Two novel neutral cadmium(II) complexes, Cd3Cl6(L1)2.11(H2O) (C1) and CdCl2L2 (C2), where L1 = N(SO2)(biphenyl)dpa and L2 = N(SO2)(4-methylbiphenyl)dpa, have been synthesized and characterized with single crystal X-ray diffraction and spectroscopic methods. The trinuclear complex C1, C48H42Cd3Cl6N6O4S2.11(H2O), crystalizes in the orthorhombic space group Pbca, with a = 19.2969(17) Å, b = 10.1998(9) Å, c = 26.569 (2) Å, Z = 4; R for 4283 observed reflections [I&gt;2σ(I)] was 0.053. This complex consists of a linear arrangement of three cadmium atoms. The central cadmium atom, located on a crystallographic inversion center, is connected by two other four bridging chlorine atoms and two oxygen atoms of each ligand. It has an almost perfect octahedral coordination environment. The outer symmetry-related cadmium atoms are in a distorted octahedral environment, and they coordinate to NNN donor L1 ligand in tridentate mode and two bridging chlorine atoms and one chlorine atom. The mononuclear complex C2, C25H23CdCl2N3O2S crystallizes in the monoclinic space group P21/c with a = 19.5525(9) Å, b = 9.6174(5) Å, c = 13.4456(6) Å, β = 100.501(1)o and Z = 4; R for 10474 observed reflections [I&gt;2σ(I)] was 0.035. The coordination about the Cd can be described as a distorted trigonal bipyramidal where the axial sites are formed by a chlorine atom and amine N of the ligand. The angles in the equatorial plane of the Cd ion range from 100.53(4)o-125.83(4)o, while the value of the axial Cl-Cd-N angle is 158.90(3)o. Both Cd(II) complexes form semi-coordination bonds with the central N atom of L1 and L2; fairly long distances, 2.728(4) Å for C1 and 2.7491(12) Å for C2, thus leading to distorted coordination geometries. The high energy absorption peaks around 200-300 nm in UV-visible spectra may be due to intra-ligand π→π* and n→π*transitions. The stretching vibration frequencies depicted by the S-N bond of L1 (923 cm-1) and L2 (920 cm-1) both appear towards higher frequencies in FTIR spectra of C1 (921 cm-1)and C2 (929 cm-1)complexes. This talk will focus on structural aspects of the first structurally characterized dipicolylamine derivatized sulfonamide complexes of cadmium.

Trinuclear and mononuclear Cd(II) complexes with the biphenyl-derived sulfonamide ligands: Synthesis, spectral, and structural analysis

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