A new octanuclear monoorganotin copper sulfide cage [(RSnCu)4(μ3-S)8]·2CHCl3 (1) (R = 2-phenylazophenyl) has been synthesized using the N→Sn intramolecular coordination approach. Complex 1 was obtained using the one pot reaction of monoorganotin trichloride, CuCl2 and Na2S·9H2O in Acetone/Methanol (1:1) solution. Complex 1 crystallizes in tetragonal P42/n space group. Formation of 1 is accompanied by the substitution of all the chlorides by sulfide ligand. The molecular structure of 1 contains four tin centers and four copper centers in distorted trigonal bipyramidal and distorted trigonal planar geometry respectively. Both Sn and Copper centers are further bridged by µ3-sulfide ligands. Closer inspection of solid state structure of 1 revealed the formation of 1-D and 2-D supramolecular architecture due to the various intermolecular interaction such as hydrogen bonding and CH–π interactions. Density functional theory (DFT) analysis of complex 1 has been performed to understand the orbital picture. The NBO analysis of complex 1 reveals three bonding interaction and two donor-acceptor interactions for tin (Sn) and three donor-acceptor interactions for copper (Cu). The AIM studies further demonstrate the clear picture of the various interactions present in the complex 1 using topological analysis scheme. These interactions are found to be ionic with partial/slight covalent characters. © 2021