Smith Graham, Wermuth Urs D
Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia.
School of Natural Sciences, Griffith University, Nathan, Queensland 4111, Australia.
Acta Crystallogr E Crystallogr Commun. 2017 Jan 17;73(Pt 2):203-208. doi: 10.1107/S2056989017000445. eCollection 2017 Feb 1.
The structures of the alkali metal (K, Rb and Cs) complex salts with 4-amino-phenyl-arsonic acid (-arsanilic acid) manifest an isotypic series with the general formula [(CHAsNO)(HO)], with = K {poly[di-μ-4-amino-phenyl-arsonato-tri-μ-aqua-dipotassium], [K(CHAsNO)(HO)], (I)}, Rb {poly[di-μ-4-amino-phenyl-arsonato-tri-μ-aqua-dirubidium], [Rb(CHAsNO)(HO)], (II)}, and Cs {poly[di-μ-4-amino-phenyl-arsonato-tri-μ-aqua-dirubidium], [Cs(CHAsNO)(HO)], (III)}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water mol-ecule, with the two hydrogen -arsanilate ligands and the second water mol-ecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I) to eight-coordinate in both (II) and (III), with overall -O bond-length ranges of 2.694 (5)-3.009 (7) (K), 2.818 (4)-3.246 (4) (Rb) and 2.961 (9)-3.400 (10) Å (Cs). The additional three bonds in (II) and (III) are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100) are generated through a number of bridging bonds involving the water mol-ecules (including hydrogen-bonding inter-actions), as well as through the arsanilate O atoms. These layers are linked across [100] through amine N-H⋯O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.
碱金属（钾、铷和铯）与4-氨基苯胂酸（-对氨基苯胂酸）形成的配合物盐的结构呈现出一个同型系列，其通式为[(CHAsNO)(HO)]，其中 = K {聚[二-μ-4-氨基苯胂酸根-三-μ-水二钾]，[K(CHAsNO)(HO)]，(I)}，Rb {聚[二-μ-4-氨基苯胂酸根-三-μ-水二铷]，[Rb(CHAsNO)(HO)]，(II)}，以及Cs {聚[二-μ-4-氨基苯胂酸根-三-μ-水二铯]，[Cs(CHAsNO)(HO)]，(III)}，其中重复的结构单元横跨包含两个独立且不同金属阳离子和一个桥连水分子的晶体学镜面，两个氢胂酸根配体和第二个水分子位于镜面之外。所有配合物中两个金属阳离子周围的键合情况相似，一个为五配位，另一个从（I）中的五配位发展到（II）和（III）中的八配位，总的 -O 键长范围为2.694 (5)-3.009 (7) （K），2.818 (4)-3.246 (4) （Rb）和2.961 (9)-3.400 (10) Å （Cs）。（II）和（III）中额外的三个键是通过水配体进行金属间桥连的结果。通过涉及水分子（包括氢键相互作用）以及胂酸根O原子的多个桥连键，生成了与（100）平行的二维配位聚合物结构。这些层通过胺N-H⋯O氢键跨[100]连接到胂酸根和水O原子受体上，形成整体的三维网络结构。
