TY - JOUR
T1 - A first exploration of isostructurality in transition metal nitroprussides
T2 - X-ray analysis, magnetic properties and DFT calculations
AU - Pérez, Hiram
AU - Di Santo, Alejandro
AU - Piro, Oscar E.
AU - Echeverría, Gustavo A.
AU - Cano, A.
AU - González, M.
AU - Rodríguez-Hernández, J.
AU - Ben Altabef, A.
AU - Frontera, Antonio
AU - Gil, Diego M.
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2021.
PY - 2021/2/7
Y1 - 2021/2/7
N2 - Five new transition metal nitroprussides with 1-methylimidazole (1-MeIm) have been synthesized and characterized by IR, XPS and UV-vis spectroscopy, thermal analysis, and powder and single-crystal X-ray diffraction. The structural analyses have revealed that the complexes Mn(1-MeIm)2[Fe(CN)5NO] (1), Fe(1-MeIm)2[Fe(CN)5NO] (2), Cu(1-MeIm)4[Fe(CN)5NO] (3), Zn(1-MeIm)2[Fe(CN)5NO] (4) and Cd(1-MeIm)2[Fe(CN)5NO] (5) are 2D coordination polymers. The supramolecular self-assembly of all the five complexes is governed by non-classical C-H⋯N hydrogen bonds and lone-pair(O)⋯π interactions. N⋯O chalcogen and π⋯π contacts are also present in the crystal packing of complexes1,2,4and5. A detailed analysis of four geometric descriptors revealed the existence of a high degree of isostructurality for the molecular pair1/2, and a moderate one for the pairs1/5and2/5. The dissimilarity index was also calculated for molecular pairs in two series of related compounds, showing that the degree of similarity is lower than those found in the pairs1/2,1/5and2/5. The results herein discussed for first time in the literature may be useful to understand property/structure relationships in these types of complexes. By using DFT calculations at the PBE0-D3/def2-TZVP level of theory and discrete models of the coordination polymers, we have analyzed cooperative lp-π/π-π/π-lp assemblies that are observed in the solid state of these compounds. This interesting assembly has been further analyzed by a combination of QTAIM, NCIplot and MEP surface calculations. The magnetic measurements indicate that compounds1-3are paramagnetic at 300 K and the Curie-Weiss constants are negative, suggesting weak antiferromagnetic coupling between the metal centers, at very low temperatures.
AB - Five new transition metal nitroprussides with 1-methylimidazole (1-MeIm) have been synthesized and characterized by IR, XPS and UV-vis spectroscopy, thermal analysis, and powder and single-crystal X-ray diffraction. The structural analyses have revealed that the complexes Mn(1-MeIm)2[Fe(CN)5NO] (1), Fe(1-MeIm)2[Fe(CN)5NO] (2), Cu(1-MeIm)4[Fe(CN)5NO] (3), Zn(1-MeIm)2[Fe(CN)5NO] (4) and Cd(1-MeIm)2[Fe(CN)5NO] (5) are 2D coordination polymers. The supramolecular self-assembly of all the five complexes is governed by non-classical C-H⋯N hydrogen bonds and lone-pair(O)⋯π interactions. N⋯O chalcogen and π⋯π contacts are also present in the crystal packing of complexes1,2,4and5. A detailed analysis of four geometric descriptors revealed the existence of a high degree of isostructurality for the molecular pair1/2, and a moderate one for the pairs1/5and2/5. The dissimilarity index was also calculated for molecular pairs in two series of related compounds, showing that the degree of similarity is lower than those found in the pairs1/2,1/5and2/5. The results herein discussed for first time in the literature may be useful to understand property/structure relationships in these types of complexes. By using DFT calculations at the PBE0-D3/def2-TZVP level of theory and discrete models of the coordination polymers, we have analyzed cooperative lp-π/π-π/π-lp assemblies that are observed in the solid state of these compounds. This interesting assembly has been further analyzed by a combination of QTAIM, NCIplot and MEP surface calculations. The magnetic measurements indicate that compounds1-3are paramagnetic at 300 K and the Curie-Weiss constants are negative, suggesting weak antiferromagnetic coupling between the metal centers, at very low temperatures.
UR - http://www.scopus.com/inward/record.url?scp=85100827849&partnerID=8YFLogxK
U2 - 10.1039/d0ce01596b
DO - 10.1039/d0ce01596b
M3 - Artículo
AN - SCOPUS:85100827849
SN - 1466-8033
VL - 23
SP - 1158
EP - 1171
JO - CrystEngComm
JF - CrystEngComm
IS - 5
ER -