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

Abstract

Hydrolysis of Bi(NO(3))(3) in aqueous solution gave crystals of the novel compounds [Bi(6)O(4)(OH)(4)(NO(3))(5)(H(2)O)](NO(3)) (1) and [Bi(6)O(4)(OH)(4)(NO(3))(6)(H(2)O)(2)]·H(2)O (2) among the series of hexanuclear bismuth oxido nitrates. Compounds 1 and 2 both crystallize in the monoclinic space group P2(1)/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) Å(3); 2, a = 9.0149(3) Å, b = 16.9298(4) Å, c = 15.6864(4) Å, β = 90.129(3)°, V = 2394.06(12) Å(3). Variation of the conditions for partial hydrolysis of Bi(NO(3))(3) gave bismuth oxido nitrates of even higher nuclearity, [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·4DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·4DMSO] (3) and [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·2DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·0.5DMSO] (5), upon crystallization from DMSO. Bismuth oxido clusters 3 and 5 crystallize in the triclinic space group P1 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) Å(3); 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) Å(3). Differences in the number of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate, DMSO) coordination modes are observed.

Homo‐ and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates

“…The hydroxido oxygen atom can be differentiated based on the elongated Bi−O bonds relative to the other μ 3 ‐oxygen atoms (Table ) and hence due to the sum of the bond valences . The bond‐valence sum varies from 2.40 to 2.53 for the μ 3 ‐oxido oxygen atoms, whereas a sum of 1.34 is observed for the μ 3 ‐hydroxido oxygen atom, which is in accordance with previous studies . Intermediate bond‐valence sums of 2.08 to 2.18 are calculated for the μ 4 ‐oxido oxygen atoms.…”

“…These clusters were obtained 1) hydrothermally, for example, [Bi 9 O 8 (OH) 6 ](OTf) 5 ; 2) from acidolysis and/or hydrolysis/condensation reactions starting from mononuclear compounds or Bi 2 O 3 , for example, [Bi 9 O 7 L 13 ] (L=Hsal, OC 6 F 5 , OCH(CF 3 ) 2 , hfac=hexafluoroacetylacetonate, OSiMe 3 ), and [Bi 9 O 8 (OH) 6 ](ClO 4 ) 5 ; or 3) from ethanolysis/ligand exchange of a preformed {Bi 9 } oxido cluster, for example, [Bi 9 O 8 (OEt) 6 (EtOH)](ClO 4 ) 5 . In contrast, the vast majority of reactions starting from [Bi 6 O 4 (OH) 4 (NO 3 ) 6 ]⋅H 2 O ( A ) in DMSO result in {Bi 38 O 45 } clusters, such as nitrates, nitrato sulfonates, nitrato anthranilate, and methacrylate, whereby [Bi 6 O 4 (OH) 4 (OTf) 6 (MeCN) 6 ] represents the only example that was obtained from cluster A by complete ligand exchange along with maintenance of the cluster core . For the more stable {Bi 38 O 45 } clusters, substitution of ligands in the periphery is usually observed without change of the cluster‐core structure .…”

“…[Bi 9 O 7 (OH)(O 3 SCH=CH 2 ) 11 (dmso) 11 ](O 3 SCH=CH 2 )⋅3 DMSO ( 4 ) crystallizes in the triclinic space group P , in which the asymmetric unit comprises one molecule of cluster 4 (Figure ). The [Bi 9 O 7 (OH)] 12+ core is built up by a central [Bi 6 O 7 (OH)] 3+ octahedron, in which the bismuth atoms occupy the corners and the oxygen atoms μ 3 ‐cap the triangular faces, as found for hexanuclear clusters, such as the starting material [Bi 6 O 4 (OH) 4 (NO 3 ) 6 ]⋅H 2 O ( A ) and other similar nitrates, [Bi 6 O 4 (OH) 4 ](ClO 4 ) 6 , [Bi 6 O 4 (OH) 4 (O 3 SNH 2 ) 6 ], [Bi 6 O 4 (OH) 4 (OTf) 6 (MeCN) 6 ], and other sulfonates . Three of the oxygen atoms are connected to one lateral bismuth atom each, located above the triangular faces of the octahedron.…”

“…The shortest Bi⋅⋅⋅O distance between the vinylsulfonate ion (O42) and the nearest bismuth atom (Bi9) of a neighboring molecule amounts to 6.25 Å. Although cationic core structures have also been described for clusters of the type [Bi 9 O 8 (OR) 6 ]X 5 (X=OTf: R=H; X=ClO 4 − : R=H, Et), these compounds exhibit significantly shorter Bi⋅⋅⋅O distances, which fall within the sum of the van der Waals radii (∑ r vdW (Bi−O)=3.57–4.09 Å) and should be regarded as coordinating ligands (Bi−O≤3.15 Å) . In addition, the core structures of these nonanuclear clusters are composed of three edge‐sharing [Bi 5 O 8 ] − pyramids, thus differing from the octahedral {Bi 6 } motif in the core of sulfonate 4 .…”

Two novel nanoscaled bismuth oxido clusters, [Bi38O45(OMc)22(C8H7SO3)2(DMSO)6(H2O)1.5]·2.5H2O and [Bi38O45(HSal)22(OMc)2(DMSO)15(H2O)]·DMSO·2H2O

“…Thus, phase separation and leaching effects are minimized. Recently, we have presented the synthesis of organic-inorganic hybrid materials based on the highly soluble [Bi 38 O 45 (OMc) 24 (DMSO) 9 ]·2DMSO·7H 2 O cluster (Miersch et al, 2011a (Andrews et al, 2006(Andrews et al, , 2012Dikarev et al, 2006;Mansfeld et al, 2011;Miersch et al, 2011bMiersch et al, , 2012. Such bismuth oxido clusters represent important model compounds for hydrolysis processes and contain a [Bi 6 O 9 ] unit in the center of the clusters, which is surrounded by 12 edge-sharing octahedral [Bi 6 O 8-x ] 2(1 + x) + units ( Figure 1 ).…”