Ruthenium(II/III)-based compounds have gained significant interest due to the biocompatibility of ruthenium, its similarity to iron, and the possibility for structural diversification through the choice of ligands. In this contribution, two novel ligands, (2-(2-methoxyethoxy)ethyl nicotinate hydrochloride) and (2-2-(2-methoxyethoxy)ethoxyethyl nicotinate hydrochloride) (pyCOO(CH2CH2O)nCH3: L2, n = 2; L3, n = 3), were synthesized and characterized via ESI-HRMS, as well as IR and NMR spectroscopies. Their structures were optimized at the B3LYP/6-311++G(d,p) level of theory, and NMR chemical shifts were predicted, along with the most important intramolecular interactions. Additionally, two neutral complexes of the general formula RuCl2(η6-p-cym) (L-κN) (L = L2: 2; L3: 3) and two cationic complexes of the general formula RuCl(η6-p-cym)(L-κN)2PF6 (L = L1: 4; L2: 5) were obtained and characterized. The optimization of the structures was performed at the B3LYP/6-31+G(d,p)(H,C,N,O,Cl)/LanL2DZ(Ru) level of theory. Structural features were described, and intramolecular stabilization interactions were outlined.