Solvothermal Syntheses and Crystal Structures of Neodymium Thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2]

Two neodymium thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] (1) and [Nd(dien)3]2[(Sn2S6)(SH)2] (2) (dien = diethylenetriamine) were synthesized by the reaction of tin and sulfur in the presence of NdCl3 and Nd2O3, respectively under solvothermal conditions. Compounds 1 and 2 crystallize in monoclinic space group P21/n. Crystallographic data for 1: a = 11.6722(16), b = 15.119(2), c = 14.1566(19) A, β = 96.213(3)°, V = 2483.6(6) A3, Z = 4. For 2: a = 11.7190(14), b = 15.2168(19), c = 14.2209(18) A, β = 95.775(4)°, V = 2523.1(5) A3, Z = 4. The nine-coordinate [Nd(trien)3]3+ complex cation formed in situ acts as the counter ion to the [Sn2S6]4− anion. The [Nd(dien)3]3+, [Sn2S6]4− and Cl– (or SH–) ions form a 3-dimensional network structure through the N–H···S and N–H···Cl hydrogen bonds. New lanthanide thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2] with 3-dimensional H-bonding network structures were synthesized in diethylenetriamine (dien) under mild solvothermal conditions.