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Crystals 2018, 8(1), 18; https://doi.org/10.3390/cryst8010018

Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds

Research Centre for Crystalline Materials, School of Science and Technology, Sunway University, No. 5 Jalan Universiti, Bandar Sunway 47500, Selangor Darul Ehsan, Malaysia
Received: 9 December 2017 / Revised: 29 December 2017 / Accepted: 31 December 2017 / Published: 4 January 2018
(This article belongs to the Special Issue Crystal Chemistry of Zinc, Cadmium and Mercury)

Abstract

The X-ray structural chemistry of zinc and cadmium 1,1-dithiolates (for example, xanthate, dithiophosphate and dithiocarbamate) with potentially bridging bipyridyl-type ligands (for example, 4,4′-bipyridine) is reviewed. For zinc, the xanthates and dithiophosphates uniformly form one-dimensional coordination polymers, whereas the zinc dithiocarbamates are always zero-dimensional, reflecting the exceptional chelating ability of dithiocarbamate ligands compared with xanthates and dithiophosphates. For cadmium, one-dimensional coordination polymers are usually found, reflecting the larger size of cadmium compared with zinc, but zero-dimensional aggregates are sometimes found. Steric effects associated with the 1,1-dithiolate-bound R groups are shown to influence supramolecular aggregation and, when formed, polymer topology in order to reduce steric hindrance; the nature of the bipyridyl-type ligand can also be influential. For the dithiocarbamates of both zinc and cadmium, in instances where the dithiocarbamate ligand is functionalised with hydrogen bonding potential, extended supramolecular architectures are often formed via hydrogen bonding interactions. Of particular interest is the observation that the bipyridyl-type ligands do not always bridge zinc or cadmium 1,1-dithiolates, being monodentate instead, often in the presence of hydrogen bonding. Thus, hydroxyl-O–HN(pyridyl) hydrogen bonds are sometimes formed in preference to M←N(pyridyl) coordinate-bonds, suggesting a competition between the two modes of association. View Full-Text
Keywords: crystal engineering; coordination polymers; hydrogen bonding; structural chemistry; zinc; cadmium; dithiocarbamate; xanthate; dithiophosphates; unusual coordination modes crystal engineering; coordination polymers; hydrogen bonding; structural chemistry; zinc; cadmium; dithiocarbamate; xanthate; dithiophosphates; unusual coordination modes
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
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Tiekink, E.R.T. Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds. Crystals 2018, 8, 18.

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