Hydrothermal synthesis, structure, and magnetic properties of the mixed-valent Np(IV)/Np(V) selenite, Np(NpO{sub 2}){sub 2}(SeO{sub 3}){sub 3}.
The reaction of NpO{sub 2} with SeO{sub 2} in the presence of CsCl at 180 {sup o}C results in the formation of Np(NpO{sub 2}){sub 2}(SeO{sub 3}){sub 3} (1). The structure of 1 consists of three crystallographically unique Np centers with three different coordination environments in two different oxidation states. Np(1) is found in a neptunyl(V), ONpO{sup +}, unit that is further ligated in the equatorial plane by three chelating SeO{sub 3}{sup 2-} anions to create a hexagonal bipyramidal NpO{sub 8} unit. A second neptunyl(V) cation also occurs for Np(2); it is bound by four bridging selenite anions and by the oxo atom from the Np(1) neptunyl cation to form a pentagonal bipyramidal, NpO{sub 7}, unit. The third neptunium center, Np(3), which contains Np(IV), is found in a distorted NpO{sub 8} dodecahedron. Np(3) is bound by five bridging selenite anions and by three neptunyl units via cation-cation interactions. The NpO{sub 7} pentagonal bipyramids and NpO{sub 8} hexagonal bipyramids share both corners and edges. Both of these polyhedra share corners via cation-cation interactions with the NpO{sub 8} dodecahedra creating a three-dimensional structure with small channels that house the stereochemically active lone pair of electrons on the selenite anions. Magnetic susceptibility data follow Curie-Weiss behavior over the entire temperature range measured (5 {<=} T {<=} 320 K). The effective moment, {mu}{sub eff} = 2.28 {mu}{sub B}, which represents an average over the three crystallographically inequivalent Np atoms, is within the expected range of values. There is no evidence of long-range ordering of the Np moments at temperatures down to 5 K, consistent with the negligible Weiss constant determined from fitting the susceptibility data. Crystallographic data: 1, orthorhombic, space group Pbca, a = 10.6216(5), b = 11.9695(6), and c = 17.8084(8) {angstrom} and Z = 8 (T = 193 K).
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 961512
- Report Number(s):
- ANL/CHM/JA-48585
- Journal Information:
- Inorg. Chem., Journal Name: Inorg. Chem. Journal Issue: 3 ; Feb. 9, 2004 Vol. 43; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- ENGLISH
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