Solvothermal Syntheses and Crystal Structures of Hexachalcogenidodistannates with Europium Complexes of Different Ethylene Polyamine Ligands

Abstract

Organic hybrid europium hexachalcogenidodistannates [{Eu(en)3}2(μ-OH)2]Sn2S6 (1), [{Eu(en)3}2(μ-OH)2]Sn2Se6 (2), and [Eu(dien)3]2[(Sn2S6)(SH)2] (3) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally synthesized by the reactions of Sn, S (or Se) and Eu2O3 in en and dien solvents, respectively. Compounds 1–3 crystallize in monoclinic space group P21/n. Crystallographic data for 1: a = 10.1158(13), b = 11.3793(14), c = 14.9487(15) A, β = 98.209(4)°, V = 1703.1(3) A3, Z = 2. For 2: a = 10.1359(19), b = 11.771(2), c = 15.423(3) A, β = 99.322(5)°, V = 1815.8(6) A3, Z = 2. For 3: a = 11.6559(10), b = 15.1677(13), c = 14.1732(13) A, β = 95.682(2)°, V = 2493.4(4) A3, Z = 2. The Eu3+ ion forms binuclear tetravalent [{Eu(en)3}2(μ-OH)2]4+ complex cation to act as counter ion to the [Sn2S6]4− and [Sn2Se6]4− anions in 1 and 2. But it is coordinated with three dien ligands to form the mononuclear trivalent [Eu(dien)3]3+ complex cation in 3. The cations and anions are connected into 3-dimensional networks via O–H···S, N–H···S, or N–H···Se hydrogen bonds, respectively. New europium hexachalcogenidodistannate [{Eu(en)3}2(μ-OH)2]Sn2S6, [{Eu(en)3}2(μ-OH)2]Sn2Se6, and [Eu(dien)3]2[(Sn2S6)(SH)2] with 3-dimensional H-bonding network structures were respectively prepared in ethylenetediamine (en) and diethylenetetriamine (dien) under mild solvothermal conditions.