Squattrito Philip J, Lambright-Mutthamsetty Kelly J, Giolando Patrick A, Kirschbaum Kristin
Department of Chemistry and Biochemistry, Central Michigan University, Mount Pleasant, Michigan 48859, USA.
College of Natural Sciences and Mathematics, University of Toledo, Toledo, OH 43606, USA.
Acta Crystallogr E Crystallogr Commun. 2019 Oct 31;75(Pt 11):1801-1807. doi: 10.1107/S2056989019014610. eCollection 2019 Nov 1.
A reaction of copper(II) carbonate and potassium 4-sulfo-benzoic acid in water acidified with hydro-chloric acid yielded two crystalline products. Tetra-aqua-bis-(4-carb-oxy-benzene-sulfonato)-copper(II) dihydrate, [Cu(OSCHCOH)(HO)]·2HO, (I), crystallizes in the triclinic space group with the Cu ions located on centers of inversion. Each copper ion is coordinated to four water mol-ecules in a square plane with two sulfonate O atoms in the apical positions of a Jahn-Teller-distorted octa-hedron. The carboxyl-ate group is protonated and not involved in coordination to the metal ions. The complexes pack so as to create a layered structure with alternating inorganic and organic domains. The packing is reinforced by several O-H⋯O hydrogen bonds involving coordinated and non-coordinated water mol-ecules, the carb-oxy-lic acid group and the sulfonate group. Hexa-aqua-copper(II) 4-carb-oxy-benzene-sulfonate, Cu(HO), (II), also crystallizes in the triclinic space group with Jahn-Teller-distorted octa-hedral copper(II) aqua complexes on the centers of inversion. As in (I), the carboxyl-ate group on the anion is protonated and the structure consists of alternating layers of inorganic cations and organic anions linked by O-H⋯O hydrogen bonds. A reaction of silver nitrate and potassium 4-sulfo-benzoic acid in water also resulted in two distinct products that have been structurally characterized. An anhydrous silver potassium 4-carb-oxy-benzene-sulfonate salt, AgK, (III), crystallizes in the monoclinic space group 2/. There are two independent metal sites, one fully occupied by silver ions and the other showing a 62% K/38% Ag (fixed) ratio, refined in two slightly different positions. The coordination environments of the metal ions are composed primarily of sulfonate O atoms, with some participation by the non-protonated carboxyl-ate O atoms in the disordered site. As in the copper compounds, the cations and anions cleanly segregate into alternating layers. A hydrated mixed silver potassium 4-carb-oxy-benzene-sulfonate salt dihydrate, AgK·2HO, (IV), crystallizes in the monoclinic space group 2/ with the Ag and K ions sharing one unique metal site coordinated by two water mol-ecules and six sulfonate O atoms. The packing in (IV) follows the dominant motif of alternating inorganic and organic layers. The protonated carboxyl-ate groups do not inter-act with the cations directly, but do participate in hydrogen bonds with the coordinated water mol-ecules. (IV) is isostructural with pure potassium 4-sulfo-benzoic acid dihydrate.
碳酸铜（II）与4 - 磺基苯甲酸钾在盐酸酸化的水中反应，生成了两种晶体产物。四水合双（4 - 羧基苯磺酸根）铜（II）二水合物，[Cu(OSCH₂CO₂H)(H₂O)₄]·2H₂O，（I），结晶于三斜空间群，铜离子位于对称中心。每个铜离子在一个正方形平面中与四个水分子配位，两个磺酸根O原子位于 Jahn - Teller 畸变八面体的顶端位置。羧酸根基团被质子化，不参与与金属离子的配位。这些配合物堆积形成一种具有交替无机和有机区域的层状结构。堆积通过涉及配位和未配位水分子、羧酸基团和磺酸基团的几个O - H⋯O氢键得到加强。六水合铜（II）4 - 羧基苯磺酸盐，Cu(H₂O)₆，（II），也结晶于三斜空间群，在对称中心有 Jahn - Teller 畸变的八面体铜（II）水合配合物。与（I）一样，阴离子上的羧酸根基团被质子化，结构由通过O - H⋯O氢键连接的无机阳离子和有机阴离子交替层组成。硝酸银与4 - 磺基苯甲酸钾在水中反应也得到了两种已进行结构表征的不同产物。无水银钾4 - 羧基苯磺酸盐，AgK，（III），结晶于单斜空间群P2₁/c。有两个独立的金属位点，一个完全被银离子占据，另一个显示62% K/38% Ag（固定）比例，在两个略有不同的位置精修。金属离子的配位环境主要由磺酸根O原子组成，无序位点中未质子化的羧酸根O原子也有一定参与。与铜化合物一样，阳离子和阴离子清晰地分离成交替层。水合混合银钾4 - 羧基苯磺酸盐二水合物，AgK·2H₂O，（IV），结晶于单斜空间群P2₁/c，Ag和K离子共享一个独特的金属位点，由两个水分子和六个磺酸根O原子配位。（IV）中的堆积遵循交替无机和有机层的主要模式。质子化的羧酸根基团不直接与阳离子相互作用，但确实参与与配位水分子的氢键形成。（IV）与纯4 - 磺基苯甲酸钾二水合物同构。
