Synthesis and structural study of Copper(I) or Silver(I) complexes of 2,11-dithia-4,5,6,7,8,9-hexahydro[3.3]paracyclophanes

The complexes of 2,1 1-dithia-4,5,6,7,8,9-hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [CU2I2(dthhpcp)2]center dot 2H(2)O1, or with Ag(l), i.e. [Ag(dthhpcp)(NO3)]center dot thf 2 and [Ag(dthpcp)(CF3COO)] 3, were prepared for structural study by single-crystal X-ray diffraction analysis. For these three complexes, dthhpcp serves as a bridging group in the polymeric structure through bridging sulfur atoms via metal, while the bonding of anion with the second metal atom forms the multi-diminished structures. Complex I is a novel two-dimensional coordination polymer composed of Cu-6 motifs, in which Cu2I2 formed a square planar unit to link the dthhpcp molecule. The two oxygen atoms of the nitrate anion as a bridge for two Ag atoms in complex 2 provides a three-dimensional channel framework of silver(l) with a tetrahydrofuran molecule as a guest inside the open cavities. In contrast, the analogous reaction with silver triflouroacetate gave a complex 3, which is composed of infinite linear chains of -Ag-dthhpcp-Ag-dthhpcp- along the a axis. Unit cell data: complex 1, orthorhombic system, space group P2(1)2(1)2(l), a = 19.2982(l 1) A b = 16.5661 (10) A, c = 25.3006(15) A, = 90 degrees, Z = 8; complex 2, orthorhombic system, space group Pna2(l), a = 8.8595(6) A, b = 12.6901(9) A, c 19.8449(14) A, P = 90 degrees, Z = 4; complex 3, monoclinic system, space group P2(1)/n, a = 8.845(3) A, b 20.841(6) A, c = 11.061(3) A, P = 107.832(6)0, Z= 4.