Supramolecular Interactions Direct the Formation of Two Structural Polymorphs from One Building Unit in a One-Pot Synthesis.
Chemistry
; 22(39): 13900-13907, 2016 Sep 19.
Article
em En
| MEDLINE
| ID: mdl-27514321
ABSTRACT
Two polymorphs of supramolecular isomers, a discrete dimer and a zig-zag chain, having the same chemical composition, [Mn(Hbit)Cl2 ] (Hbit=1-methyl-2-(1H-1,2,3-triazol-4-yl)-1H-benzo[d]imidazole), were obtained solvothermally in a one-pot synthesis. The isomers differ in a number of ways orange blocks versus pale-yellow needles, triclinic P1â¾ versus orthorhombic Pbcn, double µ2 -Cl versus alternate single and triple µ2 -Cl, coordination number 5 versus 6, and antiparallel versus parallel near-neighbor orientation of Hbit. The packing in each case is driven by the supramolecular interactions, H-bonds (N-Hâ
â
â
Cl, C-Hâ
â
â
Cl) and πâ
â
â
π overlaps, calculated to be in the range 20-36â
kcal mol-1 . Calculations gave a difference of only 2â
kcal mol-1 in favor of the dimer, which confirms with the observation of principally the dimer at short reaction time. ESI-MS spectra of the dissolved crystals reveal the same fragments with similar distributions. The presence of two fragments at m/z 286.96 [MnIV (Hbit)Cl-2H]+ and 323.94 [MnIII (Hbit)Cl2 ]+ indicates that [Mn(Hbit)Cl2 ] is the building unit in both cases; thus, the different orientations of the ligands lead to the two polymorphs stabilized by the respective supramolecular interactions. Importantly, the chain form represents the first example with alternate single and triple µ2 -Cl bridges. The magnetic interactions are weakly antiferromagnetic in both cases, with J in the range 0.07-0.34â
cm-1 ; however, high-field EPR analysis reveals moderate magneto-anisotropy with D=0.26(1)â
cm-1 , E=0.06(1)â
cm-1 and D=0.17(1)â
cm-1 , E=0.03(1)â
cm-1 , respectively.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2016
Tipo de documento:
Article