Three new metal coordination polymers of bifunctional imidazolate/tetrazolate bridges: the only example of a three-dimensional framework based on rare [Co(μ-OH)(μ-Cl)] mixed oxo-chloro-clusters.

Three new metal coordination polymers [Ni(μ-L)(HO)] (1, HL = 1-tetrazole-4-imidazole-benzene), [Co(μ-L)] (2), and [Co(μ-OH)(μ-Cl)(μ-L)(μ-L)] ·7HO (3) were hydrothermally synthesized and structurally characterized. 1 displays a neutral [Ni(μ-L)(HO)] chain built up from the Ni ions bridged by deprotonated L ligands, while 2 shows another rare neutral [Co(μ-L)] chain based on Co ions connected by two different coordination modes of the L ligand. 3 exhibits a rare [Co(μ-OH)(μ-Cl)] mixed oxo-chloro-cluster-based three-dimensional framework with large elliptical channels, which are filled by unprecedented chilopod [(HO)] chains. Both 1 and 2 show antiferromagnetic behavior, while 3 exhibits unusual spin-canting.