title: Triclinic and monoclinic polymorphs of meso-(E,E)-1,1'-[1,2-bis(4-chlorophenyl)ethane-1,2-diyl]bis(phenyldiazene): the high-yield synthesis of an unexpected product, concomitant polymorphism and configurational disorder.
abstract: Pyrazolidine-3,5-diones and their derivatives exhibit a wide range of biological activities. Seeking to explore the effect of combining a hydrocarbyl ring substituent, as present in sulfinpyrazone (used to treat gout), with a chlorinated aryl ring, as present in muzolimine (a diuretic), we explored the reaction between 1-phenylpyrazolidine-3,5-dione and 4-chlorobenzaldehyde under mildly basic conditions in the expectation of producing the simple condensation product 4-(4-chlorobenzylidene)-1-phenylpyrazolidine-3,5-dione. However, the reaction product proved to be meso-(E,E)-1,1'-[1,2-bis(4-chlorophenyl)ethane-1,2-diyl]bis(phenyldiazene), C26H20Cl2N4, and a tentative mechanism is proposed. Crystallization from ethanol produces two concomitant polymorphs, i.e. a triclinic form, (I), in the space group P-1, and a monoclinic form, (II), in the space group C2/c. In both polymorphs, the molecules lie across centres of inversion, but in (II), the molecules are subject to whole-molecule disorder equivalent to configurational disorder with occupancies of 0.6021 (19) and 0.3979 (19). There are no hydrogen bonds in the crystal structure of polymorph (I), but the molecules of polymorph (II) are linked by C-H...π(arene) hydrogen bonds into complex chains, which are further linked into sheets by C-H...N interactions.
authors.affiliation: Chemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England.
authors.forename: Shaaban K
authors.initials: SK
authors.lastname: Mohamed
authors.affiliation: Chemistry Department, Faculty of Science, Sohag University, 82524 Sohag, Egypt.
authors.forename: Sabry H H
authors.initials: SH
authors.lastname: Younes
authors.affiliation: Chemistry Department, Faculty of Science, Sohag University, 82524 Sohag, Egypt.
authors.forename: Eman M M
authors.initials: EM
authors.lastname: Abdel-Raheem
authors.affiliation: School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, England.
authors.forename: Peter N
authors.initials: PN
authors.lastname: Horton
authors.affiliation: Department of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey.
authors.forename: Mehmet
authors.initials: M
authors.lastname: Akkurt
authors.affiliation: School of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland.
authors.forename: Christopher
authors.initials: C
authors.lastname: Glidewell
mesh_terms: D001686:Biological Phenomena; D003460:Crystallization; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure
chemical_list: C000608054:1,1'-(1,2-bis(4-chlorophenyl)ethane-1,2-diyl)bis(phenyldiazene); D007097:Imines; C011981:phenyldiazene
keywords: crystal structure; diazene; hydrogen bonding; meso forms; polymorphism; synthesis; whole-molecule disorder