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Synthesis, Crystal Structure, and Thermal Properties of Na 5 [SnS 4 ]Cl·13H 2 O
Author(s) -
Lühmann Henning,
Näther Christian,
Jess Inke,
Bensch Wolfgang
Publication year - 2019
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.201900169
Subject(s) - monoclinic crystal system , crystallization , chemistry , crystallography , water of crystallization , crystal structure , differential scanning calorimetry , aqueous solution , thermogravimetry , molecule , hydrogen bond , differential thermal analysis , thermal decomposition , hydroxide , inorganic chemistry , organic chemistry , diffraction , physics , optics , thermodynamics
Reaction of Na 2 S with SnCl 4 · 5H 2 O in aqueous alkaline sodium hydroxide solution leads to the formation of Na 5 [SnS 4 ]Cl · 13H 2 O ( 1 ). The compound crystallizes monoclinic in space group P 2 1 / m with two formula units in the unit cell. In the crystal structure the Na + cations are octahedrally coordinated and are linked into layers by bridging water molecules, μ 3 bridging Cl – anions and μ 1,1 bridging S atoms of [SnS 4 ] 4– anions. Extended hydrogen bonding interactions generate a three‐dimensional network. Investigations using differential thermoanalysis, thermogravimetry, and differential scanning calorimetry shows that upon heating in open crucibles the water can be removed leading to the formation of the anhydrate that is stable at room temperature and does not transform back into compound 1 . Storage of the anhydrate in a desiccator over a water atmosphere leads first to formation of Na 4 SnS 4 · 14H 2 O followed by crystallization of the title compound. After longer storage times NaCl appears as a second crystalline phase. If the thermal measurements are performed in a self‐produced atmosphere, compound 1 transforms partly into Na 4 SnS 4 · 14H 2 O with an increasing amount of this phase with increasing temperature. Synthetic investigations reveal that crystallization of compound 1 sensitively depends on the water content of acetone, which is used for precipitation of 1 . Reacting Na 4 SnS 4 · 14H 2 O directly with NaCl afforded formation of complex mixtures.