The present work demonstrates the single crystal X-ray and DFT analysis of $ [{(2,4-CH_{3})_{2}C_{6}H_{3}O}_{2}$PS_{2}HNEt_{3}]$ (1) and $ [{(3,4-CH_{3})_{2}$ $C_{6}H_{3}O}_{2}$ $PS_{2}HNEt_{3}]$ (2) along with computational analysis of $ [{(3,5-CH_{3})_{2}C_{6}H_{3}O}_{2} $PS_{2}HNEt_{3}]$ (3) by using density functional theory (DFT) in its hybrid form B3LYP method. Compounds1 and 2 crystallize in the orthorhombic space group Pbca and triclinic space groupP1,respectively andtheir X-ray analysis reveals that phosphorus atom is coordinated to the two S and two O atoms to form tetrahedralgeometry. The structure is stabilized by cation–anion N–H.... S hydrogen bonded interactions. The structuralparameters, vibrational bands and energy gaps of frontier orbitals (HOMO–LUMO) have been calculated.The calculated geometric and spectral results matched the experimental data with good agreement. Theoreticallycalculated frontier molecular orbitals (HOMO–LUMO) and their energies suggest that charge transferoccurs within the compounds.