The synthesis, single crystal structure determination, and Raman spectrum are reported for colorless transparent tribarium disodium tetracyanamide, Ba 3Na 2(CN 2) 4. The title compound crystallizes in the space group C 2 h 5- P2 1/ c (#14, a = 6.2872 ( 5 ) Å , b = 10.0002 ( 8 ) Å , c = 17.7303 ( 16 ) Å , β = 110.454 ( 4 ) ° , V = 1044.48 ( 15 ) Å 3 , Z = 4 , R / w R = 0.0266 / 0.0543 ). Each sodium atom is surrounded by six nitrogen atoms in octahedral geometry. Sodium centered nitrogen octahedra are linked through face-sharing along the [100] direction to form one-dimensional (1D) chains. These chains are connected to each other through the carbon atoms of cyanamide and make a three-dimensional (3D) network with 1D channels along the [100] direction. Barium atoms and additional cyanamide anions reside in the channels. Each barium atom is irregularly coordinated with nitrogen and carbon from the cyanamide anions. The Raman spectrum shows symmetric vibrations of [N C N] 2− corresponding to ν sym (1241.5 cm −1) and 2 δ (1356.4 cm −1).