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

摘要

The complexes of 2,11-dithia-4,5,6,7,8,9-hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [Cu2I2(dthhpcp)_2]-2H2O 1, or with Ag(I), 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 1 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(I) 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(1), a = 19.2982(11) A b = 16.5661(10) A, c = 25.3006(15) A, beta = 90°, Z= 8; complex 2, orthorhombic system, space group Pna2(J), a = 8.8595(6) A, b = 12.6901(9) A, c = 19.8449(14) A, beta = 90°, Z = 4; complex 3, monoclinic system, space group P2(1),a = 8.845(3) A, b = 20.841(6) A,c= 11.061(3)A, beta= 107.832(6)°, Z = 4.