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Thermodynamically stable and metastable coordination polymers synthesized from solution and the solid state

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Abstract

The reaction of Fe(NCS)2 with 4-picoline in solution leads to two new discrete complexes, Fe(NCS)2(4-picoline)4·solvate (1-Fe) and Fe(NCS)2(4-picoline)2(H2O)2 (2-Fe–H2O). Upon heating, both compounds transform into two isomers with the composition [Fe(NCS)2(4-picoline)2]n (2-Fe/I and 2-Fe/II) that consist of chains and that are related by monotropy, with 2-Fe/I as the thermodynamically stable form. Upon further heating, a transformation into a more condensed chain compound of unusual structure with the composition [Fe(NCS)2(4-picoline)]n (3-Fe) is observed. The crystal structures of 2-Fe/I and 2-Fe/II were determined by Rietveld refinements, as it was found that 2-Fe/I is isotypic to the corresponding Cd compound 2-Cd/I, whereas 2-Fe/II is isotypic to [Cu(NCS)2(4-cyanopyridine)2]n which was reported recently. To retrieve structural information on 3-Fe the corresponding Cd compound (3-Cd) was synthesized and was shown to be isotypic to 3-Fe. Finally, upon heating the already known compounds [Cd(NCS)2(4-picoline)4]·0.67·4-picoline·0.33·H2O solvate (1-Cd) and [Cd(NCS)2(4-picoline)2]n (2-Cd/I) a new thermodynamically metastable modification was found (2-Cd/III) that is isotypic to [Cd(NCS)2(4-cyanopyridine)2]n and behaves monotropically to 2-Cd/I with the latter as the thermodynamically stable phase.

Graphical abstract: Thermodynamically stable and metastable coordination polymers synthesized from solution and the solid state

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Publication details

The article was received on 08 Oct 2019, accepted on 04 Nov 2019 and first published on 04 Nov 2019


Article type: Paper
DOI: 10.1039/C9CE01589B
CrystEngComm, 2020, Advance Article
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    Thermodynamically stable and metastable coordination polymers synthesized from solution and the solid state

    T. Neumann, G. Gallo, I. Jess, R. E. Dinnebier and C. Näther, CrystEngComm, 2020, Advance Article , DOI: 10.1039/C9CE01589B

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