The dinuclear diorganotin sulfide [R₂Sn(µ-S)]₂ (1) (R = 2-phenylazophenyl) was synthesized by the room temperature reaction of the N → Sn intramolecularly coordinated starting precursor R₂SnCl₂ and Na₂S·9H₂O in acetone/methanol (1:1). The molecular structure of 1 was primarily characterized by single crystal X-ray crystallography. Furthermore, 1 was also characterized by other experimental techniques, such as ¹H, ¹³C and ¹¹⁹Sn NMR, ESI-MS, FTIR spectroscopy. Complex 1 crystallized in the monoclinic P2₁/n space group. Each tin center of complex 1 is pentacoordinated and acquires a distorted trigonal bipyramidal geometry. Time dependent density functional theory (TD-DFT) analysis revealed that the transitions observed in complex 1 are predominantly of the ligand-to-ligand type. Natural bond orbital (NBO) analysis showed that complex 1 consists of three ionic bonds (2Sn-C and Sn-S) and two ligand to metal coordinate bonds (S → Sn and N → Sn). HOMO-LUMO analysis suggested that the HOMO of complex 1 is mainly sulfur based. The complex 1 showed significant bactericidal activity against both gram positive and negative bacteria.