RbMg14V crystallizes in the hexagonal P-6m2 space group. Rb(1) is bonded to six equivalent Mg(2) and six equivalent Mg(3) atoms to form RbMg12 cuboctahedra that share corners with six equivalent Rb(1)Mg12 cuboctahedra, corners with twelve equivalent Mg(1)Mg10V2 cuboctahedra, edges with six equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with twelve equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with six equivalent Mg(4)Mg12 cuboctahedra, faces with six equivalent Mg(2)Rb2Mg10 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V cuboctahedra. 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 distorted MgMg10V2 cuboctahedra that share corners with four equivalent Rb(1)Mg12 cuboctahedra, corners with six equivalent Mg(1)Mg10V2 cuboctahedra, corners with eight equivalent Mg(2)Rb2Mg10 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)RbMg10V cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(2)Rb2Mg10 cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with four equivalent Mg(1)Mg10V2 cuboctahedra, and faces with ten equivalent Mg(3)RbMg10V cuboctahedra. In the second Mg site, Mg(2) is bonded to two equivalent Rb(1), two equivalent Mg(4), four equivalent Mg(2), and four equivalent Mg(3) atoms to form distorted MgRb2Mg10 cuboctahedra that share corners with four equivalent V(1)Mg12 cuboctahedra, corners with six equivalent Mg(2)Rb2Mg10 cuboctahedra, corners with eight equivalent Mg(1)Mg10V2 cuboctahedra, edges with two equivalent Rb(1)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with eight equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent Rb(1)Mg12 cuboctahedra, faces with two equivalent Mg(1)Mg10V2 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with four equivalent Mg(2)Rb2Mg10 cuboctahedra, and faces with ten equivalent Mg(3)RbMg10V 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 equivalent Mg(3), and one V(1) atom to form distorted MgRbMg10V cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra, corners with fourteen equivalent Mg(3)RbMg10V cuboctahedra, edges with two equivalent Rb(1)Mg12 cuboctahedra, edges with two equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent V(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Mg10V2 cuboctahedra, edges with four equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with four equivalent Mg(3)RbMg10V cuboctahedra,  a faceface with one Rb(1)Mg12 cuboctahedra,  a faceface with one V(1)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with five equivalent Mg(1)Mg10V2 cuboctahedra, faces with five equivalent Mg(2)Rb2Mg10 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V 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)RbMg10V cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with six equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with six equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with three equivalent Rb(1)Mg12 cuboctahedra, faces with three equivalent Mg(1)Mg10V2 cuboctahedra, faces with three equivalent Mg(2)Rb2Mg10 cuboctahedra, faces with three equivalent V(1)Mg12 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V 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, corners with twelve equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with twelve equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent Rb(1)Mg12 cuboctahedra, faces with six equivalent Mg(1)Mg10V2 cuboctahedra, faces with six equivalent Mg(4)Mg12 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V cuboctahedra.
RbMg14V crystallizes in the hexagonal P-6m2 space group. Rb(1) is bonded to six equivalent Mg(2) and six equivalent Mg(3) atoms to form RbMg12 cuboctahedra that share corners with six equivalent Rb(1)Mg12 cuboctahedra, corners with twelve equivalent Mg(1)Mg10V2 cuboctahedra, edges with six equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with twelve equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with six equivalent Mg(4)Mg12 cuboctahedra, faces with six equivalent Mg(2)Rb2Mg10 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V cuboctahedra. All Rb(1)-Mg(2) bond lengths are 3.27 Å. All Rb(1)-Mg(3) bond lengths are 3.43 Å. 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 distorted MgMg10V2 cuboctahedra that share corners with four equivalent Rb(1)Mg12 cuboctahedra, corners with six equivalent Mg(1)Mg10V2 cuboctahedra, corners with eight equivalent Mg(2)Rb2Mg10 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)RbMg10V cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(2)Rb2Mg10 cuboctahedra, faces with two equivalent V(1)Mg12 cuboctahedra, faces with four equivalent Mg(1)Mg10V2 cuboctahedra, and faces with ten equivalent Mg(3)RbMg10V cuboctahedra. Both Mg(1)-Mg(4) bond lengths are 3.28 Å. There are two shorter (3.21 Å) and two longer (3.34 Å) Mg(1)-Mg(1) bond lengths. All Mg(1)-Mg(3) bond lengths are 3.07 Å. Both Mg(1)-V(1) bond lengths are 3.27 Å. In the second Mg site, Mg(2) is bonded to two equivalent Rb(1), two equivalent Mg(4), four equivalent Mg(2), and four equivalent Mg(3) atoms to form distorted MgRb2Mg10 cuboctahedra that share corners with four equivalent V(1)Mg12 cuboctahedra, corners with six equivalent Mg(2)Rb2Mg10 cuboctahedra, corners with eight equivalent Mg(1)Mg10V2 cuboctahedra, edges with two equivalent Rb(1)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with eight equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent Rb(1)Mg12 cuboctahedra, faces with two equivalent Mg(1)Mg10V2 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with four equivalent Mg(2)Rb2Mg10 cuboctahedra, and faces with ten equivalent Mg(3)RbMg10V cuboctahedra. Both Mg(2)-Mg(4) bond lengths are 3.21 Å. There are two shorter (3.17 Å) and two longer (3.37 Å) Mg(2)-Mg(2) bond lengths. All Mg(2)-Mg(3) bond lengths are 3.40 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 equivalent Mg(3), and one V(1) atom to form distorted MgRbMg10V cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra, corners with fourteen equivalent Mg(3)RbMg10V cuboctahedra, edges with two equivalent Rb(1)Mg12 cuboctahedra, edges with two equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent V(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Mg10V2 cuboctahedra, edges with four equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with four equivalent Mg(3)RbMg10V cuboctahedra,  a faceface with one Rb(1)Mg12 cuboctahedra,  a faceface with one V(1)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with five equivalent Mg(1)Mg10V2 cuboctahedra, faces with five equivalent Mg(2)Rb2Mg10 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V cuboctahedra. Both Mg(3)-Mg(4) bond lengths are 3.28 Å. There are two shorter (3.24 Å) and two longer (3.30 Å) Mg(3)-Mg(3) bond lengths. The Mg(3)-V(1) bond length is 3.07 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)RbMg10V cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with six equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with six equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with three equivalent Rb(1)Mg12 cuboctahedra, faces with three equivalent Mg(1)Mg10V2 cuboctahedra, faces with three equivalent Mg(2)Rb2Mg10 cuboctahedra, faces with three equivalent V(1)Mg12 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V 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, corners with twelve equivalent Mg(2)Rb2Mg10 cuboctahedra, edges with six equivalent Mg(1)Mg10V2 cuboctahedra, edges with twelve equivalent Mg(3)RbMg10V cuboctahedra, faces with two equivalent Rb(1)Mg12 cuboctahedra, faces with six equivalent Mg(1)Mg10V2 cuboctahedra, faces with six equivalent Mg(4)Mg12 cuboctahedra, and faces with six equivalent Mg(3)RbMg10V cuboctahedra.