Two new structural isomers – 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesulfonamide or N-(2,6-dimethylphenyl)-N-methylbenzenesulfonamide with chlorosulfonic acid. Both compounds have been structurally characterized by X-ray single crystal diffraction at 100 K. The crystals of 1 are triclinic: space group P1¯, a = 8.1542(2), b = 11.0728(3), c = 11.2680(3) Å, α = 116.557(3), β = 95.155(2), γ = 108.258(2)°, V = 831.97(4) Å3, Z = 2, R = 0.0251 for 2429 reflections; the crystals of 2 are monoclinic: space group P21/c, a = 11.7428(2), b = 11.3518(2), c = 12.5886(2) Å, β = 93.659(2)°, V = 1674.66(5) Å3, Z = 4, R = 0.0269 for 2622 reflections. The structure of both isomers is organized as molecular crystals. These sterically hindered organic molecules are cross-linked into framework by means of hydrogen bonds of CH⋯O type (H⋯O distances are in range 2.27(2)–2.76(2) Å). The ab initio quantum-chemical calculations of an electronic structure of the isomeric molecules of 1 and 2 have been performed using the restricted Hartree-Fock method with a 6-31G* basis set. The calculated values of charge density concentrated on the electronegative atoms of the sterically hindered molecules are in good agreement with parameters of the intramolecular hydrogen bonds. The obtained data of the kinetic investigations of the substitution reactions in aqueous solution well correlate with stereo-chemical characteristics of the both molecules of the dimethyl[methyl(phenylsulfonyl)amino]-benzenesulfonyl chloride.