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MgCo2Si is Zincblende, Sphalerite structured and crystallizes in the orthorhombic Immm space group. The structure is zero-dimensional and consists of two magnesium molecules and two Co2Si clusters. In each Co2Si cluster, Co1+ is bonded in a single-bond geometry to one Si4- atom. The Co–Si bond length is 2.10 Å. Si4- is bonded in a linear geometry to two equivalent Co1+ atoms.
MgCo2Si is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Mg2+ is bonded in a 6-coordinate geometry to six equivalent Si4- atoms. All Mg–Si bond lengths are 2.86 Å. Co1+ is bonded in a 4-coordinate geometry to four equivalent Si4- atoms. All Co–Si bond lengths are 2.47 Å. Si4- is bonded in a 8-coordinate geometry to six equivalent Mg2+ and eight equivalent Co1+ atoms.