X-ray diffraction study of bisphosphonate metal complexes: Mg, Sr and Ba complexes of (dichloromethylene)bisphosphonic acid P,P′-dibenzoyl anhydride

Kunnas-Hiltunen, Susan; Matilainen, Mervi; Vepsäläinen, Jouko; Ahlgrén, Markku

doi:10.1016/j.poly.2008.10.030

Cited by 18 publications

(12 citation statements)

References 39 publications

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“…Generally, the L2 ligand tends to chelate and/or bridge the metal atoms, and therefore the size of the ionic radii of the metal has an effect. In addition to the Co 2+ ion (ionic radius 0.745 Å 19), the L2 also binds the hexacoordinate Mg 2+ ion (ionic radius 0.72 Å 19) in a monodentate fashion 13. With hexacoordinate Ni 2+ (ionic radius 0.69 Å 19) and Zn 2+ ions (ionic radius 0.74 Å 19), the L2 ligand coordinates metals in a monodentate manner, but also bridges them to the hexacoordinate Na + ion (ionic radius 1.02 Å 19), forming polymeric chains 14.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Antioxidant Evaluation of Some New 3‐Substituted Coumarins

Hamama

Berghot

Baz

et al. 2011

Archiv der Pharmazie

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3-Acetylcoumarin (1) was utilized as a key intermediate for the synthesis of 2-aminothiazole derivative 3 via bromination of 1 to afford acetylbromide 2 followed by treatment with thiourea or via Biginelli reaction of 1. Treatment of 3 with 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, 2-methyl-4H-benzo[d][1,3]oxazin-4-one, furo[3,4-b]pyrazine-5,7-dione or 2-methyl-5,6,7,8-tetrahydro-4H-benzothieno[2,3-d][1,3]oxazin-4-one afforded diazine derivatives 4-7. Also, pyridopyrimidine 8 was obtained via a one pot reaction of 6-aminothiouracil, p-chlorobenzaldehyde and 3-acetylcoumarin. Moreover, refluxing of 6-aminothiouracil with one equivalent amount of 2 afforded the thiazolopyrimidine 9, while the pyrrolothiazolopyrimidine 10 was revealed when two equivalent amounts of 2 was used. Furthermore, treatment of enamine 11 with 2-aminobenzothiazole or 6-aminothiouracil afforded the pyrimidine derivatives 12 and 13, respectively. Transamination of enamine 11 with m-anisidine followed by cyclization of the resulting enaminone 14 gave the desired quinoline 15. Also, treatment of 11 with thiophenol in dioxane gave the mercapto derivative 16. Moreover, coupling of 11 with 4,6-dimethyl-1H-pyrazolo[3,4-b]pyridin-3-yl-diazonium chloride, followed by complete cyclization of the resulting product afforded the pyridopyrazolothiazine 19 via the intermediate 18. Furthermore, the pyrazolopyrimidine 20 was revealed via a one pot condensation of 11, 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and ammonium acetate. The thiadiazine derivatives 21-23 were obtained via treatment of 2 with the corresponding o-aminothiols. Desulphonation of 23 afforded the pyrazolotriazine 24. Finally, reaction of 2 with 2-hydroxybenzaldehyde gave benzofuran derivative 25. Representative compounds of the synthesized products were evaluated as antioxidant agents.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Antioxidant Evaluation of Some New 3‐Substituted Coumarins

Hamama

Berghot

Baz

et al. 2011

Archiv der Pharmazie

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“…[14] Our results indicated that the Cl 2 C(PO 2 O(C(O)C 6 H 5 )) 2 2-ligand (L1) can act as a bridging and a chelating ligand forming 2D layer structures by intermolecular hydrogen bonds between monomeric units and polymeric chains. Here, we report our preparation of isomorphic Ni and Zn complexes of the dibenzoyl derivative of clodronic acid:…”

Section: Introductionmentioning

confidence: 71%

“…The synthesis and characterisation of P,PЈ-dibenzoyl-dichloromethylenebis(phosphonate) disodium salt Na 2 Cl 2 C{PO 3 [C(O)C 6 H 5 ]} 2 (Na 2 L1) have been reported earlier. [12] As has been discussed before, [14] crystallisation time is an essential factor in synthesising the metal complexes of the dibenzoyl derivative. The crystals of L1 complexes need to form within a few days, or the hydrolysis product will form instead.…”

