Organic‐Inorganic Hybrid Materials: Syntheses, X‐ray Diffraction Study, and Characterisations of Manganese, Cobalt, and Copper Complexes of Modified Bis(phosphonates)  

Abstract

Abstract Four new cobalt, manganese, and copper bis(phosphonates), [Co 2 {Cl 2 C(PO 3 ) 2 }(H 2 O) 7 · 4H 2 O] ( 1 ), [Co{Cl 2 C(PO 2 O(C(O)C 6 H 5 )) 2 (H 2 O) 5 } · 2H 2 O{Cl 2 C(PO 2 O(C(O)C 6 H 5 )) 2 }{Co(H 2 O) 6 }] ( 2 ), [Mn{[Cl 2 C(PO 2 O(C(O)C 6 H 5 )) 2 ](H 2 O) 3 }] ( 3 ), and [Cu{(CH 2 C 5 H 5 N)C(OH)(PO 3 H) 2 } 2 · 4H 2 O] ( 4 ), were prepared by gel, liquid, and evaporation crystallisation methods. Compounds 1 – 4 were characterised by X‐ray single‐crystal diffraction, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The effects of metal and various substituted groups in bis(phosphonate) ligands on the structure formation of bis(phosphonates) were studied. In the structure of 1 , the clodronic acid ligand ( L1 ) is in bischelating bonding mode, and the dinuclear units of 1 are surrounded by two‐dimensional water cluster patterns. The hydrogen bond network of compound 1 is extended to a three‐dimensional framework when the phosphonate oxygen atoms serve as hydrogen‐bond acceptors. In complex 2 , the CoO 6 octahedron shares a corner of one PCO 3 tetrahedron of the dibenzoyl derivative of clodronic acid ligand ( L2 ), and forms a two‐dimensional hydrogen bonding network, which consists of [Co(H 2 O) 6 }] 2+ cations, lattice water molecules and L2 ligand molecules. Compound 3 , in turn, consists of dimeric building blocks built up of PCO 3 tetrahedra of the ligand L2 , which connect the corner‐sharing MnO 6 octahedra and form an overall 2D structure through hydrogen bonds of coordinated and crystal water molecules and phosphonate oxygen atoms. Complex 4 is among the first metal complexes of risedronic acid ( L3 ). In compound 4 , two L3 ligand molecules chelate tridentately the Cu II atom at the center of symmetry, and the monomeric units of 4 are connected to a 3D structure through hydrogen bonding of coordinated and lattice water molecules to both protonated and deprotonated phosphonate oxygen atoms and protonated nitrogen atoms in the pyridine ring.