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 language | English |
|---|---|
| Pages (from-to) | 997-1006 |
| Number of pages | 10 |
| Journal | Acta Crystallographica Section C: Structural Chemistry |
| Volume | 74 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - 1 Sep 2018 |
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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 journal › Article
}
TY - JOUR
T1 - Supramolecular structures of rhenium(I) complexes mediated by ligand planarity via the interplay of substituents
AU - Mark-Lee, Wun Fui
AU - Chong, Yan Yi
AU - Kassim, Mohammad
PY - 2018/9/1
Y1 - 2018/9/1
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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U2 - 10.1107/S2053229618010586
DO - 10.1107/S2053229618010586
M3 - Article
VL - 74
SP - 997
EP - 1006
JO - Acta crystallographica. Section C, Structural chemistry
JF - Acta crystallographica. Section C, Structural chemistry
SN - 2053-2296
IS - 9
ER -