Jean-Paul Silvestre

ÉTUDE DE LA COMPLEXATION DU CADMIUM ET DU ZINC AVEC L'ALENDRONATE (ACIDE 4-AMINO-1-HYDROXYBUTYLIDÈNE-1′1-BISPHOSPHONIQUE)

Abstract Structural study using X-ray cristallography of the complexes of the title has been done. Alendronate is already known to be a very good chelator of divalent cations and supramolecular species obtained with alendronate and these cations are very stable and make them able to be used in biological systems. Our study points out that the size of the cation strongly modifies the structure of the complex. With Cu(II) and Zn(II) which are two cations with proximate ionic radii one cation is put in the centre of the coordination system and structures are isomorphous. On the other hand, with Cd(II), a binuclear complex is obtained. Results are discussed on the basis of these structures.

Crystal structure of the gadolinium trihydrogenohydroxy-1 ethane bis(phosphonate)-1,1' trihydrate

Abstract The title complex salt Gd[C(CH3)(OH)(PO3H)(PO3)],3H2O is obtained by progressive dissolving of gadolinium carbonate in an aqueous solution of hydroxyethylidenebisphosphonic acid (HEBP). This compound crystallizes with the orthorhombic space group Pbca (n°61) and a = 9.690(1) Å, b = 9.744(2) Å, c = 20.585(4) Å, V = 1943.7(5) Å3, and Z = 8. The coordinence of Gadolinium is 8 and the corresponding polyhedra are associated two by two by sharing an edge to form centrosymmetric “bipolyhedra.” The crystal cohesion is assumed by one interligand hydrogen bond and mainly by the hydrogen bond network given by the three water molecules. This compound, where the ligand is tri-ionized, is totally different from the other known lanthanide salts (Ln = Ho, Er, Y) where mono- and di-ionized HEBP ligands coexist with the ratio 1/1.

STRUCTURE DU DIHYDROGÉNO HYDROXY-1 ÉTHANEBIS(PHOSPHONATE)-1,1′DE CADMIUM DIHYDRATE

Abstract The synthesis of the complex Cadmium 1-hydroxyethylidene-1, 1-bisphosphonate dehydrated Cd(HEBP).2H2O is described. This compound crystallizes with the monoclinic P21/n (n°14)group and a = 14.229(3)Å, b equals; 5.613(1)Å;, c equals; 11.521(3)Å, β equals; 93.06(1)°, V equals; 918.8(4) Å3, Z equals; 4. Cd is sixfold coordinated. It is bonded to one tridentate, one bidentate and one monodentate (HEBP)2− ligands. The structure is made up of chains of summit-sharing CdO6 polyhedra along the [010] direction. These chains are linked together through hydrogen bonds involving the water molecules. (HEBP)2− ligands are only linked together by weak hydrogen bonds involving also and exclusively the water molecules. The complex Hg(HEBP).2H2O synthesized by the same method is isostructural; the cell parameters are: a=14.346(4) Å, b =5.692(2) Å, c =11.621(4)Å, β=95.17(2)°, V =945(1)Å3.

Refinement by Neutron Diffraction of the Crystal Structure of Hydroxyethylidene Bisphosphonic ACID Monohydrate: C(CH 3 )(OH)(PO 3 H 2 ) 2 ·H 2 O

The neutron diffraction study of the crystal structure of C(CH 3 )(OH)(PO 3 H 2 ) 2 ·;H 2 O carried out at room temperature led to a least squares refinement based on 949 reflections with R ( F 2 ) = 0.0471 and R w ( F 2 ) = 0.0473. This compound crystallizes with the monoclinic P2 1 / c (n°;14) space group and a = 6.983(3)Å, b = 17.56(3)Å, c = 7.109(9)Å, g = 108.5(1)°;, V = 826.4Å 3 , and Z = 4. This investigation gives precise details about the hydrogen atom positions, the hydrogen bonds, and the configuration of the hydroxyethylidene bisphosphonic molecule which is then compared to that of the rubidium salt previously studied also by neutron diffraction. 2

Structure Cristalline de L'Éthylènediammonium HydroxyÉthylidènebisphosphonate

The organic complex salt [H 3 N--CH 2 --CH 2 --NH 3 ][C(CH 3 )(OH)(PO 3 H 2 )(PO 3 H)] 2 is obtained by reaction between the hydroxyethylidenebisphosphonic acid (HEBP) and the ethylenediamine (EDA) in aqueous medium. This compound, the first where the cation is an organic base, crystallizes with the monoclinic space group P2 1 / c (n°;14) and a = 6.867(1) Å, b = 11.665(2) Å, c = 10.977(2) Å, g = 101.85(4)°;, V = 861.2(2) Å 3 , Z = 2. The cohesion of the crystal structure is assumed exclusively by a dense network of hydrogen bonds between two HEDP m and between one HEDP m and one EDA 2+ .

SYNTHÈSE ET ÉTUDE STRUCTURALE D'ACIDES DIHYDROXYTÉTRAPHOSPHONIQUES ET DE SELS DE CES ACIDES. III: UN CAS D'ISOMORPHISME ENTRE LE SEL DE POTASSIUM ET L'ACIDE 1,6-DIHYDROXYHEXYLIDÈNE-1,1,6,6-TÉTRAPHOSPHONIQUE (DHHTP) HYDRATÉ

Abstract The determination by X-ray diffraction of the crystal structure of the 1,6-Dihydroxyhexylidene-1,1,6,6-tetraphosphonic acid (DHHTP) has shown that this compound cristallizes in normal conditions as an oxonium sait (1) with 2 water molecules. This compound and the Potassium sait (2) are isostructural and crystallize in the monoclinic C2/c (n°15) space group with Z = 4 and (1): a = 19.935(3)Å, b = 9.925(2)Å, c = 10.195(3)Å β = 108.51(2)°, V = 1912.8(7)Å3; (2) a = 19.914(5)Å b = 9.813(3)Å, c = 10.046(2)Å, β = 107.83(2), V = 1872.5(7)Å3. The Potassium (or Oxonium) cation is eightfold coordinated. The coordination polyhedra are grouped two by two by pooling four oxygen atoms to form ≪ bispolyhedra ≫. The ligands DHHT2− , where the hydrocarboned chain is into maximum extension, are linked together by hydrogen bonds to form molecular chains which are themselves linked together by strong hydrogen bonds. The Infrared and Raman spectra are given.