N-(ARYLSULFONYL)GLYCINES AS CYCLOMETALATING LIGANDS - CRYSTAL AND MOLECULAR-STRUCTURES OF DISODIUM BIS(MU-CHLORO)BIS[MU-N-(PHENYLSULFONYL)GLYCINATO-O,N,C]-BIS[MU-N-(PHENYLSULFONYL)GLYCINATO-O,O']TETRAPALLADATE(II) HEXAHYDRATE AND DISODIUM BIS(MU-CHLORO)BI

The interaction of N-(phenylsulfonyl)- and N-(4-tolylsulfonyl)- (N-tosyl hereafter) glycine (Bsgly and Tsgly, respectively) with Pd(II) ion at pH congruent-to 3.5 gives rise to cyclometalation reactions leading to complexes of the formulas Na2[Pd4Cl2(Bsgly-O,N,C)2(Bsgly-O,O')2].6H2O (I) and Na2[Pd4Cl2(Tsgly-O,N,C)(Tsgly-O,O')]2.4.5H2O.2TsglyH (II) (Bsgly-O,N,C and Tsgly-O,N,C = O,N,C-bonded ligand; Bsgly-O,O' and Tsgly-O,O' = carboxylate bridging ligand; TsglyH = neutral N-tosylglycine). The complexes crystallize in the triclinic P1BAR space group with a = 13.469 (4) angstrom, b = 13.636 (4) angstrom, c = 15.005 (5) angstrom, alpha = 70.94 (2)-degrees, beta = 66.32 (2)-degrees, gamma = 88.59 (2)-degrees, and Z = 2 for I and a = 17.058 (1) angstrom, 18.897 (2) angstrom, c = 13.194 (1) angstrom, alpha = 94.61 (1)-degrees, beta = 107.98 (1)-degrees, gamma = 74.32 (1)-degrees, and Z = 2 for II. Both structures consist of two tetrameric units, symmetry generated from two independent [Pd2Cl(L-O,N,C)(L-O,O')] (L = Bsgly or Tsgly) monoanions. In each tetramer one Pd(II) atom is coordinated with the deprotonated sulfonamide nitrogen and the carbon atom of the aromatic ring in the ortho position to the sulfonyl group of a ligand molecule, the bridging chlorine atom, and one oxygen atom of a bridging carboxyl from a second ligand molecule. The other crystallographically independent Pd(II) atom is coordinated with the other oxygen of the bridging carboxyl, the chlorine atom, the deprotonated sulfonamide nitrogen, and the oxygen atom of a monodentate carboxylate group forming a N,O-chelate glycine-like ring. Both of the Pd(II) atoms show a slightly distorted square-planar coordination geometry. Infrared and NMR results are also reported.