Bimetallic copper(I)-mercury(II) and copper(I)-potassium(I) coordination polymers with bridging Di- and trithiacrown ethers

摘要

The complex [Hg(SCN)(2)(1,10DT18C6)] (1) contains discrete Hg(SCN)(2) units, whose Hg atoms lie at the centre of a 1,10-dithia-18-crown-6 (1,10DT18C6) macrocycle. The essentially linear coordination of Hg in Hg(SCN)(2) is extended to hexagonal bipyramidal by weak Hg-S bonds of length 3.003(2) Angstrom to the thiacrown ether S atoms and by four additional secondary Hg-O interactions. Solvothermal reaction of CuCN and HgCl2 with 1,10DT18C6 in acetonitrile at 100degreesC affords (3)(infinity)[(CuCN)(4){(CN)(2)(1,10DT18C6)}] (2). Zigzag CuCN chains in this complex are linked by 1,10DT18C6 ligands in a mu-S1,S10 bridging manner into layers. These, in their turn, are connected through mu-[Hg(CN)(2)] units into interpenetrating 3D frameworks, in which the Hg atoms are surrounded by coordinating thiacrown ether macrocycles. (3)(infinity)[K(Cu3I4)(1,7,13TT18C6)](CH3CN)-C-. (3) can be prepared by treatment of KI and CuI with 1,7,3-trithia-18-crown-6 (1,7,13TT18C6) in acetonitrile at 100degreesC and contains anionic layers in which broken cube [Cu3I4](-) building units connect three adjacent thiacrown ether ligands. Individual layers are linked into a 3D network by the K+ counter cations.