Molecular spin-crossover (SCO) compounds are attractive for information storage and photovoltaic technologies. We compared two prototypic SCO compounds with (FeN6)-N-II (1, [Fe(phen)(2)(NCS)(2)], with phen = 1,10= phenanthroline) or (FeS6)-S-III (2, [Fe(dedtc)(3)], with dedtc = N,N'-diethyldithiocarbamate) centers, which show abrupt (1) or gradual :(2) thermally induced SCO, using K-edge X-ray absorption and K beta emission spectroscopy (XAS/XES) in a 8-315 K temperature range, Single-crystal X-ray diffraction (XRD), and density functional theory (DFT). Core-td-valence and valence-to-core electronic transitions in the XAS/XES spectra and bond lengths change from XRD provided benchmark data, verifying the adequacy of the TPSSh/TZVP DFT approach for the description of low-spin (LS) and high-spin (HS) species. Determination of the spin densities, charge distributions, bonding descriptors, and valence-level configurationS, as well as similar experimental and calculated enthalpy changes (Delta H), suggested that the varying metal ligand bonding properties and deviating electronic structures converge to similar enthalpic contributions to the free-energy change (Delta G) and thus presumably are not decisive for the differing SCO behavior of 1 and 2. Rather, SCO seems to be governed by vibrational contributions to the entropy changes (AS) in both complexes. Intra, and intermolecular interactions in crystals of 1 and 2 were identified by atoms-in-molecules analysis. Thermal excitation of individual dedtc ligand vibrations accompanies the gradual SCO in 2. In contrast, extensive inter- and intramolecular phen/NCS vibrational mode coupling may be an important factor in the cooperative SCO behavior of 1.