Section: Methodsmentioning

confidence: 98%

“…[4b,5k] The rate of hydrolysis of the L1 ligand is dependent on the pH, [12] but the pH changes in the same way in the formation of the alkaline earth metal complexes of L1 and the corresponding complexes of clodronic acid. [14] The pH values of all syntheses of 1-4 were in the range where the ligand should not hydrolyse quickly. [12] A look at the pH of previously published [13a-13b] Zn complexes of clodronic acid and its derivatives and that of the Ni and Zn complexes 1-4, shows that the Ni and Zn complexes of clodronic acid are formed at lower pH than the Ni and Zn complexes of its derivatives.…”

Section: Synthesismentioning

confidence: 99%

“…[14] The assignments of the Ni and Zn complexes 1-4 are based on earlier results, published values for similar compounds and IR tables. [19] For compounds 1 and 2 the characteristic region was observed at 1735-700 cm -1 , whereas the characteristic region for the metal complexes of clodronic acid 3 and 4 appeared in the region 1135-760 cm -1 .…”

Section: Spectroscopic Propertiesmentioning

confidence: 99%

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Syntheses, X‐ray Diffraction Study and Characterisations of Ni and Zn Complexes of Clodronic Acid and Its Dibenzoyl Derivative

et al. 2009

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Four new nickel and zinc bis(phosphonates) were prepared, and their crystal structures were determined by single‐crystal X‐ray diffractometry: [{Na2Ni3(Cl2C(PO2O(C(O)C6H5))2)(H2O)20}{Cl2C(PO2O(C(O)C6H5))2}]n (1), [{Na2Zn3(Cl2C(PO2O(C(O)C6H5))2)(H2O)20}{Cl2C(PO2O(C(O)C6H5))2}]n (2), [Ni2{Cl2C(PO3)2}(H2O)7]·4H2O (3) and [Zn2{Cl2C(PO3)2}(H2O)7]·6H2O (4). In addition, the spectroscopic and thermal properties of the compounds 1–4 were studied by infrared spectroscopy and thermogravimetric analysis. The coordination polymers 1 and 2 form, through intermolecular hydrogen bonds, 2D layer‐like structures, whereas the aqua ligands and lattice water molecules of the monomeric compounds 3 and 4 form hydrogen bonds in three dimensions giving rise to a 3D network. In the isomorphous structures 1 and 2 the octahedral Na and Ni/Zn atoms form μ‐H2O‐bridged stepped metal chains where the Cl2C(PO2O(C(O)C6H5))22– ligands (L1) are monodentately coordinated to the Na and Ni/Zn atoms, and the lattice L1 ligands are located in a trans position with respect to the chain. The isostructural Ni and Zn complexes of clodronic acid, 3 and 4, are formed by a hydrolysis method from the L1 ligand. There, the clodronate ligand acts as a bridging and chelating ligand with the octahedral Ni and Zn atoms. The bulky and hydrophopic benzoyl groups of the L1 ligand in structures 1 and 2 lead to dense packing modes. The clodronic acid ligand of structures 3 and 4, in turn, has a higher coordination flexibility and forms voids, where the water clusters are trapped by hydrogen bonds.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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

Kunnas-Hiltunen

Laurila

Haukka

et al. 2010

Zeitschrift anorg allge chemie

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Four new cobalt, manganese, and copper bis(phosphonates), [Co2{Cl2C(PO3)2}(H2O)7·4H2O] (1), [Co{Cl2C(PO2O(C(O)C6H5))2(H2O)5}·2H2O{Cl2C(PO2O(C(O)C6H5))2}{Co(H2O)6}] (2), [Mn{[Cl2C(PO2O(C(O)C6H5))2](H2O)3}] (3), and [Cu{(CH2C5H5N)C(OH)(PO3H)2}2·4H2O] (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 CoO6 octahedron shares a corner of one PCO3 tetrahedron of the dibenzoyl derivative of clodronic acid ligand (L2), and forms a two‐dimensional hydrogen bonding network, which consists of [Co(H2O)6}]2+ cations, lattice water molecules and L2 ligand molecules. Compound 3, in turn, consists of dimeric building blocks built up of PCO3 tetrahedra of the ligand L2, which connect the corner‐sharing MnO6 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 CuII 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.

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X-ray diffraction study of bisphosphonate metal complexes: Mg, Sr and Ba complexes of (dichloromethylene)bisphosphonic acid P,P′-dibenzoyl anhydride

Cited by 18 publications

References 39 publications

Synthesis and Antioxidant Evaluation of Some New 3‐Substituted Coumarins

Synthesis and Antioxidant Evaluation of Some New 3‐Substituted Coumarins

Syntheses, X‐ray Diffraction Study and Characterisations of Ni and Zn Complexes of Clodronic Acid and Its Dibenzoyl Derivative

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

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