CaMg14V crystallizes in the hexagonal P-6m2 space group. Ca(1) is bonded to six Mg(1,1) and six equivalent Mg(3) atoms to form CaMg12 cuboctahedra that share corners with six equivalent Ca(1)Mg12 cuboctahedra; corners with twelve equivalent Mg(2)Mg10V2 cuboctahedra; edges with six Mg(1,1)Ca2Mg10 cuboctahedra; edges with twelve equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent V(1)Mg12 cuboctahedra; faces with six Mg(1,1)Ca2Mg10 cuboctahedra; faces with six equivalent Mg(3)CaMg10V cuboctahedra; and faces with six equivalent Mg(4)Mg12 cuboctahedra. There are five inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Ca(1); two equivalent Mg(4); four Mg(1,1); and four equivalent Mg(3) atoms to form distorted MgCa2Mg10 cuboctahedra that share corners with four equivalent V(1)Mg12 cuboctahedra; corners with six equivalent Mg(1)Ca2Mg10 cuboctahedra; corners with eight equivalent Mg(2)Mg10V2 cuboctahedra; edges with two equivalent Ca(1)Mg12 cuboctahedra; edges with four Mg(1,1)Ca2Mg10 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with eight equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent Ca(1)Mg12 cuboctahedra; faces with two equivalent Mg(2)Mg10V2 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with four Mg(1,1)Ca2Mg10 cuboctahedra; and faces with ten equivalent Mg(3)CaMg10V 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 V(1) atoms to form MgMg10V2 cuboctahedra that share corners with four equivalent Ca(1)Mg12 cuboctahedra; corners with six equivalent Mg(2)Mg10V2 cuboctahedra; corners with eight Mg(1,1)Ca2Mg10 cuboctahedra; edges with two equivalent V(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10V2 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with eight equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent Mg(1)Ca2Mg10 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with two equivalent V(1)Mg12 cuboctahedra; faces with four equivalent Mg(2)Mg10V2 cuboctahedra; and faces with ten equivalent Mg(3)CaMg10V cuboctahedra. In the third Mg site, Mg(1) is bonded to two equivalent Ca(1), two equivalent Mg(4), four equivalent Mg(1), and four equivalent Mg(3) atoms to form distorted MgCa2Mg10 cuboctahedra that share corners with four equivalent V(1)Mg12 cuboctahedra, corners with six equivalent Mg(1)Ca2Mg10 cuboctahedra, corners with eight equivalent Mg(2)Mg10V2 cuboctahedra, edges with two equivalent Ca(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Ca2Mg10 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with eight equivalent Mg(3)CaMg10V cuboctahedra, faces with two equivalent Ca(1)Mg12 cuboctahedra, faces with two equivalent Mg(2)Mg10V2 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with four equivalent Mg(1)Ca2Mg10 cuboctahedra, and faces with ten equivalent Mg(3)CaMg10V cuboctahedra. In the fourth Mg site, Mg(3) is bonded to one Ca(1); two Mg(1,1); two equivalent Mg(2); two equivalent Mg(4); four equivalent Mg(3); and one V(1) atom to form distorted MgCaMg10V cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra; corners with fourteen equivalent Mg(3)CaMg10V cuboctahedra; edges with two equivalent Ca(1)Mg12 cuboctahedra; edges with two equivalent Mg(4)Mg12 cuboctahedra; edges with two equivalent V(1)Mg12 cuboctahedra; edges with four Mg(1,1)Ca2Mg10 cuboctahedra; edges with four equivalent Mg(3)CaMg10V cuboctahedra; edges with four equivalent Mg(2)Mg10V2 cuboctahedra;  a faceface with one Ca(1)Mg12 