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Crystal structures of two coordination isomers of copper(II) 4-sulfo-benzoic acid hexa-hydrate and two mixed silver/potassium 4-sulfo-benzoic acid salts.

ABSTRACT: 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(O3SC6H4CO2H)2(H2O)4]·2H2O, (I), crystallizes in the triclinic space group P with the Cu2+ 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(H2O)6](O3SC6H4CO2H)2, (II), also crystallizes in the triclinic space group P 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, [Ag0.69K0.31](O3SC6H4CO2H), (III), crystallizes in the monoclinic space group C2/c. 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, [Ag0.20K0.80](O3SC6H4CO2H)·2H2O, (IV), crystallizes in the monoclinic space group P21/c 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.

SUBMITTER: Squattrito PJ

PROVIDER: S-EPMC6829707 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Crystal structures of two coordination isomers of copper(II) 4-sulfo-benzoic acid hexa-hydrate and two mixed silver/potassium 4-sulfo-benzoic acid salts.

Squattrito Philip J PJ Lambright-Mutthamsetty Kelly J KJ Giolando Patrick A PA Kirschbaum Kristin K

Acta crystallographica. Section E, Crystallographic communications 20191031 Pt 11

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(O3SC6H4CO2H)2(H2O)4]·2H2O, (I), crystallizes in the triclinic space group P with the Cu2+ ions located on centers of inversion. Each copper ion is coordinated to four water mo ...[more]

PMID: 31709112

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Project description:The crystal structures of two ammonium salts of 2-amino-4-nitro-benzoic acid are described, namely di-methyl-aza-nium 2-amino-4-nitro-benzoate, C2H8N+·C7H5N2O4-, (I), and di-butyl-aza-nium 2-amino-4-nitro-benzoate, C8H20N+·C7H5N2O4-, (II). The asymmetric unit of (I) comprises a single cation and a single anion. In the anion, small twists are noted for the carboxyl-ate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13) and 3.71 (15)°, respectively; the dihedral angle between the substituents is 7.9 (2)°. The asymmetric unit of (II) comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+)-anti-periplanar] conformation, while one has a distinctive kink resulting in a (+)-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxyl-ate and nitro groups and the ring being 12.73 (6) and 4.30 (10)°, respectively, for the first anion and 8.1 (4) and 12.6 (3)°, respectively, for the second. The difference between anions in (I) and (II) is that in the anions of (II), the terminal groups are conrotatory, forming dihedral angles of 17.02 (8) and 19.0 (5)°, respectively. In each independent anion of (I) and (II), an intra-molecular amino-N-H⋯O(carboxyl-ate) hydrogen bond is formed. In the crystal of (I), anions are linked into a jagged supra-molecular chain by charge-assisted amine-N-H⋯O(carboxyl-ate) hydrogen bonds and these are connected into layers via charge-assisted ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N-O⋯π(arene) and methyl-C-H⋯O(nitro) inter-actions. In the crystal of (II), the anions are connected into four-ion aggregates by charge-assisted amino-N-H⋯O(carboxyl-ate) hydrogen bonding. The formation of ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds, involving all ammonium-N-H and carboxyl-ate O atoms leads to a three-dimensional architecture; additional C-H⋯O(nitro) inter-actions contribute to the packing. The Hirshfeld surface analysis confirms the importance of the hydrogen bonding in both crystal structures. Indeed, O⋯H/H⋯O inter-actions contribute nearly 50% to the entire Hirshfeld surface in (I).

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Crystal structures of two coordination isomers of copper(II) 4-sulfo-benzoic acid hexa-hydrate and two mixed silver/potassium 4-sulfo-benzoic acid salts.

Publications

Crystal structures of two coordination isomers of copper(II) 4-sulfo-benzoic acid hexa-hydrate and two mixed silver/potassium 4-sulfo-benzoic acid salts.

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