The crystal and solution structure of 2,4-dinitrophenyl phenylsulfide determined by X-ray crystallography and13C-NMR spin-lattice relaxation measurements

Abstract

The crystal structure of 2,4-dinitrophenyl phenylsulfide, C12H8N2O4S, has been determined by single crystal X-ray diffraction. The crystals are monoclinic, space groupP21/n, Z = 8, witha = 10.670(2),b = 8.381(4),c = 27.998(18) A, and β = 100.44(4) °. There are two crystallographically independent molecules per asymmetric unit. All intensity measurements were made at room temperature on an Enraf-Nonius CAD-4 automatic diffractometer using monochromatized MoKα radiation. The structure was solved by direct methods and refined to a finalR value of 0.032. The two independent molecules have nearly identical geometries, with the most notable difference being the torsion angles involving the sulfur atoms. Thepara-nitro groups are more nearly in the planes of the central phenyl rings than are theortho-nitro groups although there may be nonbonded attractions between the latter. The two phenyls of each molecule are nearly at right angles to each other, as necessitated by steric forces involvingortho hydrogens. The characteristic distortions of the central phenyl rings caused by differing substituent electronegativities and degrees of conjugation are noted. The13C-NMR spectrum of the compound was assigned by comparison of calculated with observed chemical shift data. Calculated chemical shifts were obtained by incrementation of the chemical shifts of diphenylsulfide with standard nitro group additivities which were adjusted for the sulfur-nitro group interaction. Where necessary, assignments were confirmed with selective excitation spin-coupled subspectra. Solution behavior of the molecule was determined from spin-lattice (T1) relaxation measurements which showed the unsubstituted ring to reorient anisotropically about the C(21)-C(24) bond axis while the substituted ring appears to be governed by the overall isotropic reorientation of the molecular framework, indicating that the sulfur-nitro group interaction restricts anisotropic reorientation about the C(11)-C(14) bond axis.