cuboctahedra;  a faceface with one V(1)Mg12 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with five Mg(1,1)Ca2Mg10 cuboctahedra; faces with five equivalent Mg(2)Mg10V2 cuboctahedra; and faces with six equivalent Mg(3)CaMg10V cuboctahedra. In the fifth Mg site, Mg(4) is bonded to three Mg(1,1); 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)CaMg10V cuboctahedra; edges with six Mg(1,1)Ca2Mg10 cuboctahedra; edges with six equivalent Mg(3)CaMg10V cuboctahedra; edges with six equivalent Mg(2)Mg10V2 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with three equivalent Ca(1)Mg12 cuboctahedra; faces with three Mg(1,1)Ca2Mg10 cuboctahedra; faces with three equivalent Mg(2)Mg10V2 cuboctahedra; faces with three equivalent V(1)Mg12 cuboctahedra; and faces with six equivalent Mg(3)CaMg10V cuboctahedra. V(1) is bonded to six equivalent Mg(2) and six equivalent Mg(3) atoms to form VMg12 cuboctahedra that share corners with six equivalent V(1)Mg12 cuboctahedra; corners with twelve Mg(1,1)Ca2Mg10 cuboctahedra; edges with six equivalent Mg(2)Mg10V2 cuboctahedra; edges with twelve equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent Ca(1)Mg12 cuboctahedra; faces with six equivalent Mg(3)CaMg10V cuboctahedra; faces with six equivalent Mg(2)Mg10V2 cuboctahedra; and faces with six equivalent Mg(4)Mg12 cuboctahedra.
CaMg14V crystallizes in the hexagonal P-6m2 space group. Ca(1) is bonded to six Mg(1,1) and six equivalent Mg(3) atoms to form CaMg12 cuboctahedra that share corners with six equivalent Ca(1)Mg12 cuboctahedra; corners with twelve equivalent Mg(2)Mg10V2 cuboctahedra; edges with six Mg(1,1)Ca2Mg10 cuboctahedra; edges with twelve equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent V(1)Mg12 cuboctahedra; faces with six Mg(1,1)Ca2Mg10 cuboctahedra; faces with six equivalent Mg(3)CaMg10V cuboctahedra; and faces with six equivalent Mg(4)Mg12 cuboctahedra. All Ca(1)-Mg(1,1) bond lengths are 3.23 Å. All Ca(1)-Mg(3) bond lengths are 3.28 Å. There are five inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Ca(1); two equivalent Mg(4); four Mg(1,1); and four equivalent Mg(3) atoms to form distorted MgCa2Mg10 cuboctahedra that share corners with four equivalent V(1)Mg12 cuboctahedra; corners with six equivalent Mg(1)Ca2Mg10 cuboctahedra; corners with eight equivalent Mg(2)Mg10V2 cuboctahedra; edges with two equivalent Ca(1)Mg12 cuboctahedra; edges with four Mg(1,1)Ca2Mg10 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with eight equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent Ca(1)Mg12 cuboctahedra; faces with two equivalent Mg(2)Mg10V2 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with four Mg(1,1)Ca2Mg10 cuboctahedra; and faces with ten equivalent Mg(3)CaMg10V cuboctahedra. Both Mg(1)-Mg(4) bond lengths are 3.17 Å. There are two shorter (3.14 Å) and two longer (3.32 Å) Mg(1)-Mg(1,1) bond lengths. All Mg(1)-Mg(3) bond lengths are 3.27 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 V(1) atoms to form MgMg10V2 cuboctahedra that share corners with four equivalent Ca(1)Mg12 cuboctahedra; corners with six equivalent Mg(2)Mg10V2 cuboctahedra; corners with eight Mg(1,1)Ca2Mg10 cuboctahedra; edges with two equivalent V(1)Mg12 cuboctahedra; edges with four equivalent Mg(2)Mg10V2 cuboctahedra; edges with four equivalent Mg(4)Mg12 cuboctahedra; edges with eight equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent Mg(1)Ca2Mg10 