Synthesis and Structure of the Group 12 Pyrimidinethiolate Complexes _∞³[Zn(S‐2‐N₂C₄H₃)₂], _∞²[Cd(S‐2‐N₂C₄H₃)₂], [Hg(S‐2‐N₂C₄H₃)₂] and[Cd(S‐2‐N₂C₄H₃)₂(tmeda)]

Abstract

The pyrimidinethiolate complexes ∞3[Zn(S‐2‐N2C4H3)2],∞2[Cd(S‐2‐N2C4H3)2] and [Hg(S‐2‐N2C4H3)2] have been prepared by reaction of MCl2 (M = Zn, Cd, Hg) with 2 equiv. of Me3SiS‐2‐N2C4H3 in organic solvents, whilst [Cd(S‐2‐N2C4H3)2(tmeda)] was obtained by recrystallisation of∞2[Cd(S‐2‐N2C4H3)2] in TMEDA at 40 °C. The structures of the complexes were determined by single‐crystal X‐ray crystallography, which shows that the different metal atoms each have different coordination environments. The zinc atom in ∞3[Zn(S‐2‐N2C4H3)2] exhibits a tetrahedral coordination with one sulfur and three nitrogen atoms from pyrimidinethiolate ligands, whereas the cadmium atoms in ∞2[Cd(S‐2‐N2C4H3)2] and [Cd(S‐2‐N2C4H3)2(tmeda)] are six‐coordinate with either three sulfur and three nitrogen atoms or two sulfur and four nitrogen atoms. In contrast, the mercury atoms in [Hg(S‐2‐N2C4H3)2] display a distorted square‐planar coordination to a pair of chelating –S‐2‐N2C4H3 ligands with additional weak Hg–S interactions to adjacent molecules. While known cadmium and zinc pyrimidinethiolate complexes consist of one‐dimensional chains, ∞3[Zn(S‐2‐N2C4H3)2] and ∞2[Cd(S‐2‐N2C4H3)2] form either three‐ or two‐dimensional polymeric networks of metal atoms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Supramolecular aggregation featuring Hg⋯S secondary-bonding interactions in crystals of mercury(ii) species augmented by computational chemistry calculations

“…24 , 89 25 (ref. 90) and 26 , 91 adopt a common motif with that of 25 shown in Fig. 7 being representative of the series.…”

Anchoring I3– via Charge-Transfer Interaction by a Coordination Supramolecular Network Cathode for a High-Performance Aqueous Dual-Ion Battery

“…266974). 30 The crystal structure of Zn-PymSH is shown in Figure 1c,d. A zinc ion is coordinated by three nitrogen atoms and one sulfur atom, which forms a distorted tetrahedral coordination environment (Figure 1c).…”

Synthesis, X-ray Diffraction, NMR and Thermolysis Studies of Cadmium Tin Sulfido Complexes

“…To the best of our knowledge, there are only the purely inorganic, supertetrahedral cluster Cs 10 [Cd 4 Sn 4 S 17 ] [1] and [{(C 6 F 5 ) 3 Ge} 2 Cd{S(SnEt 3 ) 2 }] [2]. Suitable starting materials for the solution-based synthesis of cadmium tin sulfido complexes are cadmium chalcogenolate complexes which are known in the literature with different ligands coordinating the Cd 2+ ions, e.g., tmeda-stabilized chalcogenolates [3][4][5][6][7]. Moreover, tertiary phosphine ligands have been used to synthesize complexes such as [Cd 4 (SPh) 6 (PPh 3 ) 4 ](ClO 4 ) 2 [8], [Cd(SEt)(S 2 CSEt)(P{c-hex} 3 )] 2 [9] or [Cd 17 S 4 (SH) 2 (SPh) 24 (PPh 3 ) 2 ] [10] (Et = C 2 H 5 , Ph = C 6 H 5 , c-hex = cyclo-C 6 H 11 ) and also a mixed zinc-cadmium thiophenolate complex [11].…”