The masses of 222,224,[226][227][228][229][230][231][232][233]234 Ra have been determined with the Penning-trap mass spectrometer ISOLTRAP at the ISOLDE facility at CERN, including the previously unknown mass and half-life of 233 Fr. We study the evolution of the odd-even staggering of binding energies along the francium and radium isotopic chains and of its lowest-order estimator, 3 (N ). An enhancement of the staggering of 3 (N ) is observed towards neutron number N = 146, which points to contributions beyond pairing correlations. These contributions are investigated in the Hartree-Fock and Hartree-Fock-Bogoliubov approaches, emphasizing the connections to the single-particle level density and nuclear deformation.