The Influence of Liquid on the Outcome of Halogen-Bonded Metal–Organic Materials Synthesis by Liquid Assisted Grinding

Katarina Lisac,Dominik Cinčić

doi:10.3390/cryst7120363

Abstract

In this work, we describe novel multi-component halogen bonded solids of Co(ii) complexes and 1,4-diiodotetrafluorobenzene, 14tfib. We present the important influence of liquid on the outcome of liquid assisted grinding of dichlorobis(1,10-phenantroline)cobalt(ii), CoCl2(phen)2 and 14tfib. Grinding of solid reactants with a small amount of water gives the cocrystal product [CoCl2(phen)2](14tfib) (1) while grinding with a small amount of methanol gives an ionic structure, the four-component solid [CoCl(MeOH)(phen)2]Cl(14tfib)(MeOH) (2). Both solid products were also obtained by crystallization from the solution. Single crystal X-ray diffraction reveals that the dominant supramolecular interaction in 1 is the I···Cl halogen bond between 14tfib and CoCl2(phen)2 building blocks. On the other hand, the dominant supramolecular interactions in 2 are I···Cl− charge-assisted halogen bonds between the halogen bond donor and the chloride anion as well as hydrogen bonds between the chloride anion and OH groups of coordinated and solvated methanol molecules.

Highlights

The study of multi-component materials, e.g., cocrystals and salts, has become one of the most attractive areas of research in the field of solid-state chemistry [1]
Where coordination are building blocks which contain ligandssyntheses with pendant halogen bond organic electron donor units which contain simple inorganic ligands (Cl ) [12,17], and to explore the following studies atom on halogen-bonded syntheses neutral of halogen bonding proclivityprevious of the chlorine coordinated tococrystal metal, we report with the synthesis
− ) [12,17], and to explore metal–organic electron donor units which contain simple inorganic ligands (Cl multi-component solids derived from dichlorobis(1,10-phenantroline)cobalt(II), (CoCl2(phen)2), and the halogenused bonding proclivitybond of the donor, chlorine atom coordinated to metal, we report the synthesis of 1)

Summary

Introduction

The study of multi-component materials, e.g., cocrystals and salts, has become one of the most attractive areas of research in the field of solid-state chemistry [1] Effective synthesis of such materials utilizes appropriate molecular building blocks, either neutral or ionic, and supramolecular interactions which lead to reliable motifs of molecular assembly [2,3]. Has been recognized as a reliable crystal engineering tool [5] It is an attractive interaction between a positively charged area of a covalently bound halogen atoms (Br, I) and Lewis bases (nucleophilic atoms such as O, N, S, etc.) [6,7]. Typical halogen bonds are similar to hydrogen bonds in terms of both length and directionality [8,9]. Their strength strongly depends on the surroundings to which the halogen atom is bonded and on acceptor atom basicity [10,11]

Methods

Discussion

Conclusion