Uranyl sequestering agents: Correlation of properties and efficacy with structure for UO{sub 2}{sup 2+} complexes of linear tetradentate 1-methyl-3-hydroxy-2(1H)-pyridinone ligands
- Lawrence Berkeley National Lab., CA (United States)
A rational design of uranyl sequestering agents based on 3-hydroxy-2(1H)-pyridinone ligands has resulted in the first effective agents for mammalian uranyl decorporation. In this study crystal structures of uranyl complexes with four of these agents are compared and correlated with the chemical and biological properties. These hydroxypyridinone ligands bind the uranyl ion in the equator of a pentagonal prism; a solvent molecule fills the fifth coordination site. The tetradentate ligands are composed of two hydroxypyridonate groups connected by a diamine linker via amide coupling. The dihedral angles between two pyridinone ring planes in these complexes differ as the length of linear backbone changes, giving these molecules a ruffled shape. The physical parameters (such as NMR chemical shifts) of the uranyl complexes with tetradentate Me-3,2-HOPO ligands correlate with the length of the diamine linker, as does the in vivo activity. The ligands are amides of 3-hydroxy-N-methyl-2-(1H)-4-carboxypyridone. For L{sup 1} the amine is propane amine. For the tetradentate bis-amides the linker groups are (L{sup 3}) 1,3-diaminopropane, (L{sup 4}) 1,4-diaminobutane, (L{sup 5}) 1,5-diaminopentane. Crystal data: [UO{sub 2}(L{sup 1}){sub 2}{center_dot}DMF], space group, C2/c, cell constants: a = 37.430(8) {angstrom}, b = 7.0808(14) {angstrom}, c = 26.781(5) {angstrom}, {beta} = 130.17(3){degree}, V = 5424(2) {angstrom}{sup 3}, Z = 8. [UO{sub 2}L{sup 3}{center_dot}DMSO], Pnma, a = 8.4113(1) {angstrom}, b = 16.0140(3) {angstrom}, c = 16.7339(3) {angstrom}, V = 2254.03(5) {angstrom}{sup 3}, Z = 4. [UO{sub 2}L{sup 4}{center_dot}DMSO]{center_dot}DMSO{center_dot}H{sub 2}O{center_dot}0.5C{sub 6}H{sub 12}, P2{sub 1}/n, a = 26.7382(4) {angstrom}, b = 7.4472(1) {angstrom}, c = 31.4876(2) {angstrom}, V = 6209.05(13) {angstrom}{sup 3}, Z = 8. [UO{sub 2}L{sup 5}{center_dot}DMSO]{center_dot}DMSO, Pnma, a = 7.3808(1) {angstrom}, b = 14.7403(3) {angstrom}, c = 23.134(3) {angstrom}, V = 2516.88(8) {angstrom}{sup 3}, Z = 4.
- Sponsoring Organization:
- USDOE Office of Energy Research, Washington, DC (United States); National Inst. of Environmental Health Sciences, Research Triangle Park, NC (United States)
- OSTI ID:
- 347504
- Journal Information:
- Inorganic Chemistry, Vol. 38, Issue 2; Other Information: PBD: 25 Jan 1999
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis of N-alkyl-3-hydroxy-2(1H)-pyridinones and coordination complexes with iron(III)
Functional and structural model for the molybdenum-pterin binding site in dimethyl sulfoxide reductase. Synthesis, crystal structure, and spectroscopic investigations of trichloro(quinonoid-N(8)H-6,7-dihydropterin)oxomolybdenum(IV)