The vibrational structure and binding motifs of vanadium cation-ethane clusters, V+(C2H6)n, for n = 1-4 are probed using infrared photodissociation spectroscopy in the C-H stretching region (2550-3100 cm-1). Comparison of spectra to scaled harmonic frequency spectra obtained using density functional theory suggests that ethane exhibits two primary binding motifs when interacting with the vanadium cation: an end-on η2 configuration and a side-on configuration. Determining the denticity of the side on isomer is complicated by the rotational motion of ethane, implying that structural analysis based solely on Born-Oppenheimer potential energy surface minimizations is insufficient and that a more sophisticated vibrationally adiabatic approach is necessary to interpret spectra. The lower-energy side-on configuration predominates in smaller clusters, but the end-on configuration becomes important for larger clusters as it helps to maintain a roughly square-planar geometry about the central vanadium. Proximate C-H bonds exhibit elongation and large red-shifts when compared to bare ethane, particularly in the case of the side-on isomer, demonstrating initial effects of C-H bond activation, which are underestimated by scaled harmonic frequency calculations. Tagging several of the clusters with argon and nitrogen results in nontrivial effects. The high binding energy of N2 can lead to the displacement of ethane from a side-on configuration into an end-on configuration. The presence of either one or two Ar or N2 can impact the overall symmetry of the cluster, which can alter the potential energy surface for ethane rotation in the side-on isomer and may affect the accessibility of low-lying electronic excited states of V+.