Hydrolysis Studies on Bismuth Nitrate: Synthesis and Crystallization of Four Novel Polynuclear Basic Bismuth Nitrates

Hydrolysis of Bi(NO3)(3) in aqueous solution gave crystals of the novel compounds [Bi6O4(OH)(4)(NO3)(5)(H2O)](NO3) (1) and [Bi6O4(OH)(4)(NO3)(6)(H2O)(2)]center dot H2O (2) among the series of hexanuclear bismuth oxido nitrates. Compounds 1 and 2 both crystallize in the monoclinic space group P2(I)/n but show significant differences in their lattice parameters: 1, a = 9.2516(6) angstrom, b = 13.4298(9) angstrom, c = 17.8471(14) angstrom, beta = 94.531(6)degrees, V = 2210.5(3) angstrom(3); 2, a = 9.0149(3) angstrom, b = 16.9298(4) angstrom, c = 15.6864(4) angstrom, beta = 90.129(3)degrees, V = 2394.06(12) angstrom(3). Variation of the conditions for partial hydrolysis of Bi(NO3)(3) gave bismuth oxido nitrates of even higher nuclearity, [{Bi38O45(NO3)(24)(DMSO)(26)}center dot 4DMSO][{Bi38O45(NO3)(24) (DMSO)(24)}center dot 4DMSO] (3) and [(Bi38O45(NO3)(24)(DMSO)(26)}center dot 2DMSO][{Bi38O45(N-3)(24)(DMSO)(24)}center dot 0.5DMSO] (5), upon crystallization from DMSO. Bismuth mddo clusters 3 and 5 crystallize in the triclinic space group PT both with two crystallographically independent molecules in the asymmetric unit. The following lattice parameters are observed: 3, a = 20.3804(10) angstrom, b = 20.3871(9) angstrom, c = 34.9715(15) angstrom, a = 76.657(4)degrees, beta = 73.479(4)degrees, Y = 60.228.(5)degrees, V= 12021.7(9) angstrom(3); 5, a = 20.0329(4) angstrom, b = 20.0601(4) angstrom, c = 34.3532(6) angstrom, a = 90.196(1)degrees beta = 91.344(2)degrees, gamma = 119.370(2)degrees, V = 12025.8(4) angstrom(3). Differences in the number of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate, DMSO) coordination modes are observed.