Abstract
The syntheses and crystal structures of two bimetallic mol-ecular compounds, namely, bis[bis-(6,6'-dimethyl-2,2'-bi-pyridine)-copper(I)] hexa-fluorido-zir-con-ate(IV) 1.134-hydrate, [Cu(dmbpy)2]2[ZrF6]·1.134H2O (dmbpy = 6,6'-di-methyl-2,2'-bipyri-dyl, C12H12N2), (I), and bis[bis-(6,6'-dimethyl-2,2'-bi-pyr-idine)-copper(I)] hexa-fluorido-hafnate(IV) 0.671-hydrate, [Cu(dmbpy)2]2[HfF6]·0.671H2O, (II), are reported. Apart from a slight site occupany difference for the water mol-ecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetra-hedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octa-hedral anions of fluorinated early transition metals. The tetra-hedral environments of the copper complexes are distorted owing to the steric effects of the dmbpy ligands. The extended structures are built up through Coulombic inter-actions between cations and anions and π-π stacking inter-actions between heterochiral Δ- and Λ-[Cu(dmbpy)2]+ complexes. A comparison between the title compounds and other [Cu(dmbpy)2]+ compounds with monovalent and bivalent anions reveals a significant influence of the cation-to-anion ratio on the resulting crystal packing architectures, providing insights for future crystal design of distorted tetra-hedral copper compounds.
Highlights
The syntheses and crystal structures of two bimetallic molecular compounds, namely, bis[bis(6,60-dimethyl-2,20-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate, [Cu(dmbpy)2]2[ZrF6]Á1.134H2O, (I), and bis[bis(6,60-dimethyl-2,20-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate, [Cu(dmbpy)2]2[HfF6]Á0.671H2O, (II), are reported
Apart from a slight site occupany difference for the water molecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetrahedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octahedral anions of fluorinated early transition metals
A comparison between the title compounds and other [Cu(dmbpy)2]+ compounds with monovalent and bivalent anions reveals a significant influence of the cationto-anion ratio on the resulting crystal packing architectures, providing insights for future crystal design of distorted tetrahedral copper compounds
Summary
Copper(I) complexes with distorted tetrahedral environments have been studied as catalytic active sites in electron-transfer reactions and are found in a number of proteins that contain copper (Vallee & Williams, 1968; Colman et al, 1978; Adman et al, 1978). The realization of significantly distorted tetrahedral geometry requires sufficient steric hindrance between the ligands. The methyl groups of the 6,60-dimethyl-2,20bipyridyl (C12H12N2; dmbpy) ligand create a large steric hindrance upon coordination, and, a common strategy to form distorted tetrahedral complexes is to use dmbpy or its derivatives as ligands (McKenzie et al, 1971; Burke et al, 1980). (Burke et al, 1980; Cui et al, 2005; Itoh et al, 2005; Mei et al, 2011; Bozic-Weber et al, 2012; Li et al, 2017) Here, we report two structures with [MF6]2À (M = Zr, Hf), which are the first known distorted tetrahedral copper compounds with bivalent anions
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