Cooperativity between the Dihydrogen Bond and the N⋅⋅⋅HC Hydrogen Bond in LiH–(HCN)n Complexes

The cooperativity between the dihydrogen bond and the N???HC hydrogen bond in LiH–(HCN)_n (n=2 and 3) complexes is investigated at the MP2 level of theory. The bond lengths, dipole moments, and energies are analyzed. It is demonstrated that synergetic effects are present in the complexes. The cooperativity contribution of the dihydrogen bond is smaller than that of the N???HC hydrogen bond. The three‐body energy in systems involving different types of hydrogen bonds is larger than that in the same hydrogen‐bonded systems. NBO analyses indicate that orbital interaction, charge transfer, and bond polarization are mainly responsible for the cooperativity between the two types of hydrogen bonds.