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MgTiCo2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two MgTiCo2 ribbons oriented in the (1, 0, 0) direction. Mg is bonded in a linear geometry to two equivalent Co atoms. Both Mg–Co bond lengths are 2.65 Å. Ti is bonded in a linear geometry to two equivalent Co atoms. Both Ti–Co bond lengths are 1.95 Å. Co is bonded in a linear geometry to one Mg and one Ti atom.
MgTiCo2 is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Mg is bonded in a body-centered cubic geometry to eight equivalent Co atoms. All Mg–Co bond lengths are 2.58 Å. Ti is bonded in a body-centered cubic geometry to eight equivalent Co atoms. All Ti–Co bond lengths are 2.58 Å. Co is bonded in a body-centered cubic geometry to four equivalent Mg and four equivalent Ti atoms.