Synthesis, characterization, single crystal X-ray and DFT analysis of disubstituted phosphorodithioates

Abstract Disubstituted phosphorodithioates of the type [{(2,5-CH 3 ) 2 C 6 H 3 O} 2 PS 2 HNEt 3 ] ( 1 ) and [{(3,5-CH 3 ) 2 C 6 H 3 O) 2 (PS 2 )} 2 ] ( 2 ) were synthesized and characterized by IR and NMR ( 1 H, 13 C and 31 P) spectroscopic studies and as single crystal X-ray analysis. The compound 1 crystallizes in monoclinic space group P 2 1 / c whereas compound 2 crystallizes in triclinic space group P ¯1. The X-ray analysis reveals that in compound 1 phosphorus atom is coordinated to the two S and two O atoms to form tetrahedral geometry. The structure is stabilized by cation–anion N H⋯S hydrogen bonded interactions. In compound 2 , the two phosphorus atoms have a distorted tetrahedral geometry coordinated to two (3,5-CH 3 ) 2 C 6 H 3 O groups. The molecule possesses a crystallographic center of symmetry and consists of zig-zag array of S P S S P S linkages with two diphenyldithiophosphate moieties in the trans configuration. Molecular geometries, HOMO-LUMO analysis and molecular electrostatic potential of compounds 1 and 2 are investigated by theoretical calculations using B3LYP functional with the 6-311G basis combination set in the ground state and compared with the experimental values.