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

Abstract

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), CoCl 2 (phen) 2 and 14tfib. Grinding of solid reactants with a small amount of water gives the cocrystal product [CoCl 2 (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 CoCl 2 (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.

Crystal engineering strategies towards halogen-bonded metal–organic multi-component solids: salts, cocrystals and salt cocrystals

“…8). 77,78 As a result of using different halogen bond donors, the resulting halogen bonding motifs led to different dimensionalities of the crystal structures, ranging from discrete supramolecular complexes to three-dimensional networks.…”

Halogen Bonding in N-Alkyl-3-halogenopyridinium Salts

“…To date, various Lewis bases (neutral molecules or charged species) have been employed as halogen bond acceptors in constructing halogenbonded supramolecular assemblies. These have most commonly been organic [13,14] and metal-organic [15] molecules containing electron-rich nitrogen [16][17][18][19][20][21][22][23][24][25][26] and oxygen atoms [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41], as well as inorganic anions such as halogenides [42][43][44][45][46][47][48][49][50][51][52][53][54]. The most commonly used halogen bond donors have traditionally been neutral organic molecules where a halogen atom is bonded to electron-withdrawing molecular residues.…”

Halogen‐Bonded Co‐Crystals Containing Mono‐ and Dinuclear Metal‐Organic Units: Three‐Component One‐Pot Mechanosynthesis, Structural Analysis and Magnetic Properties

“…Differences in the reaction outcome, depending on whether CuCl 2 ⋅ 2H 2 O or CuCl 2 is used, once more draw attention to the role that water molecules have in co‐crystal synthesis. Previous studies have shown that a liquid phase released from hydrate reactants can enhance [23] and autocatalyze [24] the formation of co‐crystals or, in the case of a metal‐organic system, direct reactions towards the neutral metal‐organic co‐crystal instead of the ionic co‐crystal [15b] . In this case, the presence of hydrate water evidently directs the reaction towards the formation of a co‐crystal containing the mononuclear copper(II) complex, while the absence of hydrate water directs the reaction towards the formation of co‐crystal containing the dinuclear copper(II) complex.…”