Solvothermal Syntheses, Crystal Structures, and Thermal Properties of the First Example of Selenidostannates with Mixed Ethylene Polyamine‐Coordinated Transition Metal Complexes as Counterions

Abstract

The compounds [Ni(en)3]2Sn2Se6 (1), [Ni(en)(trien)]2Sn2Se6 (2), [Co(en)(trien)]2Sn2Se6 (3), and [Ni2(trien)2(μ‐trien)]Cl4·2H2O (4) (en = ethylenediamine, trien = triethylenetetramine) were solvothermally synthesized by the reactions of NiCl2·6H2O (or CoCl2·6H2O), tin and selenium in en, mixed en/trien and trien solvents, respectively. The selenidostannates 1–3 are composed of the [Sn2Se6]4– anion and [Ni(en)3]2+ or [M(en)(trien)]2+ (M = Co, Ni) complex cations. The large dinuclear complex cation [Ni2(trien)2(μ‐trien)]4+ seems to prevent the formation of the [Sn2Se6]4– anion in the tien solvent, which indicates the different structural directing effects of the complex cations on the formation of the [Sn2Se6]4– anion. As far as we know, compounds 2 and 3 are the first examples of [Sn2Se6]4– compounds containing transition metal complexes with mixed ammine ligands. In the crystal structures of 1–4, the cations and anions are connected to three‐dimensional supramolecular networks by N–H···Se or N–H···Cl, N–H···O, and O–H···Cl hydrogen bonds.

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

“…1b). C (5) and N (8) are disordered with occupies of 54% and 46% for C (5), and 80% and 20% for N (8). The Sm 3+ ion is also in a 9-fold coordination environment involving eight N atoms from a trien and a tren, and a Cl À ion.…”

“…Both C(27) and N(21) are refined as 60% and 40%. The disordered C (5) and N (8) in 2 are refined as 54% and 46%, and 80% and 20%, respectively. Hydrogen atoms were added geometrically and refined using the riding model.…”

“…Compounds 1-3 are the first examples of Ln-containing selenidostannates synthesized in mixed ethylene polyamine solvents. The first transition metal selenidostannate prepared in the mixed ethylene polyamines is [TM(en)(trien)] 2 Sn 2 Se 6 (TM = Co, Ni) [5].…”

“…The [TM(amine) m ] n+ complex cations formed in situ act as charge compensating ions or structural components in the final ternary chalcogenostannates, depending on the structures of the amine ligands. In ethylenediamine (en) and diethylenetriamine (dien) solutions, TM n+ ions often form saturated complexes [TM(en) 3 ] n+ and [TM(dien) 2 ] n+ , which lead to compounds containing free chalcogenostannate anions, such as [M(en) 3 ] 2 Sn 2 S 6 (M = Mn, Co, Zn) [3], [M(en) 3 ] 2 Sn 2 Se 6 (M = Mn, Ni, Zn) [4,5], [Zn(en) 3 ] 2 Sn 2 Te 6 Áen [6], [M(en) 3 ] 2 Sn 2 Te 6 (M = Mn, Zn) [7], and [Ni(dien) 2 ] 2 Sn 2 S 6 [8]. The only chalcogenidostannates incorporated with TM-en complex components are [{Mn(en) 2 } 2 (l-en)(l-Sn 2 S 6 )] 1 [9] and [K 6 (MeOH) 9 ][Sn 2 Se 6 ][Cr(en) 2 (SnSe 4 )] 2 [10].…”

“…-115.62(5) 93.68(4)-114.12(5) Sn-Se-Sn 85.03(5) 84.85(4)86.32(4)N-Sm-N 63.0(3)-152.1(3) 62.0(3)-154.6(3) 65.3(3)-162.7(3) N-Sm-Cl(O) 72.86(18)-146.6(2) 68.2(3)-154.5(2) a Terminal bond length. b Bridging bond length.…”