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Solvothermal Synthesis, Crystal Structure, and Thermoanalytical Investigations of the New Layered Thioantimonate(III) [Fe(C 4 H 13 N 3 ) 2 ]Sb 6 S 10 · 0.5 H 2 O
Author(s) -
Stähler Ralph,
Näther Christian,
Bensch Wolfgang
Publication year - 2001
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 - 10.1002/1099-0682(200107)2001:7<1835::aid-ejic1835>3.0.co;2-3
Subject(s) - chemistry , monoclinic crystal system , diethylenetriamine , thermal decomposition , crystallography , crystal structure , molecule , valence (chemistry) , hydrothermal synthesis , solvothermal synthesis , hydrothermal circulation , organic chemistry , seismology , geology
The novel thioantimonate(III) [Fe(C 4 H 13 N 3 ) 2 ]Sb 6 S 10 · 0.5 H 2 O was synthesised under mild hydrothermal conditions by allowing elemental Fe, Sb, and S to react in a 50% diethylenetriamine (dien) solution. The compound crystallises in the monoclinic space group C 2/ c with a = 33.789(3), b = 8.5697(4), c = 24.620(2) Å, β = 118.411(8)°, and V = 6270.3(7) Å 3 . In the crystal structure, five SbS 3 trigonal pyramids and one SbS 4 unit are interconnected by sharing common S atoms, forming Sb 2 S 2 , Sb 4 S 4 , and Sb 5 S 5 heterocycles. The layered [Sb 6 S 10 ] 2− anion is formed by condensation of the rings in the order Sb 4 S 4 −Sb 5 S 5 −Sb 2 S 2 −Sb 5 S 5 −Sb 4 S 4 . The interconnection of the different Sb x S x heterocycles leads to the formation of a large Sb 16 S 16 ring. The special geometries of the SbS x units and their interconnection results in a new and unprecedented architecture of the four‐atoms thick thioantimonate layer. The calculated bond valence sums (BVS) for the Sb atoms range from 3.07 to 3.16 v. u., indicating that the Sb atoms are formally trivalent. The [Fe(dien) 2 ] 2+ cations and the water molecule are located between neighbouring layers. The thermal behaviour of the compound was investigated using DTA‐TG measurements. Upon heating decomposition starts at about 200 °C, which is accompanied by the removal of the organic ligands and the incorporated water molecules. In the X‐ray powder pattern of the decomposition product, the three compounds Sb 2 S 3 , FeSb 2 S 4 , and FeS could be identified.