The Phenomenon of Conglomerate Crystallization. Part 44. Counterion Control of Crystallization Pathway Selection. Part VI. The Crystallization Behavior of [Co(abap)(NO2)2]Cl (I), [Co(abap)(NO2)2]ClO4 (II), [Co(abap)(NO2)2]PF6·H2O (III) and [Co(abap)(NO2)2]I·H2O (IV)
Coordination compounds of Co(III) and the dissymmetric tripodal ligand [N-(2-aminoethyl)-N, N’-bis(3-aminopropyl)-amine] produces a series of anionic derivatives of the cation [Co(abap)(NO2)2]+ whose single crystal structures have been determined here in order to document the crystallization pathway selected by these species and to further explore the effect the counter ion has in the selection of the crystallization pathway of racemic solutions.
[Co(abap)(NO2)2]Cl and [Co(abap)(NO2)2]ClO4·H2O crystallize as conglomerates in space group P21 and P212121, respectively, while [Co(abap)(NO2)2]PF6·H2O and [Co(abap)(NO2)2]I·H2O crystallize as racemates. The conformations of the two six-membered rings in these complexes are chairs which are the expected, stable conformations. In the chloride and perchlorate complexes there are strong hydrogen bonds between anions and hydrogens of terminal nitrogens and also between the the -NO2 oxygens and those hydrogens, interactions which lock the cations into a specific dissymmetric conformation. Moreover, inter-cationic hydrogen bonds lead to the formation of spiral strings, adjacent strings being of the same helicity in the case of the conglomerates. Such strong hydrogen bonds and helical strings are noticeably absent in the case of the racemic crystals of [Co(abap)(NO2)2]PF6·H2O and [Co(abap)(NO2)2]I·H2O.
KeywordsTorsional Angle Short Hydrogen Bond Amine Hydrogen Deionized Water Solution Twist Boat
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Notes and References
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