ZrCo3B2 crystallizes in the trigonal R-3m space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 20-coordinate geometry to one Zr(1), one Zr(2), three equivalent Co(2), nine equivalent Co(1), and six equivalent B(1) atoms. In the second Zr site, Zr(2) is bonded to two equivalent Zr(1), six equivalent Co(1), and six equivalent Co(2) atoms to form distorted corner-sharing ZrZr2Co12 cuboctahedra. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 4-coordinate geometry to one Zr(2), three equivalent Zr(1), and four equivalent B(1) atoms. In the second Co site, Co(2) is bonded in a 4-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent B(1) atoms. B(1) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Co(2), four equivalent Co(1), and one B(1) atom.
ZrCo3B2 crystallizes in the trigonal R-3m space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 20-coordinate geometry to one Zr(1), one Zr(2), three equivalent Co(2), nine equivalent Co(1), and six equivalent B(1) atoms. The Zr(1)-Zr(1) bond length is 3.07 Å. The Zr(1)-Zr(2) bond length is 2.97 Å. All Zr(1)-Co(2) bond lengths are 2.82 Å. There are a spread of Zr(1)-Co(1) bond distances ranging from 2.72-2.99 Å. All Zr(1)-B(1) bond lengths are 2.62 Å. In the second Zr site, Zr(2) is bonded to two equivalent Zr(1), six equivalent Co(1), and six equivalent Co(2) atoms to form distorted corner-sharing ZrZr2Co12 cuboctahedra. All Zr(2)-Co(1) bond lengths are 2.72 Å. All Zr(2)-Co(2) bond lengths are 2.84 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 4-coordinate geometry to one Zr(2), three equivalent Zr(1), and four equivalent B(1) atoms. There are two shorter (2.02 Å) and two longer (2.03 Å) Co(1)-B(1) bond lengths. In the second Co site, Co(2) is bonded in a 4-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent B(1) atoms. All Co(2)-B(1) bond lengths are 2.19 Å. B(1) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Co(2), four equivalent Co(1), and one B(1) atom. The B(1)-B(1) bond length is 2.09 Å.