equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with twelve Mg(3,3)RbMg10Bi cuboctahedra; faces with two equivalent Bi(1)Mg12 cuboctahedra; faces with six equivalent Mg(4)Mg12 cuboctahedra; faces with six equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. All Rb(1)-Mg(1) bond lengths are 3.29 Å. All Rb(1)-Mg(3,3) bond lengths are 3.42 Å. There are five inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Rb(1), two equivalent Mg(4), four equivalent Mg(1), and four equivalent Mg(3) atoms to form distorted MgRb2Mg10 cuboctahedra that share corners with four equivalent Bi(1)Mg12 cuboctahedra; corners with six equivalent Mg(1)Rb2Mg10 cuboctahedra; corners with eight equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with two equivalent Rb(1)Mg12 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with four equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with eight equivalent Mg(3)RbMg10Bi cuboctahedra; faces with two equivalent Rb(1)Mg12 cuboctahedra; faces with two equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with four equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with ten Mg(3,3)RbMg10Bi cuboctahedra. Both Mg(1)-Mg(4) bond lengths are 3.30 Å. There are two shorter (3.24 Å) and two longer (3.33 Å) Mg(1)-Mg(1) bond lengths. All Mg(1)-Mg(3) bond lengths are 3.36 Å. In the second Mg site, Mg(2) is bonded to two equivalent Mg(4), four equivalent Mg(2), four equivalent Mg(3), and two equivalent Bi(1) atoms to form distorted MgMg10Bi2 cuboctahedra that share corners with four equivalent Rb(1)Mg12 cuboctahedra; corners with six equivalent Mg(2)Mg10Bi2 cuboctahedra; corners with eight equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with two equivalent Bi(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with eight equivalent Mg(3)RbMg10Bi cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with two equivalent Mg(1)Rb2Mg10 cuboctahedra; faces with two equivalent Bi(1)Mg12 cuboctahedra; faces with four equivalent Mg(2)Mg10Bi2 cuboctahedra; and faces with ten Mg(3,3)RbMg10Bi cuboctahedra. Both Mg(2)-Mg(4) bond lengths are 3.35 Å. There are two shorter (3.25 Å) and two longer (3.32 Å) Mg(2)-Mg(2) bond lengths. All Mg(2)-Mg(3) bond lengths are 3.25 Å. Both Mg(2)-Bi(1) bond lengths are 3.28 Å. In the third Mg site, Mg(3) is bonded to one Rb(1); two equivalent Mg(1); two equivalent Mg(2); two equivalent Mg(4); four Mg(3,3); and one Bi(1) atom to form distorted MgRbMg10Bi cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra; corners with fourteen Mg(3,3)RbMg10Bi cuboctahedra; edges with two equivalent Rb(1)Mg12 cuboctahedra; edges with two equivalent Mg(4)Mg12 cuboctahedra; edges with two equivalent Bi(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with four equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with four Mg(3,3)RbMg10Bi cuboctahedra;  a faceface with one Rb(1)Mg12 cuboctahedra;  a faceface with one Bi(1)Mg12 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with five equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with five equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. Both Mg(3)-Mg(4) bond lengths are 3.29 Å. There are two shorter (3.17 Å) and two longer (3.40 Å) Mg(3)-Mg(3,3) bond lengths. The Mg(3)-Bi(1) bond length is 3.30 Å. In the fourth Mg site, Mg(3) is bonded to one Rb(1), two equivalent Mg(1), two equivalent Mg(2), two equivalent Mg(4), four equivalent Mg(3), and one Bi(1) atom to form distorted MgRbMg10Bi cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra; corners with fourteen Mg(3,3)RbMg10Bi cuboctahedra; edges with two equivalent Rb(1)Mg12 cuboctahedra; edges with two equivalent Mg(4)Mg12 cuboctahedra; edges with two equivalent Bi(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with four equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with four equivalent Mg(3)RbMg10Bi cuboctahedra;  a faceface with one Rb(1)Mg12 cuboctahedra;  a faceface with one Bi(1)Mg12 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with five equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with five equivalent Mg(1)Rb2Mg10 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. Both Mg(3)-Mg(1) bond lengths are 3.36 Å. Both Mg(3)-Mg(2) bond lengths are 3.25 Å. Both Mg(3)-Mg(4) bond lengths are 3.29 Å. The Mg(3)-Bi(1) bond length is 3.30 Å. In the fifth Mg site, Mg(4) is bonded to three equivalent Mg(1); three equivalent Mg(2); and six Mg(3,3) atoms to form MgMg12 cuboctahedra that share corners with six equivalent Mg(4)Mg12 cuboctahedra; corners with twelve Mg(3,3)RbMg10Bi cuboctahedra; edges with six equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with six equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with six Mg(3,3)RbMg10Bi cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with three equivalent Rb(1)Mg12 cuboctahedra; faces with three equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with three equivalent Mg(1)Rb2Mg10 cuboctahedra; faces with three equivalent Bi(1)Mg12 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra. Bi(1) is bonded to six equivalent Mg(2) and six Mg(3,3) atoms to form BiMg12 cuboctahedra that share corners with six equivalent Bi(1)Mg12 cuboctahedra; corners with twelve equivalent Mg(1)Rb2Mg10 cuboctahedra; edges with six equivalent Mg(2)Mg10Bi2 cuboctahedra; edges with twelve Mg(3,3)RbMg10Bi cuboctahedra; faces with two equivalent Rb(1)Mg12 cuboctahedra; faces with six equivalent Mg(2)Mg10Bi2 cuboctahedra; faces with six equivalent Mg(4)Mg12 cuboctahedra; and faces with six Mg(3,3)RbMg10Bi cuboctahedra.