Investigation of FOX‐7 Polymorphs: new polymorphs – ϵ and ζ

• Published in: ChemistrySelect (Weinheim) 2021-12, Vol.6 (45), p.12562-12570
• Main Authors: Kushtaev, Alexander A., Yudin, Nikolay V., Kondakova, Natalia N., Ilicheva, Natalia N., Vu, Tuan Q., Zbarskiy, Vitold L.
• Format: Article
• Language: English
• Subjects: DSC; FOX-7; IR/Raman spectroscopy; polymorphism; X-ray diffraction
• ISSN: 2365-6549; 2365-6549
• DOI: 10.1002/slct.202102810

Polymorphism of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7, DADNE) has investigated by X‐ray powder diffraction (XRD), differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), IR‐spectroscopy. Two previously unknown polymorph modifications of FOX‐7 ‐ ϵ and ζ were discovered. ϵ‐FOX‐7 has prepared by hydrolysis of 2‐(dinitromethylene)‐5,5‐dinitropyrimidine‐4,6(1H,3H,5H)‐dione in a media with pH up 7–8 to Ho≈−3 and 2‐(dinitromethylene)imidazolidine‐4,5‐dione in aqueous ammonia. ϵ‐FOX‐7 is a stable and exists in temperature range 273–378 K. ζ‐polymorph of FOX‐7 can be obtained at ϵ‐FOX‐7 heating to 378–380 K. ζ→ϵ polymorph transition is a reversible and occurs at 361.7±3.1 K. At 433–453 K ζ‐FOX‐7 transforms to γ‐polymorph. ζ→γ phase transition temperature range was determined using IR‐spectroscopy because it is invisible on DSC curves. IR‐spectra of ϵ and ζ polymorphs are significantly distinct from α‐, β‐ and γ‐FOX‐7. ϵ‐FOX‐7, in contrast to monoclinic α‐polymorph, has orthorhombic type of crystal system (space group P212121). Based on received data, new scheme of FOX‐7 polymorph transition is proposed. Detail investigation of polymorph transitions of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7, DADNE) using X‐ray powder diffraction, differential scanning calorimetry, thermo gravimetric analysis, IR‐spectroscopy has allowed to discover two previously unknown polymorphs of FOX‐7 – ϵ‐ and ζ. ϵ‐ and ζ‐FOX‐7 is formed an independent parallel chain of FOX‐7 polymorph transitions, which leads to γ‐ FOX‐7 and further to δ‐FOX‐7.