Vibrational Stark probes are incisive tools for measuring local electric fields in a wide range of chemical environments. The interpretation of the frequency shift often gets complicated due to the specific interactions of the probe, such as hydrogen bonding and Lewis bonding. Therefore, it is important to distinguish between the pure electrostatic response and the response due to such specific interactions. Here we report a molecular system that is sensitive to both the Stark effect from a single ion and the explicit Lewis bonding of ions with the probe. The molecule consists of a crown ether with an appended benzonitrile. The crown captures cations of various charges, and the electric field from the ions is sensed by the benzonitrile probe. Additionally, the lone pair of the benzonitrile can engage in Lewis interactions with some of the ions by donating partial charge density to the ions. Our system exhibits both of these effects and therefore is a suitable test bed for distinguishing between the pure electrostatic and the Lewis interactions. Our computational results show that the electrostatic influence of the ion is operative at large distances, while the Lewis interaction becomes important only within distances that permit orbital overlap. Our results may be useful for using the nitrile probe for measuring electrostatic and coordination effects in complex ionic environments such as the electrode-electrolyte interfaces.