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VCo2Zn crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two VCo2Zn ribbons oriented in the (1, 0, 0) direction. V is bonded in a linear geometry to two equivalent Co atoms. Both V–Co bond lengths are 1.87 Å. Co is bonded in a linear geometry to one V and one Zn atom. The Co–Zn bond length is 2.50 Å. Zn is bonded in a linear geometry to two equivalent Co atoms.
VCo2Zn is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. V is bonded in a body-centered cubic geometry to eight equivalent Co atoms. All V–Co bond lengths are 2.48 Å. Co is bonded in a body-centered cubic geometry to four equivalent V and four equivalent Zn atoms. All Co–Zn bond lengths are 2.48 Å. Zn is bonded in a body-centered cubic geometry to eight equivalent Co atoms.