Title of article :
Silver(I) nitrate two-dimensional coordination polymers of two new pyrazinethiophane ligands: 5,7-dihydro-1H,3H-dithieno[3,4-b:3′,4′-e]pyrazine and 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine
Author/Authors :
Assoumatine, Tokouré Institute of Chemistry - University of Neuchâtel, Switzerland , Stoeckli-Evans, Helen Institute of Physics - University of Neuchâtel, Switzerland
Abstract :
The two new pyrazineophanes, 5,7-dihydro-1H,3H-dithieno[3,4-b:3′,4′-e]pyrazine, C8H8N2S2, L1, and 3,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b:6′,7′-e]pyrazine, C12H16N2S4, L2, both crystallize with half a molecule in the asymmetric unit; the whole molecules are generated by inversion symmetry. The molecule of L1, which is planar (r.m.s. deviation = 0.008 Å), consists of two sulfur atoms linked by a rigid tetra-2,3,5,6-methylenepyrazine unit, forming planar five-membered rings. The molecule of L2 is step-shaped and consists of two S–CH2–CH2–S chains linked by the central rigid tetra-2,3,5,6-methylenepyrazine unit, forming eight-membered rings that have twist-boat-chair configurations. In the crystals of both compounds, there are no significant intermolecular interactions present. The reaction of L1 with silver nitrate leads to the formation of a two-dimensional coordination polymer, poly[(μ-5,7-dihydro-1H,3H-dithieno[3,4-b;3′,4′-e]pyrazine-κ2S:S′)(μ-nitrato-κ2O:O′)silver(I)], [Ag(NO3)(C8H8N2S2)]n, (I), with the nitrato anion bridging two equivalent silver atoms. The central pyrazine ring is situated about an inversion center and the silver atom lies on a twofold rotation axis that bisects the nitrato anion. The silver atom has a fourfold AgO2S2 coordination sphere with a distorted shape. The reaction of L2 with silver nitrate also leads to the formation of a two-dimensional coordination polymer, poly[μ33,4,8,10,11,13-hexahydro-1H,6H-bis([1,4]dithiocino)[6,7-b;6′,7′-e]pyrazine-κ3S:S′:S′′](nitrato-κO)silver(I)], [Ag(NO3)(C12H16N2S4)]n, (II), with the nitrate anion coordinating in a monodentate manner to the silver atom. The silver atom has a fourfold AgOS3 coordination sphere with a distorted shape. In the crystals of both complexes, the networks are linked by C—H⋯O hydrogen bonds, forming supramolecular frameworks. There are additional C—H⋯S contacts present in the supramolecular framework of II.
Keywords :
crystal structure , thio-substituted pyrazines , pyrazinethiophanes , ortho-bis-L regioisomer , silver(I) , nitrate , two-dimensional coordination polymers , supramolecular frameworks