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The binary complexes of MCO 3 ···HF/XF (M = Zn and Cd; X = F, Cl, Br and I) have been studied using  ab initio  calculations. The carbonyl O atom is inclined to engage in a stronger H-bond or X-bond, with interaction energy up to −17 kcal/mol. The CdCO 3  complex brings out a stronger H-bond or X-bond than does the ZnCO 3  analogue. The H-bond is stronger than the X-bond for X = F and Cl, while an opposite result is obtained for X = Br and I. If the M atom in MCO 3 ···HF/XF again participates in a spodium bond with three N-bases (HCN, CH 2 NH and NH 3 ), the H-bond or X-bond is strengthened and the largest interaction energy amounts to −24 kcal/mol. In addition, the introduction of a spodium bond has a prominent effect on the geometries, orbital interaction and nature of the H-bond and X-bond.

Hydrogen and halogen bonds formed by MCO 3 (M = Zn, Cd) and their enhancement by a spodium bond