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A novel ternary nitride semiconductor, CaSnN2, with a layered rock-salt-type structure (R3̅m) was synthesized via a high-pressure metathesis reaction. The properties and structures of II-Sn-N2 (II = Ca, Mg, Zn) semiconductors were also systematically studied, and the differences among them were revealed by comparison. These semiconductor materials showed a rock-salt- or wurtzite-type structure depending on the combined effect of the synthetic conditions and the characteristics of the group II elements. Additionally, the rock-salt-type