The supramolecular architecture of arene complexes of bis(polyfluorophenyl) -mercurials

Glen B. Deacon, Craig M. Forsyth, Peter C. Junk, Timothy J. Ness, Ekaterina Izgorodina, Jens Baldamus, Gerd Meyer, Ingo Pantenburg, Julia Hitzbleck, Karin Ruhlandt

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Abstract

The 1:1 (arene)mercury complexes [HgR2(arene)] [R = C 6F4-o-NO2, C6F4-m-NO 2, C6F4-o-H, C6F5; arene = TMB (1,2,4,5-tetramethylbenzene), PMB (1,2,3,4,5-pentamethylbenzene)] are readily formed when mixtures of the mercurial and arene are crystallised from CH2Cl2 or CH2Cl2/hexane. Analogous 1:1 complexes are also formed from Hg(C6F5)2 and PhMe, whereas novel 1:2 complexes [HgR2(arene)2] result from Hg(C6F4-o-NO2)2 and PhMe or TMO (1,2,4-trimethoxybenzene) and from Hg(C6F5) 2 and TMO. In the crystalline state, the 1:1 [HgR2(arene)] complexes exist as canted columns of alternating planar HgR2 and arene layers linked by weak (Hg···C 3.2-3.5 Å) η1 or η2 π-arene-mercury interactions. For the TMB (R = C6F4-o-NO2, C6F 4-o-H, C6F5) and PhMe (R = C6F 5) complexes, the packing of neighbouring columns shows aligned, alternating fluoroarene and arene ring planes resulting in a 2D brick-wall motif with potential supramolecular components (fluoroarene-fluoroarene and fluoroarenearene stacking). For the TMB complex with R = C6F 4-m-NO2 the 2D array is distorted into a herringbone motif by weak C-H···O interactions. The 1:2 complex [Hg(C 6F4-o-NO2)2-(PhMe)2] has an analogous mercury environment to the 1:1 complexes, and the packing shows a distinct layer structure of alternating rows of PhMe and HgR2 with two PhMe units per HgR2 unit but with no inter-stack interactions. The TMO complexes have long Hg···O contacts (3.2 Å) rather than Hg···C and similarly show a layered structure, but in this case, with a single column of alternating HgR2 and pairs of TMO. Theoretical calculations for the 1:2 [HgR2(TMB)2] complexes (R = C6F4-o-NO2, C6F 4-m-NO2) are consistent with the findings from the observed crystal structures.

Original languageEnglish (US)
Pages (from-to)4770-4780
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number30
DOIs
StatePublished - Oct 2008

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Mercury
Hexanes
Brick
Crystal structure
Crystalline materials
durene
1,2,4-trimethoxybenzene

Keywords

  • Arene
  • Fluorocarbon
  • Mercury
  • Supramolecular

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

The supramolecular architecture of arene complexes of bis(polyfluorophenyl) -mercurials. / Deacon, Glen B.; Forsyth, Craig M.; Junk, Peter C.; Ness, Timothy J.; Izgorodina, Ekaterina; Baldamus, Jens; Meyer, Gerd; Pantenburg, Ingo; Hitzbleck, Julia; Ruhlandt, Karin.

In: European Journal of Inorganic Chemistry, No. 30, 10.2008, p. 4770-4780.

Research output: Contribution to journalArticle

Deacon, GB, Forsyth, CM, Junk, PC, Ness, TJ, Izgorodina, E, Baldamus, J, Meyer, G, Pantenburg, I, Hitzbleck, J & Ruhlandt, K 2008, 'The supramolecular architecture of arene complexes of bis(polyfluorophenyl) -mercurials', European Journal of Inorganic Chemistry, no. 30, pp. 4770-4780. https://doi.org/10.1002/ejic.200800615
Deacon, Glen B. ; Forsyth, Craig M. ; Junk, Peter C. ; Ness, Timothy J. ; Izgorodina, Ekaterina ; Baldamus, Jens ; Meyer, Gerd ; Pantenburg, Ingo ; Hitzbleck, Julia ; Ruhlandt, Karin. / The supramolecular architecture of arene complexes of bis(polyfluorophenyl) -mercurials. In: European Journal of Inorganic Chemistry. 2008 ; No. 30. pp. 4770-4780.
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abstract = "The 1:1 (arene)mercury complexes [HgR2(arene)] [R = C 6F4-o-NO2, C6F4-m-NO 2, C6F4-o-H, C6F5; arene = TMB (1,2,4,5-tetramethylbenzene), PMB (1,2,3,4,5-pentamethylbenzene)] are readily formed when mixtures of the mercurial and arene are crystallised from CH2Cl2 or CH2Cl2/hexane. Analogous 1:1 complexes are also formed from Hg(C6F5)2 and PhMe, whereas novel 1:2 complexes [HgR2(arene)2] result from Hg(C6F4-o-NO2)2 and PhMe or TMO (1,2,4-trimethoxybenzene) and from Hg(C6F5) 2 and TMO. In the crystalline state, the 1:1 [HgR2(arene)] complexes exist as canted columns of alternating planar HgR2 and arene layers linked by weak (Hg···C 3.2-3.5 {\AA}) η1 or η2 π-arene-mercury interactions. For the TMB (R = C6F4-o-NO2, C6F 4-o-H, C6F5) and PhMe (R = C6F 5) complexes, the packing of neighbouring columns shows aligned, alternating fluoroarene and arene ring planes resulting in a 2D brick-wall motif with potential supramolecular components (fluoroarene-fluoroarene and fluoroarenearene stacking). For the TMB complex with R = C6F 4-m-NO2 the 2D array is distorted into a herringbone motif by weak C-H···O interactions. The 1:2 complex [Hg(C 6F4-o-NO2)2-(PhMe)2] has an analogous mercury environment to the 1:1 complexes, and the packing shows a distinct layer structure of alternating rows of PhMe and HgR2 with two PhMe units per HgR2 unit but with no inter-stack interactions. The TMO complexes have long Hg···O contacts (3.2 {\AA}) rather than Hg···C and similarly show a layered structure, but in this case, with a single column of alternating HgR2 and pairs of TMO. Theoretical calculations for the 1:2 [HgR2(TMB)2] complexes (R = C6F4-o-NO2, C6F 4-m-NO2) are consistent with the findings from the observed crystal structures.",
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T1 - The supramolecular architecture of arene complexes of bis(polyfluorophenyl) -mercurials

