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The syntheses and crystal structures of two bimetallic molecular compounds, namely, bis[bis(6,6′-dimethyl-2,2′-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate, [Cu(dmbpy) 2 ] 2 [ZrF 6 ]·1.134H 2 O (dmbpy = 6,6′-dimethyl-2,2′-bipyridyl, C 12 H 12 N 2 ), (I), and bis[bis(6,6′-dimethyl-2,2′-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate, [Cu(dmbpy) 2 ] 2 [HfF 6 ]·0.671H 2 O, (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. The tetrahedral environments of the copper complexes are distorted owing to the steric effects of the dmbpy ligands. The extended structures are built up through Coulombic interactions between cations and anions and π–π stacking interactions 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 tetrahedral copper compounds. 

We report the hydrothermal syntheses and crystal structures of aquabis(2,2′-bipyridine-κ 2 N , N ′)copper(II) hexafluoridosilicate tetrahydrate, [Cu(bpy) 2 (H 2 O)][SiF 6 ]·4H 2 O (bpy is 2,2′-bipyridine, C 10 H 8 N 2 ), (I), bis(2,2′-bipyridine-3κ 2 N , N ′)-di-μ-fluorido-1:3κ 2 F : F ;2:3κ 2 F : F -decafluorido-1κ 5 F ,2κ 5 F -ditantalum(V)copper(II), [Cu(bpy) 2 (TaF 6 ) 2 ], (II), tris(2,2′-bipyridine-κ 2 N , N ′)copper(II) bis[hexafluoridotantalate(V)], [Cu(bpy) 3 ][TaF 6 ] 2 , (III), and catena -poly[[diaqua(2,2′-bipyridine-κ 2 N , N ′)copper(II)]-μ-fluorido-tetrafluoridotin-μ-fluorido], [Cu(bpy)(H 2 O) 2 SnF 6 ] n , (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C 2 , D 2 , and D 3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O—H...F and O—H...O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin. 

The crystal structures of three bridged bimetallic molecular compounds, namely, triaqua-2κ 3 O -μ-fluorido-pentafluorido-1κ 5 F -(1,10-phenanthroline-2κ 2 N , N ′)copper(II)titanium(IV) monohydrate, [Cu(TiF 6 )(phen)(H 2 O) 3 ]·H 2 O (phen is 1,10-phenanthroline, C 12 H 8 N 2 ), (I), triaqua-2κ 3 O -μ-fluorido-pentafluorido-1κ 5 F -(1,10-phenanthroline-2κ 2 N , N ′)copper(II)zirconium(IV) monohydrate, [Cu(ZrF 6 )(phen)(H 2 O) 3 ]·H 2 O, (II), and triaqua-2κ 3 O -μ-fluorido-pentafluorido-1κ 5 F -(1,10-phenanthroline-2κ 2 N , N ′)copper(II)hafnium(IV) monohydrate, [Cu(HfF 6 )(phen)(H 2 O) 3 ]·H 2 O, (III), and one molecular salt, bis[diaquafluorido(1,10-phenanthroline-κ 2 N , N ′)copper(II)] hexafluoridohafnate(IV) dihydrate, [CuF(phen)(H 2 O) 2 ] 2 [HfF 6 ]·2H 2 O, (IV), are reported. The bridged bimetallic compounds adopt Λ-shaped configurations, with the octahedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these Λ-shaped compounds are organized through both intra- and intermolecular hydrogen bonds and intermolecular π–π stacking. The salt compound [Cu(phen)(H 2 O) 2 F] 2 [HfF 6 ]·H 2 O displays an isolated square-pyramidal Cu(phen)(H 2 O) 2 F + complex linked to other cationic complexes and isolated HfF 6 2− anions through intermolecular hydrogen-bonding interactions.