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Background Design of new metal complexes is an interesting field for development of new functional molecular based materials. In this process by the usage of mixed functional ligands one can precisely tune the physical and chemical properties of those metal complexes. However, it is difficult to obtain the desired complex in many cases for factors like different coordination abilities of the ligands and the types of anions have a great influence on the structure. Results A series of five copper(II) complexes [Cu(Bipy) (5-TPC) 2(H2O)] (1), [Cu(Phen) (5-TPC) 2(H2O)] (2), [Cu(NO3) (4,7-Phen) (5-TPC) (H2O)].H2O (3), [Cu(Bipy) 2(5-TPC)]2.(ClO4)2 (4), and [Cu2(Bipy)4(H2PO4)] (5) (where Bipy = 2,2'-bipyridine, Phen = 1,10-phenanthroline, 4,7-Phen = 4,7-hydroxy-1,10-phenanthroline, 5-TPC = 5-chloro-2 thiophene carboxylate) has been synthesized and characterised using single crystal X-ray diffraction studies. In all the compounds, the N,N' ligand coordinates in a bidentate chelating manner and the copper has a square pyramidal geometry. Conclusions Complexes (1,2) are expected to be isostructural due to similarity of the N.N'-chelating ligands used, but due to the difference in supramolecular architectures no similar unit cells were observed. This is important in crystal engineering point of view. Complexes (1-4) possess the neutral mononuclear and complex (5) possesses a dinuclear entity. These entities are connected by intermolecular interactions like X...π, H...X, (X = Cl) generating supramolecular architectures. [ABSTRACT FROM AUTHOR]

Background The usage of polynuclear metal clusters as secondary building units (SBU's) in designing of metal organic frameworks (MOF's) is a field of current interest. These metal clusters have attracted a great deal of attention not only due to their interesting structural topologies but also due to promising physical and chemical properties. In this regard various d,f block (transition and lanthanide) metal clusters have been widely investigated so far. Less attention is paid to construction of heavy p-block Pb(II) clusters. Results Two mixed ligand Pb(II) clusters have been synthesized with bipy(2,2'-Bipyridine), phen(1,10-Phenanthroline), quin (8-Hydroxy quinolinate) and 5-tpc (5-chloro thiophene 2- carboxylate). They have been characterized by elemental analysis, IR, TGA and X-ray crystallography. X-ray diffraction analysis reveals that the complexes [Pb4(quin)4(bipy)2(5- tpc)4] (1) and [Pb4(quin) 4(phen) 2(5-tpc)4] (2) are tetranuclear. The complexes show a slight variation in unit cell parameters, due to the replacement of bipy and the phen ligands. Both complexes contain two types of Pb(II) ions which differ in the coordination geometry around the Pb(II) ion. Conclusions In both complexes the four lead ions Pb1,Pb2, Pb1i and Pb2i lie on the same plane bridged by the 5-tpc anions. Pb1 and Pb2 of both complexes contain a 5-tpc and quin coordinated in a bidentate chelating bridging fashion. In addition the Pb2 and Pb2i ions alone contain a bipy and phen in a bidentate chelating fashion in (1) and (2) respectively. An additional notable feature in both of these complexes are the bridging ability of the quin oxygen which forms a network of coordination bonds in between the four Pb(II) ions. In both complexes the individual units are self-assembled by C-H---Cl/C-H---S hydrogen bonding interactions to generate 2-D aggregates. [ABSTRACT FROM AUTHOR]

