The tetraazamacrocyclic ligand 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMC) has been used to bind a variety of first-row transition metals but to date the crystal structure of the cobalt(II) complex has been missing from this series. The missing cobalt complex chlorido(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane-κN)cobalt(II) chloride dihydrate, [CoCl(CHN)]Cl·2HO or [CoCl(TMC)]Cl·2HO, crystallizes as a purple crystal. This species adopts a distorted square-pyramidal geometry in which the TMC ligand assumes the trans-I configuration and the chloride ion binds in the syn-methyl pocket of the ligand. The Co ion adopts an S = 3/2 spin state, as measured by the Evans NMR method, and UV-visible spectroscopic studies indicate that the title hydrated salt is stable in solution. Density functional theory (DFT) studies reveal that the geometric parameters of [CoCl(TMC)]Cl·2HO are sensitive to the cobalt spin state and correctly predict a change in spin state upon a minor perturbation to the ligand environment.
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