NMR Crystallography Comparative Studies of Chiral (1<i>R</i>,2<i>S</i>,3<i>R</i>,5<i>R</i>)‑3-Amino-6,6-dimethylbicyclo[3.1.1]heptan-2-ol and Its <i>p</i>‑Toluenesulfonamide Derivative

Abstract

The crystal structure of (1<i>R</i>,2<i>S</i>,3<i>R</i>,5<i>R</i>)-3-amino-6,6-dimethyl-2-hydroxybicyclo­[3.1.1]­heptane <b>1</b> was determined and it is presented in reference to the structure of (1<i>R</i>,2<i>S</i>,3<i>R</i>,5<i>R</i>)-3-(<i>p</i>-tosylamino)-6,6-dimethyl-2-hydroxybicyclo­[3.1.1]­heptane <b>2</b>. ¹H and ¹³C chemical shifts parameters for both structures and for whole unit cells were calculated by using the GIPAW (gauge including projector augmented waves) method. Theoretically calculated chemical shift tensor parameters were verified by ¹³C CP MAS, 2D PASS, and ¹³C–¹H FSLG HETCOR results to obtain a full structural assignment for ¹³C and ¹H resonances in the solid-state. PISEMA MAS experiment was performed to determine the molecular dynamics of aminoalcohol <b>1</b>. The comparison of two structures, obtained after all-atom positions optimization after the GIPAW calculations, revealed small conformational differences consistent with the single-crystal X-ray diffaction results