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Ca12[Mn19N23] and Ca133[Mn216N260]: structural complexity by 2D intergrowth

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Ovchinnikov,  Alexander
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Bobnar,  Matej
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Prots,  Yurii
Yuri Prots, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Borrmann,  Horst
Horst Borrmann, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Sichelschmidt,  Jörg
Jörg Sichelschmidt, Physics of Quantum Materials, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Grin,  Yuri
Juri Grin, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Höhn,  Peter
Peter Höhn, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Ovchinnikov, A., Bobnar, M., Prots, Y., Borrmann, H., Sichelschmidt, J., Grin, Y., et al. (2018). Ca12[Mn19N23] and Ca133[Mn216N260]: structural complexity by 2D intergrowth. Angewandte Chemie, 130, 11753-11767. doi:10.1002/ange.201804369.


Cite as: http://hdl.handle.net/21.11116/0000-0001-9376-4
Abstract
Two new calcium nitridomanganates, Ca12[Mn19N23] (P3, a = 11.81341(3) Å, c = 5.58975(2) Å, Z = 1) and Ca133[Mn216N260] (P‐3, 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 the former compound 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 latter phase, which classifies as a complex metallic alloy (CMA). Both crystal structures possess 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 Mn atoms in both structures carries a localized magnetic moment, while for most Mn species the magnetism is quenched due to metal‐metal bond formation.