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Two penta-coordinate complexes of the general formula [CLn)(NCS)]ClO4, where L1 = bis[(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]-[(3,4-dimethoxypyridin-2-yl)methyl]amine and L2 = bis[(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]-[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]amine, have been synthesized and thoroughly characterized. Each of the cobalt(ii) atoms is penta-coordinated in the CoN5 donor set with a distorted square-pyramidal geometry in [CL1)(NCS)]ClO4·MeOH (1), while the vicinity of the central atom can be described as a distorted trigon

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