Kristall‐ und Molekülstruktur eines neuartigen Trimetallamacrocyclus: cyclo‐Tri[nickel‐μ‐[1,1,1′,1′‐tetraethyl‐3,3′‐terephthaloyl‐bis‐thioureato(2‐)‐S,O:O′,S′]]

Abstract

Die Struktur der Titelverbindung wurde durch Röntgenkristallstrukturanalyse bestimmt. Die Verbindung kristallisiert triklin in der Raumgruppe P1 mit den Gitterkonstanten a = 13,900, b = 15,403, c = 16,615 Å, δ = 84,01, β = 70,61, γ = 89,64° und Z = 2. Die Lösung der Struktur erfolgte mit direkten Methoden. Der abschließende R‐Wert betrug R = 0,073 für 2284 beobachtete Reflexe. Das Molekül besitzt eine zyklische Struktur, bestehend aus drei Molekülen des quadridentaten Liganden und drei Nickel‐Atomen. Der gebildete Ring ist ein 27gliedriger Trimetallamacrocyclus. Die Nickel‐Atome bilden ein nahezu gleichseitiges Dreieck mit Abständen von 10,25 Å, 10,45 Å und 10,45 Å. Das Molekül ist relativ planar.

AgI Metallacoronates and HgII Metallacryptates Derived from a Catechol‐Based Aroylbis(N,N‐diethylthiourea)

“…The coordination chemistry of aroyl( N , N ‐dialkylthioureas) has been dominated for a long time by metal complexes with bidentate benzoylthioureas, HL benz Because of their hard oxygen and soft sulfur donor atoms and an acidic amido group, such compounds are versatile ligands and form stable complexes with a large number of metal ions. However, the structural coordination chemistry of the HL benz ligands as well as of the related bis(thioureas) H 2 L meta or H 2 L para has mainly focused on metal ions that prefer square‐planar or pseudo‐planar coordination environments such as Ni 2+ , Pd 2+ ,, Pt 2+ ,, and Cu 2+ . Additionally, a few examples of tris complexes with M 3+ ions have been reported, and the coordination chemistry of rhenium and technetium with such ligands is relatively well explored .…”

Polymorphism in bipodalO,O′-dimethylN,N′-(m-phenylenedicarbonyl)bis(thiocarbamate)

“…Substituted acylthioureas with the general motif RC(O)NH-C(S)N(R H ) 2 have been studied extensively as a result of their coordination chemistry, particularly with the softer transition metal ions (Hoyer et al, 1986;Ko È hler et al, 1986;Ko È nig et al, 1983Ko È nig et al, , 1986Richter et al, 1989;Schro È der et al, 2000). We have extensively studied these molecules and their bipodal analogues, (R H ) 2 NC(S)NHC(O)RC(O)NHC(S)N(R H ) 2 , as part of an investigation examining their potential uses in the platinum group metal industry (Bourne et al, 2005;Hallale et al, 2005;Koch et al, 1999).…”

First metallamacrocyclic complexes of Pt(iv) with 3,3,3′,3′-tetraalkyl-1,1′-phenylenedicarbonylbis(thioureas): synthesis by direct or electrolytic oxidative addition of I2, Br2 and Cl2

“…This organised self-assembly occurs as a result of the tendency of the S,O-donating acylthioureas to coordinate to these metals in a predominantly cis fashion. [3][4][5][6][7][8] We found that metallamacrocyclic complexes with well-defined metal-to-ligand ratios are exclusively formed depending on the relative substitution positions of the carbonylthiourea moieties on the phenylene spacer: meta substitution (H 2 L m ; Scheme 1) leads to 2 : 2 complexes (cis-[M 2 (L m -S,O) 2 ] with M = Ni, Pd, Pt; Scheme 1), and para substitution (H 2 L p ; Scheme 1) to 3 : 3 metallamacrocycles (cis-[M 3 (L p -S,O) 3 ] with M = Ni, Pd, Pt; Scheme 1). [5][6][7][8] The structural characterisation of 2 : 2 metallamacrocycles of Ni(II) and Pt(II) with 3,3,3 ,3 -tetraethyl-1,1 -isophthaloylbis-(thiourea) 5, 8 and of Pd(II) with 3,3,3 ,3 -tetra(n-butyl)-1,1isophthaloylbis(thiourea), 6 has been reported, and crystallo-Ni(II) with 3,3,3 ,3 -tetraethyl-1,1 -terephthaloylbis(thiourea).…”