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

Abstract

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 ∞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(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.

Synthesis and Crystal Structures of Lithium, Sodium, and ­Potassium Derivatives of 2‐(Methylthio)aniline and 2‐(Phenylthio)aniline

“…Like in the case of the lithium and sodium derivatives 1 and 3 the thioether coordination is relatively weak (K-S: 331.0(1)-353.1(1) pm). Similar K-S distances have been observed for some thiocrownether complexes (CCDC refcode OBOFIV, [25] RALGAM [20] ). Potassium arene π interactions are frequently observed in potassium amide chemistry.…”

Preparation and characterisation of divalent hard and soft metal (M = Ca, Co, Cu, Zn, Cd, Hg and Pb) complexes of 1,10-dithia-18-crown-6: structural versatility

“…A similar mercury(II) coordination sphere, [Hg(L)(SCN) 2 ], with an axial NCS-Hg-SCN unit and hexagonal plane was reported by the Sheldrick group. 16 However, the Hg-O(ether) bonds [Hg1-O1 2.9260( 18), Hg1-O2 2.8474( 19) Å] show fairly elongated distances and longer than that of the Hg-O(nitrate) bond [2.680( 2) Å], suggesting that the negatively charged nitrato oxygen is bonded more strongly to the mercury(II) centre. The elongation of the Hg-O(ether) bonds is due to the higher coordination number.…”

Heterometallic Coordination Polymers Assembled from Trigonal Trinuclear Fe2Ni-Pivalate Blocks and Polypyridine Spacers: Topological Diversity, Sorption, and Catalytic Properties

“…Thus, an underlying net of 2 is composed of the 4-connected Fe and Ni nodes (topologically equivalent), 3-connected μ 3 -L 2 and μ 3 -O nodes, as well as 2-connected μ 2 -Piv linkers (Figure a and Figure S10, Supporting Information). This trinodal 3,3,4-connected net possesses a rare 3,3,4L40 topology , expressed by the point symbol of (3 3 .9 2 .10) 3 (3 3 )­(9 3 ), with the (3 3 .9 2 .10), (3 3 ), and (9 3 ) indices corresponding to the Fe/Ni, μ 3 -O, and μ 3 -L 2 nodes, respectively. This network can be reduced further to a uninodal 3-connected net with the hcb [Shubnikov hexagonal plane net (6,3)] topology and the point symbol of (6 3 ) (Figure a), after treating the heterometallic [Fe 2 Ni­(μ 3 -O)­(μ-Piv) 6 ] blocks as the 3-connected cluster nodes.…”