The First Thiostannate Compound with Copper(II) Synthesized Under Ambient Conditions: Crystal Structure, Electronic and Thermal Properties

Abstract

The new compound {[Cu(cyclam)] 2 [Sn 2 S 6 ]} n ·2nH 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 ] 4anions 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 dis- IntroductionThe integration of transition metals into thiostannate frameworks significantly alters the crystal structures and properties of the inorganic framework. Pure inorganic bulk thiostannates, respectively tin sulfides containing transition metals are prepared using the high temperature route, [1] by reaction of elements in an inert flux, [2] in reactive fluxes [3] or by mechanical alloying combined with spark plasma sintering. [4] In the past, it was demonstrated that the solvothermal method is most promising for the generation of thiostannates containing transition metal complexes. Considering only compounds that contain the [Sn 2 S 6 ] 4anion, saturated complexes with the cations Mn 2+ , Co 2+ , Ni 2+ and Zn 2+ are observed with bi-and tridentate amine molecules like en (en = ethylenediamine), dap (dap = 1,2-diaminopropane), 1,2-dach (1,2-dach = 1,2-diaminocyclohexane), 2amp (2amp = 2-(aminomethyl)pyridine), dien (dien = diethylenetriamine) and aepa (aepa = N-2-aminoethyl-1,3-propandiamine), as exemplified by the compounds [M(en) 3 ] 2 [Sn 2 S 6 ] (M = Mn, Co, Ni and Zn), [5,6] [Ni(dap) 3 ] 2 [Sn 2 S 6 ]·2H 2 O, [6] [Ni(1,2dach) 3 ] 2 [Sn 2 S 6 ]·4H 2 O, [7] [M(dien) 2 ] 2 [Sn 2 S 6 ] (M = Co and Ni), [7,8] [Ni(2amp) 3 ] 2 [Sn 2 S 6 ]·9.5H 2 O [9] and [Ni(aepa) 2 ] 2 [Sn 2 S 6 ]. [7] In contrast, tetra-and pentadentate amines like tren (tren = tris- [a]

Directed Dehydration as Synthetic Tool for Generation of a New Na4SnS4 Polymorph: Crystal Structure, Na+ Conductivity, and Influence of Sb‐Substitution

“…[9,[20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Applying suitable precursors, the preparation of thiostannates at room temperature was also reported. [36][37][38][39][40][41] These examples demonstrate the broad variety of synthetic approaches established in the thiostannate chemistry.…”

“…Thiostannates with protonated amine molecules, transition metal cations, or transition metal complexes as counter ions compensating the negative charge of the [Sn x S y ] n − anions were mostly prepared under solvothermal conditions [9, 20–35] . Applying suitable precursors, the preparation of thiostannates at room temperature was also reported [36–41] . These examples demonstrate the broad variety of synthetic approaches established in the thiostannate chemistry.…”

Crystalline chalcogenidometalate-based compounds from uncommon reaction media

“…Furthermore, the solvothermal approach enables the preparation of inorganic-organic hybrid compounds containing amine molecules, ammonium counterions derived in situ from them or transition-metal complexes that were generated in situ by combining donor solvent molecules with metal ions from the reaction mixture. [25][26][27][28][29][30] An example of a compound synthesized by using solvothermal methods is (MeNH 3 ) 0.75 [Cu 1.25 GeSe 3 ], which features a 3D-{[Cu 1. 25 GeSe 3 ] n 0.75nÀ } open framework with methylammonium cations as counterions.…”

Gezielte Dehydratisierung als Synthesewerkzeug zur Herstellung eines neuen Na4SnS4‐Polymorphs: Kristallstruktur, Na+‐Leitfähigkeit und Einfluss der Sb‐Substitution

“…Thiostannate mit protonierten Aminmolekülen, Übergangsmetallkationen oder Übergangsmetallkomplexen als Gegenionen, die die negative Ladung der [Sn x S y ] n − ‐Anionen kompensieren, wurden meist unter solvothermalen Bedingungen hergestellt [9, 20–35] . Bei Verwendung geeigneter Ausgangsverbindungen wurde auch über die Bildung von Thiostannaten bei Raumtemperatur berichtet [36–41] . Diese Beispiele belegen die große Vielfalt der Syntheseverfahren, welche in der Chemie der Thiostannate etabliert sind.…”