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[Cd 3 Cu]CuP 10 , [Cd 3 Cu] Cluster Stabilized in an Adamantane‐Like Polyphosphide Substructure
Author(s) -
Bawohl Melanie,
Nilges Tom
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200801414
Subject(s) - isostructural , crystallography , substructure , adamantane , chemical formula , crystal structure , tetragonal crystal system , chemistry , metal , thermal decomposition , space group , tin , zintl phase , materials science , x ray crystallography , diffraction , metallurgy , physics , structural engineering , organic chemistry , engineering , optics
[Cd 3 Cu]CuP 10 is the first representative of the adamantane‐like polyphosphides featuring a metalloid, tetrahedral [ M 3 X ] heterocluster, containing only d 10 ions. It was prepared by the mineralization concept for polyphosphides using CuI as the mineralizer species. The title compound crystallizes cubic in the space group F $/bar{4}$ 3 m (No. 216), with a = 10.479(2) Å and V = 1150.9(4) Å 3 . It is isostructural to the tin containing coinage‐metal polyphosphides [ M 3 Sn]CuP 10 with M = Cu, Ag, Au. A perfect orientation disorder of the [Cd 3 Cu] heterocluster relative to the space diagonals of the cubic cell is present, which is characteristic for the metalloid substructure of this class of compounds. EDX measurements substantiated the refined composition within the standard deviation of the experiment. A slow decomposition of [Cd 3 Cu]CuP 10 was proven by DSC measurements and annealing experiments. The DSC spectra of different samples showed a broad exothermic effect starting at 573 K, which could be identified as a decomposition to new phases. Preliminary results of a single crystal structure determination of the main phase after decomposition pointed towards realized structure units closely related to the title compound, the Cu 2 P 20 and the [Ag 3 Sn]P 7 structure type. A detailed examination of the structural features of this new compound is still in progress.