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 HgCl 2 with 1, 10DT18C6 in acetonitrile at 100 °C affords   ∞ 3 [(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.   ∞ 3 [K(Cu 3 I 4 )(1, 7, 13TT18C6)]·CH 3 CN ( 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 [Cu 3 I 4 ] — building units connect three adjacent thiacrown ether ligands. Individual layers are linked into a 3D network by the K + counter cations.