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with two equivalent V(1)Mg12 cuboctahedra; faces with four equivalent Mg(2)Mg10V2 cuboctahedra; and faces with ten equivalent Mg(3)CaMg10V cuboctahedra. Both Mg(2)-Mg(4) bond lengths are 3.23 Å. There are two shorter (3.22 Å) and two longer (3.23 Å) Mg(2)-Mg(2) bond lengths. All Mg(2)-Mg(3) bond lengths are 3.09 Å. Both Mg(2)-V(1) bond lengths are 3.23 Å. In the third Mg site, Mg(1) is bonded to two equivalent Ca(1), two equivalent Mg(4), four equivalent Mg(1), and four equivalent Mg(3) atoms to form distorted MgCa2Mg10 cuboctahedra that share corners with four equivalent V(1)Mg12 cuboctahedra, corners with six equivalent Mg(1)Ca2Mg10 cuboctahedra, corners with eight equivalent Mg(2)Mg10V2 cuboctahedra, edges with two equivalent Ca(1)Mg12 cuboctahedra, edges with four equivalent Mg(1)Ca2Mg10 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with eight equivalent Mg(3)CaMg10V cuboctahedra, faces with two equivalent Ca(1)Mg12 cuboctahedra, faces with two equivalent Mg(2)Mg10V2 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with four equivalent Mg(1)Ca2Mg10 cuboctahedra, and faces with ten equivalent Mg(3)CaMg10V cuboctahedra. Both Mg(1)-Mg(4) bond lengths are 3.17 Å. All Mg(1)-Mg(3) bond lengths are 3.27 Å. In the fourth Mg site, Mg(3) is bonded to one Ca(1); two Mg(1,1); two equivalent Mg(2); two equivalent Mg(4); four equivalent Mg(3); and one V(1) atom to form distorted MgCaMg10V cuboctahedra that share corners with four equivalent Mg(4)Mg12 cuboctahedra; corners with fourteen equivalent Mg(3)CaMg10V cuboctahedra; edges with two equivalent Ca(1)Mg12 cuboctahedra; edges with two equivalent Mg(4)Mg12 cuboctahedra; edges with two equivalent V(1)Mg12 cuboctahedra; edges with four Mg(1,1)Ca2Mg10 cuboctahedra; edges with four equivalent Mg(3)CaMg10V cuboctahedra; edges with four equivalent Mg(2)Mg10V2 cuboctahedra;  a faceface with one Ca(1)Mg12 cuboctahedra;  a faceface with one V(1)Mg12 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with five Mg(1,1)Ca2Mg10 cuboctahedra; faces with five equivalent Mg(2)Mg10V2 cuboctahedra; and faces with six equivalent Mg(3)CaMg10V cuboctahedra. Both Mg(3)-Mg(4) bond lengths are 3.23 Å. There are two shorter (3.21 Å) and two longer (3.24 Å) Mg(3)-Mg(3) bond lengths. The Mg(3)-V(1) bond length is 3.08 Å. In the fifth Mg site, Mg(4) is bonded to three Mg(1,1); 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)CaMg10V cuboctahedra; edges with six Mg(1,1)Ca2Mg10 cuboctahedra; edges with six equivalent Mg(3)CaMg10V cuboctahedra; edges with six equivalent Mg(2)Mg10V2 cuboctahedra; faces with two equivalent Mg(4)Mg12 cuboctahedra; faces with three equivalent Ca(1)Mg12 cuboctahedra; faces with three Mg(1,1)Ca2Mg10 cuboctahedra; faces with three equivalent Mg(2)Mg10V2 cuboctahedra; faces with three equivalent V(1)Mg12 cuboctahedra; and faces with six equivalent Mg(3)CaMg10V cuboctahedra. V(1) is bonded to six equivalent Mg(2) and six equivalent Mg(3) atoms to form VMg12 cuboctahedra that share corners with six equivalent V(1)Mg12 cuboctahedra; corners with twelve Mg(1,1)Ca2Mg10 cuboctahedra; edges with six equivalent Mg(2)Mg10V2 cuboctahedra; edges with twelve equivalent Mg(3)CaMg10V cuboctahedra; faces with two equivalent Ca(1)Mg12 cuboctahedra; faces with six equivalent Mg(3)CaMg10V cuboctahedra; faces with six equivalent Mg(2)Mg10V2 cuboctahedra; and faces with six equivalent Mg(4)Mg12 cuboctahedra.