久保埜 公二

The asymmetric unit of the title compound is composed of two independent ion pairs of 4-(dimethylamino)pyridin-1-ium 8-hydroxyquinoline-5-sulfonate (HDMAP⁺·HqSA⁻, C₇H₁₁N₂ ⁺·C₉H₆NO₄S⁻) and neutral N,N-dimethylpyridin-4-amine molecules (DMAP, C₇H₁₀N₂), co-crystallized as a 1:1:1 HDMAP⁺:HqSA⁻:DMAP adduct in the monoclinic system, space group Pc. The compound has a layered structure, including cation layers of HDMAP⁺ with DMAP and anion layers of HqSA⁻ in the crystal. In the cation layer, there are intermolecular N—H...N hydrogen bonds between the protonated HDMAP⁺ molecule and the neutral DMAP molecule. In the anion layer, each HqSA⁻ is surrounded by other six HqSA⁻, where the planar network structure is formed by intermolecular O—H...O and C—H...O hydrogen bonds. The cation and anion layers are linked by intermolecular C—H...O hydrogen bonds and C—H...π interactions.

In the title compound, [Na(C₂₂H₁₉N₄O₄S)(CH₃CN)]_n, the Na^I atom adopts a distorted square-pyramidal coordination geometry, formed by one N and one O atom of the qunolinol moiety in the ligand, two O atoms of sulfonate moieties of two adjacent ligands and the N atom of the coordinated acetonitrile solvent. The Na^I atom is located well above the mean basal plane of the square-based pyramid. The apical position is occupied by a sulfonate O atom of a neighboring ligand. Three N atoms of the bis(pyridin-2-ylmethyl)amine moiety in the ligand are not coordinated by the sodium atom. The molecule forms an intramolecular bifurcated O—H...[N(tertiary amine),N(pyridine)] hydrogen bond, generating S(6) and S(5) rings. In the crystal, four molecules are linked by four Na—O(sulfonato) bridged coordination bonds, forming a supramolecular centrosymmetric tetramer unit comprising an eight-membered ring, and generating a two-dimensional network sheet. The molecules of different sheets form intermolecular C—H...O hydrogen bonds, and thereby a three-dimensional network structure.