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]·H2O (2) among the series of hexanuclear bismuth
oxido nitrates. Compounds 1 and 2 both crystallize
in the monoclinic space group P21/n but show significant differences in their lattice parameters: 1, a = 9.2516(6) Å, b = 13.4298(9) Å, c = 17.8471(14) Å, β
= 94.531(6)°, V = 2210.5(3) Å3; 2, a = 9.0149(3) Å, b = 16.9298(4) Å, c = 15.6864(4) Å,
β = 90.129(3)°, V = 2394.06(12) Å3. Variation of the conditions for partial hydrolysis of Bi­(NO3)3 gave bismuth oxido nitrates of even higher nuclearity,
[{Bi38O45(NO3)24(DMSO)26}·4DMSO]­[{Bi38O45(NO3)24(DMSO)24}·4DMSO] (3) and
[{Bi38O45(NO3)24(DMSO)26}·2DMSO]­[{Bi38O45(NO3)24(DMSO)24}·0.5DMSO] (5),
upon crystallization from DMSO. Bismuth oxido clusters 3 and 5 crystallize in the triclinic space group P1̅ both with two crystallographically independent
molecules in the asymmetric unit. The following lattice parameters
are observed: 3, a = 20.3804(10) Å, b = 20.3871(9) Å, c = 34.9715(15)
Å, α = 76.657(4)°, β = 73.479(4)°, γ
= 60.228(5)°, V = 12021.7(9) Å3; 5, a = 20.0329(4) Å, b = 20.0601(4) Å, c = 34.3532(6) Å,
α = 90.196(1)°, β = 91.344(2)°, γ = 119.370(2)°, V = 12025.8(4) Å3. Differences in the number
of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate,
DMSO) coordination modes are observed.