Spontaneous self-assembly is one of the available synthetic routes to achieve structurally versatile and unique crystal complexes with selected metal-ligand combinations in the spirit of pseudohalides. In this endeavour, we designed a novel 1D coordination polymer (CP), (Cd)(Pb)(L)(η 1 -NCS)(η 1 -SCN) n ( 1 ), using a compartmental Salen ligand (H 3 L) in the presence of NaSCN. The characterization of the CP was accomplished using several spectroscopic techniques: MALDI-TOF, PXRD, SEM, EDX mapping, and single-crystal X-ray crystallography. The CP crystallizes in the monoclinic space group P 2 1 / c with Z = 4. SCXRD reveals Cd( ii ) and Pb( ii ) metal ions fulfilled distorted square pyramidal and hemi-directed coordination spheres. Cd( ii ) is placed in the inner N 2 O 2 and heavier Pb( ii ) in the outer O 4 compartments of the de-protonated form of the ligand L 2− . Supramolecular interactions in the intricate crystal structure produced attractive molecular architectures of the compound. The flexible aliphatic -OH pendent group coordinates with the Pb( ii ) ions. This unique binding further elevates the supramolecular crystal topographies. The supramolecular interactions were authenticated by Hirshfeld surface analysis (HSA). The observation of the recurring unconventional tetrel bonds was rationalized by DFT calculations and surface plots of molecular electrostatic potential (MEP). In the 1D polymeric chain in the complex, the O-atom of the -OH groups shows a tetrel bonding interaction with the Pb atom. We have found that the combination of QTAIM/NCI and QTAIM/ELF plots helps reveal the nature of these contacts. Moreover, the QTAIM/ELF plot determines the donor-acceptor interaction between the O-atom and the Pb atom, establishing the σ-hole. Agreeably, the σ-hole interaction also helps Pb( ii ) serve as a Lewis acid in the complex. Finally, spodium and tetrel bonds are formed, possible thanks to a hemi-directional coordination sphere of the Pb atoms in the polymer described. We report σ-hole interaction/spodium/tetrel bonding and other non-covalent interactions in a heteronuclear Pb( ii )-Salen coordination polymer using DFT, HSA, QTAIM/NCI, and QTAIM/ELF plots. The non-covalent interactions predominantly drive the formation of extended architectures.