Bimetallic Copper(I)‐Mercury(II) and Copper(I)‐Potassium(I) Coordination Polymers with Bridging Di‐ and Trithiacrown Ethers

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)Å 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 100 °C affords [(CuCN)4{Hg(CN)2(1, 10DT18C6)}] (2). Zigzag CuCN chains in this complex are linked by 1, 10DT18C6 ligands in a μ‐S1, S10 bridging manner into layers. These, in their turn, are connected through μ‐[Hg(CN)2] units into interpenetrating 3D frameworks, in which the Hg atoms are surrounded by coordinating thiacrown ether macrocycles. [K(Cu3I4)(1, 7, 13TT18C6)]·CH3CN (3) can be prepared by treatment of KI and CuI with 1, 7, 3‐trithia‐18‐crown‐6 (1, 7, 13TT18C6) in acetonitrile at 100 °C 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.