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 C Struct Chem. 2017 Apr 1;73(Pt 4):325-330. doi: 10.1107/S205322961700314X. Epub 2017 Mar 8.
Structures having the unusual protonated 4-arsonoanilinium species, namely in the hydrochloride salt, CHAsNO·Cl, (I), and the complex salts formed from the reaction of (4-aminophenyl)arsonic acid (p-arsanilic acid) with copper(II) sulfate, i.e. hexaaquacopper(II) bis(4-arsonoanilinium) disulfate dihydrate, (CHAsNO)Cu(HO)·2HO, (II), with copper(II) chloride, i.e. poly[bis(4-arsonoanilinium) [tetra-μ-chlorido-cuprate(II)]], {(CHAsNO)[CuCl]}, (III), and with cadmium chloride, i.e. poly[bis(4-arsonoanilinium) [tetra-μ-chlorido-cadmate(II)]], {(CHAsNO)[CdCl]}, (IV), have been determined. In (II), the two 4-arsonoanilinium cations are accompanied by [Cu(HO)] cations with sulfate anions. In the isotypic complex salts (III) and (IV), they act as counter-cations to the {[CuCl]} or {[CdCl]} anionic polymer sheets, respectively. In (II), the [Cu(HO)] ion sits on a crystallographic centre of symmetry and displays a slightly distorted octahedral coordination geometry. The asymmetric unit for (II) contains, in addition to half the [Cu(HO)] ion, one 4-arsonoanilinium cation, a sulfate dianion and a solvent water molecule. Extensive O-H...O and N-H...O hydrogen bonds link all the species, giving an overall three-dimensional structure. In (III), four of the chloride ligands are related by inversion [Cu-Cl = 2.2826 (8) and 2.2990 (9) Å], with the other two sites of the tetragonally distorted octahedral CuCl unit occupied by symmetry-generated Cl-atom donors [Cu-Cl = 2.9833 (9) Å], forming a two-dimensional coordination polymer network substructure lying parallel to (001). In the crystal, the polymer layers are linked across [001] by a number of bridging hydrogen bonds involving N-H...Cl interactions from head-to-head-linked As-O-H...O 4-arsonoanilinium cations. A three-dimensional network structure is formed. Cd compound (IV) is isotypic with Cu complex (III), but with the central CdCl complex repeat unit having a more regular M-Cl bond-length range [2.5232 (12)-2.6931 (10) Å] compared to that in (III). This series of compounds represents the first reported crystal structures having the protonated 4-arsonoanilinium species.
已测定了具有不寻常质子化4-胂酸苯胺鎓物种的结构，即在盐酸盐CH₅AsNO₂·Cl (I) 中，以及由 (4-氨基苯基)胂酸（对氨基苯胂酸）与硫酸铜反应形成的复盐，即六水合铜 (II) 双(4-胂酸苯胺鎓) 二硫酸盐二水合物 (CH₅AsNO₂)₂Cu(H₂O)₆₂·2H₂O (II)，与氯化铜反应形成的复盐，即聚[双(4-胂酸苯胺鎓) [四-μ-氯合铜 (II)]] {(CH₅AsNO₂)₂[CuCl₄]} (III)，以及与氯化镉反应形成的复盐，即聚[双(4-胂酸苯胺鎓) [四-μ-氯合镉 (II)]] {(CH₅AsNO₂)₂[CdCl₄]} (IV)。在 (II) 中，两个4-胂酸苯胺鎓阳离子伴随着[Cu(H₂O)₆]阳离子和硫酸根阴离子。在同型复盐 (III) 和 (IV) 中，它们分别作为{[CuCl₄]}或{[CdCl₄]}阴离子聚合物片层的抗衡阳离子。在 (II) 中，[Cu(H₂O)₆]离子位于晶体学对称中心，呈现出略微扭曲的八面体配位几何构型。(II) 的不对称单元除了半个[Cu(H₂O)₆]离子外，还包含一个4-胂酸苯胺鎓阳离子、一个硫酸根二价阴离子和一个溶剂水分子。广泛的O-H...O和N-H...O氢键连接所有物种，形成整体三维结构。在 (III) 中，四个氯配体通过反演相关[Cu-Cl = 2.2826 (8) 和2.2990 (9) Å]（此处原文有误，推测应为2.2826 (8) 和2.2990 (9) Å），四方扭曲八面体CuCl₄单元的另外两个位置由对称产生的Cl原子供体占据[Cu-Cl = 2.9833 (9) Å]，形成平行于(001) 的二维配位聚合物网络子结构。在晶体中，聚合物层通过许多涉及头对头连接的As-O-H...O 4-胂酸苯胺鎓阳离子的N-H...Cl相互作用的桥连氢键在[001]方向上相连。形成三维网络结构。镉化合物 (IV) 与铜配合物 (III) 同型，但中心CdCl₄配合物重复单元的M-Cl键长范围[2.5232 (12)-2.6931 (1)(此处原文有误，推测应为(III)中的2.9833 (9) Å) 相比更规则。这一系列化合物代表了首次报道的具有质子化4-胂酸苯胺鎓物种的晶体结构。
