On the Incorporation of Transition Metal Atoms into Thiostannates: Synthesis, Crystal Structures and Spectroscopic Properties of [Ni(en)₃]₂Sn₂S₆, [Ni(dap)₃]₂Sn₂S₆ · 2 H₂O, [Co(tren)]₂Sn₂S₆, and [Ni(tren)]₂Sn₂S₆

Abstract

The four new thiostannates [Ni(en)3]2Sn2S6 (1) (en = ethylenediamine), [Ni(dap)3]2Sn2S6 · 2 H2O (2) (dap = 1, 2‐diaminopropane), [Co(tren)]2Sn2S6 (3) and [Ni(tren)]2Sn2S6 (4) (tren = tris(2‐aminoethyl)amine) were prepared under solvothermal conditions. In all compounds [Sn2S6]4— anions are observed as the common structural motif. This anion is composed of two SnS4 tetrahedra sharing a common edge. In compounds 1 and 2 the transition metal cations are coordinated each by three amine ligands and therefore solvent separated complex cations as well as discrete [Sn2S6]4— anions are found. In compounds 3 and 4 the coordination around the transition metal ions cannot be completed by the organic ligands and the [Sn2S6]4— anions are connected to the transition metal cations via terminal S atoms. In both compounds the [Sn2S6]4— anion acts as a bidentate ligand connecting two transition metal cations by terminal S atoms. The Co2+ cations in compound 3 are in a fivefold environment of one tetradentate tren ligand and one S atom forming discrete[Co(tren)]2Sn2S6 units. In compound 4 the Ni2+ ions are in a sixfold environment of one tetradentate tren ligand and two S atoms of two symmetry related [Sn2S6]4— anions. This connection mode leads to formation of “zig‐zag‐like” Ni—Sn2S6 chains which are directed along the crystallographic c‐axis. The spectroscopic properties of compounds 1 to 3 were investigated using Raman spectroscopy. Differences in the spectra of 1 and 2 compared to 3 are observed which are caused by the covalent bonding between the Co2+ ions and the Sn2S64— anions in 3.

Solvothermal Syntheses of Two New Thiostannates and an In‐Situ Energy Dispersive X‐ray Scattering Study of Their Formation

“…These values match well with data published in literature. [12,48] (6) 2.392 (2) 2.405 (2) 2.407 (2) 2.414 (2) 3.1678 (18) Cu ( (5) 2.238 (2) 2.357 (3) 2.446 (3) 2.7755 (18) 3.052 (2) Sn (2)…”

“…[8][9][10] In addition, the integration of transition metals (TM) into the network alters the physical and chemical properties. [11] Thiostannates containing transition metals are for example [Ni(en) 3 ] 2 Sn 2 S 6 , [Co(tren)] 2 Sn 2 S 6 (tren = tris(2-aminoethyl)amine), [Ni(tren)] 2 Sn 2 S 6 , [12] (1,4-dabH 2 )Ag 2 SnS 4 (1,4-dab = 1,4-diaminobutane), [13] (DBUH)CuSnS 3 (DBU = 1,5-diazabicyclo[4.3.0]non-5-ene), (1,4-dabH 2 )Cu 2 SnS 4 , [14] [Ni(dien) 3 ] 2 Sn 2 S 6 (dien = diethylenetriamine) [15] or [M(en) 3 ] 2 Sn 2 S 6 (M = Mn, Co, Zn). [16] Sn(IV) is the most common oxidation state in thiostannates and tin sulfides.…”

Solvothermal syntheses and characterizations of the first example of lanthanide selenidostannates prepared in mixed ethylene polyamines

“…But in the presence of tetradentate triethylenetetramine (trien) and tris(2-aminoethyl)amine (tren), and pentadentate tetraethylenepentamine (tepa) ligands, or bidentate ligands with higher steric hindrance (such as 1,10-Phenanthroline, phen), unsaturated TM-amine complexes can be formed, and TM-incorporated chalcogenidostannates are obtained. The examples include {[Mn(trien)] 2 SnS 4 }Á4H 2 O [11], [{TM(tren)} 2 (l-Sn 2 S 6 )] (TM = Co, Ni) [12], [{TM(tepa)} 2 (l-Sn 2 S 6 )] (TM = Fe, Co, Ni) [13], [{TM(phen)} 2 (l-Sn 2 Se 6 )] (TM = Mn, Fe) [14], [{Zn(trien)} 2 (l-SnTe 4 )], and [{Zn(tren)} 2 (l-Sn 2 Te 6 )] [15]. The unsaturated coordination site of TM center in TM-amine complexes is completed by the chalcogen atom of the chalcogenidostannate anions in these compounds.…”

Solvothermal Syntheses and Characterization of a Series of New Selenidostannates with Lanthanide Complexes as Counterions

“…Saturated transition-metal complexes (TMCs) act as structure-directing agents and counterions, such as [M(en) 3 ] 2 [Sn 2 S 6 ] (en = ethylenediamine; M = Mn, Co, Zn, Ni) [4][5][6], [Ni(dien) 3 [7,8], [M(en) 3 ] 2 [Sn 2 Te 6 ] (M = Mn, Zn) [9] and [Mn(en) 3 ] 2 [Sn 2 Te 6 ]Á4H 2 O [10]. Unsaturated TMCs that act as either decorating groups or bridging groups can bond directly to [Sn 2 Q 6 ] 4-anions to form a new class of organic hybrid chalcogenidostannates, as exemplified by [{Mn(en) 2 } 2 (l-en) (l-Sn 2 S 6 )] [11], [{M(tren)} 2 (l-Sn 2 S 6 )] (tren = tris(2-aminoethyl)amine; M = Ni and Co) [2a], and [M(tepa)] 2 (l-Sn 2 Se 6 ) (tepa = tetraethylenepentamine; M = Fe, Co, Mn) [12,13].…”