Room Temperature Synthesis of New Thiostannates by Slow Interdiffusion of Different Solvents

The new compounds [Ni(L-1)][Ni(L-1)Sn2S6](n)center dot 2H(2)O (I) and [Ni(L-2)](2)[Sn2S6]center dot 4H(2)O (II) containing the macrocyclic ligands L-1(L-1= 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane) and L-2(L-2= 1,8-diethyl-1,3,6,8,10,13-hexaazacyclotetradecane) were prepared at room temperature by overlaying an aqueous solution of Na4SnS4 center dot 14H(2)O with the [Ni(L-1)](ClO4)(2)complex dissolved in CH3CN (I) or by overlaying a solution of the [Ni(L-2)](ClO4)(2)complex dissolved in DMSO with an aqueous solution of Na4SnS4 center dot 14H(2)O (II). The slow interdiffusion of the two solvents guarantees supersaturation in the interface region of the solvents so that crystallization of the compounds occurs. In the structure ofIone Ni(2+)cation has bonds to S(2-)anions of the thiostannate anion thus generating chains along [100]. This cation is in an octahedral environment of four N atoms of L(1)and two S atoms of the [Sn2S6](4-)anion. The second [Ni(L-1)](2+)complex exhibits a square-planar coordination geometry. These [Ni(L-1)](2+)complexes and water molecules are located between the chains. In the structure ofIIisolated [Sn2S6](4-)anions and [Ni(L-2)](2+)cations are observed. The Ni(2+)cations are fourfold coordinated by N atoms of the L(2)ligand and feature also a square planar environment.