Alkali Cation Ligating Chains and Sheets of the Macrocycle 1, 7‐Dithia‐18‐Crown‐6 with Bridging Iodo‐ and Thiocyanatocuprate(I) Units

Abstract

Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer 1[(CuI)2(1, 7‐DT18C6)2] (1) in which 1, 7‐DT18C6 ligands bridge (CuI)2 rings into double chains. 1D polymers of the type 1[M{(Cu3I4)(1, 7‐DT18C6)}] (M = K, 2; M = Cs, 3) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu6I8]2— units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields 2[{Na(CH3CN)2} {(CuSCN)2(1, 7‐DT18C6)}][Cu(SCN)2] (4), in which 1[(CuSCN)2] double chains are linked through macrocycles into sheets. Infinite 1[{Cu(SCN)2}—] chains compensate the charge of the Na+ cations. Complex 1 can imbibe 0.90 mol CsNO3 per mol of 1, 7‐DT18C6 pairs.

Two-Dimensional Square-Grid versus One-Dimensional Double-Stranded Networks: Counterion Regulation of the Formation of Macrocycle-Based Copper(I) Coordination Frameworks

“…The Cu coordination sphere has a distorted tetrahedral shape, with the “tetrahedral” angles falling in the range 100.29(8)−123.94(8)°. The bond distances to sulfur [Cu−S1 2.333(3) Å, Cu−S2 ii 2.302(2) Å] are reasonably similar and compare well to those found in other copper(I)−thia macrocyclic complexes. , Four other examples of thia macrocycles yielding coordination polymers incorporating double-stranded 1D copper(I) halides are known 2 Double-stranded 1D structure of 3 , {[Cu( 1 )I](CH 3 CN)} n .…”

“…A distortion from tetrahedral at the copper(I) is apparent with the C21−Cu−N22 i angle being 130.3(2)°, while the smallest angle, S1−Cu−S2 ii , is 95.20(5)°. The Cu−S bond distances [Cu−S1 2.4171(14), Cu−S2 ii 2.4678(15)] are about 0.1 Å longer than those found in other four-coordinate copper(I) systems (≈2.35 Å). , The 2D sheets of 2 , which are considerably puckered due to the distorted tetrahedral geometry of the copper atoms, have a mean plane parallel to (200). The dimensions of each rectangular unit, incorporating Cu atoms at each corner, were observed to be approximately 4.9 and 10.3 Å.…”

Copper(I) Pseudohalide Coordination Polymers containing Macrocyclic Methylcycloarsoxane (CH3AsO)n (n = 4, 5) or 1, 7‐Dithia‐18‐crown‐6 Bridging Units. Kupfer(I)‐Pseudohalogenid‐haltige Koordinationspolymere mit den Makrozyklen Methylcycloarsoxan (CH3AsO)n (n = 4, 5) oder 1, 7‐Dithia‐18‐Krone‐6 als Brückenliganden

“…A µ-NCS bridging role is, in fact, more characteristic for the thiocyanate ligand in CuSCN coordination polymers and typical building units are 1 ϱ [Cu(SCN)] single chains [15,16], staircase double chains [13,15,17] and sheets [18,19] Metal mediated expansion of ethylcycloarsoxane to (C 2 H 5 AsO) 5 pentamers has previously been confirmed for [K{cyclo-(C 2 H 5 AsO) 5 [5]. The observed pentagonal antiprismatic coordination polyhedra in these complexes exhibit a typical longitudinal distortion and this is also the case for the κ 10 O potassium environment in 2,whose degree of stretching can be gauged by comparison of the K-M distance of 1.89 (1) 14 (1,10DT18C6) 3 }·CH 3 CN] [23].…”

Influence of the Reaction Sequence on the Complexation of an NS4-Macrocycle with CdII and CuI Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic CuI Complex

“…Crown ethers are one of the simplest macrocycle categories and have opened the era of alkali-metal coordination chemistry in synthetic inorganic chemistry. − As well as possessing central cavities, crown ethers have frequently been tuned by substituting their O heteroatoms by N donors to achieve endocyclic recognition (metal-in-cavity, Chart a) of certain metal ions, − while S-containing crown ethers (thiacrowns or thiamacrocycles) often form exocyclic complexes in which metal ions exist outside the cavity (Chart b) because of the electron sufficiency of S donors. − The use of such exocoordination is synthetically attractive for the construction of novel metallosupramolecular entities and coordination networks based on macrocyclic ligand building blocks. − …”

“…Beyond endo- or exocoordinated complexes, endo/exocoordinated ones (Chart c), in which two metal ions exist both inside and outside the macrocyclic cavity, appear to be promising entities for producing new rich and varied supramolecular coordination chemistry. − Thus, the endo/exocoordination of macrocycles raises the following fundamental questions or issues: (i) how to network macrocycles using exocoordination, (ii) how to control the endo- and exocoordination, (iii) how to facilitate the preparation of endo/exocoordinated products, and (iv) exploration of applications of endo/exocoordination. Some structures of the isolated products, including discrete and networked products based on the endo- or exocoordination modes, are influenced by the anion, interdonor distance, and flexibility of the cavity. − Some soft metal complexes of thiamacrocycles associated with endo- or exocoordination modes have been integral to explaining the operation of anion-controlled chemosensors and chiral inversion. − Despite advances in exocoordination-based networking, − homonuclear endo/exocoordinated complexes are less explored. − Thus, the development of new synthetic methods for homonuclear endo/exocoordinated complexes remains a challenge.…”