Supramolecular structures of rhenium(I) complexes mediated by ligand planarity via the interplay of substituents

Wun Fui Mark-Lee, Yan Yi Chong, Mohammad Kassim

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The crystal and molecular structures of two ReI tricarbonyl complexes, namely fac-tricarbonylchlorido[1-(4-fluorocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2]-rhenium(I), [ReCl(C17 H12 FN3 O)(CO)3], (I), and fac-tricarbonylchlorido[1-(4-nitrocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2 ]rhenium(I) acetone monosol-vate, [ReCl(C17 H12ClN4O3)(CO)3].C3 H6 O, (II), are reported. The complexes form centrosymmetric dimers that are linked into one-dimensional columns by C—H…Cl and N—O…H interactions in (I) and (II), respectively. C—H…Cl interactions in (II) generate two R1 2(7) loops that merge into a single R1 2(10) loop. These interactions involve the alkene, pyrazole and benzene rings, hence restricting the ligand rotation and giving rise to a planar conformation. Unlike (II), complex (I) exhibits a twisted conformation of the ligand and a pair of molecules forms a centrosymmetric dimer with an R2 2(10) loop via C—H…O interactions. The unique supramolecular structures of (I) and (II) are determined by their planarity and weak interactions. The planar conformation of (II) provides a base for appreciable π–π stacking interactions compared to (I). In addition, an N—O…π interaction stabilizes the supramolecular structure of (II). We report herein the first n→π* interactions of ReI tricarbonyl complexes, which account for 0.33 kJ mol1. Intermolecular C—H…Cl and C— H…O interactions are present in both complexes, with (II) showing a greater preference for these interactions compared to (I), with cumulative contributions of 48.7 and 41.5%, respectively. The influence of inductive (fluoro) and/or resonance (nitro) effects on the π-stacking ability was further supported by LOLIPOP (localized orbital locator-integrated π over plane) analysis. The benzene ring of (II) demonstrated a higher π-stacking ability compared to that of (I), which is supported by the intrinsic planar geometry. The HOMA (harmonic oscillator model of aromaticity) index of (I) revealed more aromaticity with respect to (II), suggesting that NO2 greatly perturbed the aromaticity. The Hirshfeld fingerprint (FP) plots revealed the preference of (II) over (I) for π–π contacts, with contributions of 6.8 and 4.4%, respectively.

Original languageEnglish
Pages (from-to)997-1006
Number of pages10
JournalActa Crystallographica Section C: Structural Chemistry
Volume74
Issue number9
DOIs
Publication statusPublished - 1 Sep 2018

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Rhenium
rhenium
Conformations
Ligands
Carbon Monoxide
Benzene
Dimers
ligands
Alkenes
interactions
Acetone
Molecular structure
Olefins
Crystal structure
Molecules
Geometry
pyrazole
benzene
dimers

Keywords

  • Computational chemistry
  • Crystal structure
  • Hirshfeld surface analysis
  • n-to-π*
  • Planarity
  • Rhenium(I) complexes
  • Supramolecular architectures
  • Tubular column
  • Weak interactions

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Supramolecular structures of rhenium(I) complexes mediated by ligand planarity via the interplay of substituents. / Mark-Lee, Wun Fui; Chong, Yan Yi; Kassim, Mohammad.

In: Acta Crystallographica Section C: Structural Chemistry, Vol. 74, No. 9, 01.09.2018, p. 997-1006.

Research output: Contribution to journalArticle

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abstract = "The crystal and molecular structures of two ReI tricarbonyl complexes, namely fac-tricarbonylchlorido[1-(4-fluorocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2]-rhenium(I), [ReCl(C17 H12 FN3 O)(CO)3], (I), and fac-tricarbonylchlorido[1-(4-nitrocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2 ]rhenium(I) acetone monosol-vate, [ReCl(C17 H12ClN4O3)(CO)3].C3 H6 O, (II), are reported. The complexes form centrosymmetric dimers that are linked into one-dimensional columns by C—H…Cl and N—O…H interactions in (I) and (II), respectively. C—H…Cl interactions in (II) generate two R1 2(7) loops that merge into a single R1 2(10) loop. These interactions involve the alkene, pyrazole and benzene rings, hence restricting the ligand rotation and giving rise to a planar conformation. Unlike (II), complex (I) exhibits a twisted conformation of the ligand and a pair of molecules forms a centrosymmetric dimer with an R2 2(10) loop via C—H…O interactions. The unique supramolecular structures of (I) and (II) are determined by their planarity and weak interactions. The planar conformation of (II) provides a base for appreciable π–π stacking interactions compared to (I). In addition, an N—O…π interaction stabilizes the supramolecular structure of (II). We report herein the first n→π* interactions of ReI tricarbonyl complexes, which account for 0.33 kJ mol1. Intermolecular C—H…Cl and C— H…O interactions are present in both complexes, with (II) showing a greater preference for these interactions compared to (I), with cumulative contributions of 48.7 and 41.5{\%}, respectively. The influence of inductive (fluoro) and/or resonance (nitro) effects on the π-stacking ability was further supported by LOLIPOP (localized orbital locator-integrated π over plane) analysis. The benzene ring of (II) demonstrated a higher π-stacking ability compared to that of (I), which is supported by the intrinsic planar geometry. The HOMA (harmonic oscillator model of aromaticity) index of (I) revealed more aromaticity with respect to (II), suggesting that NO2 greatly perturbed the aromaticity. The Hirshfeld fingerprint (FP) plots revealed the preference of (II) over (I) for π–π contacts, with contributions of 6.8 and 4.4{\%}, respectively.",
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AU - Kassim, Mohammad

