Adducts of main group cations with neutral and anionic second row species (H2S, SH-, and PH2-) are calculated to be severely bent, the inclination angle often being less than 90 degrees. The corresponding adducts of H2O, OH-, and NH2- favor the aligned conformation (inclination angle 180 degrees). Analysis of the wave functions of Li+: Na+, K+, Be2+, Mg2+, and Ca2+ adducts shows that a preference for off-axis binding arises when the combined effects of covalency and the electrostatic ion-quadrupole term outweigh the usually dominant ion-dipole binding. Adducts of the radical cations Be+, Mg+, and Ca+ display the same conformational preferences as do the compounds of closed shell cations.