ja6b06024_si_002.cif (335.73 kB)

Metal Nitrides Grown from Ca/Li Flux: Ca6Te3N2 and New Nitridoferrate(I) Ca6(LixFe1–x)Te2N3

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posted on 01.08.2016, 00:00 by Matthew J. Dickman, Susan E. Latturner
Two new tellurium-containing nitrides were grown from reactions in molten calcium and lithium. The compound Ca6Te3N2 crystallizes in space group Rc (a = 12.000(3)­Å, c = 13.147(4)­Å; Z = 6); its structure is an anti-type of rinneite (K3NaFeCl6) and 2H perovskite related oxides such as Sr3Co2O6. The compound Ca6(LixFe1–x)­Te2N3 where x ≈ 0.48 forms in space group P42/m (a = 8.718(3)­Å, c = 6.719(2)­Å; Z = 2) with a new stuffed anti-type variant of the Tl3BiCl6 structure. Band structure calculations and easily observable red/green dichroic behavior indicate that Ca6Te3N2 is a highly anisotropic direct band gap semiconductor (Eg = 2.5 eV). Ca6(LixFe1–x)­Te2N3 features isolated linear N–Fe–N units with iron in the rare Fe1+ state. The magnetic behavior of the iron site was characterized by magnetic susceptibility measurements, which indicate a very high magnetic moment (5.16μB) likely due to a high degree of spin–orbit coupling. Inherent disorder at the Fe/Li mixed site frustrates long-range communication between magnetic centers.