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N2 - The crystal and molecular structures of two ReI tricarbonyl complexes, namely fac-tricarbonylchlorido[1-(4-fluorocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2]-rhenium(I), [ReCl(C17 H12 FN3 O)(CO)3], (I), and fac-tricarbonylchlorido[1-(4-nitrocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2 ]rhenium(I) acetone monosol-vate, [ReCl(C17 H12ClN4O3)(CO)3].C3 H6 O, (II), are reported. The complexes form centrosymmetric dimers that are linked into one-dimensional columns by C—H…Cl and N—O…H interactions in (I) and (II), respectively. C—H…Cl interactions in (II) generate two R1 2(7) loops that merge into a single R1 2(10) loop. These interactions involve the alkene, pyrazole and benzene rings, hence restricting the ligand rotation and giving rise to a planar conformation. Unlike (II), complex (I) exhibits a twisted conformation of the ligand and a pair of molecules forms a centrosymmetric dimer with an R2 2(10) loop via C—H…O interactions. The unique supramolecular structures of (I) and (II) are determined by their planarity and weak interactions. The planar conformation of (II) provides a base for appreciable π–π stacking interactions compared to (I). In addition, an N—O…π interaction stabilizes the supramolecular structure of (II). We report herein the first n→π* interactions of ReI tricarbonyl complexes, which account for 0.33 kJ mol1. Intermolecular C—H…Cl and C— H…O interactions are present in both complexes, with (II) showing a greater preference for these interactions compared to (I), with cumulative contributions of 48.7 and 41.5%, respectively. The influence of inductive (fluoro) and/or resonance (nitro) effects on the π-stacking ability was further supported by LOLIPOP (localized orbital locator-integrated π over plane) analysis. The benzene ring of (II) demonstrated a higher π-stacking ability compared to that of (I), which is supported by the intrinsic planar geometry. The HOMA (harmonic oscillator model of aromaticity) index of (I) revealed more aromaticity with respect to (II), suggesting that NO2 greatly perturbed the aromaticity. The Hirshfeld fingerprint (FP) plots revealed the preference of (II) over (I) for π–π contacts, with contributions of 6.8 and 4.4%, respectively.

AB - The crystal and molecular structures of two ReI tricarbonyl complexes, namely fac-tricarbonylchlorido[1-(4-fluorocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2]-rhenium(I), [ReCl(C17 H12 FN3 O)(CO)3], (I), and fac-tricarbonylchlorido[1-(4-nitrocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN2 ]rhenium(I) acetone monosol-vate, [ReCl(C17 H12ClN4O3)(CO)3].C3 H6 O, (II), are reported. The complexes form centrosymmetric dimers that are linked into one-dimensional columns by C—H…Cl and N—O…H interactions in (I) and (II), respectively. C—H…Cl interactions in (II) generate two R1 2(7) loops that merge into a single R1 2(10) loop. These interactions involve the alkene, pyrazole and benzene rings, hence restricting the ligand rotation and giving rise to a planar conformation. Unlike (II), complex (I) exhibits a twisted conformation of the ligand and a pair of molecules forms a centrosymmetric dimer with an R2 2(10) loop via C—H…O interactions. The unique supramolecular structures of (I) and (II) are determined by their planarity and weak interactions. The planar conformation of (II) provides a base for appreciable π–π stacking interactions compared to (I). In addition, an N—O…π interaction stabilizes the supramolecular structure of (II). We report herein the first n→π* interactions of ReI tricarbonyl complexes, which account for 0.33 kJ mol1. Intermolecular C—H…Cl and C— H…O interactions are present in both complexes, with (II) showing a greater preference for these interactions compared to (I), with cumulative contributions of 48.7 and 41.5%, respectively. The influence of inductive (fluoro) and/or resonance (nitro) effects on the π-stacking ability was further supported by LOLIPOP (localized orbital locator-integrated π over plane) analysis. The benzene ring of (II) demonstrated a higher π-stacking ability compared to that of (I), which is supported by the intrinsic planar geometry. The HOMA (harmonic oscillator model of aromaticity) index of (I) revealed more aromaticity with respect to (II), suggesting that NO2 greatly perturbed the aromaticity. The Hirshfeld fingerprint (FP) plots revealed the preference of (II) over (I) for π–π contacts, with contributions of 6.8 and 4.4%, respectively.

KW - Computational chemistry

KW - Crystal structure

KW - Hirshfeld surface analysis

KW - n-to-π

KW - Planarity

KW - Rhenium(I) complexes

KW - Supramolecular architectures

KW - Tubular column

KW - Weak interactions

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