One mononuclear cobalt(II) compound of the type [Co(bnzd)₂(NCS)₂(OH₂)₂] (1) (bnzd = benzidine) has been isolated through a single-pot reaction of the molecular building components in MeOH-H₂O solvent mixture at room temperature and characterized by physico-chemical and spectroscopic methods. The crystal structure of complex 1 has an octahedral geometry with trans, trans, trans orientations in the order (N$^a$,N$^a$), (N$^t$,N$^t$), (O$^w$,O$^w$) [N$^a$ = N(amine), N$^t$ = N(thiocyanate) and O$^w$ = O(water)]. In crystalline state, individual units of 1 are associated by weak cooperative O-H…N, O-H…S and N-H…S hydrogen bonds resulting in a 3D network structure. The compound is redox active and shows luminescence in MeOH solution. Thermal decomposition pattern of 1 reveals the presence of two coordinated water molecules. Variabletemperature magnetic susceptibility measurement shows significant orbital contribution and numerical matrix diagonalization method gives the best fit parameters: 𝛼 = A^∗k = 1.43; 𝜆 = −130 cm^-1; 𝛥 = −864 cm^-1; TIP = 0.000975; R = $1.19 \times 10^{−4}$.