Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Inorg Chem. 2011 Sep 5;50(17):8621-9. doi: 10.1021/ic201175u. Epub 2011 Aug 3.
Three Th(IV) sulfates, two new and one previously reported, have been synthesized from aqueous solution. In all of the compounds, the sulfate anions coordinate the Th(4+) metal center(s) in a monodentate manner with Th-S distances of 3.7-3.8 Å. Th(SO(4))(2)(H(2)O)(7)·2(H(2)O) (1; P2(1)/m, a = 7.224(1) Å, b = 12.151(1) Å, c = 7.989(1) Å, ss =98.289(2)°) and Th(4)(SO(4))(7)(H(2)O)(7)(OH)(2)·H(2)O (2; Pnma, a = 18.139(2) Å, b = 11.173(1) Å, c = 14.391(2) Å) each contain 9-coordinate monomeric (1,2) and dimeric (2) Th(IV) cations in monocapped square antiprism geometry. Alternatively, Th(OH)(2)SO(4) (3; Pnma, a = 11.684(1) Å, b = 6.047(1) Å, c = 7.047(1) Å) is built from chains of hydroxo-bridged, 8-coordinate Th(4+) centers. Whereas 1 adopts a molecular structure, 2 and 3 both exhibit 3D architectures. Differences in the dimensionality and the topology of 1-3 are manifested in the local coordination environment about the Th(IV) centers, the formation of oligomeric Th(4+) species, and the extended connectivity of the sulfate ligands. Herein, we report the syntheses and characterization of 1-3 as well as the atomic correlations of 1 in solution, as determined by high-energy X-ray scattering (HEXS).
三种三价（IV）硫酸盐，两种新的和一种以前报道过的，已从水溶液中合成。在所有化合物中，硫酸根阴离子以单齿配位方式与 Th(4+) 金属中心配位，Th-S 距离为 3.7-3.8 Å。Th(SO(4))(2)(H(2)O)(7)·2(H(2)O)（1；P2(1)/m，a = 7.224(1)Å，b = 12.151(1)Å，c = 7.989(1)Å，ss =98.289(2)°)和 Th(4)(SO(4))(7)(H(2)O)(7)(OH)(2)·H(2)O（2；Pnma，a = 18.139(2)Å，b = 11.173(1)Å，c = 14.391(2)Å）分别含有 9 配位的单体（1,2）和二聚体（2）Th(IV)阳离子，其在单帽四方反棱柱几何形状中。或者，Th(OH)(2)SO(4)（3；Pnma，a = 11.684(1)Å，b = 6.047(1)Å，c = 7.047(1)Å）是由羟桥连接的，8 配位 Th(4+)中心的链构成的。虽然 1 采用分子结构，但 2 和 3 均显示 3D 架构。1-3 的维度和拓扑结构的差异体现在 Th(IV)中心的局部配位环境、寡聚 Th(4+)物种的形成以及硫酸盐配体的扩展连接性上。在这里，我们报告了 1-3 的合成和表征，以及通过高能 X 射线散射（HEXS）确定的 1 在溶液中的原子相关性。
