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New Cd(II) and Hg(II) complexes of five previously known dithiophosphonic acids ((p-MeO-C6H4)PS(SH)(OR), HL n , (n= 1-5); R= 3-pentyl-, HL 1 ; R=1-phenyl-1-propyl-, HL 2 ; R= 4-tertbutylbenzyl-, HL 3 ; R= diphenylmethyl-, HL 4 ; R= 4-tert-butylcyclohexyl-, HL 5 ) were prepared and characterized. To do this, the dithiophosphonic acids involved were treated with stoichiometric amount of the corresponding metal salts in methyl alcohol. The complexes came of as powdery crystals and were recrystallized from chloroform. The pure complexes were characterized by using elemental analyses as well as mass-(ESI), FTIR-, Raman-, NMR-( 1 H, 13 C, 31 P) spectroscopies.

Thionation of 3-methylbutylmagnesium bromide with Lawesson's Reagent (LR) gave 4-methoxyphenyl (3-methylbutyl)dithiophosphinic acid (DTPA), and the latter was converted to the ammonium salt (NH 4 L = Ammonium 4-methoxyphenyl (3-methylbutyl) dithiophosphinate). The complex, trans-bis[4-methoxyphenyl(3-methylbutyl) dithiophosphinato] nickel(II) [NiL 2 ], was prepared by the reaction of NH 4 L with NiCl 2 .6H 2 O in EtOH. Bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) [(CoL 2 ) 2 ] was also prepared in the same way. The structures of the complexes have been characterized by elemental analysis, FTIR, 1 H, 13 C, 31 P NMR and X-ray diffraction. The single crystal X-ray structures of [NiL 2 ] and [(CoL 2 ) 2 ] show that the nickel complex is square planar while the cobalt counterpart has tetrahedral coordination with a dimeric structure. Bond lengths, angles, torsion angles and dihedral angles are correlated to the structures and also compared with the literature data on similar compounds.

Key indicators: single-crystal X-ray study; T = 100 K; mean (C-C) = 0.002 Å; disorder in main residue; R factor = 0.029; wR factor = 0.077; data-to-parameter ratio = 18.3.In the centrosymmetric binuclear title complex, [Zn 2 (C 11 H 14 -NO 2 ) 4 (C 10 H 14 N 2 O) 2 ], the two Zn II ions [ZnÁ Á ÁZn = 2.8874 (3) Å ] are bridged by four 4-(diethylamino)benzoate (DEAB) ligands. The four nearest O atoms around each Zn II ion form a distorted square-planar arrangement, the distorted square-pyramidal coordination being completed by the pyridine N atom of an N,N-diethylnicotinamide (DENA) ligand at a distance of 2.0484 (12) Å . The dihedral angle between the benzene ring and the carboxylate group is 4.89 (6) in one of the independent DEAB ligands and 7.13 (7) in the other. The benzene rings of the two independent DEAB ligands are oriented at a dihedral angle of 86.58 (5) . The pyridine ring is oriented at dihedral angles of 31.17 (4) and 58.38 (4) with respect to the two benzene rings. In the crystal, weak intermolecular C-HÁ Á ÁO interactions link the molecules into a three-dimensional network. Two weak C-HÁ Á Á interactions are also present. The two ethyl groups of one of the DEAB ligands are disordered over two orientations, with occupancy ratios of 0.798 (5)

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