[NH3(CH2)(8)NH3](3)[V15O36(CL)](NH3)(6)(H2O)(3) - SYNTHESIS AND STRUCTURE DETERMINATION OF A NOVEL CENTERED TRICOSAHEDRAL CLUSTER COMPOUND RELATED TO THE MULLER-TYPE STRUCTURE

A new microstructured mixed-valence oxovanadate with formula [NH3(CH2) (8)NH3](3) [V15O36(Cl)](NH3)(6)(H2O)(3) has been prepared hydrothermal ly (443 K, autogeneous pressure) by prolonged heating (5 days) of an a queous mixture of NH2(CH2)(8) NH2 and V2O5 in acidic HCl (1M) medium. Its structure was solved by single-crystal X-ray diffraction at two te mperatures (293 and 150 K). It is hexagonal (space group P6(3)/mmc, Z = 2) with cell parameters a = 18.730(3)Angstrom, c = 11.040(3)Angstrom and V = 3354.1(5)Angstrom(3) at 293 K and a = 18.626(3)Angstrom, c = 10.961(3)Angstrom, and V = 3293.2(5)Angstrom(3) at 150 K. Spherical cl uster shells, [V15O36], built up from the linkage of 15 VO5 square pyr amids, encapsulate the Cl- anionic species. Six [V15O36(Cl)](6-) clust ers run along the threefold axis to form infinite pseudohexagonal one- dimensional channels (diameter 12.841 Angstrom) inside which three [NH 3(CH2)(8) NH3](2+) chains are accommodated. Application tests in recha rgeable lithium cells are presented. (C) 1998 Academic Press.