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CdP 2 N 4 and MnP 2 N 4 – Ternary Transition‐Metal Nitridophosphates
Author(s) -
Pucher Florian J.,
Karau Friedrich W.,
Schmedt auf der Günne Jörn,
Schnick Wolfgang
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600042
Subject(s) - chemistry , crystallography , transition metal , superstructure , crystallite , metal , nitride , ternary operation , crystal structure , stereochemistry , catalysis , biochemistry , oceanography , organic chemistry , layer (electronics) , computer science , programming language , geology
The ternary transition‐metal nitridophosphates CdP 2 N 4 and MnP 2 N 4 have been synthesized under high‐pressure high‐temperature conditions (5–8 GPa, 1000–1300 °C) by using the multianvil technique. Cd and Mn azides can be used as the starting materials, however, with respect to safety considerations, it is much more advantageous to start from metal powders and phosphorus nitride imide, HPN 2 . Both nitridophosphates crystallize in a structure closely related to the megacalsilite structure type. As a result of the known issues concerning superstructures with this type of structure, TEM investigations were performed on CdP 2 N 4 , which revealed that the megacalsilite superstructure is not equally pronounced in all crystallites. By adding NH 4 Cl as mineralizer, single crystals were obtained that exhibit unequally pronounced superstructure reflections. Consequently, an averaged structural model was used and refined by the Rietveld method [ P 6 3 22, a = 16.7197(3), c = 7.6428(2) Å, V = 1850.3(2) Å 3 , R p = 0.0671, wR p = 0.0869 for CdP 2 N 4 and P 6 3 22, a = 16.5543(2), c = 7.5058(2) Å, V = 1781.3(1) Å 3 , R p = 0.0526, wR p = 0.0697 for MnP 2 N 4 ]. The 31 P NMR spectra exhibit four signal groups at (6.4, 4.8), 0.8, and –9.7 ppm with pronounced shoulders belonging to the same phase in an approximate area ratio of 4.8:1.1:2.0, thereby proving at least eight P sites.