Oxydiacetato Complexes of Thorium(IV), the Crystal Structures of Tetra-aquo Bis(oxydiacetato) thorium(IV) Hexahydrate and Di(sodium nitrate) Disodium Tris(oxydiacetato) thorium(IV).

The crystal and mol. structure of Th(oda)2(H2O)4.6H2O (I, H2oda = O(CH2CO2H)2) and Na2[Th(oda)3].2NaNO3 (II) were detd. from 3-dimensional x-ray diffraction data and refined by least squares to R = 0.049 and Rw = 0.049 for 2265 independent reflections for I and to R = 0.024 and Rw = 0.023 for 2196 independent reflections for II. Crystal parameters are as follows: I, tetragonal, space group P41212, a 10.335(2), c 20.709(5) Å, and Z = 4; II, monoclinic, space group C2/c, a 17.096(5), b 9.451(2), c 16.245(4) Å, β 107.8(1), and Z = 4. In both compds. the Th-atom lies on a crystallog. 2-fold axis. The coordination no. of Th in I is 10 (bicapped square antiprism geometry), the compd. is monomeric, the 2 oda ligands are tridentate to the metal, and 4 H2O complete the coordination sphere; in II the coordination no. of Th is 9 (tricapped trigonal prism geometry) with 3 oda ligands tridentate to the metal; the [Th(oda)3]2- and NO3- anions are held together through the Na ions which are coordinated both to the oda carboxylic O and to the nitrate O. I was prepd. from Th(NO3)4 and Hoda.