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ZrCo3B2 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Zr2+ is bonded in a hexagonal planar geometry to six equivalent B3- atoms. All Zr–B bond lengths are 2.81 Å. Co+1.33+ is bonded in a square co-planar geometry to four equivalent B3- atoms. All Co–B bond lengths are 2.07 Å. B3- is bonded in a 9-coordinate geometry to three equivalent Zr2+ and six equivalent Co+1.33+ atoms.
Zr2(Co7B2)3 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Zr is bonded in a distorted tetrahedral geometry to four equivalent Co atoms. All Zr–Co bond lengths are 2.49 Å. There are three inequivalent Co sites. In the first Co site, Co is bonded in a cuboctahedral geometry to twelve equivalent Co atoms. All Co–Co bond lengths are 2.52 Å. In the second Co site, Co is bonded to one Zr and three equivalent B atoms to form a mixture of corner and edge-sharing CoZrB3 tetrahedra. All Co–B bond lengths are 2.08 Å. In the third Co site, Co is bonded in a distorted bent 150 degrees geometry to one Co and two equivalent B atoms. Both Co–B bond lengths are 2.10 Å. B is bonded in a 8-coordinate geometry to eight Co atoms.
ZrCo3B2 crystallizes in the trigonal R-3m space group. The structure is three-dimensional and consists of one Zr2(Co3B2)3 framework and three zirconium molecules. In the Zr2(Co3B2)3 framework, Zr2+ is bonded in a hexagonal planar geometry to six equivalent B3- atoms. All Zr–B bond lengths are 2.66 Å. There are two inequivalent Co+1.33+ sites. In the first Co+1.33+ site, Co+1.33+ is bonded in a distorted square co-planar geometry to four equivalent B3- atoms. All Co–B bond lengths are 2.05 Å. In the second Co+1.33+ site, Co+1.33+ is bonded in a square co-planar geometry to four equivalent B3- atoms. All Co–B bond lengths are 2.21 Å. B3- is bonded in a 9-coordinate geometry to two equivalent Zr2+, six Co+1.33+, and one B3- atom. The B–B bond length is 2.10 Å.