Substituted-benzoate complexes of nickel(II) of the types bidentate [Ni(mcN 3 )(Bz)](PF 6 ) and monodentate [Ni(mcN 3 )(Bz)(H 2 O)](PF 6 ) have been prepared by acid-base reaction between the hydroxo complexes [Ni(mcN 3 )(μ-OH)] 2 (PF 6 ) 2 (mcN 3 =2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene (Me 3 -mcN 3 ) or its 9-methyl derivative (Me 4 -mcN 3 )) and the corresponding benzoic acid. The paramagnetic nickel(II) complexes have been characterized in solution by NMR spectroscopy. The influence of the substituents on the hyperfine shift patterns for substituted-benzoate complexes of nickel(II) has been studied. The substituent effects upon the coordination mode of substituted benzoates have been established by X-ray diffraction.