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The Role of the Bi3+ Lone Pair Effect in Bi(H3O)(SO4)2, Bi(HSO4)3, and Bi2(SO4)3
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-02-22 , DOI: 10.1021/acs.inorgchem.1c03893 Matthias Hämmer 1 , Jakoah Brgoch 2, 3 , Philip Netzsch 1 , Henning A Höppe 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-02-22 , DOI: 10.1021/acs.inorgchem.1c03893 Matthias Hämmer 1 , Jakoah Brgoch 2, 3 , Philip Netzsch 1 , Henning A Höppe 1
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Three new members in the Bi2O3–SO3–H2O system are identified by single crystal X-ray diffraction and Rietveld refinement after a fundamental examination of this phase space. Bi(H3O)(SO4)2 crystallizes in space group P21/c (no. 14, a = 1203.5(4), b = 682.9(2), c = 821.2(2) pm, β = 102.99(1)°, 861 independent reflections, 88 refined parameters, wR2 = 0.14) homeotypic with Nd(H3O)(SO4)2 featuring edge-sharing BiO9 polyhedra. Bi(HSO4)3 crystallizes in a new structure type in space group P1 (no. 2, a = 492.04(7), b = 910.8(1), c = 1040.8(2) pm, α = 85.443(5)°, β = 86.897(5)°, γ = 74.542(4)°, 3227 independent reflections, 154 refined parameters, wR2 = 0.05) comprising dimers of edge-sharing BiO8 polyhedra. For Bi2(SO4)3, a new modification crystallizing in space group P21/n (no. 14, a = 1308.03(7), b = 473.25(3), c = 1452.61(8) pm, β = 100.886(2)°, 3189 independent reflections, 155 refined parameters, wR2 = 0.03) isotypic to Sb2(SO4)3 with noncondensed BiO7 polyhedra is presented. The role of the Bi3+ lone pair effect as elucidated by density functional theory (DFT) calculations is discussed for all three compounds with respect to their structural and optical properties. Additionally, the Bi3+ lone pair activity is compared to the recently reported borosulfates Bi(H3O)[B(SO4)2]4 and Bi2[B2(SO4)6]. Geometrical calculations based on structural data are correlated with electron localization function (ELF) calculations to establish the origin of the direction and strength of the lone pair stereoactivity of Bi3+ in oxidic compounds. Finally, the thermal properties of the three compounds are reported.
中文翻译：
Bi3+ 孤对效应在 Bi(H3O)(SO4)2、Bi(HSO4)3 和 Bi2(SO4)3 中的作用
在对该相空间进行基本检查后，通过单晶 X 射线衍射和 Rietveld 细化确定了 Bi 2 O 3 –SO 3 –H 2 O 系统中的三个新成员。Bi(H 3 O)(SO 4 ) 2结晶在空间群P 2 1 / c (no. 14, a = 1203.5(4), b = 682.9(2), c = 821.2(2) pm, β = 102.99 (1)°，861 个独立反射，88 个精化参数，wR 2 = 0.14) 同型与 Nd(H 3 O)(SO 4 ) 2具有共享边缘的 BiO 9多面体。Bi(HSO 4 ) 3在空间群P 1 (no. 2, a = 492.04(7), b = 910.8(1), c = 1040.8(2) pm, α = 85.443(5) °, β = 86.897(5)°, γ = 74.542(4)°, 3227 个独立反射, 154 个精化参数, wR 2 = 0.05) 包括边缘共享 BiO 8多面体的二聚体。对于 Bi 2 (SO 4 ) 3 ，在空间群P 2 1 / n中结晶的新变体（第 14 号，a= 1308.03(7), b = 473.25(3), c = 1452.61(8) pm, β = 100.886(2)°, 3189 次独立反射, 155 个细化参数, wR 2 = 0.03) 同型到 Sb 2 (SO 4 ) 3与非凝聚 BiO 7多面体呈现。通过密度泛函理论 (DFT) 计算阐明的 Bi 3+孤对效应的作用针对所有三种化合物的结构和光学性质进行了讨论。此外，将 Bi 3+孤对活性与最近报道的硼硫酸盐 Bi(H 3 O)[B(SO 4 ) 2 ] 4进行了比较和 Bi 2 [B 2 (SO 4 ) 6 ]。基于结构数据的几何计算与电子定位函数 (ELF) 计算相关，以确定氧化化合物中 Bi 3+孤对立体活性的方向和强度的起源。最后，报告了这三种化合物的热性能。
更新日期：2022-02-22
中文翻译：
Bi3+ 孤对效应在 Bi(H3O)(SO4)2、Bi(HSO4)3 和 Bi2(SO4)3 中的作用
在对该相空间进行基本检查后，通过单晶 X 射线衍射和 Rietveld 细化确定了 Bi 2 O 3 –SO 3 –H 2 O 系统中的三个新成员。Bi(H 3 O)(SO 4 ) 2结晶在空间群P 2 1 / c (no. 14, a = 1203.5(4), b = 682.9(2), c = 821.2(2) pm, β = 102.99 (1)°，861 个独立反射，88 个精化参数，wR 2 = 0.14) 同型与 Nd(H 3 O)(SO 4 ) 2具有共享边缘的 BiO 9多面体。Bi(HSO 4 ) 3在空间群P 1 (no. 2, a = 492.04(7), b = 910.8(1), c = 1040.8(2) pm, α = 85.443(5) °, β = 86.897(5)°, γ = 74.542(4)°, 3227 个独立反射, 154 个精化参数, wR 2 = 0.05) 包括边缘共享 BiO 8多面体的二聚体。对于 Bi 2 (SO 4 ) 3 ，在空间群P 2 1 / n中结晶的新变体（第 14 号，a= 1308.03(7), b = 473.25(3), c = 1452.61(8) pm, β = 100.886(2)°, 3189 次独立反射, 155 个细化参数, wR 2 = 0.03) 同型到 Sb 2 (SO 4 ) 3与非凝聚 BiO 7多面体呈现。通过密度泛函理论 (DFT) 计算阐明的 Bi 3+孤对效应的作用针对所有三种化合物的结构和光学性质进行了讨论。此外，将 Bi 3+孤对活性与最近报道的硼硫酸盐 Bi(H 3 O)[B(SO 4 ) 2 ] 4进行了比较和 Bi 2 [B 2 (SO 4 ) 6 ]。基于结构数据的几何计算与电子定位函数 (ELF) 计算相关，以确定氧化化合物中 Bi 3+孤对立体活性的方向和强度的起源。最后，报告了这三种化合物的热性能。
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