Homochiral Column Structure of rac- and Λ-Tris(ethylenediamine)cobalt(III) Cyclotriphosphate Dihydrate in Crystal Structures and Cation−Anion Association in Aqueous Solution

rac- and Λ-tris(ethylenediamine)cobalt(III) cyclotriphosphate dihydrate with the chemical formulas rac-[Co(en)3]P3O9·2H2O (1) and Λ-[Co(en)3]P3O9·2H2O (2) were synthesized, and their crystal structures were determined by single-crystal X-ray analyses. In 1, the cationic complex molecule [Co(en)3]3+ with the Δ or Λ enantiomer and cyclotriphosphate anion are alternately arrayed and connected by multiple hydrogen bonds to form a homochiral column structure. Adjacent homochiral columns with different chirality for 1 are connected by intercolumn hydrogen bonds through P3O9 3- anions, as the bridging groups, to form a tetrameric cyclic cylindrical structure, while the adjacent columns with the same chirality are connected for 2 to form the cyclic cylindrical structure. All 6 amino groups per [Co(en)3]3+ participate in the formation of 12 hydrogen bonds, in which 8 hydrogen bonds contribute to the construction of a homochiral column and the remaining 4 hydrogen bonds contribute to the intercolumn interactions. The circular dichroism spectrum of the aqueous solution of Λ-[Co(en)3]3+ changes drastically when excess P3O9 3- is added, and this change is explained by ion-pair formation. The thermodynamic association constant of [Co(en)3]3+ with P3O9 3-, calculated from the conductivity data, was log K = 4.26 at 25 °C.