拓展铀酰亚碲酸盐显著的结构多样性：K[UO(2)Te(2)O(5)(OH)]、Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O、β-Tl(2)[UO(2)(TeO(3))(2)]及Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2)的水热制备与结构

Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

作者信息

Almond Philip M, Albrecht-Schmitt Thomas E

机构信息

Department of Chemistry, Auburn University, Auburn, AL 36849, USA.

出版信息

Inorg Chem. 2002 Oct 21;41(21):5495-501. doi: 10.1021/ic025820m.

DOI:10.1021/ic025820m

PMID:12377045

Abstract

The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)Te(2)O(5)(OH)].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)UO(2)(TeO(3))(2)(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional UO(2)(TeO(3))(2) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta = 94.416(1) degrees, Z = 4.

摘要

在温和水热条件下，使二氧化铀（乙酸）₂·2H₂O与K₂TeO₃·H₂O、Na₂TeO₃和TlCl，或Na₂TeO₃和Sr(OH)₂·8H₂O反应，分别生成K[UO₂Te₂O₅(OH)]（1）、Tl₃[(UO₂)₂Te₂O₅(OH)]·2H₂O（2）和β-Tl₂[UO₂(TeO₃)₂]（3），或Sr₃UO₂(TeO₃)₂₂（4）。1的结构由四方双锥的U(VI)中心组成，这些中心由末端氧原子团和亚碲酸根阴离子配位。这些UO₆单元跨越由共角的四方锥TeO₄多面体组成的一维链，形成二维层。氧化碲链中交替共角的氧原子被质子化，形成短/长键合模式。在1中发现的由共角TeO₄单元组成的一维链在2中也存在。然而，在2中有两种不同的链，一种是交替共角的氧原子被质子化的链，另一种是链未被质子化的链。2中的铀酰部分由来自亚碲酸根链的五个氧原子配位，形成七配位的五角双锥U(VI)。3和4的结构都包含由四方双锥U(VI)中心构成的一维[UO₂(TeO₃)₂]²⁻链，这些中心由亚碲酸根阴离子桥连。3和4中的链的区别在于，3中所有的锥状亚碲酸根阴离子具有相同的取向，而4中链两侧的亚碲酸根阴离子具有相反的取向。在4中，还存在额外的孤立TeO₃²⁻阴离子。晶体学数据：1，正交晶系，空间群Cmcm，a = 7.9993(5) Å，b = 8.7416(6) Å，c = 11.4413(8) Å，Z = 4；2，正交晶系，空间群Pbam，a = 10.0623(8) Å，b = 23.024(2) Å，c = 7.9389(6) Å，Z = 4；3，单斜晶系，空间群P2(1)/n，a = 5.4766(4) Å，b = 8.2348(6) Å，c = 20.849(3) Å，β = 92.329(1)°，Z = 4；4，单斜晶系，空间群C2/c，a = 20.546(1) Å，b = 5.6571(3) Å，c = 13.0979(8) Å，β = 94.416(1)°，Z = 4。