Abstract: | BaClSCN and Na4Mg(SCN)6: Two New Thiocyanates of the Alkaline Earth Metals The reaction of BaCl2 and NaSCN yielded single crystals of BaClSCN (P 21/m, Z = 2, a = 588.6(1) pm, b = 465.8(1) pm, c = 864.4(2) pm, β = 100.20(3)°, Rall = 0.0214). According to X‐ray single crystal investigations, the structure consists of anionic SCN– and Cl– layers, respectively, alternating in 001] direction. The SCN–‐ions are connected via the N and the S atoms to the cations. Na4Mg(SCN)6 (P 3 1c, Z = 2, a = 863.8(1) pm, c = 1399.3(2) pm, Rall = 0.0870), which was obtained from a melt of NaSCN and MgCl2, consists of anionic layers with the cations between the sheets. The holes are filled altenatingly by Na+ or Na+ and Mg2+. Regarding only the C‐atoms of the SCN– group, the structure can be described as a hexagonal closest packing whith the cations occupying 5/6 of the octahedral voids. |