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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.
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.