N. Henry, M. Evain, P. Deniard
Nov 15, 2003
Citations
0
Influential Citations
46
Citations
Journal
Journal of Solid State Chemistry
Abstract
Abstract The bismuth basic nitrate [Bi6O4.5(OH)3.5]2(NO3)11 crystallizes in the monoclinic space group P21 with a=15.850(3) A , b=14.986(3) A , c=18.230(4) A , β=107.329(17)° and V=4133.7(14) A 3 (Z=4) . Its structure has been determined from 120 K , twinned crystal X-ray data (16 781 reflections, 683 parameters, R=0.0703). It is built upon [Bi6Ox(OH)8−x](10−x)+, x=4 and x=5 hexanuclear complexes and nitrate groups. The polycationic entities are linked to the nitrate anions either by hydrogen bonds or through bismuth–oxygen coordination. Even at 120 K , the [Bi6O4(OH)4]6+ and [Bi6O5(OH)3]5+ polycations could not be observed as such, the crystal structure refinement only detecting an average [Bi6O4.5(OH)3.5]5.5+ polycation. To prove the presence of both hexanuclear complexes in the structure, we report the existence of a correlation between the bismuth-linked oxygen bond-valence parameters and the presence, or not, of hydroxyl groups. Moreover, the Raman spectrum of the new anhydrous bismuth basic nitrate is compared to those of [Bi6O5(OH)3](NO3)5·3H2O, [Bi6O4(OH)4](NO3)6·4H2O, and two yet uncharacterized bismuth nitrates.