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The First Thiostannate Compound with Copper(II) Synthesized Under Ambient Conditions: Crystal Structure, Electronic and Thermal Properties
Author(s) -
Benkada Assma,
Reinsch Helge,
Bensch Wolfgang
Publication year - 2019
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.201900924
Subject(s) - cyclam , chemistry , crystallography , unpaired electron , copper , crystal structure , electron paramagnetic resonance , octahedron , crystallinity , aqueous solution , molecule , crystallite , inorganic chemistry , metal , organic chemistry , nuclear magnetic resonance , physics
The new compound {[Cu(cyclam)] 2 [Sn 2 S 6 ]} n · 2 n H 2 O containing Cu(II) was synthesized at room temperature reacting aqueous solutions of Na 4 SnS 4 · 14H 2 O and of [Cu(cyclam)](ClO 4 ) 2 . A crystalline precipitate consisting of small crystallites was formed after a very short reaction time of 2 h. Structure analysis reveals that [Sn 2 S 6 ] 4– anions are joined by the [Cu(cyclam)] 2+ cations via Cu–S bonds generating layers which are stacked along the crystallographic a‐axis. The Cu(II) centers are in a distorted octahedral environment of four N and two S atoms. The distortion is reflected in the EPR spectrum that displays the A ∥ lines characteristic for Cu 2+ ( I = 3/2) and due to g ∥ > g ⊥ > 2.0023, the unpaired electron is located in the d x 2 – y 2 orbital. The crystal water molecules can be removed at elevated temperatures, while crystallinity of the sample is mainly retained. Storage of the dehydrated sample on air leads to water uptake and recovery of the pristine compound.