AU - Deacon, Glen B.

AU - Forsyth, Craig M.

AU - Junk, Peter C.

AU - Ness, Timothy J.

AU - Izgorodina, Ekaterina

AU - Baldamus, Jens

AU - Meyer, Gerd

AU - Pantenburg, Ingo

AU - Hitzbleck, Julia

AU - Ruhlandt, Karin

PY - 2008/10

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N2 - The 1:1 (arene)mercury complexes [HgR2(arene)] [R = C 6F4-o-NO2, C6F4-m-NO 2, C6F4-o-H, C6F5; arene = TMB (1,2,4,5-tetramethylbenzene), PMB (1,2,3,4,5-pentamethylbenzene)] are readily formed when mixtures of the mercurial and arene are crystallised from CH2Cl2 or CH2Cl2/hexane. Analogous 1:1 complexes are also formed from Hg(C6F5)2 and PhMe, whereas novel 1:2 complexes [HgR2(arene)2] result from Hg(C6F4-o-NO2)2 and PhMe or TMO (1,2,4-trimethoxybenzene) and from Hg(C6F5) 2 and TMO. In the crystalline state, the 1:1 [HgR2(arene)] complexes exist as canted columns of alternating planar HgR2 and arene layers linked by weak (Hg···C 3.2-3.5 Å) η1 or η2 π-arene-mercury interactions. For the TMB (R = C6F4-o-NO2, C6F 4-o-H, C6F5) and PhMe (R = C6F 5) complexes, the packing of neighbouring columns shows aligned, alternating fluoroarene and arene ring planes resulting in a 2D brick-wall motif with potential supramolecular components (fluoroarene-fluoroarene and fluoroarenearene stacking). For the TMB complex with R = C6F 4-m-NO2 the 2D array is distorted into a herringbone motif by weak C-H···O interactions. The 1:2 complex [Hg(C 6F4-o-NO2)2-(PhMe)2] has an analogous mercury environment to the 1:1 complexes, and the packing shows a distinct layer structure of alternating rows of PhMe and HgR2 with two PhMe units per HgR2 unit but with no inter-stack interactions. The TMO complexes have long Hg···O contacts (3.2 Å) rather than Hg···C and similarly show a layered structure, but in this case, with a single column of alternating HgR2 and pairs of TMO. Theoretical calculations for the 1:2 [HgR2(TMB)2] complexes (R = C6F4-o-NO2, C6F 4-m-NO2) are consistent with the findings from the observed crystal structures.

AB - The 1:1 (arene)mercury complexes [HgR2(arene)] [R = C 6F4-o-NO2, C6F4-m-NO 2, C6F4-o-H, C6F5; arene = TMB (1,2,4,5-tetramethylbenzene), PMB (1,2,3,4,5-pentamethylbenzene)] are readily formed when mixtures of the mercurial and arene are crystallised from CH2Cl2 or CH2Cl2/hexane. Analogous 1:1 complexes are also formed from Hg(C6F5)2 and PhMe, whereas novel 1:2 complexes [HgR2(arene)2] result from Hg(C6F4-o-NO2)2 and PhMe or TMO (1,2,4-trimethoxybenzene) and from Hg(C6F5) 2 and TMO. In the crystalline state, the 1:1 [HgR2(arene)] complexes exist as canted columns of alternating planar HgR2 and arene layers linked by weak (Hg···C 3.2-3.5 Å) η1 or η2 π-arene-mercury interactions. For the TMB (R = C6F4-o-NO2, C6F 4-o-H, C6F5) and PhMe (R = C6F 5) complexes, the packing of neighbouring columns shows aligned, alternating fluoroarene and arene ring planes resulting in a 2D brick-wall motif with potential supramolecular components (fluoroarene-fluoroarene and fluoroarenearene stacking). For the TMB complex with R = C6F 4-m-NO2 the 2D array is distorted into a herringbone motif by weak C-H···O interactions. The 1:2 complex [Hg(C 6F4-o-NO2)2-(PhMe)2] has an analogous mercury environment to the 1:1 complexes, and the packing shows a distinct layer structure of alternating rows of PhMe and HgR2 with two PhMe units per HgR2 unit but with no inter-stack interactions. The TMO complexes have long Hg···O contacts (3.2 Å) rather than Hg···C and similarly show a layered structure, but in this case, with a single column of alternating HgR2 and pairs of TMO. Theoretical calculations for the 1:2 [HgR2(TMB)2] complexes (R = C6F4-o-NO2, C6F 4-m-NO2) are consistent with the findings from the observed crystal structures.

KW - Arene

KW - Fluorocarbon

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