Synthesis, Structural Characterization, Conformational and Topological Classification of Different Salts in the 2,2-Dimethylpropane-1,3-diamine/HCl/H2O-System

Abstract

The reaction of 2,2-dimethylpropane-1,3-diamine (dmpn) with an excess of concentrated aqueous hydrochloric acid yielded colorless crystals of 2,2-dimethylpropane-1,3-diaminium dichloride, dmpnH2Cl2 (1), in addition to small amounts of a monohydrate, dmpnH2Cl2∙H2O (2). The compounds were studied via X-ray crystallography, IR and Raman spectroscopy, NMR spectroscopy and thermal analysis. Single crystal structure determinations on 1 and 2 showed that dmpnH2Cl2 exists in two polymorphic forms, 1a and 1b. The crystal structure of 1b showed to be much more complex than that of 1a. In the crystal structure of 2, four (dmpnH2)2+ cations and eight chloride anions form a cage constructed by N−H∙∙∙Cl hydrogen bonds. In the center of these cages water dimers with a O∙∙∙O distance of 2.776 (8) Å are present. In addition, a conformational analysis of the 2,2-dimethylpropane-1,3-diaminium cation was performed. The results are compared to the experimental findings of 1a, 1b, 2 and other related hydrogen bonded salt structures from the Cambridge crystallographic structure database (CCDC). Last, a topological classification of the solid-state structures of 1a and 2 was performed and the simplified topological networks are discussed.