Technische Universität Chemnitz, Institut für Chemie, Strasse der Nationen 62, 09111 Chemnitz, Deutschland.
Inorg Chem. 2012 Sep 3;51(17):9376-84. doi: 10.1021/ic301148p. Epub 2012 Aug 17.
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) (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.
在水溶液中水解 Bi(NO3)3 得到了两种新型化合物 Bi(6)O(4)(OH)(4)(NO3))(5)(H2O) (1) 和 [Bi(6)O(4)(OH)(4)(NO3))(6)(H2O)(2)]·H2O (2) 的晶体，它们都是六核铋氧化硝酸盐系列中的一员。化合物 1 和 2 都在单斜空间群 P2(1)/n 中结晶，但晶格参数有显著差异：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。改变 Bi(NO3)3 的部分水解条件，得到了更高核数的铋氧化硝酸盐，[{Bi(38)O(45)(NO3))(24)(DMSO)(26)}·4DMSO][{Bi(38)O(45)(NO3))(24)(DMSO)(24)}·4DMSO] (3) 和 [{Bi(38)O(45)(NO3))(24)(DMSO)(26)}·2DMSO][{Bi(38)O(45)(NO3))(24)(DMSO)(24)}·0.5DMSO] (5)，它们是通过在 DMSO 中结晶得到的。铋氧化簇合物 3 和 5 都在三斜空间群 P1 中结晶，每个不对称单元中有两个结晶学上独立的分子。观察到以下晶格参数：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。观察到了 DMSO 分子（配位和非配位）数量和配体（硝酸盐、DMSO）配位模式的差异。
