Kristallstrukturen der „supramolekularen“ 1,4-Diazabicyclo[2.2.2]octan- Quecksilber(II)-Komplexe [Hg(dabco)I₂] und [Hg(dabco)(SCN)₂] / Crystal Structures of the “Supram olecular” 1,4-Diazabicyclo[2.2.2]octane Mercury(II) Complexes [Hg(dabco)I₂] and [Hg(dabco)(SCN)₂]

Abstract

Reactions of 1,4-diazabicyclo[2.2.2]octane (“dabco”) with K2[HgI4] or Hg(SCN)2 yield crystals of [Hg(dabco)I2] (1) and [Hg(dabco)(SCN)2] (2). 1 crystallizes monoclinically, space group P21/a. Z = 4, a = 1211.6(5), b = 682.3(6), c = 1430.4(3) pm, β = 98.90(5)°; 2 is orthorhombic, space group Pmmn, Z = 2, a - 740.5(3), b = 609.1(4), c = 1220.0(8) pm. In 1 HgI2 groups are connected by bridging dabco molecules to give a chain structure. The Hg atoms are tetrahedrally coordinated. In 2 the Hg atoms are bridged by two SCN ligands and the chains thus formed are again interconnected by bridging dabco molecules, whereby layers are formed. The coordination polyhedron for the Hg atoms is a distorted octahedron.

catena-Poly[[chloridomercury(II)]-μ-1,4-diazabicyclo[2.2.2]octane-κ2N:N′-[chloridomercury(II)]-di-μ-chlorido]

“…It is noteworthy that mercury(II) metal halide-daco materials are relatively rare, and to the best of our knowledge, only one halide-daco complex has been reported previously, viz. HgI 2 -daco (Pickardt et al, 1995). This complex, [HgI 2 (daco)] n , also exhibits a zigzag one-dimensional structure, but here the I-atoms are all terminally coordinated to the metal centers, while in the title complex one of the Cl atoms act as a bridging atom.…”

“…For a related structure, see: Pickardt et al (1995). For functional materials, see: Chen, Kang & Su (2006); Fang et al (2009); Liu et al (2007); Ma et al (2009); Tranchemontagne et al (2009); Uemura et al (2009); Xue et al (2008).…”

Three-Dimensional Silver-dabco Coordination Polymers with Zeolitic or Three-Connected Topology

“…While there are a number of examples of dabco-containing coordination polymers, the majority of these also involve another type of bridging ligand or anion, and it is surprising that the chemistry of simpler M-dabco systems remains relatively unexplored. Examples where dabco is the sole linking ligand are unusual and include one-dimensional (1D) coordination chains, , a 2D hexagonal network of 6 3 topology of [Ag(dabco) 3 (H 2 O)]­·(3-fluorobenzenecarboxylate), and a series of networks where dabco ligands bridge between M 2 I 2 dimers or between Cu 4 X 4 or higher ordered metal clusters where X = I or Cl. , The latter feature 3D coordination polymer structures with an extraordinary range of topologies. Recently, a luminescent [Cu 4 I 4 (dabco) 2 ] coordination polymer was reported with a zeolitic mtn type structure, and very large pores .…”

Kristallstrukturen „supramolekularer”︁ (Benzo-18-krone-6)kaliumtetrathiocyanatometallate: Ein dimerer Komplex {[K(Benzo-18-krone-6)]2[Hg(SCN)4]}2und zwei isomere Komplexe [K(Benzo-18-krone-6)][Cd(SCN)3] mit kettenförmigen Trithiocyanatocadmat-Anionen

“…Beide Isomere haben als wesentliche Baugruppen [Cd(SCN) 3 ± ] ∞ -Ketten, die sich im Kristall entlang der Schraubenachsen ziehen, also in Richtung der kristallographischen b-Achse in der monoklinen bzw. der a-Achse in der orthorhombischen Modifikation.…”