Structural Analyses of tetrathiadodecahydro[3.3.3.3]paracyclophane Complexes with Copper(I) and Silver(I)

Abstract

The preparation and X-ray structures of complexes of 2,11,20,29-tetrathia-4e,5,6,7e,8,9,22e,23,24,25e,26,27dodecahydro[3.3.3.3]cyclophane (2) (tTTDHPCP) with Cu(I), i.e. [Cu 2 I 2 (tTTDHPCP)]·thf 3, and with Ag(I), i.e. [Ag 2 (tTTDHPCP)(CF 3 COO) 2 ] 4, are reported. The sulfur atoms of compound 2 bind with metals to serve as the bridge in the polymeric structures, while anions interact with other metal atoms forming multi-dimensional structures. Complex 3 is a novel three-dimensional coordination polymer composed of Cu 4 motifs, in which (CuI) 2 forms a square planar unit to link the compound 2 molecules with a THF molecule situated outside the open cavities. In contrast, the Ag atom in complex 4 serves as a bridge for two compound 2 molecules, providing a two-dimensional channel framework. Unit cell data: complex 3, monoclinic system, space group P2 (1)/n, a = 14.1935(19) Å, b = 13.7879(19) Å, c = 22.222(3) Å, = 107.888(3)°, Z = 4.; complex 4, triclinic system, space group P-1, a = 9.4736(7) Å, b = 12.0619(8) Å, c = 18.0914(10) Å, = 80.1260(10)°, Z = 2.

Designs of 3-Dimensional Networks and MOFs Using Mono- and Polymetallic Copper(I) Secondary Building Units and Mono- and Polythioethers: Materials Based on the Cu–S Coordination Bond

“…The significantly larger macrocyclic ligand L12 dissolved in THF reacts with CuI in MeCN in a 1:1 molar ratio to generate red-brown crystals of composition [(Cu 2 I 2 )(L12)•THF] n [54]. The X-ray structure (monoclinic, P2(1)/n) reveals the presence of 3D network built upon rhomboid dimers as SBUs (Fig.…”

2,2′-Ethylenebis(1,3-dithiane) as a polydentate μ2-, μ4- and μ5-assembling ligand for the construction of sulphur-rich Cu(i), Hg(ii) and heterometallic Cu(i)/Hg(ii) coordination polymers featuring uncommon network architectures

“…12 The cyclophane derivative 2,11,20,29-tetrathia-dodecahydro[3.3.3.3]cyclophane reacts with CuI in MeCN in a 1 : 1 molar ratio to generate a 3D CP built upon rhomboid dimers as SBUs. 13 In a collaborative work, our group has reported on the network assembly of octadentate thioether-decorated octasilsesquioxanes with CuI salts under mild conditions yielding 3D POSS-based CPs incorporating dinuclear or closed-cubane-type SBUs. 14 The tetradentate thioether functionalized silanes Si(CH 2 SR) 4 (R = Me or Ph) were found to react with HgBr 2 yielding 1D CPs, where HgBr 2 moieties are connected by doubly bidentate chelating thioether ligands.…”

1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers

“…We are also aware of a CP [(Cu( 2 -Cl)Cu)}( -oxathietane)] n containing a somewhat similar inorganic CuCl ribbon. However, in this Cu(II) compound, the stepped chain is constituted of doublybridge CuCl 2 units ligated via the S-donor site of 1,4-oxathietane [30]. At the first glance, there is some resemblance between the one-dimensional ribbons of…”