Deacon, Glen B., Forsyth, Craig M., Junk, Peter C., Ness, Timothy J., Izgorodina, Ekaterina, Baldamus, Jens, Meyer, Gerd, Pantenburg, Ingo, Hitzbleck, Julia, and Ruhlandt-Senge, Karin (2008) The supramolecular architecture of arene complexes of bis(polyfluorophenyl)mercurials. European Journal of Inorganic Chemistry, 2008 (30). pp. 4770-4780.

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Abstract

The 1:1 (arene)mercury complexes [HgR2(arene)] [R = C6F4-o-NO2, C6F4-m-NO2, 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 center dot center dot center dot C 3.2-3.5 angstrom) eta(1) or eta(2) pi-arene-mercury interactions. For the TMB (R = C6F4-o-NO2, C6F4-o-H, C6F5) and PhMe (R = C6F5) 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 fluoroarene-arene stacking). For the TMB complex with R = C6F4-m-NO2 the 2D array is distorted into a herringbone motif by weak C-H center dot center dot center dot O interactions. The 1:2 complex [Hg(C6F4-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 center dot center dot center dot O contacts (3.2 angstrom.) rather than Hg center dot center dot center dot 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, C6F4-m-NO2) are consistent with the findings from the observed crystal structures.

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