Two zigzag-type paddlewheel Ru dimer chains with N, N, N', N'-tetramethyl-p-phenylenediamine (TMPDA) were synthesized in a solvated form (1-DCE; DCE: dichloroethane) and a non-solvated form (2), according to the Ru dimer used. Compound 1-DCE underwent crystal-to-crystal transition to its solvent-free species (1), with a characteristic structural change with respect to the contraction/expansion of solvent-accessible space. Following this transition, only 1 exhibited gate-open-type gas sorption behavior for N-2, O-2, NO, and CO2. The structures of the 1, Gas were determined by the Rietveld method based on their powder X-ray diffraction patterns under gas atmospheres.