Crystal structures of [(l2-L1)dibromidodicopper( II)] dibromide and poly[[(l2-L1)diiodidodicopper( I)]-di-l-iodido-dicopper(I)], where L1 is 2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane

The reaction of the hexathiapyrazinophane ligand, 2,5,8,11,14,17-hexathia- [9.9](2,6,3,5)-pyrazinophane (L1), with copper(II) dibromide led to the formation of a binuclear complex, [2-2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)- pyrazinophane]bis[bromidocopper(II)] dibromide, [Cu2Br2(C16H24N2S6)]Br2, (I). The complex possesses inversion symmetry with the pyrazine ring being situated about a center of symmetry. The ligand coordinates to the copper(II) atom in a bis-tetradentate manner and the copper atom has a fivefold NS3Br coordination environment with a distorted shape. The reaction of ligand L1 with copper(I) iodide also gave a binuclear complex, which is bridged by a Cu2I2 unit to form a two-dimensional coordination polymer, poly [[2-2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane]tetra-iodido-tetracopper(I)], [Cu4I4- (C16H24N2S6)]n, (II). The binuclear unit possesses inversion symmetry with the pyrazine ring being located about a center of symmetry. The Cu2I2 unit i s also located about an inversion center. The two independent copper(I) atoms are both fourfold coordinate. That coordinating to the ligand L1 in a bistridentatemanner has an NS2I coordination environment and an irregular shape, while the second copper(I) atom, where L1 coordinates in a bismonodentate manner, has an SI3 coordination environment with an almost perfect tetrahedral geometry. In the crystal of I, the cations and Br anions are linked by a number of C-HS and C-HBr hydrogen bonds, forming a supramolecular network. In the crystal of II, the two-dimensional coordination polymers lie parallel to the ab plane and there are no significant inter-layer contacts present.