A systematic experimental and theoretical study of the crystalline state of six chloronitrobenzenes

Experimental and computational searches for the crystal structures of the five commercially available isomers of dichloronitrobenzene and 3,4-dinitrochlorobenzene were performed to assess the relationship between functional group interactions and steric requirements in determining the solid forms. Experimentally, this resulted in the first crystal structure determination of 2,4-dichloronitrobenzene, two solvates of 3,4-dichloronitrobenzene and one of 3,4-dinitrochlorobenzene. Additionally, low temperature redeterminations of the crystal structures were obtained for 2,5-dichloronitrobenzene, 3,4-dichloronitrobenzene, and both the β- and γ-forms of 3,4-dinitrochlorobenzene. The searches for energetically feasible structures of each of these compounds showed a wide variety of distributions leading to varying degrees of clarity of prediction of the solid state behavior. These range from 2,3-dichloronitrobenzene, which only adopts the crystal structure that was clearly the most thermodynamically stable of all five isomers, through complex systems, which show a range of low energy minima indicating possible polymorphism and solvate formation, to 2,4-dichloronitrobenzene, which can conformationally distort and adopts a complicated Z′ = 2 crystal structure.