[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

摘要

A new microstructured mixed-valence oxovanadate with formula [NH3(CH2)(8)NH3](3) [V15O36(Cl)](NH3)(6)(H2O)(3) has been prepared hydrothermally (443 K, autogeneous pressure) by prolonged heating (5 days) of an aqueous 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 temperatures (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 cluster shells, [V15O36], built up from the linkage of 15 VO5 square pyramids, encapsulate the Cl- anionic species. Six [V15O36(Cl)](6-) clusters run along the threefold axis to form infinite pseudohexagonal one-dimensional channels (diameter 12.841 Angstrom) inside which three [NH3(CH2)(8) NH3](2+) chains are accommodated. Application tests in rechargeable lithium cells are presented. (C) 1998 Academic Press. [References: 21]