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

S.A. Barnett, Andrea Johnston, A.J. Florence, Sarah L. Price, Derek A. Tocherr

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

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.
LanguageEnglish
Pages24-36
Number of pages12
JournalCrystal Growth and Design
Volume8
Issue number1
DOIs
Publication statusPublished - 2008

Fingerprint

1-chloronitrobenzene
Dinitrochlorobenzene
Crystal structure
Crystalline materials
crystal structure
Isomers
isomers
clarity
polymorphism
Polymorphism
complex systems
Functional groups
Large scale systems
solid state
requirements

Keywords

  • chloronitrobenzenes
  • crystalline state
  • crystal structures

Cite this

Barnett, S.A. ; Johnston, Andrea ; Florence, A.J. ; Price, Sarah L. ; Tocherr, Derek A. / A systematic experimental and theoretical study of the crystalline state of six chloronitrobenzenes. In: Crystal Growth and Design. 2008 ; Vol. 8, No. 1. pp. 24-36.
@article{9115cb47589f4507a6c9848b33227df9,
title = "A systematic experimental and theoretical study of the crystalline state of six chloronitrobenzenes",
abstract = "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.",
keywords = "chloronitrobenzenes, crystalline state, crystal structures",
author = "S.A. Barnett and Andrea Johnston and A.J. Florence and Price, {Sarah L.} and Tocherr, {Derek A.}",
year = "2008",
doi = "10.1021/cg070131c",
language = "English",
volume = "8",
pages = "24--36",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "1",

}

A systematic experimental and theoretical study of the crystalline state of six chloronitrobenzenes. / Barnett, S.A.; Johnston, Andrea; Florence, A.J.; Price, Sarah L.; Tocherr, Derek A.

In: Crystal Growth and Design, Vol. 8, No. 1, 2008, p. 24-36.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A systematic experimental and theoretical study of the crystalline state of six chloronitrobenzenes

AU - Barnett, S.A.

AU - Johnston, Andrea

AU - Florence, A.J.

AU - Price, Sarah L.

AU - Tocherr, Derek A.

PY - 2008

Y1 - 2008

N2 - 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.

AB - 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.

KW - chloronitrobenzenes

KW - crystalline state

KW - crystal structures

U2 - 10.1021/cg070131c

DO - 10.1021/cg070131c

M3 - Article

VL - 8

SP - 24

EP - 36

JO - Crystal Growth and Design

T2 - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 1

ER -