Molecular spin qubits have demonstrated immense potential in quantum information science research due to the addressability of electron spins using microwave frequencies, and the scalability and tunability of molecular systems. Exemplary in this regard is the holmium polyoxometalate, [Na₉Ho(W₅O₁₈)₂]·35H₂O (HoW₁₀), which features an accessible atomic clock transition at 9.4 GHz; however, the coherence time of this molecule is limited by spin-phonon coupling driven decoherence processes. To limit these decoherence pathways, materials need to be designed to reduce energy overlap between spin and phonon states, and this necessitates developing a better understanding on how structural modifications impact the vibrational landscape for classes of complexes. Herein we conducted a full investigation into the fundamental structural and vibrational properties of the lanthanide Lindqvist polyoxometalate series, [Na₉Ln(W₅O₁₈)₂]·xH₂O (Ln = La(III)–Lu(III), except Pm(III)) (LnW₁₀), to assess how structural changes effect vibrational characteristics and to elucidate pathways to improve the coherence properties of HoW₁₀. Single crystal X-ray diffraction results revealed four distinct structural polymorphs in complexes 1–14 wherein first coordination spheres were identical, and differences manifested as changes in lattice packing. Interestingly, the subtle changes in packing exhibited by the four polymorphs were found to impact distortions away from ideal D_4d symmetry for each of the LnW₁₀ complexes. Raman and far-infrared (FIR) spectra of complexes 1–14 were collected to identify vibrational modes present in low energy regions and peak fitting assignments were made according to literature precedents. Qualitative and Partial least squares (PLS) analysis show correlations between complex structural parameters with the low energy Raman and FIR vibrational modes of interest. Overall, this investigation shows that the second coordination sphere plays an integral role in modulation of the structural and vibrational characteristics of LnW₁₀ complexes, which makes it a viable route for tuning spin and vibrational manifolds of species within this series.