Abstract
A new heterometallic CuI-NiII coordination polymer, poly[[tetra-μ3-iodido-μ2-iodido-bis-(μ3-piperidine-1-di-thio-carbamato)propio-nitrilepenta-copper(I)nickel(II)] chloro-form monosolvate], {[CuI5NiIII5(C6H10NS2)2(C3H5N)]·CHCl3} n , has been synthesized and structurally characterized. This coordination polymer consists of an NiII mononuclear unit of NiII(Pip-dtc)2 (Pip-dtc- is piperidine-1-di-thio-carbamate) and a penta-nuclear copper(I) cluster unit of Cu5I5(CH3CH2CN). The NiII ion, which lies on an inversion centre, is surrounded by four S atoms in a square-planar coordination geometry while all CuI ions have distorted tetra-hedral coordination geometries. In the penta-nuclear copper(I) cluster unit, a mirror plane passes through one CuI ion and three I ions. All the S atoms in NiII(Pip-dtc) are also coordinated by the CuI ions, forming an infinite zigzag chain structure along the b-axis direction. The chains are weakly connected by solvent CHCl3 mol-ecules via Cl⋯I [3.653 (1) Å] and Cl⋯S [3.4370 (1) Å] short-contact inter-actions.
Highlights
Chemical contextThe crystal engineering of coordination polymers is one of the most attractive areas in the field of materials science because their characteristic assembled structures and electronic states bearing features of organic–inorganic hybrid materials have new chemical and/or physical properties such as catalytic activity (Yaghi et al, 2003), gas adsorption (Kitagawa et al, 2004), conductivity (Givaja et al, 2012), magnetism (Sato et al, 1996) and optical properties (Watanabe et al, 2017)
Kento Himoto,a Toshiya Horii,a Shoki Oda,a Shimpei Suzuki,a Kunihisa Sugimoto,b Takashi Okubo,a* Masahiko Maekawac and Takayoshi Kuroda-Sowaa
The NiII ion, which lies on an inversion centre, is surrounded by four S atoms in a square-planar coordination geometry while all CuI ions have distorted tetrahedral coordination geometries
Summary
The crystal engineering of coordination polymers is one of the most attractive areas in the field of materials science because their characteristic assembled structures and electronic states bearing features of organic–inorganic hybrid materials have new chemical and/or physical properties such as catalytic activity (Yaghi et al, 2003), gas adsorption (Kitagawa et al, 2004), conductivity (Givaja et al, 2012), magnetism (Sato et al, 1996) and optical properties (Watanabe et al, 2017). The design and synthesis of coordination polymers have drawn much interest; in particular, the establishment of a rational synthetic method for preparing heterometallic coordination polymers is important in developing the chemistry of coordination complexes because of the unique coordination networks created by the combination of several metal ions with versatile coordination geometries (Ghosh et al, 2018). Metal complexes with dithiocarbamate (dtc) derivatives are some of the most useful building units to form heterometallic coordination polymers (Engelhardt et al, 1988, 1989; Healy et al, 1989; Tokoro et al, 1995; Okubo et al, 2012) because one can employ a variety of mononuclear metal complexes as building units for coordination polymers owing to the coordination ability of the sulfur atoms in the dithiocarbamate complexes.
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