Ca12[Mn19N23] and Ca133[Mn216N260]: Structural Complexity by 2D Intergrowth

Two new calcium nitridomanganates, Ca12[Mn19N23] (P3, a=11.81341(3) Å, c=5.58975(2) Å, Z=1) and Ca133[Mn216N260] (P3‾ , a=39.477(1) Å, c=5.5974(2) Å, Z=1), were obtained by a gas–solid reaction of Ca3N2 and Mn with N2 at 1273 K and 1223 K, respectively. The crystal structure of Ca12[Mn19N23] was determined from high‐resolution X‐ray synchrotron powder diffraction data, whereas single‐crystal X‐ray diffraction was employed to establish the crystal structure of the Ca133[Mn216N260] phase, which classifies as a complex metallic alloy (CMA). Both crystal structures have 2D nitridomanganate layers containing similar building blocks but of different levels of structural complexity. Bonding analysis as well as magnetic susceptibility and electron spin resonance measurements revealed that only a fraction of the Mn atoms in both structures carries a localized magnetic moment, while for most Mn species the magnetism is quenched as a result of metal–metal bond formation. Die Calciumnitridomanganate Ca133[Mn216N260], das als komplexe metallische Legierung (CMA) klassifiziert wird, und Ca12[Mn19N23] sind aus komplexen Nitridomanganatschichten aufgebaut. Nur ein Teil der Mn‐Atome trägt lokalisierte magnetische Momente, bei den übrigen Mn‐Atomen ist der Magnetismus durch die Bildung von Metall‐Metall‐Bindungen ausgelöscht.