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Ca2ZnSn crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Ca2ZnSn ribbons oriented in the (1, 0, 0) direction. Ca is bonded in a linear geometry to one Zn and one Sn atom. The Ca–Zn bond length is 3.21 Å. The Ca–Sn bond length is 2.99 Å. Zn is bonded in a linear geometry to two equivalent Ca atoms. Sn is bonded in a linear geometry to two equivalent Ca atoms.
Ca2ZnSn is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ca is bonded in a body-centered cubic geometry to four equivalent Zn and four equivalent Sn atoms. All Ca–Zn bond lengths are 3.29 Å. All Ca–Sn bond lengths are 3.29 Å. Zn is bonded in a body-centered cubic geometry to eight equivalent Ca atoms. Sn is bonded in a body-centered cubic geometry to eight equivalent Ca atoms.