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Coordination chemistry of anticrowns: Complexation of cyclic trimeric perfluoro-o-phenylenemercury with nitro compounds

“…3.254 (5) Hg(1)-C(1) 2.075(6) Hg(2)-O (1) 2.953 (5) Hg (1)-C (14) 2.062 (6) Hg (3)-O(2) 2.858 (6) Hg(2)-C(2) 2.080(7) N(1)-O (1) 1.235 (7) Hg(2)-C (7) 2.076 (6) (1) 1.453 (8) Hg(3)-C (13) 2.078 (7) C(1)-Hg (1) 119.8 (6) the centroids of the Hg 3 C 6 macrocyclic units onto the plane parallel to these units are shifted with respect to one another by 3.00 Å . The mutual orientation of the neighbouring macrocycles in the dimers corresponds to an eclipsed conformation.…”

“…The formation of cofacial dimers was also observed earlier in the crystal packing of the pyramidal 1:1 complex of 1 with n-butyronitrile (HgÁ Á ÁHg 3.372 and 3.512 Å , HgÁ Á ÁC 3.58 and 3.59 Å ). These dimers are linked in the crystal with each other through additional shortened HgÁ Á ÁF contacts (3.28 and 3.44 Å ) as well [10]. The pyramidal 1:1 complex of 1 with acetone is also associated in the crystal into cofacial dimers due to shortened intermolecular HgÁ Á ÁHg (3.512 Å ) and HgÁ Á ÁC (3.402 and 3.483 Å ) contacts [11].…”

“…Hg (1) (1) 3.345 (5) Hg(1)-C(1) 2.071(6) Hg(3A)-O(2) a 3.075 (5) Hg(1)-C (14) 2.075(6) Hg(2)- C(19) 3.304 (7) Hg(2)-C(2) 2.083(6) Hg(2)- C(20) 3.193 (7) Hg(2)-C (7) 2.082 (6) (1) 1.220 (7) Hg(3)-C (13) 2.071 (6) C (1) (6) a Symmetry transformation 1 + x, y, z was used to generate equivalent atoms. Fig.…”

“…Finally, in the 1:3 complex of 1 with 1-nitropyrene, the NO 2 group in all three nitroarene ligands behaves as a monodentate Lewis base and is coordinated only to one Lewis acidic Hg site of 1. Note, in the previously described 1:3 complexes of 1 with DMSO [13], ethyl acetate [2a,2c,13] and acetone [2d], two of three Lewis basic species are cooperatively coordinated by all mercury centres of 1, forming the corresponding bipyramidal fragment. A characteristic structural feature of complexes 4 and 6 is also the mutually parallel arrangement of 1 and the aromatic rings of the nitroarene units as well as the presence of shortened Hg-C contacts between the Hg sites of 1 and the carbon atoms of the nitro derivative.…”

“…As part of our ongoing research into binding and catalytic properties of anticrowns, we have previously described a series of complexes of cyclic trimeric perfluoro-o-phenylenemercury 3 (1), containing three Hg atoms in a planar nine-membered ring [4], with different anionic species (Cl À , Br À , I À , SCN À , closo-[B 10 [2a,2c,3k]. The ability of 1 to coordinate neutral Lewis bases such as nitriles [2a,2c], carbonyl compounds [2a,2c,2d,3c], arenes [2d,3n], metallocenes [3i,3j], azulene [3a], 6-(N,N-dimethylamino) pentafulvene [3a], polyynes [3b], dimethyl sulfide [3o] and some others has also been established.…”