AbstractThe reproducible formation, in mild conditions, of three new 1D zigzag coordination polymers using sulfonylcalix[4]arene (TCASO2), metal M2+ cations (M=Co or Zn) and rigid planar N‐shaped linkers (stilbene‐4,4′‐dicarboxylic acid (1‐2H) or azobenzene‐4,4′‐dicarboxylic acid (2‐2H)) is reported. The obtained coordination compounds (1‐TCASO2Zn3, 1‐TCASO2Co3 and 2‐TCASO2Zn3) are characterized in the crystalline phase using single crystal and powder X‐ray diffraction (XRD and XRPD), TGA and IR‐spectroscopy. The three compounds present the same coordination pattern and 1‐TCASO2Zn3 and 2‐TCASO2Zn3 reveal to be isostructural. Due to a high porosity and amount of accommodated solvent molecules hosted in the network, the generated rigid 1D chains are capable to undergo a reversible dynamic solid‐state transformation in terms of crystal packing, accompanied with release/uptake of DMSO molecules leading to compression/stretching of the unit cell along one of the crystallographic axis which was attested by Rietveld refinement on XRPD data.