Background: Lead is a heavy toxic metal element in biological systems and is one of the major pollutants as a result of its widespread use in industries. In spite of its negative roles the coordination chemistry of Pb(II) complexes is a matter of interest. The N,N'-bidentate aromatic bases such as BPY,4-BPY and PHEN (BPY = 2,2'bipyridine, 4-BPY = 4,4'-dimethyl-2,2'-bipyridine, PHEN = 1,10-Phenanthroline) are widely used to build supramolecular architectures because of their excellent coordinating ability and large conjugated system that can easily form π-π interactions among their aromatic moieties. A series of novel Pb(II) complexes in concert with 5-CTPC, 5-BTPC (5-CTPC = 5-chlorothiophen-2-carboxylate, 5-BTPC = 5-bromothiophen-2-carboxylate) and corresponding bidentate chelating N.N' ligands have been synthesized and characterized. Results: Five new Pb (II) complexes [Pb(BPY)(5-CTPC)2] (1), [Pb(4-BPY)(5-CTPC)2] (2), [Pb2(PHEN)2(5-CTPC)4] (3), [Pb(4-BPY)(5-BTPC)2] (4) and [Pb2(PHEN)2(5-BTPC)2(ACE)2] (5) have been synthesized. Even though in all these complexes the molar ratio of Pb, carboxylate, N,N-chelating ligand are the same (1:2:1), there is a significant structural diversity. These complexes have been characterised and investigated by elemental analysis, IR, 1H-NMR,13C-NMR, TGA, and photoluminescence studies. Single crystal X-ray diffraction studies reveal that complexes (1, 2) and (4) are mononuclear while (3 and 5) are dinuclear in nature which may result from the chelating nature of the ligands, various coordination modes of the carboxylates, and the coordination geometry of the Pb(II) ions. Conclusions: The observation of structures 2,4 and 3,5 show the structural changes made just chloro/bromo substituent of the thiophene ring. A detailed packing analysis has been undertaken to delineate the role of valuable non covalent interactions like X...π, H...X, (X = Cl/Br). A quadruple hydrogen bond linking the monomeric units and generating a supramolecular architecture is observed in (1). The metal bite unit comprised of PbN2C2 (i.e. Pb-N-C-C-N-Pb) is the repeating unit in all the five complexes and they have almost same geometrical parameters. This metal bite has been identified as the self assembly unit in complexes. [ABSTRACT FROM AUTHOR]

Background: Various dinuclear copper (II) complexes with octahedral geometry have been reported. The majority of these complexes contain N containing aromatic rings as axial ligands. There are also a few cases where the solvent used in the reaction occupies the axial position of the dinuclear copper (II) complex. This may occur by planned synthesis or some times by serendipity. Here we report some four copper (II) complexes containing solvent and or N containing heterocyclic ring as the axial ligand. Results: Four compounds, each containing dinuclear Copper (II) units (with the most robust, frequently occurring paddle wheel structures) were synthesized and characterised by single crystal X-ray diffraction and by IR spectroscopy. The compounds 1 & 2 have the general formula Cu2(RCOO) 4 (L) 2 [(for (1) RCOO= 4-Chloro Benzoate, L= Isopropanol; for 2 RCOO= Benzoate, L= 2-Amino-4,6-dimethyl pyrimidine )] while 3 & 4 have the general formula, Cu2 (RCOO) 4 (S) 2 Cu2 (RCOO) 4 (L) 2 [RCOO=5-Chloro-thiophene-2-carboxylate L= 2-Amino-4,6-dimethyl pyrimidine, for 3 S= ethanol; for 4 S= methanol ]. A wide range of hydrogen bonds (of the O-H...O, N-H...O and N-H...N type) and p-p stacking interactions are present in the crystal structures. Conclusions: All compounds contain the dinuclear units, in which two Cu (II) ions are bridged by four syn, syn-η¹ η¹ µ carboxylates, showing a paddle-wheel cage type with a distorted octahedral geometry. The compounds 1 & 2 contain a single dimeric unit while 3 & 4 contain two dimeric units. The structures 3 and 4 are very interesting co-crystals of two paddle wheel molecules. Also it is interesting to note that the compounds 3 & 4 are isostructural with similar cell parameters. Both the compounds 3 & 4 differ in the solvent molecule coordinated to copper in one of the dimeric units. In all the four compounds, each of the copper dimers has an inversion centre. Every copper has a distorted octahedral centre, formed by four oxygen atoms (from different carboxylate) in the equatorial sites. The two axial positions are occupied by copper and the corresponding ligand. [ABSTRACT FROM AUTHOR]