The crystal and molecular structures of two phenanthroline hydrochlorides have been determined at 173 K. 1,10‐Phenanthrolin‐1‐ium chloride, C12H9N2+·Cl−, crystallizes in two stacks of exactly planar molecules. Both stacks are approximately parallel to the (02) plane and the planes composing the different stacks enclose an angle of 13.29 (3)°. Tris(1,10‐phenanthrolin‐1‐ium) dichloride (hydrogen chloride) chloride chloroform solvate, 3C12H9N2+·2Cl−·HCl·Cl−·CHCl3, displays an interesting network of Cl− mediated hydrogen bonds between the two different phenanthrolinium moieties and between a phenanthrolinium and the chloroform solvate. In addition, a hydrogen bond between the HCl and the third Cl− ion is formed. The C—N—C angle at the protonated N atoms is, in all phenanthrolinium units of both structures, significantly larger than the C—N—C angle at the non‐protonated N atom.
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