VCo4 is alpha La-derived structured and crystallizes in the trigonal R-3m space group. V(1) is bonded to six equivalent V(1) and six equivalent Co(1) atoms to form VV6Co6 cuboctahedra that share corners with six equivalent V(1)V6Co6 cuboctahedra; corners with six Co(2,2)Co12 cuboctahedra; edges with six equivalent V(1)V6Co6 cuboctahedra; edges with six Co(2,2)Co12 cuboctahedra; edges with twelve equivalent Co(1)V3Co9 cuboctahedra; faces with six equivalent V(1)V6Co6 cuboctahedra; and faces with twelve equivalent Co(1)V3Co9 cuboctahedra. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent V(1), three equivalent Co(2), and six equivalent Co(1) atoms to form CoV3Co9 cuboctahedra that share corners with three equivalent Co(2)Co12 cuboctahedra; corners with nine equivalent Co(1)V3Co9 cuboctahedra; edges with six equivalent V(1)V6Co6 cuboctahedra; edges with nine Co(2,2)Co12 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; faces with six equivalent V(1)V6Co6 cuboctahedra; faces with six equivalent Co(2)Co12 cuboctahedra; and faces with six equivalent Co(1)V3Co9 cuboctahedra. In the second Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. In the third Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. In the fourth Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. In the fifth Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra.
VCo4 is alpha La-derived structured and crystallizes in the trigonal R-3m space group. V(1) is bonded to six equivalent V(1) and six equivalent Co(1) atoms to form VV6Co6 cuboctahedra that share corners with six equivalent V(1)V6Co6 cuboctahedra; corners with six Co(2,2)Co12 cuboctahedra; edges with six equivalent V(1)V6Co6 cuboctahedra; edges with six Co(2,2)Co12 cuboctahedra; edges with twelve equivalent Co(1)V3Co9 cuboctahedra; faces with six equivalent V(1)V6Co6 cuboctahedra; and faces with twelve equivalent Co(1)V3Co9 cuboctahedra. All V(1)-V(1) bond lengths are 2.52 Å. All V(1)-Co(1) bond lengths are 2.57 Å. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent V(1), three equivalent Co(2), and six equivalent Co(1) atoms to form CoV3Co9 cuboctahedra that share corners with three equivalent Co(2)Co12 cuboctahedra; corners with nine equivalent Co(1)V3Co9 cuboctahedra; edges with six equivalent V(1)V6Co6 cuboctahedra; edges with nine Co(2,2)Co12 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; faces with six equivalent V(1)V6Co6 cuboctahedra; faces with six equivalent Co(2)Co12 cuboctahedra; and faces with six equivalent Co(1)V3Co9 cuboctahedra. All Co(1)-Co(2) bond lengths are 2.49 Å. All Co(1)-Co(1) bond lengths are 2.52 Å. In the second Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. There are three shorter (2.48 Å) and six longer (2.52 Å) Co(2)-Co(2,2) bond lengths. In the third Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. All Co(2)-Co(1) bond lengths are 2.49 Å. All Co(2)-Co(2) bond lengths are 2.52 Å. In the fourth Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. All Co(2)-Co(1) bond lengths are 2.49 Å. There are three shorter (2.48 Å) and six longer (2.52 Å) Co(2)-Co(2,2) bond lengths. In the fifth Co site, Co(2) is bonded to three equivalent Co(1) and nine Co(2,2) atoms to form CoCo12 cuboctahedra that share corners with three equivalent V(1)V6Co6 cuboctahedra; corners with three equivalent Co(1)V3Co9 cuboctahedra; corners with six equivalent Co(2)Co12 cuboctahedra; edges with three equivalent V(1)V6Co6 cuboctahedra; edges with nine equivalent Co(1)V3Co9 cuboctahedra; edges with twelve Co(2,2)Co12 cuboctahedra; faces with six equivalent Co(1)V3Co9 cuboctahedra; and faces with twelve Co(2,2)Co12 cuboctahedra. All Co(2)-Co(1) bond lengths are 2.49 Å. All Co(2)-Co(2) bond lengths are 2.52 Å.