Complexes of Ni II with new ligands N¢,N¢¢-bis(3-carboxy-1-oxoprop-2-enyl), 2-Amino-N-arylbenzamidine (C 21 H 17 N 3 O 6 ), N¢,N¢¢-bis(3-carboxy-1-oxopropanyl) 2-Amino-N-arylbenzamidine (C 21 H 21 N 3 O 6 ) and N¢,N¢¢-bis (3-carboxy-1-oxophenelenyl) 2-Amino-N-arylbenzamidine (C 29 H 21 N 3 O 6 ) have been synthesized and characterized by elemental analyses, vibrational spectra, electronic spectra, TOF-mass spectra, magnetic susceptibility measurements, thermal studies and X-ray powder diffraction studies. Vibrational spectra indicate coordination of amide and carboxylate oxygen of the ligands along with two water molecules giving a MO 6 weak field octahedral chromophore. Electronic spectra and magnetic susceptibility measurements reveal octahedral geometry for Ni II complexes. The elemental analyses and mass spectral data have justified the ML complexes. Kinetic and thermodynamic parameters were computed from the thermal data using Coats and Redfern method, which confirm first order kinetics. The crystal data: C 21 H 19 N 3 O 8 Ni is orthorhombic, space group P mmm , a = b = 9.015360(Å ), c = 10.554430(Å ), V = 572.11A 3 ; C 21 H 23 N 3 O 8 Ni is monoclinic, space group P 2/m , a = 15.08206(Å ), b = 5.358276(Å ), c = 9.898351(Å ), V = 671.58A 3 ; C 29 H 23 N 3 O 8 Ni is tetragonal, space group P 4/m , a = b = 6.328104(Å ), c = 9.82213(Å ), V = 393.33A 3 . Molecular structures of the complexes have been optimized by MM2 calculations and supported octahedral arrangements around Nickel(II) ions.