A Basic Bismuth(III) Dodecahydro‐closo‐Dodecaborate Hydrate: [Bi6O4(OH)4][B12H12]3·10H2O

Abstract

AbstractThe reaction of Bi2O3 with an aqueous solution of(H3O)2[B12H12] leads to a basic bismuth(III) dodecahydro‐closo‐dodecaborate hydrate in the shape of colorless, hexagonally plate‐shaped single crystals. The new compound with the formula [Bi6O4(OH)4][B12H12]3·10H2O crystallizes in the monoclinic space group P21/c(a = 1837.15(9), b = 1810.64(9), c = 1360.28(7) pm, β = 90.867(3)°) with four formula units per unit cell. The crystal structure contains six crystallographically independent Bi3+ cations forming an octahedral (Bi3+)6 cluster with eight oxygen atoms capping all octahedral faces. Four of these particles represent oxide anions, whereas the other four belong to hydroxide groups. These eight oxidic ligands themselves arrange around the (Bi3+)6 cluster in the shape of a trigonal dodecahedron. Furthermore seven water molecules are situated around each cationic [Bi6O4(OH)4]6+ complex to complete the coordination sphere of every Bi3+ cation and three more serve to fill up voids in the crystal structure. In addition, direct hydrogen contacts of the quasi‐icosahedral [B12H12]2– anions to the bismuth(III) cations occur. Despite this fact the icosahedral shape of these charge‐compensating [B12H12]2– cluster anions is only slightly distorted.