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Two multinuclear complexes synthesized from Cu(NO3)2 and 6,6'-di-hydroxy-bipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6'-di-hydroxy-bipyridine-2κ(2) N,N')[μ-6-(6-hy-droxy-pyridin-2-yl)pyridin-2-olato-1:2κ(3) N,N':O (2)](μ-hydroxido-1:2κ(2) O:O')(μ-nitrato-1:2κ(2) O:O')(nitrato-1κO)dicopper(II), [Cu2(C10H7N2O2)(OH)(NO3)2(C10H8N2O2)] or [Cu(6-OH-6'-O-bpy)(NO3)(μ-OH)(μ-NO3)Cu(6,6'-dhbp)], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water-ethanol mixture at neutral pH. The hexa-nuclear complex bis-(μ3-bi-pyridine-2,2'-diolato-κ(3) O:N,N':O')tetra-kis-(6,6'-di-hydroxy-bipyridine-κ(2) N,N')tetra-kis-(μ-hydroxido-κ(2) O:O')bis-(methanol-κO)tetra-kis-(μ-nitrato-κ(2) O:O')hexa-copper(II), [Cu6(C10H6N2O2)2(CH4O)2(OH)4(NO3)4(C10H8N2O2)4] or [Cu(6,6'-dhbp)(μ-NO3)2(μ-OH)Cu(6,6'-O-bpy)(μ-OH)Cu(6,6'dhbp)(CH3OH)]2, (II), with a 1:1 NO3-OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intra-molecular O-H⋯O hydrogen bonding. Inter-molecular O-H⋯O hydrogen bonding links symmetry-related mol-ecules forming chains along [100] for complex (I) with π-stacking along [010] and [001]. Complex (II) forms inter-molecular O-H⋯O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].

Crystal structures of bis- and hexakis[(6,6′-dihydroxybipyridine)copper(II)] nitrate coordination complexes